Advances in Colloid and Interface Science 293 (2021) 102449

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Advances in Colloid and Interface Science

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

Historical Perspective

Enhanced oil recovery from fractured carbonate reservoirs using

nanoparticles with low salinity water and surfactant: A review on
experimental and simulation studies
Gideon Dordzie, Morteza Dejam ⁎
Department of Petroleum Engineering, College of Engineering and Applied Science, University of Wyoming, 1000 E. University Avenue, Laramie, WY 82071-2000, USA

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

Available online 18 May 2021 Nearly half of the world's oil reserves are found in carbonate reservoirs, which have heterogeneous formation
characteristics and are naturally fractured. Because of the permeability contrast between the matrix and fracture
network in these reservoirs, primary and secondary oil recovery processes are ineffective. Consequently, there
Keywords: has been a growing interest in enhanced oil recovery (EOR) from fractured carbonate reservoirs (FCRs) over
Fractured carbonates the past years and many successful attempts have involved the use of different thermal or non-thermal EOR
Low salinity water methods to improve oil recovery. Nonetheless, many researchers have recently directed their studies towards
Nanoparticles the use of low salinity water (LSW), nanoparticles (NPs), and surfactant (LNS) as EOR agents in carbonates be-
Surfactant cause they are environmentally friendly and incur low costs. Several studies have reported the successful appli-
Enhanced oil recovery cation of the solutions of LSW, NPs, and surfactants either as individual solutions or in combinations, to carbonate
formations. The challenges associated with their implementations such as fines migration for LSW flooding, sur-
factant adsorption onto the pore walls, and instability of NPs under harsh conditions, have also been identified in
literature and addressed. However, relatively few investigations have been conducted on FCRs to study the effec-
tiveness of these LNS EOR applications in the presence of fractures. This review, therefore, presents the reports of
EOR in FCRs using LNS and identifies the mechanisms that influence these results. It has been shown that fines
migration could either promote EOR or reduce recovery based on the occurrence of formation damage. In addi-
tion, surfactants with the tendency to form micro-emulsions will be efficient for EOR applications in FCRs. Finally,
LNS solutions show promising results with emerging techniques such as alternating injection, which could be ap-
plied in FCRs. The findings from this study set the stage for future investigations into EOR in FCRs.
© 2021 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Background of oil recovery mechanisms in fractured reservoirs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Key parameters of imbibition mechanisms in fractured reservoirs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Proposed solutions to EOR challenges in fracture systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. EOR in FCRs using LSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Overview of LSWF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Mechanisms governing EOR in FCRs using LSW. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. EOR in FCRs using surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1. Overview of surfactant flooding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2. Mechanisms of wettability alteration in FCRs using cationic, anionic, non-ionic, and zwitterionic surfactants . . . . . . . . . . . . . . . . 10
5. EOR in FCRs using NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6. Synergism among LNS solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7. EOR in FCRs using different combinations of LNS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7.1. LSW and surfactant as EOR agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7.2. Combination of LSW and NPs as EOR agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

⁎ Corresponding author.
E-mail address: mdejam@uwyo.edu (M. Dejam).

https://doi.org/10.1016/j.cis.2021.102449
0001-8686/© 2021 Elsevier B.V. All rights reserved.
G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

7.3. Combination of NPs and surfactants as EOR agents in fractured systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

7.4. Combination of LNS as EOR agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
8. Results from simulation studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
9. Limitations in the application of LNS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
10. Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
11. Future prospects and recommendations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

1. Introduction
Historically, the production of oil from the reservoir goes through
three stages namely: primary, secondary, and tertiary or enhanced oil
recovery (EOR) [1]. Usually, less than 30 to 40% of the original oil in
place (OOIP) is produced with primary and secondary methods of re-
covery [2,3], which makes EOR methods of great interest to researchers.
EOR is ideally the last phase of oil production, which involves the intro-
duction of chemicals or thermal energy to improve the production of oil.
However, it is not necessarily performed at the end of the secondary re-
covery phase but can be employed at any time when thermal energy or
chemicals are needed to stimulate the production of oil. Fractured-
cavity and fractured-porous media are examples of such systems that
might require EOR at the early stages of oil production. EOR for reser-
voirs with a high recovery factor involves the reduction of the residual
oil saturation to the lowest possible value while in reservoirs with a
low recovery factor, increasing the recovery rate is crucial [4]. It has
been reported that more than half of the world's oil reserves are found
in carbonate reservoirs [5]. However, most carbonate reservoirs
(about 80%) are naturally fractured and the oil recovery from fractured
reservoirs is relatively lower than those from unfractured reservoirs [6].
This low recovery has been attributed to the permeability and
storability contrasts between the matrix pores and the fractures,
which mostly render waterflooding methods ineffective, especially
under oil-wet conditions [7–10]. It has therefore become necessary for
researchers to investigate efficient, cost-effective, and environmentally
friendly EOR methods to recover more oil from fractured carbonate res-
ervoirs (FCRs).
The use of various forms of chemical flooding as shown in Fig. 1 for
improving oil recovery in carbonate reservoirs has been under investi-
gation for several years. Although most studies consider carbonate
rocks to be naturally fractured, relatively few studies have considered
the use of verified fractured carbonates or laboratory-created fractures
in their experimental or simulation studies. The use of low salinity
water (LSW) or smart water, nanoparticles (NPs), and surfactant as an
individual, paired or combined solutions (abbreviated as LNS) for EOR
purposes have been of interest to most researchers recently due to the
low costs involved and their effectiveness [11,12]. For this review,
smart water would be referred to as LSW.
Despite the controversies surrounding the mechanisms influencing
the incremental oil recovery observed during low salinity waterflooding
(LSWF) [13], several studies have reported that it is a suitable method to
recover more oil from the reservoir [14–21]. Other studies have ex-
tended the investigation to fractured carbonates and also have reported
additional oil recovery with LSWF [9,22,23]. One of the major challenges
associated with LSWF is fines migration [24–26]. NPs have the ability to
reduce fines migration and are often injected with LSW during EOR [27].
In addition, it has been reported that NPs alter the wettability of frac-
tured micromodels [28] and so can be suitable candidates for EOR appli-
cations in fractured carbonate rocks. Also, when surfactants are added to
NPs, they get adsorbed onto the surface of the NPs and therefore are not
adsorbed onto the surface of the pores in the reservoir [29]. The use of

Fig. 1. Summary of chemical flooding methods employed in EOR (after [2]).

