Chinese Journal of Chemical Engineering 28 (2020) 1995–2009

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Chinese Journal of Chemical Engineering

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Review

Emerging applications of nanomaterials in chemical enhanced oil

recovery: Progress and perspective
Najeebullah Lashari 1,2,⁎, Tarek Ganat 1
1
Department of Petroleum Engineering, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia
2
Department of Petroleum and Gas Engineering, Dawood University of Engineering & Technology, M.A Jinnah Road, Karachi-74800, Pakistan

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

Article history: In enhanced oil recovery, different chemical methods utilization improves hydrocarbon recovery due to their fas-
Received 14 April 2020 cinating abilities to alter some critical parameters in porous media, such as mobility control, the interaction be-
Received in revised form 14 May 2020 tween fluid to fluid, and fluid to rock surface. For decades the use of surfactant and polymer flooding has been
Accepted 17 May 2020
used as tertiary recovery methods. In the current research, the inclusion of nanomaterials in enhanced oil recov-
Available online 24 May 2020
ery injection fluids solely or in the presence of other chemicals has got colossal interest. The emphasis of this re-
Keywords:
view is on the applicability of nanofluids in the chemical enhanced oil recovery. The responsible mechanisms are
Chemical enhanced oil recovery an increment in the viscosity of injection fluid, decrement in oil viscosity, reduction in interfacial and surface ten-
Mechanisms sion, and alteration of wettability in the rock formation. In this review, important parameters are presented,
Nanoparticles which may affect the desired behavior of nanoparticles, and the drawbacks of nanofluid and polymer flooding
Polymeric and the need for a combination of nanoparticles with the polymer are discussed. Due to the lack of literature
Nanofluids in defining the mechanism of nanofluid in a reservoir, this paper covers majorly all the previous work done on
the application of nanoparticles in chemical enhanced oil recovery at home conditions. Finally, the problems as-
sociated with the nano-enhanced oil recovery are outlined, and the research gap is identified, which must be ad-
dressed to implement polymeric nanofluids in chemical enhanced oil recovery.
© 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd.
All rights reserved.

1. Introduction The most common polymer used in CEOR is HPAM (partially

Hydrocarbon is the primary source of energy for humankind and is
perceived to be a primary energy source in the near future [1]. Majorly,
the petroleum fields are in the declining phase, as it is estimated that ap-
proximately 60% to 70% of total oil remains in the reservoir by
employing conventional hydrocarbon (HCS) recovery techniques [2].
It is vital to maintain the recovery of HCS and exploit new reservoirs
to cope with the increasing demand for energy. Therefore, the use of
HCS recovery techniques is foreseeably essential. In Enhanced Oil Re-
covery (EOR), the different methods are available such as thermal,
chemical, and gas injection. Among these methods, the application of
the polymer flooding a chemical enhanced oil recovery (CEOR) method
has received prior attention due to its higher efficiency, lower capital
expenses, and techno-economic feasibility [3–5].
In CEOR, different additives are used to increase HCS, specifically
in polymer flooding different polymers (natural as well as synthetic
polymers) have been proposed according to their application, and
among these synthetic polymers are derivatives of polyacrylamides.
⁎ Corresponding author at: Department of Petroleum Engineering, Universiti Teknologi
PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia.
E-mail address: najeeb_17007123@utp.edu.my (N. Lashari).
hydrolyzed polyacrylamide) due to its cost, availability, and easy
handling [6]. Generally, the HPAM performance relies on its degree
of hydrolysis (DOH) and molecular weight (MW). A shown in
Fig. 1. During hydrolysis, the (CONH2) amide groups transform into
(COO-) carboxyl group.
Numerous projects due to insufficient reservoir data or unclear
problems with polymer system failed in past, but in these recent
years, the synthesis of novel polymers have got much attention and ex-
tensive laboratory and field test have been carried out. Howsoever the
limitations with available polymers such as chemical degradation, ther-
mal change, and chemical behavior of polymer rheology are challenges
to cope. The most common polymer HPAM is also prone to high temper-
atures and high saline environments [7–9]. The HPAM is prone to shear
degradation and temperature resistance in practical applications. In the
CEOR application, the HPAM in saline conditions can be used up to 70 °C
[7,10,11]. Despite the fact several approaches have been presented to
improve the performance of polymer flooding, the application of
nanomaterials in the enhancement of the rheological characteristics of
polymer aqueous solution in EOR is still an ongoing subject.
The recent advancements in the field of nanotechnology give direc-
tion in introducing new and advanced technologies that are more effec-
tive and environment friendly. In a broader scope, nanotechnology is

https://doi.org/10.1016/j.cjche.2020.05.019
1004-9541/© 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
1996 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009
the field of applied engineering whose studies are on the molecular and
atomic scale (100 or smaller nm) [12–15]. The nanometer is equivalent
to the billionth part of a meter, as one molecule of water is one-tenth the
nanometer size (Fig. 2). Nanotechnology is the interaction, control, and
manipulation of atoms to formulate different systems, materials, com-
ponents, and structures of a nanoscale [16].
The behavior of material changes due to change in size as material
shrinks to nanoscale the quantum effect and high surface to volume
ratio of nanoparticles (NP) alters the characteristic of material like melting
point, chemical reactivity, electrical conductivity, mechanical strength
and fluorescence color as gold NP at nanoscale instead of yellow, their
color becomes red to purple [17]. The nanofluid is a solution containing
NP with specific characterizations in colloidal suspension form. This mul-
tiphase fluid system having different components changes the character-
istics of the base fluid. The Brownian motion is responsible for the random
path flow of nanofluid molecules in the fluid system. The main quintes-
sential issues with nanofluid are its stability in the solution as being so
small in dimensions and so light in mass that they could remain in sus-
pension in the base fluid [18]. The other forces may alter the stability of
nanofluids like surface charges of NP and van der Waals forces [12].
Moon et al. [19] examined the stability of NP; the total value of attractive
as well as repulsive (van der Waal) forces states the nanofluid stability.
According to results obtained, if van der Waals forces are more significant
than of those attractive forces, the NP in nanofluid will remain stable
without any agglomeration. The value of zeta potential and charge den-
sity controls the stability of nanofluid [20].
Moreover, the use of NP in the petroleum sector has only been uti-
lized for the last few years, as Fig. 3 states the trend of SPE papers
discussing nanotechnology (Data for 2017–2019 obtained from
Onepetro) [21]. In the past few years, different studies have proven
the enthralling results of nanofluid application in improving the perfor-
mance of injectant fluids to enhance oil recovery. Current research in
nanotechnology has shown that we can control rheology and enhance
HCS recovery by adding NP in polymer flooding [22,23]. Several exper-
iments have been carried out by researchers by using various nano-
assisted polymer flooding for crude oil recovery like (ZnO2, SiO2 assisted
polymer flooding, clay nano-polymer, Fe3O4 nano-polymer flooding)
the recovery rates for every NP vary depending on the number of as-
pects like reservoir oil composition, reservoir conditions, the salinity
of reservoir, composition, and concentration of injecting fluid, etc. The
Fig. 1. Chemical structure of polymer HPAM.
application of NP in enhancing the viscosity and stability of HPAM solu-
tions is recently reported [24].
The current research has demonstrated that NP have a positive effect
on EOR [26–28]. NP can enhance mobility control and improve the stabil-
ity of emulsion in EOR processes. The NP, as an EOR agent, tend to reduce
interfacial tension (IFT) and change the wettability of rock media [29]. The
parameters like size, concentration, composition affect the performance
of NP, for that different types of NP have been considered when used as
injectant fluids. The effect of these NP has become an essential measure
for improved and stable oil production in reservoirs [30,31].
Most of the review articles in this field have focused on common ap-
plications of nanotechnology and not focused on systematic mecha-
nisms of Nano-CEOR. The main objective of this article is to identify
the mechanism and potential of NP in CEOR and to asses and review
current advancements. Firstly, we discuss the performance and draw-
backs of NP with related processes based on previous research pub-
lished. Secondly, we investigate the mechanisms of NP influencing
CEOR and finally, the significant results from peer research on utilizing
NP in CEOR till date are summarized.
2. Applicability of Nanoparticles in Enhanced Oil Recovery
Nanotechnology provides a novel approach in controlling petroleum
recovery processes. Through NP, the recovery of HCS improves by im-
proving geo-mechanism of reservoir resulted due to modifications in
reservoir characteristics. NP have unique characteristics that can be
used to get the desired results [32]. These properties are reactivity of
chemicals, active surfaces, and higher specific area. NP significantly in-
crease HCS recovery employing different properties listed in Table 1.
In literature, several experimental studies have been carried out on
nano flooding in the last few decades. Most of the research work in
this area highlights nanofluid flooding. The given Table 2 report's exper-
imental research carried out on nanofluid flooding. The number of NP
like silica, graphene, carbon nanotubes (CNT), alumina, titanium, and
many more showed improved results in oil recovery.
NP has unique properties with various effects in different conditions
in porous media and fluids. Different NP and their interaction with poly-
mer are discussed. Silica NP has widely been used in flooding due to its
availability and physio-chemical properties, with specific characteristics
 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009 1997

