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REVIEW
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Low Salinity Water–Polymer Flooding in Carbonate Oil

Reservoirs: A Critical Review
Fabio Pedro Nascimento, Verônica de Jesus Pereira, Ladislane dos Santos Bastos,
Gloria Meyberg Nunes Costa, and Silvio Alexandre Beisl Vieira de Melo*
Dedicated to Professor José Carlos Pinto on the occasion of his 60th birthday.

oil toward the production well. Water flood

Low salinity water–polymer flooding (LSWPF) is an emerging hybrid enhanced is usually the favorite secondary recovery
oil recovery (EOR) method that uses the synergetic effects of low salinity method because it is cheaper than gas. Also,
water (LSW) and polymers to enhance both the microscopic and macroscopic water is relatively abundant in the produc-
sweep efficiencies. Polymer flooding is an EOR method that aims to increase tion facilities. However, water viscosity is
relatively low, requiring polymer addition to
water viscosity and improve the mobility ratio of the injected fluid to the
increase it.
reservoir. It enhances mobility control and reduces water relative permeability, Polymer flooding (PF) is a CEOR method
reaching a more favorable condition for sweep efficiency. LSW is an EOR that involves adding polymers to increase
method that aims to change wettability by exploiting crude oil and reservoir water viscosity. Increasing water viscosity
rock interactions. It allows for improving oil recovery when the injected water improves the mobility ratio of the injected
fluid to the reservoir fluid due to increased
has a very low salinity compared to seawater or formation water. The literature
sweep efficiency reaching a more favorable
reports LSWPF studies applied to sandstone reservoirs. However, LSWPF condition. Also, it allows for improving mo-
applications in carbonate reservoirs still lack. This review critically analyzes bility control and reducing the water’s rela-
LSWPF as an alternative to Polymer flooding using seawater in carbonate tive permeability.
reservoirs. Compared to water flooding, PF avoids
fingering phenomena, i.e., when only wa-
ter is injected, it flows through the porous
media faster than oil, and a significant portion of the reservoir
1. Introduction is not contacted by water. Consequently, the amount of oil recov-
Despite the energy transition and the incentives for renewable re- ered by water flooding is less than by PF. Adding small amounts
sources, the world demand for oil and gas is increasing. So, dis- of water-soluble polymers decreases water mobility compared to
covering new reservoirs and employing tertiary production meth- oil, and the water sweeps the oil as a piston without forming
ods to recover residual oil will continue to be necessary. These fingers.
methods are referred to as enhanced oil recovery (EOR). Among PF has been widely applied in sandstone rocks, but much
the type of EOR methods, one of the most important is chemi- fewer reports of PF in carbonate rocks are available in the liter-
cally enhanced oil recovery (CEOR), representing about 11% of ature. Oil recovery is generally relatively poor in carbonate for-
worldwide projects. mations due to their oil-wet nature and geological heterogeneity,
EOR methods are tertiary because the primary and secondary which is higher than in sandstone reservoirs. However, investi-
recovery processes precede them. Oil production exploits the dif- gating EOR in these systems is crucial because they cover most
ferential pressure between the reservoir and the well in primary worldwide oil reservoirs.
recovery. In contrast, a second recovery is necessary when this Low salinity water (LSW) flooding or smart water flooding is
pressure is not enough to keep the production economically fea- another CEOR method where the injected water has a very low
sible. So, gas or water is injected into the reservoir to push the salinity compared to seawater or formation water. LSW injection