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G. Dordzie and M. Dejam
NPs as EOR agents is a relatively new research area but has proven to be
a very promising means to enhance oil recovery in carbonate reservoirs
[30,31]. However, very few investigations have been conducted to in-
vestigate their effectiveness in fractured systems, especially FCRs.
On the other hand, many studies have investigated EOR in fractured
systems using surfactants as chemical agents. As a result of most FCRs
being oil-wet in nature [32] and having a permeability contrast between
the matrix and the fractures in them, the concept of wettability alter-
ation and interfacial tension (IFT) modifications have become crucial
in the discussion of incremental oil recovery in fractured reservoirs. Un-
like NPs, different studies have been conducted experimentally to inves-
tigate the impact of surfactant flooding on EOR in fractured systems.
The synergism among LNS solutions and their potential in EOR appli-
cations for carbonate rocks have been stated in literature. Different
studies [11,33] have explained that LNS combined solutions yielded
the lowest IFT and thus produced the maximum oil removal from cal-
cium carbonate surfaces.
Among several applications, the application of chemical EOR in car-
bonate reservoirs has been practiced over the past years [34]. Recently,
investigators have been studying ways to enhance oil recovery in FCRs
by including the use of LSW, surfactants, NPs, and their combinations.
However, a complete understanding of the impact of LSW, the different
types of surfactants, and NPs as well as their combined solutions on EOR
in FCRs using experimental and simulation studies is still needed and
has to be comprehensively discussed to be used as a guide for effective
design of an EOR method in FCRs. Therefore, this review seeks to pro-
vide an overview of the impacts of LNS fluids and their combined solu-
tions on EOR in fractured carbonates and the future applications that
need exploitation. Additionally, this review seeks to outline the emerg-
ing techniques and LNS solutions that are promising for EOR in FCRs and
their applications in simulation studies. Besides, a detailed explanation
of the importance of mechanisms such as fines migration and formation
of micro-dispersions as indicated by recent studies has been included in
this review. The details of this work are organized into various parts to
reveal the oil recovery reported in literature and to explain the mecha-
nisms responsible for the recovery in FCRs. First, a background of recov-
ery in FCRs is presented which discusses the forces at play during
conventional waterflooding and explains the inefficiencies with regards
to fractured systems. Then, the EOR results from FCRs using the LNS so-
lutions and their combinations are presented. The mechanisms that in-
fluence these recoveries in the FCRs are also discussed. Furthermore, the
emerging techniques of LNS solutions used in carbonate reservoirs are
revealed and the need for their application in fractured carbonates are
stated. Finally, different simulation results regarding EOR in FCRs
using LNS solutions are presented and the summary and conclusions
drawn from this review are highlighted.
2. Background of oil recovery mechanisms in fractured reservoirs
Traditional waterflooding is mostly defective in fractured systems
such as FCRs because most FCRs are oil-wet or mixed-wet in nature. Nu-
merous studies have explained the mechanisms involved during
waterflooding in FCRs. It has been observed that recovery mechanisms
in fractured chalk blocks are changed with an alteration in wettability
[35,36]. A matrix-by-matrix block waterflooding under strongly
water-wet conditions reveals that the dominant mechanism governing
the recovery of oil was spontaneous imbibition. However, it was ob-
served that at moderately water-wet conditions, the formation of a dis-
tributed waterfront introduced a viscous component, which swept
across the fracture and recovered more oil [37]. A mechanism to obtain
recovery via viscous component through capillary continuity across
open fractures in fractured reservoirs has as a result been proposed
[38]. Graue et al. [39] investigated the impact of viscous displacement
as an oil recovery mechanism and the effects of fracture permeability
on recovery in fractured chalks at moderately water-wet conditions. Ac-
cording to them [39], an increase in the capillary number enhances oil
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Advances in Colloid and Interface Science 293 (2021) 102449
production in less water-wet fractured reservoirs. It has been concluded
that the presence of fractures in the moderately water-wet chalk blocks
did not influence the flow of the waterfront during waterflooding [39].
Additionally, a reduction in the fracture-matrix permeability ratio in-
creased the oil recovered via viscous components.
Nuclear tracer imaging (NTI) is a method used to observe fluid flow
in fractured carbonates to examine how oil recovery mechanisms are
impacted by fractures. Several works on waterflooding in fractured car-
bonates using NTI have reported that the wettability condition of the
matrix blocks is significant for oil recovery since the mechanisms re-
sponsible for the oil recovery change with wettability [35].
Ersland et al. [40] also explained that the main mechanism responsi-
ble for oil recovery in a strongly water-wet fractured system is the spon-
taneous imbibition of water into the matrix blocks from the fracture
network until the spontaneous imbibition endpoint is reached. How-
ever, it was observed that the oil was displaced by a uniformly dispersed
waterfront at moderately water-wet conditions, which made the pres-
ence of fractures in the chalk less significant. Therefore, the displace-
ment of oil was attributed to the component of viscous forces
introduced by the waterfront propagation through capillary contacts.
A similar observation was made with magnetic resonance imaging
(MRI), where the oil recovery under moderately water-wet conditions
was attributed to the formation of water bridges and the introduced vis-
cous component [38,40]. Fig. 2 shows how wetting phase bridges are
formed in a fracture-matrix system. At strongly water-wet conditions
(Iw = 1.0), the water gradually gathers at the bottom of the fracture
and becomes continuous. The water droplets accumulate at the outlet
of the matrix at less water-wet conditions (Iw = 0.6 and Iw = 0.3).
Eventually, the droplets may form a bridge with the next matrix block
and could be held in place when the IFT between the oil and water is
high. It is noted that Sw represents the water saturation and Iw repre-
sents the Amott index to water.
According to Aspenes et al. [42], the presence of a substantial
amount of capillary continuity would enable viscous forces in less
water-wet fractured chalk to drive oil to the production wells.
Despite these studies on capillary continuity having the potential to
recover oil in less water-wet fractured carbonates during waterflooding,
several investigations have reported EOR methods to be more effective.
Furthermore, the presence of fractures in carbonates has been experi-
mentally shown to reduce sweep efficiency and so needs to be highly
considered. For instance, Lian et al. [43] studied the characteristics of
the relative permeability curves in the matrix and naturally fractured
cores as well as the impact of stress sensitivity of fracture on recovery
factors. The presence of fractures increased the oil saturation to over
30% and resulted in an early water breakthrough. Fig. 3 shows the dis-
placement efficiency of different cores before and after creating the frac-
tures. In addition, it was observed that the critical water saturation
Fig. 2. The formation of wetting phase bridges (fracture crossing) (after [41]).
G. Dordzie and M. Dejam
Fig. 3. Displacement efficiencies of different cores before and after fracture creation. The
experimental data were extracted from [43].
increases with increasing confining stress, which reduces fracture and
matrix permeabilities. Furthermore, the sweep efficiency decreases
with increasing confining pressure for constant differential pressure.
The forces that govern the flow of fluid into the matrix from the
fracture are capillary, gravitational or buoyancy, and viscous forces
[7,44–47]. In order to investigate free imbibition, capillary, and viscous
forces are investigated at static conditions [48]. For instance, the capil-
lary pressure remains the same at all water-oil contact areas for a
block immersed totally in water as shown in Fig. 4. However, the grav-
itational pressure is dependent on the depth and has its maximum ef-
fect at the bottom of the block.
Although both capillary and gravitational forces affect water imbibi-
tion into the matrix pores positively, only the dominant one governs the
displacement of fluid. The equation proposed for impermeable lateral
faces is as follows [48].
Pc þ g ðH−Z ÞΔρ
U¼ μw
kkrw
Z þ kkμ oro ðH−Z Þ
where g is the gravitational acceleration, H is the block height, k indi-
cates matrix permeability, kro and krw represent oil and water relative
permeabilities, respectively, Pc is the capillary pressure, U is the velocity
of imbibition, Z is the height of the waterfront in the block, and Δρ rep-
resents the difference between oil and water densities [48].
Fig. 4. Schematic of capillary and gravitational forces during imbibition (after [48]). The
arrows show the magnitude of the forces at all water-oil contacts and not the direction
of the forces.
Advances in Colloid and Interface Science 293 (2021) 102449
Gravitational forces are dominant when the block height is high
or at the start of the capillary imbibition, where the capillary forces
are small. On the other hand, when the displacement front is well
advanced or the block height is very small, capillary forces domi-
nate and govern the displacement. Furthermore, the pore struc-
ture, rock permeability, wettability, and the viscosity of the
injected and displaced fluids affect the spontaneous imbibition
process [48]. However, for in-situ reservoir applications and up-
scaling laboratory studies to field conditions, dynamic imbibition
experiments are required to factor in the effects of viscous forces
on the matrix-fracture flow [45].
Two dimensionless numbers called capillary number (Nca) and
bond number (Bo) relate the three forces together as shown in
Eqs. (2) and (3).
μu
N ca ¼ ð2Þ
σ
where μ and u are viscosity and velocity of the injected phase, respec-
tively, and σ is the IFT between two phases. In heterogeneous forma-
tions, as in carbonates, an incremental change in Nca leads to an
increment in oil recovery [7].
2
Δρgd
Bo ¼ ð3Þ
σ
where d represents the pore diameter. It has been shown that at a Bo less
than 10, capillary forces become dominant. As shown by the Bo formula,
reducing IFT promotes gravity segregation and freeing the oil phase by
buoyancy.
In naturally fractured reservoirs, the free imbibition is a crucial
process to ensure the displacement of oil from the matrix for in-
crement in the oil recovery. However, due to the oil-wetness of
FCRs, they require wettability alteration from oil or mixed-wet
to water-wet conditions to ensure the imbibition process in the
reservoir [48].
2.1. Key parameters of imbibition mechanisms in fractured reservoirs
ð1Þ
The key parameters of imbibition mechanisms in fractured reser-
voirs are listed as follows [48].
i. IFT: The capillary-gravity ratio (CGR) as expressed in Eq. (4) can be
used to indicate the increase or decrease in oil recovery. When the
CGR increases, oil recovery decreases.
 