Fig. 2. Nanoscale margin differentiated based on different materials and measuring techniques.

(hydrophobic to hydrophilic). Theoretical and experimental studies car-
ried by Ju et al. [42] stated about hydrophilic silica NP for EOR, the con-
centration of 2.0% to 3.0% of silica NP injected in core flooding, in
conclusion, the NP may adsorb on to rock interface altering the wettabil-
ity of rock surface and improving HCS recovery factor. The polymer
nanocomposite for CEOR was also studied. The dispersion of silica NP
in the polymer (polyacrylamide) was carried out by Maghzi et al. [22].
The experiment was conducted in glass micromodel to analyze
rheological characteristics of a mixture (PAM (Polyacrylamide) and sil-
ica NP), the pseudoplastic behavior of polymer was improved by adding
0.1 wt% of silica NP ultimately improving the viscosity of the fluid; as a
result, additional recovery of 10% is noticed. Giraldo et al. [43] studies
examined the coating mechanism of Aluminum oxide based NP through
which it can change sandstone core wettability from oil-wetness to
water-wetness, as shown in Fig. 4. Sharma et al. [44] formed a combina-
tion of silica NP, polymer, and surfactant and after flooding concluded

1400

1200
Number of SPE Publications

1000

800

600

400

200

0
1992-1994 1995-1996 1997-2000 2001-2004 2005-2008 2009-2012 2013-2016 2017-2019
Year

Fig. 3. Number of SPE publications based on nanotechnology. Data obtained from [21,25]
1998 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009

Table 1 mobility is about 140 times the silicon mobility, which is 2

Properties of nanoparticles to improve hydrocarbon recovery
Altering viscosity and density of the fluid
Fluid Properties Reducing IFT
Emulsion formation
Altering Conductivity and specific heat
Rock Properties Modifying rock and oil interactions
Modifying wettability
that NP could lower IFT and stabilize emulsion in result getting addi-
tional recovery of more than 20% compared to conventional SP flooding.
The rise in temperature reduces the efficiency of both traditional as well
as surfactant polymer flood, but in contrast, the mixture of nanofluid
shows stable behavior at raised temperature, resulting in to be an effec-
tive solution for high-temperature EOR techniques.
Aluminum oxide also reduces IFT but not necessarily gives higher
recovery rates alone other factors like sweep efficiency and rheolog-
ical properties also play a part in improving HCS recovery. Several
metallic NP have been studied by Harun et al. [45] like NiO, CuO,
and Fe2O3 on carbonate cores. The results obtained from experimen-
tation showed that Fe2O3 NP did not improve recovery factor up to
mark only reaching up to 57% ultimate recovery of oil; on another
hand, NiO and CuO were able to achieve up to 85%. Similar to other
metallic NP NiO is no exception for EOR, but due to its ability to
alter rock wettability and viscosity enhancement, NiO is proved to
be a positive NP agent in EOR [46].
CNT is a cylindrical carbon-based structure in the range of nano size.
The two major CNT's have been studied extensively, which are single-
walled and multi-walled carbon nanotubes. In flooding experiments in
Berea cores and sand packs carried out by Kadhum et al. [47] with the
help of MWCNT resulted in stable dispersion and propagation of NP at
high temperature high salinity (HTHS) conditions achieving more than
80% NP effluent after HCS recovery.
Graphene, among other materials, has appeared as a focus point by
many researchers due to its exceptional thermal and mechanical prop-
erties and have a high surface area [48–50]. These single-layer atomic
thin carbon sheets, when incorporated carefully, may enhance proper-
ties of host polymers at even low concentration. Graphitic carbon NP
are members of a similar group due to their sp2 carbon atom arrange-
ment in hexagonal structure [51]. Graphene is a carbon allotrope in
2D structure, a hexagonal lattice of sp2 hybridization, having a common
structure show some similar properties, but due to different shapes and
sizes, their behavior differs in different conditions as shown in Fig. 5. The
elementary structure of all other allotropes is graphene, including CNT,
graphite, fullerene, and other related elements (charcoal, carbon fiber,
amorphous carbon) [52].
Generally, graphene is a combination of closely packed carbon atoms
of a single layer, resulting in a 2D honeycomb lattice plane. The bonding
of surrounding carbons forms a benzene ring of sp2 hybridization with
each atom denoting an unpaired electron. So far, at room temperature,
the most conductive material is graphene having conductivity and resis-
tance of 106 S·m−1 and 31 Ω·sq.−1 respectively [54]. Graphene's
× 105 cm2·V−1 ⋅s-1[55]. Graphene also has very high mechanical
strength and thermal conductivity and the hardest and robust crystal
structure, among other materials. Elastic modulus of graphene is
1.1 TPa, and its tensile strength is 125 GPa; similarly, the strength
limit of graphene is much higher, which is 42 N·m−1 (100 times the
steel's strength) [56]. The graphene's specific surface area and thermal
conductivity are about 2630 m2·g−1 and 5 × 103 W·m-1·K-1, respec-
tively thermal conductivity being much higher than that of copper,
which is (401 W·m-1·K-1) [57]. Graphene is a multifunctional rein-
forced material which can improve mechanical, chemical, and thermal
properties when added to polymer even at very low concentration
[58]. Graphene oxide (GO) is a quasi-two-dimensional layered structure
organic matter, and the GO layer contains hydroxyl, carboxyl, and epoxy
groups [59]. These functional groups make GO easy to absorb sex mole-
cules, and polymers form a complex with their physicochemical
interaction's materials, which in turn improves the properties of the
material. The GO structure possesses mixed sp2- sp3- hybridized car-
bons. GO is hydrophilic, having excellent stability in water. Instead of
surfactant, the GO is used as a surface-active agent that can reduce oil-
water contact (O/W) IFT, and can also interact with rock, altering its
wettability [60].
To improve the stability of NP, different polymers are being used as
coating material or stabilizers [61]. NP comprised of at least a single
polymer as a component are considered as polymeric nanofluids [30].
The two general methods are available in the literature regarding the
formulation and synthesis of polymeric nanofluid. In polymer nano
grafting (PNG), the polymers are grafted to or from NP, different pro-
cesses for polymer grafting are solvent evaporation, dialysis, and poly-
merization of monomers. On the other hand, polymer nanosuspension
(PNS) is formed by mixing the polymer with NP to form a solution.
These polymeric nanofluids formed tend to increase the mobility of oil
and alteration of wet rock surface during the EOR process [62].
In summary, the number of NP through different mechanisms has
proven to be an attractive EOR agent like SiO, Al, TiO, ZnO. Howsoever
other NP like FeO, ZrO, NiO have relatively given decent outcomes in
the sense of improving the recovery rate of oil. Among all these NP,
the graphene and its allotropes (CNT) have given better results at very
low concentrations. Therefore, there is a massive gap in combining sev-
eral NP with different polymers to uncover the potential and extend the
behavioral understanding of their mechanisms.
3. Multidimensional Nanoparticle for Enhanced Oil Recovery
In experimental studies, the use of various dimensional NP for oil re-
covery has been carried out. SiO2, among other zero-dimensional NP,
has been utilized to improve recovery factor (RF) of oil. Given Table 3 il-
lustrates various dimensional materials used in EOR flooding. In a one-
dimensional category number of nanomaterials has been used like car-
bon nanofiber and carbon nanotubes for incremental oil recovery.
Change in the geometrical structure of the particle can significantly
alter the emulsion properties like reducing IFT, stabilization of emulsion,