allows changing the wettability and other properties by interact-
ing with crude oil and reservoir rock, aiming for a more desirable
F. P. Nascimento, V. de J. Pereira, L. dos S. Bastos, G. M. N. Costa, condition for oil recovery.
S. A. B. Vieira de Melo
Programa de Pós-Graduação em Engenharia Industrial
LSW can produce up to 10% extra crude oil compared to water
Escola Politécnica flooding, with some advantages such as lower capital cost, ease of
Universidade Federal da Bahia injection, and availability of water. As an alternative to PF using
Rua Aristides Novis, 2, Federação, Salvador, Bahia 40210-630, Brazil seawater, LSW can be combined with PF, considerably decreas-
E-mail: sabvm@ufba.br ing polymer consumption. The literature reports some studies
The ORCID identification number(s) for the author(s) of this article on low salinity water–polymer flooding (LSWPF), mainly in sand-
can be found under https://doi.org/10.1002/mren.202300007 stone reservoirs. However, a critical analysis of LSWPF in carbon-
DOI: 10.1002/mren.202300007 ate reservoirs still lacks.

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Figure 1. Comparison of displacement front stability for a) waterflooding
and b) PF.
This review focuses on the following:
1) The fundamental concepts to develop a hybrid EOR method
by the combination of LSW and PF (LSWPF);
2) The effect of hybrid LSWPF on residual oil saturation: capil-
lary desaturation;
3) The LSWPF recovery mechanisms:
i) wettability modification using LSW;
ii) the role of potential determining ions (PDIs) and pH;
iii) favorable mobility ratio from PF;
iv) enhanced polymer stability using LSW;
v) LSW effect on polymer retention;
vi) impact of polymer on LSW performance;
4) Potential risks associated with LSWPF;
5) Lab-scale studies.
To better understand the synergistic effects of hybrid LSW and
PF on oil recovery, the following two sections separately address
the PF and the LSW flooding, respectively, followed by another
one on LSWPF.
2. Polymer Flooding (PF)
2.1. Mechanisms of Polymer Applications for EOR
If only the conventional oil recovery method with fresh water is
employed, the oil recovery factor will be low. Any EOR aims to
get the mobility ratio (M), i.e., the ratio of displacing phase mo-
bility to displaced phase mobility, less than 1.0. When the dif-
ference between oil and water viscosity expressed by a mobil-
ity ratio is greater than 1.0, the fingering process and the rela-
tively rapid breakthrough will occur. Since the water tends to fol-
low the path of least resistance, viscous fingering is created, as
shown in Figure 1a. Consequently, this injection significantly re-
duces the reservoir’s volumetric sweep efficiency (macroscopic
displacement efficiency) by water flooding.[1]
The injection of large water volumes to increase oil produc-
tion with a high recovery rate is only possible if measures are
taken to improve sweep efficiency. Solving this problem requires
using polymeric solutions with a non-Newtonian behavior with
adjustable rheological properties.[2]
This flooding enhances the viscosity of displacing fluid and
decreases the mobility ratio. In addition to this efficiency, the vis-
coelastic nature of the polymers also increases the microscopic
efficiency. This method reduces the hydrodynamic instability of
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the oil–water displacement front due to the unfavorable oil and
water viscosity ratio in reservoir conditions. Therefore, a stable
displacement front is observed, which means the mobility ratio
is less than 1.0, and occurs a piston-like flow (Figure 1b).
According to Needham and Doe,[3] there are three effects by
which polymer solutions may lead to an increase in oil recovery
in comparison to conventional water flooding: 1) by decreasing
the water/oil mobility ratio, 2) through the effects of polymers
on oil fractional flow increase as a consequence of the reduction
of the mobility ratio, and 3) by diverting the injected water from
zones that have been swept.