Pc σf ðθÞ√ ϕk
CGR ¼ ¼ ð4Þ
ΔρgH ΔρgH
where ϕ is the porosity, θ is the contact angle, and f is a function of θ.
i. Wettability: Capillary imbibition does not significantly affect recov-
ery in intermediate and oil-wet systems.
ii. Temperature: Increasing the temperature can result in additional oil
recovery via a reduction in the viscosity of the displaced fluid and oil
expansion.
iii. Rock porosity and permeability.
iv. Block size: Increasing the surface area between the oil and water will
make the capillary forces more effective.
Co-current and counter-current imbibition of water are the pro-
cesses that govern fluid flow during the recovery of oil in fractured res-
ervoirs [8]. The co-current imbibition occurs when the wetting or
displacing phase flows in the same direction as the displaced phase,
while counter-current imbibition occurs when the wetting and the
non-wetting (produced) phases flow opposite to each other [49]. Capil-
lary imbibition is counter-current while the viscous drive is co-current.
In addition, capillary forces encourage counter-current imbibition in
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G. Dordzie and M. Dejam
water-wet carbonates while gravity forces favor co-current imbibition.
Also, due to the flow of the non-wetting phase through the inlet of the
wetting phase during counter-current imbibition, capillary back pres-
sure is introduced and therefore a finite capillary pressure will be re-
quired to produce the oil [50].
It has been inferred that gravity can improve the recovery of oil on
silicon micromodels during spontaneous imbibition followed by forced
imbibition at low IFT. Alshehri and Kovscek [7] reported a 7% of im-
proved recovery factor that was achieved because of the gravitational
effect. They also concluded that successful incremental oil recovery
due to gravity does not require ultra-low IFT since the recovery factor
increased by only 4% of OOIP with a reduction in IFT from 40 mN/m to
3 mN/m. This explanation is in agreement with other studies which
are reported in this review.
2.2. Proposed solutions to EOR challenges in fracture systems
One of the options employed to mitigate the challenges of recovery
in fractured reservoirs is to add polymers or foams to the injection
fluid [51]. Alternatively, surfactants are added to reduce the IFT between
oil and water hence allowing gravity drainage to segregate the oil and
water. The oil diffuses out of the matrix by buoyancy into the fracture
for production [7]. As mentioned earlier, EOR methods are employed
in the recovery of oil from oil-wet or mixed-wet FCRs because the
entry pressure needs to be overcome in secondary waterflooding,
which is impractical [7]. The EOR methods assist to reduce the entry
pressure, which makes the imbibition possible. Some of the proposed
methods to increase the recovery of oil in fractured carbonates include:
i. Injecting LSW [20].
ii. Injecting surfactants/alkaline solutions, which would diffuse into the
matrix from the fracture and alter wettability and increase imbibi-
tion into the matrix, hence increase recovery of oil [52].
iii. The use of membrane technology to create hydrostatic pressure via
osmosis [53], which displaces the oil out of the fracture by
counter-current imbibition [49].
iv. Injection of supercritical CO2, CO2-foam, and N2-foam into fractured
reservoirs [51].
v. Addition of polymers to injecting fluids [54].
vi. The use of microbial flooding [55].
Recently, several investigations have focused on modifying water-
flooding performance in fractured systems by the use of LSW, NPs,
and surfactants because of the less cost involved in comparison to the
other methods [56].
3. EOR in FCRs using LSW
3.1. Overview of LSWF
Generally, brine composition and salinity affect the recovery of oil.
Ionic compositions can produce up to a maximum of 85% oil during
EOR [57–67]. Reports from investigations on the use of LSW in FCRs in-
dicate that LSW improves the recovery of oil when used alone or com-
bined with other solutions. It has been observed that seawater (SW) is
a more suitable candidate for EOR in carbonates than formation water
[68]. SW and its ionic modifications change the wettability of chalk res-
ervoirs to a more water-wet condition and thereby increasing sponta-
neous imbibition of water from the fractures into the matrix blocks
[5,67,69,70]. However, the presence of high sulfate content in SW
would cause souring and scaling, hence rendering it an unfavorable
method [68]. The oil recovery in fractured carbonates depends on the
orientation of the fractures to the direction of flow of fluids [71]. As re-
ported by several investigations, the increase in oil recovery in carbon-
ate reservoirs is not limited to the injection of LSW, but chemically
tuned high salinity water (HSW) and formation water are suitable
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Advances in Colloid and Interface Science 293 (2021) 102449
candidates as well. Although these different water formulations recover
oil in carbonates, LSWF at concentrations below 10,000 ppm [72] is still
intensively investigated for EOR purposes in carbonates because it elim-
inates the occurrence of souring and scaling [72].
One advantage of LSWF is that it incurs a lower capital expenditure
(CAPEX) and operational expenditure (OPEX) compared to other EOR
methods [25]. It has been explained that the highest oil recovery is
achieved by an optimum combination of the divalent ions of Mg2+,
Ca2+, and SO2− 4 (MCS), which are referred to as potential determining
ions (PDIs) [25,73–76]. Some studies have also reported increased oil
recoveries specifically for fractured carbonate systems with the use of
LSW and with modifications in some cases. For example, Alhuraishawy
et al. [77] observed a 10% increase in oil recovery using LSWF in a frac-
tured carbonate model and an additional 18% increase with a second
LSWF, which contained preformed particle gels (PPGs) for conformance
control as shown in Fig. 5. Additionally, Gachuz-Muro and Sohrabi [32]
observed a tertiary recovery of 15.28% with the injection of low salinity
seawater (LSSW) after a secondary SW injection process. Furthermore,
Zekri et al. [23] reported a recovery of 82.64% via sequential flooding
of SW diluted 10 times (SW/10), followed by SW diluted 50 times
(SW/50), and then SW with 6 times increment in sulfate concentration
(SW 6 × SO2− 4 ). In unfractured carbonate cores, however, Zekri et al.
[23] recovered 76% of oil with the same sequential flooding scenario.
3.2. Mechanisms governing EOR in FCRs using LSW
The main mechanism identified to be crucial during LSWF is wetta-
bility alteration [78,79] although IFT changes are also probable during
LSWF and therefore LSWF could be applied in water-wet reservoirs. As
explained by Shariatpanahi et al. [61], the reactions between the ions
of Ca2+, Mg2+, and SO2−4 and the rock lead to the removal of the carbox-
ylic material as shown in Fig. 6a, hence resulting in wettability alteration
of the rock. These reactions, including the substitution of Ca2+ on the
rock surface by Mg2+ as shown in Fig. 6b, are enhanced by temperature
(90 °C and above) [20,61]. Usually, the flooding of water through frac-
tured carbonates recovers less than 5% of oil because of early water-
cut as the water passes through the fractures freely with little flow
into the matrix pores. Some controversies have emerged concerning
the improved oil recovery due to the multi-ion exchange (MIE) mecha-
nism [80]. Nonetheless, Zhang et al. and Strand et al. [5,67] explained
that the MIE mechanism is significant in FCRs because the removal of
the carboxylic group in the oil from the chalk surface by MCS ions in-
creases the flow of water into the matrix pores.
Some studies have entirely focused on investigating the geochemical
interactions occurring at rock/brine interfaces to understand the
60
50
40
Oil recovery (%)
30 Seawater [32]
LSSW [32]
Waterflooding 1 [77]
PPG [77]
20
Waterflooding 2 [77]
LSWF 1 [77]
LSWF 2 (Containing PPG) [77]
10
0
0 5 10 15 20 25 30
Pore volume injected
Fig. 5. Oil recovery during LSWF with different modifications in fractured carbonate cores.
The experimental data were extracted from [32,77].
G. Dordzie and M. Dejam
Fig. 6. Schematic demonstration of the mechanism for SW-induced wettability alteration (after [67]): (a) the mechanism suggested when the dominant ions are Ca2+ and SO2−
(b) the mechanism proposed when the dominant ions at higher temperature are Mg2+ and SO2− 4 .
underlying mechanisms influencing LSWF [81]. As a result of the reduc-
tion in the salinity of LSW, the electrical double layer (EDL), which refers
to the two charged layers formed at the surface of a colloid particle dis-
persed in a continuous phase, expands and thickens the water film on
the rock surface and hence alter the wettability to a more water-wet
state [80]. It has been observed from a direct visualization experiment
that the presence of micro-dispersions from the interaction between
brine and crude oil is responsible for the alteration of wettability.
Micro-dispersions are defined as packets of nano-scale brines engulfed
in polar oil components [82–84]. The tendency of the various crude
oils to form micro-dispersions was further investigated by AlHammadi
et al. [72,85]. They investigated the relationship between micro-
dispersions and additional oil recovery from carbonate rocks using
LSW and crude oil with a high tendency to form micro-dispersions. Ad-
ditional oil recovery of 6.3% was observed for crude oil with the highest
tendency to form micro-dispersions with brine whereas no additional
recovery was recorded for crude oil which did not form micro-
dispersions with brine [72,85].
It was observed that similar geochemical effects took place in all core
floods, which attributes the main cause of the additional oil recovery to
the formation of micro-dispersions from the crude oil/brine interac-
tions. The size of the micro-dispersions causes the pore throats to be
blocked and thereby enabling the LSW to be directed towards unswept
oil-containing pores [14]. The formation of micro-dispersions as shown
in Fig. 7, occurs as a result of the interaction between the oil blob, which
is adhered onto the rock surface, and LSW. The surface-active agents in
the oil then surround the water micro-dispersions (WMD), which
causes the oil to be detached from the rock surface.
Fig. 7. A diagrammatic representation of the surface-active agents of oil in (a) HSW and (b) LSW environments (after [72]).
6
Advances in Colloid and Interface Science 293 (2021) 102449
4 and
The surface-active agents adhere to the rock surface in Fig. 8a and
thereby causing oil-wetness whereas they form micro-dispersions in
Fig. 8b causing the removal of the oil from the rock surface and hence
water-wetness. Additionally, water molecules are said to form solvation
shells around the surface-active materials (SAMs) at the oil/water inter-
face [81], forming partitioned (PRT) SAMs. In the LSW environment,
these solvation shells are broken and the heads of the SAMs, which
are in high concentration, tend to surround water molecules forming
WMD. Consequently, the SAMs do not interact effectively at the oil/
water interface and thereby increasing IFT. On the contrary, the pres-
ence of high concentration of Ca2+ and Mg2+ ions in HSW screens the
oil/brine interface and thereby reducing the concentration of SAMs rel-
ative to the LSW environment. The highly concentrated ions of Ca2+ and
Mg2+ are hydrated by water molecules and the SAMs present at the oil/
water interface encourage oil/water interactions, which reduces the IFT.
Again, the formation of WMD and PRT SAMs causes the wettability al-
teration from oil-wet to water-wet in LSWF. It should be noted that
WMD and PRT SAMs are almost absent in HSW but noticeable in LSW.
Another mechanism of concern during LSWF in fractured systems is
fines migration. As already stated, some studies have identified fines mi-
gration to be the cause of formation damage and subsequent reduction
in oil recovery while others indicate that it increases oil recovery. Re-
cently, Chequer et al. [24] explained the mechanism of fines migration
causing either a reduction or an increase in oil recovery due to forma-
tion damage.
As demonstrated in Fig. 9a, the capture of fines in the pore throats
tends to divert the water flux into unswept zones and thereby improv-
ing sweep efficiency. Fig. 9b shows the reduction in the permeability to
G. Dordzie and M. Dejam
Fig. 8. Schematic representation for the mechanism of water micro-dispersion formation
and surface-active material partitioning in (a) HSW and (b) LSW environments (after
[81]).
water by the fines in the high permeable zone, which diverts the water
flux into the low permeable zone and consequently increasing sweep ef-
ficiency. However, LSWF can cause a counter water flux diversion from
the low permeable zone to the high permeable zone when there is high
permeability damage in the low permeable region [24]. Consequently,
an early water breakthrough would be observed, and hence reducing
the oil recovery. Table 1 shows the EOR reports for FCRs using LSW.
4. EOR in FCRs using surfactants
4.1. Overview of surfactant flooding
Generally, surfactant flooding and the mechanisms associated with
it have been studied in diverse ways and for different conventional
and unconventional reservoir systems [86–90] because of their
surface-acting tendency in reducing IFT and changing wettability [91].
Several researchers have investigated EOR in fractured systems by
using surfactants as chemical agents and have conducted experiments
to investigate the impact of surfactant flooding on EOR in fractured sys-
tems [4,52]. Mejia et al. [92] studied the effectiveness of surfactant
flooding in high permeability oil-wet fractured porous media using
free imbibition, core flooding experiments, and micromodels to repre-
sent FCRs. They concluded that recovery from fractured systems
through surfactant flooding occurs at different rates and is a function
of the mechanism responsible for the recovery. According to them, vis-
cous displacement is the fastest recovery mechanism during surfactant
flooding in fractured media and although wettability alteration and IFT
7
Advances in Colloid and Interface Science 293 (2021) 102449
Fig. 9. A schematic representation of (a) fines migration and formation damage by size
exclusion in the pore throat and (b) increased displacement efficiency in heterogeneous
formations caused by fines migration (after [24]).
reduction enhance oil recovery from the matrix pores, they are often
slow processes. Chen and Mohanty [52] investigated EOR in fractured
oil-wet dolomite rocks at harsh reservoir conditions of high tempera-
ture and high salinity via surfactant flooding to study the synergistic ef-
fects of wettability alteration and IFT reduction on decreasing residual
oil saturation (Sor) and the mechanisms associated with the recovery.
They observed that the imbibition of surfactant via gravitational forces
recovered the most oil over capillary-driven imbibition. They inferred
that there exists a collaboration between wettability alteration and IFT
reduction, which impacts EOR positively. According to Chen and
Mohanty [52], there are two ways of utilizing this synergy to reduce
the Sor significantly. First, a cationic surfactant, which alters wettability,
or an IFT-reducing anionic surfactant can be used. Second, the use of
what they referred to as “divalent ion scavengers” in anionic surfactants
have the tendency to reduce the mobile divalent cations in hard brine as
shown in Fig. 10 and ensure the discharge of monomers from the surfac-
tant micelles and thereby changing the wettability by the adsorption of
the surfactant monomers. Previously, Chen and Mohanty [93] explained
that anionic surfactants could alter the wettability of carbonate rocks
and hence increase the oil recovery upon the addition of ethylene di-
amine tetra-acetic (EDTA) acid.
Also, Gupta et al. [94] identified anionic and non-ionic surfactants
that altered the wettability of fractured carbonate rocks from oil-wet
to water-wet conditions. The contact angle reduced with increasing
temperature for all the anionic and non-ionic surfactants tested. They
inferred that the majority of surfactants recovered approximately
35–70% of OOIP via gravity drainage and a reduction in IFT recovers
more oil if the rock is oil-wet but slows oil recovery if the rock is
water-wet. There is, therefore, a consensus that surfactants can alter
the wettability of fractured carbonates from oil-wet to water-wet [95].
G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