Table 2
Different nanoparticles utilized an EOR agent to recover remaining oil in place

NP Type Concentration /wt% Additional Oil Recovery Factor /% Fluids Porous Media Reference

Silica 0.1–3 19 Brine Water Sandstone rock Micromodel [33]

Nano Clay 0.1–1 5 Brine Water Sandstone Core [19]
Carbon Nanotubes 0.01–0.1 31 Nanofluid Glass beads [34]
Iron Oxide 0–0.64 28 Brine Water Glass beads [35]
Titanium Dioxide 2–2.5 4.2 Water Glass micromodel [36]
Graphene Nanosheets 0.005–0.01 15.2 Brine Water Sandstone Core [37]
Ferric oxide Chitosan 0.01–0.03 10.8 Sea Water Carbonate sand Packs [38]
Zinc Oxide 0.1 10.4 Brine Water Sand Packs [39]
Multi-Walled Carbon Nanotubes 0.1–0.3 18.5 Nanofluid Glass beads [40]
Silica / Graphene 0.01–0.1 14 Brine Water Glass micromodel [41]
 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009 1999

Fig. 4. Wettability alteration at a concentration of 100 ×10-6 of Al2O3. The figure was obtained from [43].

change in the wettability which is very important for flooding at reser-
voir conditions [63]. Simulation and numerical studies state that two-
dimensional materials are more favorable for emulsion stabilization
compared to zero- and one-dimensional material [64].
4. Performance of Nanoparticles in EOR Processes
NP behavior and performance rely on different factors such as their
size selection, the concentration of NP and, the environment in which
utilized. The following parameters play an essential part in NP
performance.
4.1. Nanoparticles concentration
NP concentration plays a critical role in the EOR process. By increas-
ing the concentration of NP, disjoining pressure tends to increase leads
to increased repulsive forces. Displacement efficiency also improves by
increasing concentration due to enhanced NP viscosity. Reduction in IFT
in reservoir fluids and high wettability alteration at rock surface can also
be achieved by increasing concentration [74]. Based on these observa-
tions, a higher concentration is promising in improving recovery rates.
Despite these results, the NP concentration has limitations, and if
injected above defined criteria, NP tends to block the rock pores and ul-
timately reduce the recovery of oil. When concentration is too high, NP
tends to coagulate, and agglomerate and this phenomenon chokes the
pore throats due to the accumulation of NP around inlet and results in
poor displacement efficiency [75].
surface. It concludes that an increase in salinity seems to enhance NP ad-
sorption on rock interface, ultimately increasing HCS recovery.
4.3. Temperature
The effect of temperature is ambiguous and hard to explain since it
involves different variables. Like temperature have a negative impact
on zeta potential by increasing temperature, the zeta potential of parti-
cle tends to decrease; due to which, instability of NP is observed, which
results in reduced oil recovery due to NP agglomeration [20]. At high
temperature, the reduction in IFT can improve oil recovery due to in-
creased Brownian motion or weak molecular interaction [77]. Abdullahi
et al. [78] studied the impact of NP types along with HPAM aqueous so-
lution viscosity at HTHS conditions and concluded that by adding NP in
polymer, the solution viscosity loss was controlled by the interaction of
NP with cations and improving molecular repulsion of polymer ulti-
mately controlling viscosity loss. The effect of temperature is dual in na-
ture, impacting both the reservoir systems as well as nanofluids.
Therefore, the temperature effect on HCS recovery cannot be general-
ized. Further studies in this aspect are required to understand the role
of temperature on different processes better.

4.2. Salinity

There are numerous ways of representing salinity, commonly

expressed as TDS (Total dissolved solid). As NaCl being the most com-
mon salt present in saline water, we usually take mass content of NaCl
as the salinity (represented in wt% or ×10-6). The stability of NP disper-
sion is significantly affected by salinity in reservoir fluids. Increment in
salinity causes a reduction in the zeta potential of NP, resulting in ag-
glomeration of particles [20]. According to Hedraningrat et al. [75], by
injecting stable silica, it can change the rock formation wettability to
medium or partially water-wet. Due to enhanced physicochemical in-
teraction, the adsorption of NP is noticed high in saline conditions.
Khadum et al. [71] studied SWCNT and MWCNT in high brine concen-
trations, by addition of different polymers, the dispersion and suspen-
sion of NP improved and gave improved recovery of oil. Likewise, the
research carried out by Kanj et al. [76] concludes that salinity increment
doesn't affect NP transport instead increases adsorption on a rock Fig. 5. Graphene Structure. The figure obtained from [53].
2000 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009

Table 3
Categories of nanoparticles used in EOR

Dimension Nanomaterial Reference

Zero [46] [65] [66]

SiO2, Al2O3, Mg2O3, TiO2
dimensional [67] [68]
One Carbon nanotubes, Cotton nanofibers, Bacterial
[69] [70] [71]
dimensional cellulose nanocrystals
Two Graphene, Graphene oxide, Reduced graphene, [37] [60] [72]
dimensional fluorographene [73]

5. Drawbacks of Nanofluid and Polymer in Chemical Enhanced Oil

Recovery

The high molecular weight polymers are mixed with the base fluid
(injection water), resulting in a higher viscosity of the injected fluid, fi-
nally improving the recovery of remaining oil in place. The by-passed oil
recovery is possible due to improved mobility ratio (Mr), while the
polymers viscoelastic behavior recovers residual oil from the reservoir
[79], but these polymers cannot sustain its properties in HTHS environ-
ment [80] [81]. The carboxylate groups in the polymer chain are
surrounded by salt (Na + cations) in the saline environment shielding
the charge, in result reducing carboxylate groups, increasing the thin-
ness of the electric double layer on the polymer backbone, ultimately re-
ducing thing viscosity of the polymer. The occurrence of Mg2+ and Ca2+
will further reduce the viscosity of polymer result in precipitating poly-
mer from solution [82]. At high reservoir temperature, the degree of hy-
drolysis of polymer increases, which is not favorable because polymers
usually in such conditions precipitate due to the charge effect of divalent
ions [83]. By observing inverse conditions where no precipitation takes
place, cations actively interact with the carboxyl group of polymers
resulting in a reduction of viscosity. High DOH is due to a high temper-
ature causing variations in rheological behavior, and characteristics of
the polymeric system in result causing phase separation [81]. Due to
this phase separation, the pores of fluid flow are blocked, ultimately re-
ducing the efficiency of polymer flooding in CEOR.
NP has been used in EOR for decades; the use of NP in saline con-
ditions and solvents has been experimented and presented as a via-
ble solution to problems faced by conventional CEOR techniques like
polymer flooding. Nonetheless, when NP goes under high tempera-
ture, and high saline conditions they use to agglomerate and aggre-
gate due to their smaller size as there attraction to each other is
stronger [30] [84]. Due to this mobility ratio is affected, and as a re-
sult, the required surface functionality at the rock-oil interface is
Fig. 7. Wedge-film enclosing nanoparticles showing in the structural disjoining pressure
gradient at the wedge apex. The figure was obtained from [25].
not achieved. This separation of NP from injection fluid eventually
leads to blockage of pore channels [85]. To overcome the problems
discussed above and to improve the efficiency of the CEOR technique,
researchers have incorporated both polymer as well as NP to formu-
late highly efficient and more stable injection fluid. With several ex-
perimental results, researchers have proposed that with optimum
concentration of polymer and nanomaterial novel, polymeric
nanofluid can be formed having improved characteristics, thermal
properties, and saline tolerance behavior if compared to individual
NP or polymer [86,87]. At high temperature, the negative charge on
rock surface increases, which repels ionic polymers to adsorb,
whereas the presence of NP in polymer further promotes in reducing
adsorption and mechanical entrapment due to the smaller size of NP.
The polymeric nanofluid governs several forces relying, on solution
conditions, and it carries properties of NP present in the fluid. The
product of NP and polymer forms different fluid, having different
electrical, magnetic, thermal, mechanical and rheological fluid char-
acteristics, which improves the recovery rate of oil from the reservoir
[30]. Generally, synthesis and formulation of polymeric nanofluid is
carried out by two methods defined earlier, in the first method the
synthesis is carried out by chemical grafting into or grafting of poly-
mer on surface of nanomaterial and is known as PNG and in second

100
ZrO2 (High concentrtion)
90
Hydrocarbon recovery (OOIP)/%

ZrO2 (Low concentrtion)

80 Distilled Water

70

60

50

40

30

20

10

0
0 50 100 150 200
Time/h

Fig. 6. Spontaneous imbibition of different concentrations of ZrO2 nanoparticles at 70 °C in

oil-wet oil-saturated core plugs. The data were obtained from [93]. Fig. 8. Polymeric nanofluid in 3 wt% electrolyte solution The data were obtained from [78]
 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009
Fig. 9. Effect of salinity on HPAM and Polymeric nanofluid at 70 °C. The data were obtained
from [78]
method the formulation is performed by the physical blending of NP
and polymer in the form of mixture and referred as PNS.
6. Mechanism of Polymeric Nanofluid in Chemical Enhanced Oil
Recovery
In EOR, the polymeric nanofluid flooding has been ascribed to the
properties of novel NP, which tend to improve the stability of fluid
and to reduce adsorption. The addition of NP helps in improving poly-
mer rheology, reducing IFT, altering the wettability of rock pores, and
in result enhances the mobility of injecting fluid in the reservoir.
6.1. Nanoparticle influence on the change in wettability
Wettability is an affinity of the fluids adherences toward rock inter-
face in the presence of other immiscible liquid. Reservoir wettability di-
rectly relates to fluid–fluid or solid–fluid interactions [88]. Several
techniques are available to analyze the wettability like contact angle
measurements, surface imaging test, spontaneous imbibition, and zeta
potential measurements. Wettability is responsible for controlling the
distribution and location of fluid in porous media, influencing capillary
pressure, and relative permeability resulting in incremental oil recovery
[89–91]. The reservoirs are categorized based on their wetness of fluid,
i.e., mixed-wet, water-wet, and oil-wet. In the aspect of contact angle
Fig. 10. Rheological behavior of HPAM and polymeric nanofluid after degradation at 70 °C for a) 7 and b) 14 days. The figure was obtained from [111]
2001
measurement, water wet are those surfaces which have contact angle
θ b 90° and those having θ N 90° is oil-wet.
In comparison to oil-wet rocks, water-wet rocks are more favorable
in oil extraction. There are several techniques to alter the wettability of
formation to enhance HCS recovery. Changing oil-wet or mixed-wet
surface to water-wet surface shows a decrement in capillary force and
increment in the mobility of the oil phase.
The application of surfactant for wettability alteration is well docu-
mented in the literature [92], but several other studies have concluded
that NP have more significant impacts on altering the wettability of for-
mation and, ultimately, oil recovery. Karimi et al. [93] performed a spon-
taneous imbibition technique to check the wettability effect of NP at 70
°C and concluded that due to the mechanism of disjoining pressure, the
NP tends to alter the wettability of rock interface and improve recovery
rate as shown in Fig. 6. Similarly, Rasoul et al. [94] used SiO2, TiO2 and
CaCO3 NP to investigate wettability effect by spontaneous imbibition
method and concluded that the primary mechanism in altering the wet-
tability of the rock is by a structural disjoining pressure gradient. NP
layers near the contact point are high enough to remove oil from the
rock surface.
NP, in comparison, to surfactants whose main deliverability is to re-
duce IFT, adsorb at formation interface, and change the wettability (due
to the partition coefficient of NP in oil and water phases). By applying
the DLVO theory, Radnia et al. [95] studied the contact angle measure-
ment. The optimum concentration of GO when interacted with rock sur-
face it altered the wettability from oil-wet (150°) to mixed wet
condition (90°). The main effect on altering wettability was GO concen-
tration, salinity and PH of developed fluid.
Polymeric nanofluids are also able to alter the wettability of porous
media. Moreover, the different scientist has analyzed the effect of SiO2
NP in changing wettability, including Ju et al. [96], Azarshin et al.
[97,98]. Maghzi et al. [99] investigated flooding experiments (five-spot
glass micromodel) to check the wettability alteration through NP, a hy-
brid solution of silica, and polyacrylamide. Wettability measurements
concluded that polymeric fluid strongly altered the wettability of
media to the water-wet. The flooding experiments showed an improved
recovery rate of 10% compared to conventional flooding. Furthermore,
Sedaghat et al. [100] in their experimental studies concluded that poly-
meric nanofluid (PNS) altered the wettability of glass micromodel to
medium to the high water-wet surface using SiO2 and TiO2 nano poly-
mer suspension respectively.
6.2. Nanoparticles influence on the disjoining pressure mechanism
It is critical to understand the multifaceted nature of the interactions
among nanofluid particles and solid substrate (rock), it is crucial to
comprehend the improved spreading phase of nanofluid on the surface
underneath the motion of the structural disjoining strain gradient. The
2002 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009