Table 1
Literature reports on EOR in fractured systems using LSW.

Reference Methodology Rock type Injected fluids Experimental Conclusions

condition

Zekri et al. [23] Core flooding Fractured and Sequential flooding of 90 °C • The oil recovery from the fractured core was 82.64% of OOIP.
unfractured SW/10, SW/50, and • EOR from the unfractured core was 76% of OOIP.
limestone cores SW 6 × SO2−4
H. Gachuz-Moro et al. [32] Core flooding Naturally • SW for secondary injec- 92 °C • 37.65% of OOIP was obtained as oil recovery with SW and 1.8%
fractured tion and brine for EOR with brine.
carbonate rocks • LSSW diluted 10 times, • 36.81% secondary recovery was obtained with SW, 15.28% EOR
followed by SW, and was recorded with LSSW diluted 10 times, and an additional
LSSW diluted 50 times 1.10% was obtained for LSSW diluted 50 times.
Shariatpanahi et al. [61] Spontaneous Low-permeable High salinity seawater 110 °C Secondary oil recovery of 40%, which increased to 50% with
imbibition naturally (HSSW) and modified SW HSSW and ~ 63% by modified SW.
fractured
limestone
Alhuraishawy et al. [77] Core flooding Fractured LSW and brine – 10% increase in oil recovery by LSW was obtained, which
carbonate cores increased to 18% with conformance control.

However, the poor sweep efficiency of the injected surfactants in oil-
wet FCRs causes ineffective wettability alteration. Mostly, the wettabil-
ity alteration occurs at the surface of the fractures because of the slow
transport of fluids into the matrix through diffusion and gravitational
forces. It is proposed that an economically beneficial way to enhance
oil recovery and improve the volumetric sweep efficiency in oil-wet
fractured reservoirs is to initially flush with surfactant [95].
An integrated EOR has been proposed which is cost-effective be-
cause it involves the application of wettability alteration treatment to
the fractures only. The stages involved include:
i. Pre-flooding of surfactants for surface wettability changes of the
fractures. This would create bridges of the wetting phase in the frac-
tures and thereby ensuring capillary continuity.
ii. Reduction of fracture flows via mobility control. This is usually
achieved by the use of foams or polymer gels.
iii. Sweeping of the matrix through viscous displacement. Since the mo-
bility in the fractures is reduced, further injection of fluids will direct
flows into the matrix to volumetrically sweep the oil out of the ma-
trix blocks. Capillary continuity, which is established by wetting
phase bridges, is crucial [96–99] and ensures the mobilization of
oil from a wide area of the reservoir [95].
Fig. 10. A schematic representation of the interaction among anionic surfactant micelles,
monomers, and precipitates and the resultant effect on the adsorption of monomers for
wettability alteration (after [52]).
Gupta and Mohanty [100] explained that at a fixed concentration of
anionic surfactant, contact angle and IFT have an equal optimal value of
salinity. Again, for a given constant salinity value, IFT reduces with in-
creasing concentration of surfactant. It has been shown that the
ethoxylation of anionic surfactants increases the magnitude of the
changes in wettability on a calcite surface. The ethoxylation of surfac-
tants involves the addition or modification of the ethylene oxide (EO)
units in the hydrophilic head [101], which would increase its hydrophi-
licity and enable it to withstand high temperature and high salinity en-
vironments [102]. It is also explained that anionic surfactants could be
used to treat fractured reservoirs [103,104]. Anionic surfactants are rel-
atively cheaper than cationic surfactants and are most effective at rela-
tively lower concentrations (~0.1 wt%) [46].
For slightly fractured reservoirs, drilling directional wells such that
the wells are perpendicular to the fractures will aid in enhancing oil re-
coveries. This is however not the case for highly fractured oil-wet car-
bonate reservoirs due to the flow of the injected water through the
fractures without being imbibed into the pore spaces in the matrix
blocks [46]. Fig. 11 demonstrates the effects of gravitational and capil-
lary forces during surfactant and brine injection in a cylindrical core.
When an oil-wet core is in a brine solution, the capillary pressure is neg-
ative and thereby opposing the imbibition of the brine into the rock
from the sides as shown in Fig. 11a. In this case, gravitational forces pro-
mote the imbibition of the brine by co-current imbibition. The addition
of surfactant solutions reduces the IFT and subsequently decreases the
capillary pressure. However, the capillary pressure in the oil-wet rock
(Fig. 11b) still opposes free imbibition if the wettability of the rock re-
mains unaltered and co-current imbibition via gravitational forces pre-
vails as the dominant mechanism. The injection of surfactants, which
alters the rock to a more water-wet condition (Fig. 11c), causes the cap-
illary pressure to be positive. Gravitational and capillary forces both
contribute to the oil recovery in this case and the oil is produced by
co- and counter-current imbibition, respectively [48].
Also, the effect of micro-emulsion formation during surfactant injec-
tion into oil-wet fractured carbonates has been explained in literature
[105]. Fig. 12a shows the flow of oil out of the matrix blocks into the
fracture via gravity drainage during surfactant injection at the initial
time (t1). The presence of the surfactant reduces the capillary forces,
which aids the imbibition by gravitational forces. At a later time (t2),
the injected surfactant solutions mix with the oil in the matrix to form
micro-emulsions (Fig. 12b), which are more viscous than the surfactant
solution. The micro-emulsions further displace the oil in the matrix and
fracture as shown in Fig. 12c. Since the micro-emulsions are heavier,
they tend to finger through the surfactant and mix with the oil to
form more micro-emulsions. The injection of surfactant at the bottom
of the fractured system is in the form shown by the dashed line in
Fig. 12a [106]. It is worth mentioning that the micro-emulsion formed
during the surfactant flooding process can serve as a mobility control

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G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

Fig. 11. A schematic demonstration of the action of capillary and gravitational forces during (a) brine imbibition, (b) surfactant imbibition under oil-wet conditions, and (c) surfactant
imbibition under water-wet conditions (after [48]).

agent, which is less costly and less complex compared to polymers or
foams [105].
Surfactant flooding has been reported to be successful in FCRs by dif-
ferent investigations. For instance, Mejia et al. [108,109] and Lu et al.
[108,109] observed an enhancement in the oil recovery from fractured
carbonates during surfactant flooding as shown in Fig. 13a. The injection
of 2 pore volumes (PV) of surfactant slug produced an oil recovery of
37% while a 0.3 PV surfactant slug, followed by a brine drive produced
an oil recovery of 25%. Comparing the slug size of surfactants injected
to the oil produced, it has been inferred that the larger surfactant slug
size was inefficient [108]. Similarly, a surfactant flooding process
followed by a brine drive produced a cumulative oil recovery of 65% of
OOIP. It has also been revealed that an increase in the viscosity (μ) of
the micro-emulsion during surfactant flooding, increased the oil recov-
ery (Figs. 13b). Besides, a reduction in flow rate of injecting fluid
(q) seems to be favorable for EOR in fractured carbonates as shown in
(Fig. 13b), where the highest recovery was obtained by using a 0.005
ml/min. Surfactant flooding has been shown to enhance the oil recovery
in FCRs as shown in Fig. 14a and further reduce the oil saturation, espe-
cially with an increase in the micro-emulsion viscosity from 30 cp to 50
cp as shown in Fig. 14b.
Surfactant solutions have also increased the oil recovery in fractured
carbonates, even in low permeability systems (24 mD), when the oil re-
covery is observed over time as shown in Fig. 15a and b. Sulfonate sur-
factants tend to enhance the oil recovery under a high salinity-high
temperature (HS-HT) condition larger than in a low salinity-high

Fig. 12. A schematic representation of the flow regimes and oil displacement during surfactant flooding (after [105,107]): (a) the action of gravitational forces as a result of IFT reduction,
(b) the flow regions in existence, and (c) the viscous crossflow due to the formation and flow of micro-emulsions. It is noted that pin is the inlet pressure, pout is the outlet pressure, and Δp
is the change in pressure.

9
G. Dordzie and M. Dejam
(a)
80
2 PV of surfactant flooding [108]
0.3 PV of surfactant flooding [108]
Surfactant flooding under HT-HS condition [110]
60
Oil recovery (%)
40
20
0
0.0 0.5 1.0
Pore volume injected
(b)
100
Micro-emulsion surfactant flooding, µ = 75 cp [105]
Micro-emulsion surfactant flooding, µ = 0.5 cp [105]
Surfactant flooding, µ = 0.5 cp, q = 0.05 ml/min [105]
80 Surfactant flooding, µ = 0.5 cp, q = 0.01 ml/min [105]
Surfactant flooding, µ = 30 cp, q = 0.01ml/min [105]
Surfactant flooding, q = 0.005 ml/min [108]
Surfactant flooding, q = 0.01 ml/min [108]
Oil recovery (%)
Surfactant flooding, q = 0.04 ml/min [108]
60
40
20
0
0 1 2 3
Pore volume injected
Fig. 13. Oil recovery for different surfactant injection scenarios: (a) the injection of
different surfactant slug sizes and (b) the injection of surfactants with different
viscosities and injection flow rates. The experimental data were extracted from
[105,108,110].
temperature (LS-HT) environment (Fig. 15b). Additionally, the injection
of the same PV of surfactants at a lower flow rate in fractured carbonates
is suitable for EOR purposes as can be seen from Fig. 15b. Although the
higher flow rate recovers oil faster, the efficiency of recovery is associ-
ated with the lower flow rate [108].
4.2. Mechanisms of wettability alteration in FCRs using cationic, anionic,
non-ionic, and zwitterionic surfactants
According to various studies, the performance of wettability alter-
ation in reservoirs is a function of the ionic state of the surfactant used
[112]. There is a consensus that cationic surfactants increase the oil
recovery by wettability alteration to a more water-wet condition
[87,101,113–116]. Additionally, Standnes and Austad [87,113,117] and
several others [87,113,117] revealed that cationic surfactants can alter
the wettability of carbonate rocks from oil-wet to water-wet conditions
better than anionic surfactants. Standnes and Austad [113] explained
that the ionic head of cationic surfactants pairs up with the ions of the
acidic components of crude oil adsorbed on the carbonate rock surface
via electrostatic interactions, which is responsible for the wettability al-
teration from oil-wet to water-wet. The proposed ion-pair formation
removes the crude oil layer from the carbonate surface and thereby re-
vealing the water-wetness of the rock. Anionic surfactants on the other
hand were said to alter wettability by forming a monolayer on the car-
bonate rock surface via surfactant tail-adsorbed crude oil lipophilic
Advances in Colloid and Interface Science 293 (2021) 102449
interactions. The adsorbed layer with the hydrophilic head of the surfac-
tant lying on the carbonate surface could alter the wettability to a more
water-wet state [113]. Salehi et al. [118] performed a different investi-
gative study approach to confirm the afore-described explanation pro-
posed by Standnes and Austad [113]. They used Berea sandstones
(instead of carbonate chalks) under oil-wet conditions with anionic sur-
factants to prove the ion-pair formation effect on the wettability alter-
ation and incremental oil recovery. The principle used here is that
positively charged crude oil components should interact with the an-
ionic surfactant via electrostatic forces, which should alter the wettabil-
ity and recover more oil as the case of carbonate rocks was proposed. It
was concluded that the hypothesized ion-pair formation and the ad-
sorption of a monolayer of surfactant via lipophilic interactions are the
two dominant mechanisms for wettability alteration in carbonate
rocks. Moradi et al. [119] also added that the migration of chemical
groups from the rock to the oil because of the hydrophobic nature of
1.5 2.0
the ion pairs contributes to the wettability alteration. According to
Mohajeri et al. [28], cationic surfactants performed a better alteration
of wettability than anionic SDS surfactants in fractured glass models.
Vatanparast et al. [87] concluded that the presence of anionic surfac-
tants does not encourage the imbibition of water into oil-wet cores. Al-
though it has been shown that the critical micelle concentration (CMC)
of cationic surfactants does not affect the oil recovery in carbonates
[115], cationic surfactants were later shown to alter the wettability of
carbonate rocks effectively above their CMC [87]. While a mixture of
cationic surfactant and dilute non-ionic surfactant could increase recov-
ery up to 80% [120], a mixture of cationic and anionic surfactants would
reduce the wettability alteration ability.
In investigating the effects of cationic surfactants on oil-wet carbon-
ate rocks, Kumar et al. [121] showed that dodecyltrimethylammonium
bromide (DTAB) and hexadecyltrimethylammonium bromide (CTAB)
surfactants yielded lower IFT and surface tension as well as greater wet-
4 5 6
tability alteration than benzyltrimethylammonium bromide (BTAB)
and tetrabutylammonium bromide (TBAB) and the higher the carbon
atom, the higher the decrease in the CMC of the surfactant. According
to Salehi et al. [118], systems containing surfactants with high charged
density heads or tails could increase the extent of wettability more
and increase oil recovery. Also, surfactants with high charged density
heads like Gemini surfactants are suitable for reservoir systems with
ion-pair formation as the mechanism for wettability alteration while
surfactants with high charged density tails like Bolaform surfactants
are suited for systems where adsorbed monolayer of surfactants govern
the wettability alteration [118]. Gemini surfactants have been shown to
have great potential in IFT reduction and wettability alteration more
than conventional monomeric surfactants [122] and so can yield posi-
tive results in EOR application in sandstones but require further studies
for their usage in carbonate rocks [12], especially in FCRs. Mobilization
of oil by surfactant solutions such as surfactant/alkali solutions tend to
produce further oil recoveries because of the reduction in IFT [45].
Some studies, although relatively few, have reported that non-ionic
surfactants could change the wettability of oil-wet carbonates at high
concentrations or in saline environments towards water-wetness
[123–125]. One of the promising non-ionic surfactants for FCRs is the sa-
ponin surfactant, which can be extracted from Ziziphus spina-christi
trees. Nonetheless, they are mostly used as co-surfactants with ionic
surfactants [101] because of their instability in high temperature and
high saline environments [126,127]. Anionic surfactants tend to reduce
IFT and alter wettability to intermediate or water-wet conditions
at extremely low concentrations (~0.05 wt%) [128]. Lu et al. [109] re-
vealed a formulation of surfactants, which seemed to be stable in ex-
tremely harsh reservoir conditions of high temperature, high salinity
brine, and low API gravity oil. It was concluded that a mixture of
Guerbet alkoxy carboxylate surfactant and internal olefin sulfate (IOS)
reduced the oil saturation in a highly fractured rock to 0.14, although
only a small amount of the combination was used. This is promising
and needs more experiments to explore its full application in fractured
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G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

(a) (a)
100 60

50
80

40
Oil recovery (%)

Oil recovery (%)

60

30 Brine injection, k = 276 mD [4]

Surfactant flooding, k = 24 mD [4]
40 Waterflooding [105] Primary waterflooding [111]
Surfactant flooding [105] 20 Surfactant flooding [111]

20
10

0 0
0 2 4 6 8 10 0.1 1 10 100 1000
Pore volume injected Time (hour)
(b) (b)
120 80
Waterflooding Surfactant flooding
70

100
60
Oil saturation (%)

Oil recovery (%)

50
80

40

60 30
Sulfonate surfactant flooding, HS-HT [94]
20 Sulfonate surfactant flooding, LS-HT [94]
40 Micro-emulsion, µ = 50 cp [92] Surfactant flooding, q = 0.04 ml/min [108]
Micro-emulsion, µ = 13 cp [92] 10 Surfactant flooding, q = 0.01 ml/min [108]
Surfactant flooding, q = 0.005 ml/min [108]
20 0
0.0 0.5 1.0 1.5 2.0 0 200 400 600 800 1000
Pore volume injected Time (hour)