nanofluid interface with dynamic dividing of the oil-strong contact,

Fig. 11. Comparison of the IFT values of silica–graphene nanohybrids in deionized water
and synthetic brine (4 wt% NaCl) The data was obtained from [41].
available theories do not fully explain the EOR phenomenon by using NP
as injectant fluid. The disjoining pressure is the primary mechanism to
change the wettability of the rock–oil–water system [64,92,94].
The NP within the 3-segment contact area opt to arrange themselves
right into a wedge-like shape and force themselves among the discon-
tinuous segment and the rock surface, as shown in Fig. 7, NP that are
available in the mass liquid persistently drive the NP in the bound dis-
trict forward and confer a great force known as the structural disjoined
pressure [25]. The particles structural phenomena realize that the struc-
tural disjoining pressure at the wedge film is higher at the tip in com-
parison to the mass meniscus. Resulting in a higher push at the oil-
and in the long run, disengages the oil drop.
In structural disjoining pressure, the main forces driving this mech-
anism are electrostatic repulsion force between NP and Brownian mo-
tion among NP. Besides, structural disjoining pressure mainly relies on
the type of base fluid, nanoparticle size, salinity, and temperature.
Moreover, the force bestowed by a solitary NP are is incredibly frail;
however, when a lot of tiny NP are is available, the force exerted at a ver-
tex can be upwards of 50 kPa [20]. ShamsiJazeyi et al. [101], suggested
that structural disjoining is the mean parameter resulting in disjoining
pressure. Electrostatic, solvation, and van der Waals forces are different
forces that can influence the disjoining pressure as well. Specifically,
electrostatic forces can be exceptionally compelling in increasing the ca-
pacity of wettability modification by NP. In the process of NP enclosed
with a polyelectrolyte, electrostatic charges may result in the structural
disjoining pressure and can improve the spreading of phase containing
NP. According to Almahfood et al. [92], the inclusion of surfactants in NP
improves the stability of the solution and helps in recovering more oil
by disjoining pressure mechanism. There is still a huge gap in determin-
ing the best combination of two materials to act as driving fluid as we
know that at low temperatures, the performance of surfactant is well
but in high temperature, the precipitation takes place and CMC (critical
micelle concentration) value of surfactant also play an important role in
formulating nano-surfactant fluid.
6.3. Increase in solution viscosity
In the EOR recovery process, due to high displacement of injection
fluid causes viscous fingering and, as a result, gives poor sweep efficiency
to achieve better sweep efficiency, it is vital to control the mobility value
of injectant. Usually, polymer flooding has been used as a viscosifying
agent to improve sweep efficiency [81], but in HTHS conditions, these
polymers often degrade by reducing their viscosity and sweep efficiency.
Nanomaterials have been suggested for enhancing polymer viscosity and

25
Wettability alteration
Foam Stability
Emulsion Stability
IFT reduction
20
Percent of nanofluid application

15

10

0
2000 2002 2004 2006 2008 2010 2012 2014 2016 2018
Year

Fig. 12. Application of nanofluid in EOR utilizing different mechanisms in past years. The data obtained from [32].
 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009 2003

Table 4
Oil recovery by the hybrid suspension of HPAM polymer with different nanoparticles

Author Nanoparticle Possible EOR mechanism Polymer Temperature Salinity Porous Additional
Media Oil
Recovery

Sandstone
Cheraghian [109] Nano Clay 85 °C 2 wt% 5%
Core
Increase in viscosity of polymer by addition of NP
Sandstone
Cheraghian [133] SiO2 25 °C 2 wt% 8%
Core
Rezaei, Abdi-Khangah, Improvement in shear-thinning behavior of polymer and resistance
Mohebbi, Tatar and Clay NP in thermal degradation of the polymer due to improved viscosity of 70 °C 10 wt% Sand Pack 14%
Mohammadi [132] a fluid
HPAM
Khalilinezhad and Decrement in polymer adsorption on rock media and increment in
Clay / SiO2 35 °C 1.5 wt% Sand Pack 10%
Cheraghian [131] polymer viscosity
Abdullahi, Rajaei, Junin and Al2O3, SiO2, Improving rheological behavior of polymer and decreasing
70 °C 3 wt% Sand Pack 15%
Bayat [78] TiO2 polymeric nanofluid adsorption in porous media
Cao, Song, Wang, Zhu, Wang,
Modified Superior interfacial activity and strong stability due to interaction
Zhao, Miao and Zhang 90 °C 3.16 wt% Sand Pack 17.30%
Nano Silica between polymer chains and Nano silica
[134]

to improve the stability of polymer solution in high temperatures and
high saline conditions. NP forms a networking structure through bonding
(hydrogen bonding), which in result thickens the solution, ultimately af-
fecting fluid viscosity. Research carried by Zehghami et al. [102] states that
due to polarity of water silica NP have low viscosity enhancement while
in polymer fluid even at low shear rate silica NP considerably enhances
its pseudoplastic behavior and prevent polymer from degradation to
much extent in harsh environment (high salinity) by avoiding polymer
to interact with ions and plays role as substitute for polymer to attract cat-
ions. Nguyen et al. [103] used GO in polymer to improve its viscosity, ther-
mal stability in a saline environment, the hydrophilicity of both polymer
and NP integrates the functional groups and distribute among polymer
chain network. In the experimental work of Maghzi et al. [22], the impact
of NP on the polymer in different saline concentrations was investigated.
Degradation of polymer was drastically reduced by the addition of silica
NP with polymer fluid. The recovery factor was improved by increasing
the concentration of NP. A comparative values state that polymeric
nanofluids flooding have the highest recovery factor if compared to con-
ventional water and polymer flooding [98]. Furthermore, different scien-
tist studied rheological behavior of polymeric nanofluid and proposed it
to be the main mechanism in improving HCS recovery includes Hu et al.
[104], Haruna et al. [105], Tongwa et al. [106], Liu et al. [107] and
Khandavalli et al. [108]. The effect of temperature and salinity on HPAM
and polymeric nanofluid was investigated by Abdullahi et al. [78]; in his
studies, he analyzed the performance of HPAM in comparison to poly-
meric nanofluid in the presence of electrolyte as shown in Fig. 8.
Cheraghian et al. [109] studied nano-clay polymer fluid in which hybrid
formulation of polymeric nanofluid formed by adding nano-clay in the
polymer solution; it significantly improves the viscosity and stability of
the solution at HTHS conditions. The number of metallic NP like FeO
[110] and TiO2 [36] have also shown improved sweep efficiency in the
EOR process.
Similarly, the change in viscosity due to high temperature on poly-
meric nanofluid and conventional polymer HPAM was analyzed and at
various concentrations of silica in HPAM, 0.1 wt% of NP in HPAM
showed low viscosity reduction defined in Fig. 9 [78]. Similar work
was carried out by Giraldo et al. in which he studied the rheological be-
havior of silica on HPAM at high temperature at different aging dura-
tions and concluded that due to NP inclusion, the viscosity of polymer
could be improved as shown in Fig. 10 [111].
a reduction in capillary forces and subsequently of IFT in the
water-oil interface [112]. For EOR applications IFT reduced up to
the order of 10-3 mN·m−1 favors high mobilization of remaining
oil from the reservoir. To reduce IFT at the oil–water interface,
surfactants are used [113–115]. NP also play the same role as a
surfactant; it irreversibly adsorbs fluidic interface to reduce IFT,
resulting in stabilized fluids, which reduce mobility ratio
between displacing and displaced fluid, thus, improving areal
and vertical sweep efficiency of oil in reservoir [116]. In compari-
son to conventional emulsion stabilization by colloidal particles or
surfactants, NP have specific characteristics and better results. At
first, NP can gain its morphological characteristics with the change
in volume as they behave in a kinetically controlled system [12].
Secondly, NP are a hundred times smaller if compared to colloidal parti-
cles, which can travel at much distance in the reservoir without a signifi-
cant retention problem [117]. Ultimately, emulsions stability through NP
can sustain high pressure, temperature, and salinity [30]. Zargartalebi
et al. [27] used silica along with surfactant to check the mechanistic effect
on IFT reduction, by using two categories of silica one hydrophilic and
other slightly hydrophobic NP, when mixed with surfactant it caused a
rapid reduction in IFT. Furthermore, number of researchers have investi-
gated the effect of NP in reducing IFT including Aurand et al. [118], Al
Shafey et al. [119], Kothari et al. [120], Moslan et al. [121], Roustaei
et al. [122], Joonaki et al. [123] and Roustaei et al. [124]. According
to Zhang et al. [117], the stable oil–water emulsion using an aqueous
suspension of NP was formed, and its transportation in glass bead
pack displayed a clear front of emulsion bank, sustaining its charac-
teristics (high apparent viscosity). Tajik et al. [41] in his experimen-
tal work formed a nanohybrid of silica and graphene NP and

6.4. Reduction in interfacial tension and emulsion stability

IFT is free energy at the surface existing in between two liquids

(immiscible). It determines the distribution of fluid in the forma-
tion and is one of the means to increase HCS recovery. Improve- Fig. 13. Ultimate HCS recovery, oil production rate with passage of time, and water cut
ment in the microscopic efficiency of HCS recovery occurs due to during water flooding [131].
2004 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009

Table 5
Summary of various nanoparticles and their mechanisms responsible for additional oil recovery

Year Reference Chemical Possible Mechanism Nanomaterial Change in Reduction Change in Porous Media AOR
Viscosity in IFT Wettability /%

NP: Al2O3 PNF,

SiO2 PNF
Rock:
Gbadamosi, Junin, Partially hydrolyzed Increment in Size: 15–20 nm 5–10 mPa·s
111.8° to Sandstone
2019 Manan, Agi, Oseh and polyacrylamide (HPAM. 20 viscosity. C: 0.1 wt% increment N/A 10–12
25.1° P: 15.20%
Usman [139] MDa) Change in wettability D: NA in viscosity
K:168.2 md
Oil: Crude oil
pH: NA
NP: SiO2, Al2O3,
TiO2
Different surfactants (oleic Size: 15–20 nm Rock:
Disjoining pressure. 63.5° ±
Kuang, Saraji and Piri acid, polyacrylic acid, a C: 0.1 wt% 54 to 5×10-5 Sandstone
2018 Reduction in IFT. N/A 2.0° to 6.2
[140] cationic, an anionic, and a D: 0.10 g·cm−3 N⋅cm-1 P: 19%–23%
Change in wettability 142° ±2.9°
non-ionic) Oil: Heavy K:150–185 md
crude oil
pH: NA
NP: CNT
Size: NA
Soleimani, Baig,
C: 0.3 wt% Glass bead
Yahya, Khodapanah, 27.43 to
2018 Sodium dodecyl sulfate Reduction in IFT D: 1.02 g·cm−3 NA NA P: 33% 18.57
Sabet, Demiral and 18.65×10-5 N⋅cm-1
Oil: Dubai crude K:2190 md
Burda [40]
oil
pH: 3–5
NP:
Sulphonated
Graphene
Rock:
Radnia, Rashidi, sodium Size: NA
Change in wettability 14.49 to 165° to Sandstone
2018 Nazar, Eskandari and dodecylbenzenesulfonates C: 0.001 wt% NA 14
and reduction in IFT 1.73×10-5 N⋅cm-1 107° P: 25.8%
Jalilian [141] (SDBS) D: 1.12 g·cm−3
K:132 md
Oil: degassed
crude oil
pH: NA
NP: ZnO2
Size: 55–117.1
Rock: Sand
nm
Adil, Lee, Mohd Zaid, sodium P:
C: 0.03 wt% 13.38 to
2018 Ahmad Latiff and dodecylbenzenesulfonate NA NA 37.37%–39.33% 7.05
D: 5.1 g·cm−3 11.60×10-5 N⋅cm-1
Alnarabiji [39] (SDBS) K: 284–303
Oil: Tapis crude
md
oil
pH: NA
NP: SiO2
Size: 11–14 nm
Rock:
Moradi, Pourafshary, C: 0.1 wt%–1 wt%
Reduction in IFT and 13.62 to Carbonate
Farahani, Mohammadi NA D: 1.01 g·cm−3 NA 122° to 16° 20
change in wettability 10.69×10-5 N⋅cm-1 P: 10.33%
and Emadi [142] Oil: Iranian
K:2.83 md
crude oil
pH: 3–5
NP: Fe2O3
Reduction in IFT and Size: 15–20 nm
Rock:
Rezvani, Riazi, Tabaei, altering wettability C: 0.03 wt%
26.32 to Carbonate
2018 Kazemzadeh and Chitosan to more water D: 5.1 g·cm−3 NA 160° to 96° 12.8
14.47×10-5 N⋅cm-1 P: 23%
Sharifi [38] wetness, reduction in Oil: black crude
K: 556 md
oil viscosity oil
pH: NA
NP:
silica–graphene
nanohybrid
Tajik, Shahrabadi, Size: NA Rock: Sand
18.01 to
2018 Rashidi, Jalilian and tetramethylsilane Reduction in IFT C: 0.17 wt% NA NA P: 36.97% 32
6.20×10-5 N⋅cm-1
Yadegari [41] D: NA K:11 md
Oil: degassed
crude oil
pH: NA
NP: Graphene
janus
Reduction in IFT and nanosheets Rock:
Luo, Wang, Zhu, Tang,
altering wettability Size: NA 10 to Sandstone
2017 Zhu, Bao, Willson, octadecylamine NA 150° to 79° 7.5
to more water C: 0.001 wt% 1×10-5 N⋅cm-1 P: 21%–25%
Yang and Ren [143]
wetness D: 1.12 g·cm−3 K:43–137 md
Oil: crude oil
pH: NA
AfzaliTabar, Alaei, Reduction in IFT and NP:
Bazmi, Ranjineh SDBS and 2-Propanol as altering wettability MWCNT/SiO2, 53.90 to
2017 NA 143° to 58° NA NA
Khojasteh, alcoholic co-surfactant to more water graphene/SiO2 29.82×10-5 N⋅cm-1
Koolivand-Salooki, wetness Size: NA
 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009 2005