Fig. 14. EOR during surfactant flooding: (a) increment in oil recovery via surfactant Fig. 15. Oil recovery in fractured carbonates using surfactant solutions, (a) comparison of
flooding and (b) a further reduction in oil saturation with an increase in the viscosity of oil recovery from brine injection with surfactant flooding, (b) the effect of surfactant
micro-emulsions. The experimental data were extracted from [92,105]. injection rate, salinity, and temperature on the oil recovery. The experimental data were
extracted from [4,94,108,111].

rocks. Therefore, it has been shown that the mechanisms governing the
mobilization of oil in the matrix pores are wettability alteration and re-
duction of the IFT between oil and water for oil-wet FCRs. Reducing IFT
results in an increase in bond number, which leads to a subsequent flow
of surfactant into the matrix pores by gravity. The reduction in IFT will
also reduce the oil recovery when the wettability of the formation is al-
tered from oil-wet to water-wet by the surfactant because of the reduc-
tion in capillary forces. However, if there is no wettability alteration,
lowering IFT will only increase oil recovery by increasing the bond num-
ber [129]. Oil recovery from fractured reservoirs during surfactant
flooding has been divided into various stages [129], which are outlined
as follows.
i. The maintenance of surfactant concentration in fractures at maxi-
mum level,
ii. The flow of surfactant from fractures into matrix blocks,
iii. Displacement of the oil from matrix blocks into fractures,
iv. Transport of collected oil from fractures to production wells.
Table 2 presents the reports of EOR in FCRs using surfactants.
5. EOR in FCRs using NPs
There is a consensus on the abilities of NPs to change the wettability
and IFT as well as reduce fines migration in the reservoir during LSW
flooding in several works [78,130–132]. Nwidee et al. [133] revealed
that ZrO2 nanofluids could be suitable candidates for altering wettability
in oil-wet fractured limestone formations when appropriate concentra-
tions and longer exposure times are used. They observed that at ambi-
ent conditions, 0.005 wt% of the ZrO2 nanofluids produced the highest
wettability alteration (from 152° to 44°). Recently, Olayiwola and
Dejam [134] reported that the size, concentration, and effective charges
of the NPs solution have significant impacts on the wettability and IFT
mechanisms that influence EOR in carbonate reservoirs. It has been ex-
plained in different studies that NPs have the tendency to reduce fines
migration in reservoirs. However, the fines migration prevention ability
is a function of the salinity of the reservoir. Olayiwola and Dejam
[134,135] explained in detail the behavior of NPs in various saline con-
ditions of the reservoir. The impact of solutions of NPs on the oil recov-
ery is dependent on the stability of NPs [136]. NPs have the ability to
reduce IFT and alter the wettability of strongly oil-wet carbonate rocks
to water-wet, especially as modified nanocomposites [137]. However,
they are rather combined with other fluids such as LSW and surfactants
for EOR applications in reservoirs because of their unstable nature in sa-
line environments [31,134]. Another application of NPs is the use of
surface-modified NPs for EOR purposes [138]. Experimental investiga-
tions reveal that the surface modification of silica NPs using hydrophilic
and hydrophobic agents could enhance their wettability alteration ten-
dency and hence improve their influence in EOR applications. However,
the challenge is to develop the surface-modified NPs suitable for harsh
reservoir conditions of high salinity, high temperature, and high

11
G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

Table 2
Literature reports on EOR from fractured systems using surfactant flooding.

Reference Methodology Rock type Injected fluids Experimental Conclusions

condition

Alamdari et al. [129] Spontaneous Fractured Non-ionic surfactant 80 °C Surfactant flooding yielded 40% recovery of oil in
imbibition and carbonate rock (NEODOL ethoxylate 91–8) fractured cores and 24% in unfractured cores.
forced imbibition
using a centrifuge
Gupta et al. [94] Spontaneous Fractured Anionic and non-ionic surfactants 25–90 °C 35–70% of OOIP was recovered through wettability
imbibition carbonate rock alteration and gravity drainage.
Chen and Mohanty [52] Spontaneous Fractured Cationic surfactant, anionic – Capillary-driven imbibition recovered 56.4%,
imbibition dolomite rock surfactant, and ultra-low IFT gravity-driven imbibition recovered 69.7%, and
surfactant formulations gravity drainage aided by ultra-low IFT recovered
(Guerbert alkoxy sulfate and alkali) 54.7% of OOIP.
Adibhatla et al. [128] Spontaneous Fractured Dilute anionic surfactant – An oil recovery of 20–42% of OOIP in 50 days was
imbibition carbonate rock obtained, which increased to 60% in 200 days.
Lu et al. [109] Core flooding and Fractured Guerbert alkoxy carboxylates and 100 °C • The oil saturation was reduced from 0.412 to
spontaneous carbonate rock IOS 0.140.
imbibition • The surfactant formulation yielded an oil recovery
of 33.3% of OOIP in 17 days during the static imbi-
bition. The oil saturation was reduced to 0.39
during this period.
Meija et al. [108] Core flooding Fractured Surfactant slugs in different sizes 78 °C Larger surfactant slugs yielded the highest recovery
carbonate rock followed by brine injection (37% of OOIP) but are inefficient when the oil
produced is compared with the slug size injected.
Gupta et al. [100] Spontaneous Fractured Sulfate surfactant and disulfonate 90 °C The sulfate surfactant recovered 53% of OOIP in 30
imbibition carbonate rock surfactant days while the disulfonate surfactant recovered 30%.
Babadagli et al. [111] Capillary imbibition Fractured chalk Cationic, non-ionic, and anionic 20 °C All surfactant concentrations above CMC produced
surfactants higher oil recoveries. Cationic surfactants yielded
the highest recovery during primary surfactant
injection while non-ionic surfactants yielded the
highest recovery during secondary injection.
Babadagli et al. [4] Spontaneous Naturally Non-ionic surfactant 40 and 80 °C The surfactant flooding produced double the oil
imbibition fractured recovery of the brine injection (5% to 10%).
carbonate rock
Parra et al. [105] Core flooding Fractured Surfactant formulation containing 78 °C An increase in the micro-emulsion viscosity from
dolomite and sulfonate, salt, alkali, and 0.5cp to 75cp increased the oil recovery by 40% of
limestone rocks carboxylate OOIP.
Mejia et al. [92] Spontaneous Fractured glass Surfactant mixture containing IOS – The viscous crossflow yielded a recovery of ~40%.
imbibition and a micromodel
micromodel
experiment

pressure [139]. The mechanisms that influence EOR using NPs are listed
as follows [140–142].
i. Disjoining pressure: This refers to the pressure needed to remove
fluids adhered to the surface of solid surfaces such as reservoir
rocks [141]. It also involves the forces of attraction and repulsion
that exist between two thin layers of fluid surfaces [142]. The
disjoining pressure is affected by the size of NPs, the concentration
of NPs, charge density, salinity, temperature, and surface properties
[142].
ii. Viscosity control: NPs can enhance sweep efficiency and confor-
mance during polymer flooding and consequently are used as vis-
cosity control agents [142].
iii. Wettability alteration: NPs alter the wettability of surfaces via ad-
sorption on the solid surface (coating approach) or by the displace-
ment of the adsorbed fluid molecule from the solid surface by the
disjoining pressure due to the formation of a wedge film (cleaning
approach) [141,142].
iv. IFT reduction: The adsorption of NPs onto the surface of fluids can
reduce the IFT between them [142].
v. Pore channel plugging: An increase in the size of NPs may cause for-
mation damage by plugging the pore channels and consequently re-
ducing recovery [140].
In FCRs, the extent of fracture-matrix interaction is crucial for incre-
mental oil recovery. One might infer that, since the size of NPs is very
small relative to the pore sizes, they could easily be transported from
the fractures into the matrix to alter wettability and improve recovery.
However, very few experiments have been conducted to verify this for
FCRs [143]. NPs have rather been combined with other chemicals like
surfactants in FCRs to investigate their impacts on EOR as will be
discussed in detail later in this study. Nevertheless, the application of
NPs in carbonates for EOR purposes is still a new area [144] and exper-
imental data are limited for NPs in fractured carbonate systems. It seems
that NPs have been applied as stability and conformance control agents
for CO2-foam injection in heterogeneous and fractured systems but are
seldom applied alone for EOR applications because of their instability at
high temperature and high saline conditions [12]. Nwidee et al. [145] in-
vestigated the influence of nickel oxide (NiO) and zirconium oxide
(ZrO2) emulsions on the wettability alteration of fractured oil-wet lime-
stone reservoirs and hence their applicability in EOR. It was observed
that both NiO and ZrO2 altered the wettability from oil-wet to water-
wet with increasing concentration of NPs (0.004–0.05 wt%), exposure
time, and salinity [145]. Additionally, it was inferred that ZrO2 changed
the wettability more favorably than NiO and so are better EOR agents in
FCRs as was observed in their previous study [133]. Recently, Zhang
et al. [143] explained from their experimental studies on EOR in frac-
tured porous media using “polymeric nanofluid” that NPs are most ef-
fective in water-wet or mixed-wet fractured porous media but might
not yield desirable EOR in oil-wet fractured systems. While 23.8% addi-
tional oil was recovered under water-wet conditions, only 6% was re-
corded in oil-wet mode. According to Zhang et al. [143], the retention
of NPs in the pore throats reduces the permeability of the reservoir
and consequently impedes the flow of injected fluids. The characteriza-
tion of the transport and retention of NPs is still a developing area and
has not been entirely understood. They reported that the contact

12
G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

angle observed with the use of nanofluids in oil-wet systems is large and
the structural disjoining pressure is insufficient to cause the removal of
more oil from the surface of the porous media [143]. However, Al-
Anssari et al. [146] reported that NPs are good wettability alteration
agents for oil-wet calcites. They further concluded that the injection of
solutions of NPs through the wellbore would be transported into the
matrix from the fractures and displace the oil through wettability alter-
ation. However, an experiment was not conducted to verify this hypoth-
esis [146]. Since Nwidee et al. [145] reported a promising result in their
case, it could be inferred that the use of actual fractured rocks and differ-
ent NPs might yield positive EOR results different from those observed
by Zhang et al. [143]. Nonetheless, more experiments are needed to
substantiate incremental oil recovery in oil-wet fractured systems
using NPs.