Table 5 (continued)

Year Reference Chemical Possible Mechanism Nanomaterial Change in Reduction Change in Porous Media AOR
Viscosity in IFT Wettability /%

Motiee and Rashidi C: 0.3 wt%

[144] D: 1.02 g·cm−3
Oil: Dubai crude
oil
pH: 3–5
NP: SiO2, TiO2
and Al2O3
Rock:
Size: 22 nm
Youssif, El-Maghraby, Sandstone
permeability C: 0.1 wt%
2017 Saleh and Elgibaly NA NA NA NA P: 19.4%–21.7% 12.7
impairment D: 1.02 g·cm−3
[145] K: 325–587
Oil: black crude
md
oil
pH: NA
NP: (SiO2,
SiO2A) formed
by TEOS, Al2O3
Taborda, Franco, Size: NA 33%
Reducing oil viscosity
2016 Lopera, Alvarado and non-ionic surfactant C: 1.0 wt% reduction in NA NA NA 16
in HPHT conditions
Cortés [146] D: 0.96 g·cm−3 oil viscosity
Oil: Heavy
crude oil
pH: NA
NP: methylated
graphene oxide
(GOM) Viscosity
Comparison of
Nguyen, Ngo, Bui, Size: NA retainment
viscosity loss after
2014 Pham, Dinh and AM, ATBS and NVP C: 0.17 wt% of 46.3% NA NA NA 20
aging of injection
Nguyen [103] D: NA after 28
fluid
Oil: degassed days aging
crude oil
pH: NA
NP: SiO2
Size: 21–40 nm
C: 0.01 wt%–1 Rock:
Decreasing IFT and
Hendraningrat, Li and wt% 19.2 to Sandstone
2013 NA increasing water NA 54° to 22° 4.69
Torsæter [74] D: 1.01 g·cm−3 7.9×10-5 N⋅cm-1 P: 33%
wetness of core
Oil: Degassed K:2190 md
crude oil
pH: 3–5
NP: Al2O3
Size: 35 nm
C: 0.01 wt%–1 Rock:
Giraldo, Benjumea,
Anionic Surfactant Altering wettability wt% 104°–142° Sandstone
2013 Lopera, Cortés and NA NA NA
(PRNS-X) of sandstone core. D: NA to 0° P: 33%
Ruiz [43]
Oil: Heavy K:2190 md
crude oil
pH: 9.3

Additional Oil Recovery (AOR), Concentration (C), Density (D), Porosity (P), Permeability (K), NA (Not Applicable)

investigated different IFT values at different concentrations and con-
cluded that IFT value in the presence of functionalized nanohybrid of
silica–graphene could be reduced more than 60%. As shown in Fig 11,
the addition of nanohybrids in brine solution facilitated in reducing
IFT in saline conditions.
Polymeric nanofluids compared to bare NP have improved emulsifica-
tion characteristics due to surface activity of polymeric chains. The pres-
ence of polymer cause more stabilized emulsion against creaming, and
these emulsions exhibit sustainable behavior due to the 3D network
structure formed due to irreversible bridging of NP and polymeric chains
[125]. Also, the viscosity of emulsions formed is controlled by polymer
and improving mobility ratio by controlling the mobility of the displaced
phase [112]. The utilization of different NP due to unique characteristics
poses different mechanisms in improving HCS recovery, as discussed in
this review. The contribution of each mechanism based on nanofluid ap-
plication is shown in Fig. 12, the overall trend of each mechanism in-
creases with increasing year, which states that the use of NP as an EOR
agent is more effective compared to conventional techniques.
6.5. Current research in core flooding experiment
In literature, the use of core flooding in the petroleum industry is
well documented. The purpose of performing a core flood is to ob-
serve the impact of injection fluids and analyzing the HCS recovery
rate at HCS reservoir conditions. According to Mohajeri [126], the ad-
dition of NP in surfactant improves HCS recovery significantly. This
improvement in recovery is for C12TAB/ZrO 2 when compared to
SDS (sodium dodecyl sulfate)/ZrO2 . Results of Rahimi et al. [127]
work shows that addition of NP in SDS surfactant can improve the
oil recovery, in their study different concentrations of SDS solutions
and hydrophilic NP on a sandstone core plug were investigated.
The 11 % additional oil recovery in oil production was recorded
when an SDS concentration of 0.25 wt% and Aerosil 200 Silica NP
concentration of 0.1 wt% was used. The addition of NP affects differ-
ent mechanisms when compared to surfactants, which are responsi-
ble for EOR like change in rheological properties, reduction in IFT,
and alteration of rock wettability.
2006 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009
6.5.1. Use of polymeric nanofluid in core flooding experiment
With available literature work, it is proved that incorporation of NP
and polymer together results in improved HCS recovery even at high
temperatures and saline conditions. Liu et al., with its star-like poly-
meric nanofluid, performed core flooding in sandstone cores in high
temperature 82 °C and high saline condition (4 wt% total dissolved
solids) and resulted in 20% an additional HCS recovery compared to con-
ventional HPAM [128]. Similar experimental studies were carried out by
Pu et al. [129] by performing core flood experiments using polymeric
nanofluid recovered HCS recovery of 16% compared to the conventional
polymer which was 9.9%, and they proposed to check the performance
of polymeric nanofluid at high temperature and high saline conditions.
Ponnapati et al. [130], in his studies, used polymeric nanofluid to check
the transport mechanism of fluid in core in the presence of 1 wt% NaCl,
after performing various core flood experiments, they got an 11% incre-
mental recovery rate. Wetness of glass surface from oil to water was
studied by Maghzi et al. [99], This change in wettability ultimately im-
proved HCS recovery compared to convention HPAM solution by
performing micromodel flooding. In result due to PNS suspension oil re-
covery is increased up to 10%. They also observed that by increasing salt
concentration HCS recovery decreased in conventional HPAM flooding,
on contrary when core flooding was performed with polymeric
nanofluid additional 10% RF was achieved due to improved physio-
chemical characteristics of polymeric nanofluid [22]. Graphene-based
amphiphilic nanosheets were employed to enhance recovery rate; the
core flooding experiments resulted in an incremental oil recovery of
15% compared to a previously reported recovery rate of 4.7% performed
in same conditions (0.01 wt% concentration) [37]. Furthermore, accord-
ing to experimental results by Abdullahi et al. [78], core flooding in the
sand pack achieved an additional 15% HCS recovery by using different
NP (Al2O3, SiO2, TiO2) along with HPAM. Besides, according to
khalilinezhad et al. [131], a 3D simulations and validated model of the
pilot field shows that water cut, breakthrough time and ultimate oil re-
covery improved when polymeric nanofluid was used as injecting fluid
in comparison with polymer fluid Finally, Rezaei et al. [132] in his stud-
ies analyzed improved rheological behavior of polymer by adding clay
NP which in result showed 33% incremental oil recovery in comparison
with conventional polymer flooding. Given Table 4 highlights the re-
sults for additional RF achieved through the polymeric fluid.
6.6. Reservoir modeling and simulation
The studies carried out in simulating NP as an EOR agent are limited
in number. The NP addition in injectant fluid enhances the mechanism
efficiency like change in wettability and reduction in IFT; the forces
causing this change are capillary pressure and relative permeability
[135]. Khalilinezhad et al. [131] investigated the NP effect on the flow
behavior of injectant fluid in porous media by engaging numerical
simulations through UTCHEM (University of Texas Chemical
Compositional Simulator) a multi-component, multiphase 3D
simulator. The feature of this simulator is that it can simulate
laboratory-scale experiments along with various chemical specimens.
After performing experimental core flooding, the simulation modeling
was validated and compared to polymer injection; the 10% incremental
recovery was recorded by using polymeric nanofluid (Fig. 13). The ad-
sorption of NP on sandstone surface and rheological results were vali-
dated through the polymer shear thinning model and concluded that
the inclusion of NP in polymer reduces the retention and adsorption
in sandstone whereas rheological behavior is shear dependent [136].
According to Soares et al. [137], the ferrofluid, when used as the injec-
tant fluid, causes less permeability impairment with little retention. The
numerical model developed discussed the role of NP for trapped oil mobi-
lization. They analyzed the symmetrical configuration of the HCS segment
along with NP in pore geometry fenced by the saline environment. The
experimental studies were carried out on a pore-scale model relying on
a 2D sinusoidal snap-off geometrical trapping of a discrete oil ganglion;
as a result, it was concluded that ferrofluids (NP dispersed in base fluid)
have potential to recover more oil from a reservoir. Furthermore,
Abdelfatah et al. [138] developed a mathematical model combining
convection-diffusion and Darcy equation to investigate NP transportation
and fluid flow behavior and their interaction in porous media. After
validation of experimental and simulated results, it was concluded that
different mechanisms like injection rate, NP size, and concentration and
permeability have a dominant contribution in transporting NP in porous
media.
7. Summary of Different Nano EOR Mechanism
In EOR, the research on the use of NP as an EOR agent is of keen in-
terest to the scientific community. The various mechanisms are respon-
sible for improving HCS recovery.
Table 5 emphasizes the summarized experimental work on nano-
technology implication in the upstream petroleum industry.
8. Challenges and Directions for Future Work
In experimental work, even though NP joined with polymer are
demonstrated to be potential competitors in EOR forms, yet their
use in field applications is extremely restricted. Fundamentally, nu-
merous challenges must be settled before this innovation is actual-
ized in practical field implications. These challenges are as per the
following:
1. The problems associated with NP are different, when NP go under
high temperature and high saline conditions, they use to agglomer-
ate and aggregate due to their smaller size as their attraction to
each other is stronger, it is pivotal to form homogeneous suspensions
of NP and use physio-chemically compatible polymers to improve
their stability.
2. The selection of NP is of keen importance, as the number of factors
needs to be considered for optimization of NP selection such as com-
patibility of physical as well as chemical nature of NP (metallic, non-
metallic, magnetic, organic or inorganic). The cost of NP also plays a
vital role as in the current market; the most expensive NP are of mag-
netic nature.
3. The composite of two or more than two NP should be utilized in EOR
injectant fluid. The interaction of hydrophilic and partially hydropho-
bic NP can give prosperous results. The fumed silica recently has
given positive results in improving the viscosity of conventional
polymer at HTHS conditions.
4. The accessible trial studies directed utilizing 2D NP also demon-
strated their ability as EOR additives. In any case, the experimental
work carried out on such NP is less, and more studies are directed
using silica NP. This is most likely because of the accessibility of
silica's over 2D NP. In this manner, leading investigative work on var-
ious kinds of 2D NP like graphene derivatives is essential to test their
ability to enhance HCS recovery.
5. The effect of temperature is dual in nature, impacting both reservoir
systems as well as nanofluids; therefore, the temperature effect on
HCS recovery is essential to consider and observe the mechanisms af-
fected due to change in temperature.
6. The experiments carried out through core flood by using NP, or poly-
meric nanofluid is limited. Performing these experiments is
extensively vital to optimize HCS recovery.
7. The reservoir simulated modeling of fluids containing NP should be
studied to help exploration and production operators in implementing
nanofluid in real conditions and can prove as a standing guideline for
EOR flooding technology.
Therefore, it is essential to address these challenges and try to over-
come current limitations.
Moreover, building numerical models for different polymeric
 N. Lashari, T. Ganat / Chinese Journal of Chemical Engineering 28 (2020) 1995–2009
nanofluids can be more useful to analyze and understand the drive
mechanisms for HCS recovery. These models are meant to help in
choosing the exceptional and appropriate nanofluid mechanisms for
the future application of these in the field.
9. Conclusions
The implication of chemical EOR is not recognized globally yet. How-
soever, China, along with other countries like Canada and the USA, are
playing a pivotal role in implicating chemical EOR techniques,
i.e., polymer flooding, surfactant flooding, polymer surfactant flooding,
alkaline surfactant polymer flooding recovery techniques. In the present
research, the emphasis on chemical-based recovery techniques to im-
prove oil recovery is noticed. Aside from application in drilling, explora-
tion, and production technology, lately, the use of NP in EOR has got
much research attention. In this article, the critical review of the current
research development in the use of NP in CEOR is presented. The devel-
opment in formulating polymeric nanofluid by using additives (NP) to
improve polymer solution properties is studied. A new class of polymer
nanocomposite is discussed using NP for the harsh subsurface condi-
tions. NP integration with the polymer may enhance the thermal con-
ductivity, improve viscosifying properties, reduce IFT and alter the
wettability of porous media. The NP have a tendency to improve the
functional ability of stimulated fluids due to their nanosized interaction
at the O/W interface, resulting in reduced IFT.
Therefore, there is a huge gap in combining several NP with different
polymers to uncover the potential and extend the behavioral under-
standing of their mechanisms. Furthermore, the research work is
needed to comprehend a better understanding of mechanisms and en-
hance the potential of polymeric nanofluid for CEOR. Practically most
of the nanofluid CEOR mechanisms are ambiguous in understanding at
this point and ought to be researched efficiently with increasingly con-
trolled experiments. In any case, nanomaterials in CEOR may have an
extraordinary future.
Acknowledgements
We acknowledge the financial support from Dawood University of
Engineering and Technology Karachi, Pakistan, under the project:
“Strengthening of DUET” and Department of Petroleum Engineering,
Universiti Teknologi PETRONAS, Malaysia.
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