6. Synergism among LNS solutions

A recent effort of Zhong et al. [147] has investigated the synergistic

effects among LNS solutions in both sandstone and carbonate reservoirs.
NPs are stable in deionized water at ambient conditions. However, the
salinity of the solution and the concentration of the NPs affect their sta-
Fig. 16. A schematic representation of the different combinations of LNS solutions for EOR
bility [134]. LSW could increase the stability of NPs by increasing their applications in FCRs.
surface potential and therefore promote their impact on EOR. Addition-
ally, various types of surfactants have been reported to increase the dis-
persion stability of NPs. For instance, Hidayat Chai et al. [148] reported
containing SDS solutions was dependent on the ions present and
that the surface modification of ZnO NPs with SDS surfactants increased
followed the order of Mg2+ > SO2− 4 > Ca
2+
and consequently yielded
the zeta potential of the pure ZnO NPs from −14.2 mV to −45.4 mV.
oil recoveries of 55%, 46%, and 31%, respectively. Additionally, carboxyl-
NPs have been used to prevent the adsorption of surfactants onto the
ate non-ionic surfactant (AEC 938) yielded the highest oil recovery (61%
pore walls of the reservoir and thereby increasing the performance of
of OOIP) in a spontaneous imbibition experiment on carbonate rocks
the surfactants in wettability and IFT alterations [149]. Zhong et al.
compared to the sulfonate anionic surfactant (IOS 20–24) and
[149] observed that smaller sizes and high concentrations of SiO2 NPs
polyethoxylated non-ionic surfactant (C13EO12) when combined with
tend to decrease the extent of adsorption of the surfactant solutions
LSW [151]. Again, the addition of AEC 938 to a combination of C13EO12
on the rocks. Other studies have also indicated that a combination of
and LSW showed an impressive recovery of 74% of OOIP and therefore
LSW and surfactants have an additional improvement in oil recovery
reveals the tendency of a combination of LSW and non-ionic and anionic
[119]. Therefore, the various combinations of LNS solutions have high
surfactants to enhance the recovery of oil in carbonate reservoirs. Sev-
potentials in EOR applications.
eral other experimental investigations have shown that a combination
The main mechanisms involved in the EOR in FCRs using LNS com-
of LSW and surfactant has great potentials for EOR in carbonate reser-
bined solutions are wettability and IFT alteration. Mohajeri et al. [28]
voirs [152–154]. After the injection of 2 PV of different solutions, it
showed that the addition of SDS anionic surfactant to ZrO2 NPs yielded
was observed that the combination of LSW and surfactant containing
the minimum IFT reduction (80%) between oil and water in the frac-
an increase in sulfate concentration by 2.5 times (SW-2.5S) produced
tured glass micromodel compared to cationic CTAB surfactant (70%).
the highest oil recovery (Fig. 17) [119]. Additionally, increasing the con-
However, the combination of CTAB surfactant and ZrO2 NPs generated
centration of surfactant solution to an optimal value will reduce the IFT
a higher wettability alteration. Ultimately, the oil recovered by the wet-
and contact angles (Fig. 18) [119].
tability alteration of CTAB was higher than the IFT reduction ability of
SDS surfactant. Furthermore, Mohajeri et al. [28] revealed that the
nano-surfactant combination increases the viscosity by at least twice
that of surfactant alone and so provides mobility control, which aids in 80

matrix-fracture transport of fluid. Distilled water

SW
SW-2.5S
7. EOR in FCRs using different combinations of LNS 60 SW-2.5S + Surfactant
Oil recovery (%)

Although more experiments are needed for further investigations, a

few experimental studies have reported the outcome in recovery with
the combination of LNS solutions. Fig. 16 shows the various combina- 40
tions of LNS solutions possible for applications in fractured systems.

7.1. LSW and surfactant as EOR agents

20

In general, a combination of LSW and surfactant has been identified

as a suitable tool for IFT reduction and wettability alteration in carbon-
ate reservoirs. Mohammadi et al. [150] investigated the ability of a mix- 0
ture of LSW and SDS surfactant to reduce IFT and alter the wettability in Surfactant/Aqueous solution
carbonate rocks via spontaneous imbibition. They concluded that the
combination of SDS and LSW solutions reduced the IFT and altered the Fig. 17. Oil recovery in carbonates after injecting approximately 2 PV of different solutions,
wettability of the rock to a more water-wet state. According to including the combination of LSW and surfactant. The experimental data were extracted
Mohammadi et al. [150], the wettability alteration ability of the LSW from [119].

13
G. Dordzie and M. Dejam
50
45
IFT versus surfactant concentration
Contact angle versus surfactant concentration
40
IFT (mNm/m)
35
30
25
20
15
10
0.0 0.2 0.4 0.6 0.8
Surfactant concentration (wt%)
Fig. 18. The effect of surfactant concentration on the IFT and contact angle. The
experimental data were extracted from [119].
7.2. Combination of LSW and NPs as EOR agents
A recent effort by Sadatshojaei et al. [155] studied the IFT change and
the wettability alteration of a carbonate core using silica NPs coupled
with LSW. They revealed that increasing the concentration of the silica
NPs is favorable for reducing IFT, changing the wettability to a more
water-wet condition, and increasing the viscosity of the NPs-LSW for-
mulation, which improves the displacement efficiency. Furthermore,
Sadatshojaei et al. [155] explained that increasing the salinity of LSW
(above 6000 ppm especially) decreases the stability of the NPs and re-
sults in a reduction in wettability alteration ability of the NPs-LSW
combination.
The sequential injection of NPs after LSWF is successful in altering
the wettability of the carbonate rock and reduce the IFT [156]. There ex-
ists an amorphous structure of NPs as shown by the transmission elec-
tron microscopy (TEM) image in Fig. 19 when it reacts with brine in
the pores, which detaches the oil from the rock and alters the wettabil-
ity to a more water-wet condition faster than LSW (Fig. 19). Further-
more, Hamouda and Abhishek [157] and Abishek et al. [158] also
revealed that the combination of LSW and NPs would result in less for-
mation damage and chalk dissolution.
Fig. 19. Schematic representation of the interaction among the NPs, oil, and LSW in the pores of the reservoir (after [156]).
Advances in Colloid and Interface Science 293 (2021) 102449
180
7.3. Combination of NPs and surfactants as EOR agents in fractured systems
160 The combination of NPs and surfactant solutions has been proven
to impact EOR positively [159–166]. The challenge of adsorption
Contact angle (degree)
140 of surfactants onto the rock surface has been extensively discussed
by Belhaj et al. [167]. Consequently, some researchers have investi-
gated and shown that surfactants are adsorbed onto the surface of
120
NPs, which would reduce their adsorption onto the rock surface
[29,134,168]. Subsequently, the use of NPs and surfactant solutions
100 has been studied for various reservoir systems but few experimental
studies have been conducted for FCRs in literature. For example, the
80 synergistic effect of the combination of ZnO NPs and SDS surfactant
has been investigated by Moghadam and Azizian [169]. It was con-
cluded that the addition of ZnO NPs to SDS reduced the interfacial ten-
60
sion faster than the use of SDS alone. Additionally, Nwidee et al. [170]
1.0
studied the wettability alteration of oil-wet limestone using combina-
tions of NPs (NiO and ZrO2) and surfactants (Triton X-100 and C16TAB)
under temperature conditions up to 70 °C. They explained that the use
of the NiO/C16TAB, NiO/Triton X-100, ZrO2/C16TAB, and ZrO2/Triton X-
100 NPs-surfactant formulations altered the wettability of the lime-
stone chalk better than the individual surfactant solutions [170]. It
was also observed that the ZrO2/C16TAB formulation performed the
best for all temperature conditions tested. It is worth mentioning
that the surfactants act as a bridge between NPs and the base fluid
in a surfactant-NPs formulation and the ratio of the concentration of
surfactant to NPs determines their surface properties [140]. A low con-
centration ratio results in the adsorption of a monolayer of surfactants
onto the surface of the NPs, which results in a hydrophobic surface. On
the other hand, a high concentration ratio results in the adsorption of a
bi-layer of surfactant onto the surface of the NPs, which may result in
higher stability and hence favor wettability alteration and IFT reduc-
tion [140].
According to Mohajeri et al. [28], the addition of 100 ppm of ZrO2
(ZrO2 100) solution to 3000 ppm of CTAB (CTAB 3000) and 2000 ppm
of SDS (SDS 2000) surfactants resulted in more oil recoveries compared
to water injection and 3000 ppm of ZrO2 solution (ZRSL 3000) and CTAB
or SDS surfactant solutions as shown in Fig. 20. Fig. 21 shows the ten-
dency of NPs and surfactant combinations in reducing IFT and altering
the wettability of a fractured micromodel. Besides, the emulsion formed
by NPs and surfactants alters their rheological properties and results in
effective surfactant action on oil recovery [28].
14
G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

60
noted that the size, concentration, and effective charges of the NPs solu-
Water tion have significant impacts on the wettability alteration and IFT reduc-
ZRSL 3000
50 SDS 2000
tion that influence EOR in carbonate reservoirs [134]. The alternating
CTAB 3000 injection of LNS solutions was observed to be highly effective in carbon-
ZrO2 100 + SDS 2000 ates [156]. It is worth mentioning that this alternating injecting of LNS
40 ZrO2 100 + CTAB 3000 should be investigated for FCRs as well.
Oil recovery (%)

30
8. Results from simulation studies

20 Among several simulation investigations conducted on carbonate

10
0 ative permeability curves to represent physical or chemical interactions
Fig. 20. The effects of the combination of NPs and surfactants on the oil recovery in a
fractured system. The experimental data were extracted from [28].
7.4. Combination of LNS as EOR agents
Researchers have investigated the abilities of NPs to change the wet-
tability and IFT as well as reduce fines migration in the reservoir during
LSW flooding, especially leading to EOR [78,130–132]. It should be
reservoirs, some have studied the impact of temperature, wettability al-
teration, and IFT reduction of LNS solutions in fractured systems on EOR
at field conditions. The results from the recent simulation studies are
presented and discussed. Aljuboori et al. [26] simulated LSWF using rel-
that are not included in the fine-scale and field-scale models. They in-
ferred from the fine-scale and field-scale model results that LSWF is
suitable for recovery from FCRs. The field-scale model showed a high
oil production rate of 32,000 BPD by the end of year fourteen whereas
high salinity waterflooding (HSWF) recorded 25,000 BPD. Additionally,
it has been revealed that LSWF tends to increase oil recovery from the
matrix even with small changes in kr in the numerical simulation
model [9]. Fig. 22a and b show the increment in the oil recovery with
time using the simulation model with kr changes.

(a)
(a)
0.6
20
Surfactant/NPs only
Surfactant + NPs 0.5
Oil recovery (fraction)

15
0.4
IFT (mN/M)

0.3
10
HSWF
0.2
LSWF, tertiary mode, maximum kr alteration
LSWF, tertiary mode, average kr alteration

0.1 LSWF, tertiary mode, minimum kr alteration

5

0.0
0 2 4 6 8 10
0 Time (year)
SDS CTAB ZRSL
(b)
(b) 0.6
120

0.5
100 Without ZrO2 NPs
With ZrO2 NPs
Oil recovery (fraction)

0.4
Contact angle (degree)

80

0.3 LSWF, SP, maximum kr alteration

LSWF, DP, maximum kr alteration
60
LSWF, SP, average kr alteration
0.2 LSWF, DP, average kr alteration
LSWF, SP, minimum kr alteration
40
LSWF, DP, minimum kr alteration
0.1
HSWF, SP
HSWF, DP
20
0.0
0 2 4 6 8 10
0 Time (year)
Crude Oil SDS CTAB ZRSL

Fig. 22. The effect of LSWF on the oil recovery, showing (a) the level of kr changes (b) the
Fig. 21. The effects of NPs and surfactant solutions on the (a) IFT and (b) wettability. The impact of single-porosity (SP) and dual-porosity (DP) models. The data were extracted
experimental data were extracted from [28]. from [9,26].

15
G. Dordzie and M. Dejam Advances in Colloid and Interface Science 293 (2021) 102449

70 (a)
1.0
60 Surfactant flooding [108]
Waterflooding + Decreased mobility [108] Water-wet core
Surfactant flooding + No phase trapping [108] Oil-wet core
50 Surfactant + Brine injection [109] 0.8
Waterflooding [45]
Oil recovery(%)

Alkaline flooding [45]

Oil recovery (fraction)

Surfactant flooding [45]
40
0.6
30

20 0.4

10
0.2

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore volume injected 0.0
0.01 0.1 1 30
IFT (mN/m)
Fig. 23. The effect of surfactant flooding on the oil recovery. The data were extracted from
[45,108,109].
(b)
70
Cummulative oil recovery after 1.5 PVI
There is a consensus from various numerical simulations as shown in Wettability alteration only
60
Fig. 23 that surfactant flooding is also a suitable candidate for field appli- IFT reduction only

Cummulative oil recovery (%)

cation of EOR in fractured carbonate rocks [45,108]. IFT reduction + Wettability alteration
50
The sensitivity of the oil recovery in the various simulation models to
IFT reduction and wettability alteration is shown in Fig. 24. The oil re-
covery is fastest for high IFT in the water-wet conditions while the 40

fastest oil recovery was recorded for the lowest IFT value under oil-
wet conditions (Fig. 24a). Also, a combination of IFT reduction and wet- 30
tability alteration yielded the highest oil recovery after 1.5 PV injection
surfactant slug followed by brine drive (Fig. 24b). 20
The simulation results show that LNS solutions have the tendency to
improve oil recovery in FCRs at a field scale. Nonetheless, the different 10
combinations proposed need to be investigated for FCRs in order to fur-
ther simulate the EOR applications at a field scale. Also, various models 0
have been developed in the attempt to characterize the behavior of
nanofluids and LSWF in the reservoir [171–176]. However, most of Fig. 24. The effect of IFT reduction and wettability alteration on the oil recovery in
these models are limited to physical interactions and do not incorporate fractured carbonates using simulation models and showing (a) sensitivity to time and
chemical interactions in their development. (b) sensitivity after 1.5 pore volume injection (PVI). The data were extracted from
[94,110].

9. Limitations in the application of LNS

The formulation of surfactants to stabilize and prevent the aggrega-
tion of NPs at harsh reservoir conditions is still required to extend labo-
ratory findings to field operations. The existing theoretical models and
numerical studies do not entirely characterize the behavior of nano-
fluids in the reservoir. Also, the upscaling of the application of NPs to
field-scale is still a challenge. This stems from the uncertainty on the
stability of nanofluids at harsh reservoir conditions and the limited
experimental studies in this area. It should be noted that the combina-
tion of LNS for EOR applications could increase the operational costs of
the EOR process.
10. Summary and conclusions
This study presented a comprehensive review of the application of
LNS solutions in FCRs and the mechanisms that influence the enhance-
ment of the oil recovery. The major findings of this review are described
as follows.
• LSWF has been successfully applied in FCRs and potential determining
ions at optimum concentrations aid in the wettability alteration to a
more water-wet condition, which is favorable for EOR in FCRs. Further
explanations from recent works have shown that the formation of
micro-dispersions is the main mechanism responsible for the wetta-
bility alteration in carbonate rocks. Simulation results have also dem-
onstrated the potential of LSWF EOR applications at a field scale.
• Surfactant flooding has also been successfully applied in FCRs. Mobil-
ity control during surfactant flooding is crucial in ensuring the effi-
ciency of the flooding process. Although mobility control agents are
often used, surfactants with the tendency to form micro-emulsions
can be used as substitutes because they are equally effective and
even less costly.
• NPs are rarely applied as EOR agents in FCRs although they showed
promising results with few investigations. Doubts arise with their ap-
plications in oil-wet fractured reservoirs. However, it could be as a re-
sult of the lack of their application in actually fractured carbonate rocks.
• Synergism among the LNS solutions has been established and found to
have great potentials for EOR applications in FCRs. For instance, a com-
bination of LSW and NPs would reduce formation damage and chalk
dissolution. Surfactants tend to adsorb onto the surface of NPs and
are therefore prevented from adsorbing onto the pore walls. A combi-
nation of LSW and surfactant are more effective in increasing oil recov-
ery than their individual solutions. Alternating injection of LNS
solutions in carbonates has been reported to be highly effective in mit-
igating the challenges that occur during the injection of their individual
solutions in carbonates. Therefore, the alternating injection method
should be extended to FCRs.
• Recent simulation results have confirmed the effectiveness of the EOR
application of LNS solutions in carbonate reservoirs. Nonetheless, fur-
ther experimental data are required for applications in FCRs at a field
scale.

16
G. Dordzie and M. Dejam
11. Future prospects and recommendations
Overall, the application of LNS in EOR is promising and should be ex-
tended to FCRs. A combination of LSW and surfactant, LSW and NPs, and
NPs and surfactant have been successfully applied in various carbonate
systems. Therefore, their application in FCRs and applicability under
field conditions are highly recommended for investigation. Other pros-
pects and recommendations are outlined as follows.
• Surface-modified NPs are promising in enhancing oil recovery but fur-
ther theoretical and experimental investigations are required for their
applications in harsh reservoir conditions and FCRs.
• The application of environmentally friendly surface-modified NPs is
strongly recommended for FCRs.
• This review shows that the application of NPs for EOR purposes in
fractured systems such as FCRs needs to be investigated because
there is currently very little attention paid to this area.
• The use of a mixture of different NPs has not been adequately investi-
gated in literature and therefore novel applications could be discov-
ered in this area especially for FCRs.
• The stability of NPs remains a concern under field conditions and
hence the need for the investigation of their applications under
harsh reservoir conditions.
Declaration of Competing Interest
The authors declare that there is no conflict of interest.
Acknowledgments
The financial support from the Department of Petroleum Engineer-
ing in the College of Engineering and Applied Science at the University
of Wyoming is gratefully appreciated.
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