The following factors determine the mechanism of PF: a) cap-
illary number increase due to the increase of the injected polymer
solution viscosity compared to water without polymer. From this
viewpoint, this method is particularly effective in heterogeneous
formation and high-viscosity oil. Water-soluble polymers used
in PF are anionic surfactants (surface active agents) that will re-
duce the system’s surface tension. Regarding the non-Newtonian
properties of polymer solution, water-soluble polymers used in
PF exhibit pseudoplastic rheological behavior. To increase the
area sweep efficiency, injecting liquids with opposite behavior
is preferable, i.e., if the liquid flows fast, its viscosity increases
(shear-thickening) or dilatant rheology. This performance allows
a more stable water–oil bank.[4]
In a porous medium, the polymer solution can exhibit dilatant
rheology caused by changes in molecular conformation involving
the formation of additional links between two chains that occur
due to coil-stretched transitions of the polymer chains. Polymer
solutions, such as Xanthan, are characterized by shear-thinning
rheology. In this case, viscosity is low at a high shear rate. Poly-
mer retention includes adsorption, mechanical entrapment, and
hydrodynamic retention, which can reduce the polymer flood effi-
ciency delaying oil movement and recovery. Therefore, minimal
polymer adsorption is required. Both oil and connate water are
displaced during the PF. Polymer adsorption from the injected
solution occurs due to the direct interaction between this solu-
tion and the reservoir. Then, a layer of water with a low polymer
concentration forms due to the decrease in the polymer concen-
tration of the solution. In PF, an increase in reservoir sweeping
can occur due to polymer adsorption on the rock surface, which
reduces the mobility of the polymeric solution and decreases the
permeability. However, polymer adsorption increases with reduc-
ing permeability. Thus, high adsorption can cause a displacement
front of the water with low polymer content, reducing the effi-
ciency of the process because the oil is mainly displaced by water,
which lacks the advantages of the high viscosity of the polymer.
The most critical mechanism in polymer flow for improving
oil recovery is the decrease of the mobility ratio due to the vis-
cosity increase of the displacement fluid.[5] However, according
to Gbadamosi et al.,[1] two other mechanisms are fundamental:
huge permeability reduction and viscoelasticity.
2.1.1. Huge Permeability Reduction
In waterflooding, due to heterogenous reservoirs (different lay-
ers with different permeability), mobility of the injected water is
faster than oil. This behavior results from the high permeable lay-
ers where water flows more easily. Therefore, significant areas of
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Figure 2. Typical PF.
the reservoir are not contacted by water. This process results in
elevated amounts of oil and gas trapped. To increase the recov-
ery factor by adding a water-soluble polymer solution can form
a molecular layer of polymer onto the pore walls due to adsorp-
tion. As this film, assumed to be of uniform thickness, contacts
the water in a water-wet reservoir, it swells, reducing the pore
sizes and generating resistance for the water flow solution. At
the same time, it allows the oil to flow. The available pore area
also reduces due to the tails, loops, and protruding ends from
the flowing polymer.[6]
2.1.2. Viscoelasticity
Polymers used in PF are viscoelastic, i.e., exhibit viscous and
elastic characteristics when undergoing deformation. Therefore,
polymer macromolecules expand and contract by stretching and
recoiling when flowing in porous media. The current assessment
indicated that PF could improve sweep and displacement effi-
ciency.
Three mechanisms are responsible for the polymer viscoelas-
tic effects on oil mobilization: the pulling mechanism, stripping
mechanism, and mechanism of oil thread flow.[7]
The oil lodged at rock fractures and pores not well connected
cannot be displaced by water flooding because of the configura-
tion constraints of the oil. With the polymer solution’s viscoelas-
ticity increasing, the residual oil in the not well-connected pores
decreases (a pulling mechanism).
The residual oil adheres to the rock surface in an oil-wet core,
forming a continuous oil film. The experimental investigation re-
ported by Wang et al.[8] with measured velocity profiles of water
and polyacrylamide (PAM) solution in a capillary indicates that
the force to “strip” the oil film off the tube wall was more sub-
stantial for the polymer solution (a stripping mechanism). Due
to heterogenous microscopic pores and capillary forces, a frac-
tion of the trapped oil may be displaced by polymer solution with
a combination of pulling and stripping mechanisms.[7,8]
After the waterflood, the residual oil became isolated oil
droplets. Then, the polymer solution pulled the oil into oil
columns. These oil columns form “oil threads.” Because of the
cohesive force of the oil/water interfaces, it was also possible to
develop new oil droplets (mechanism of oil thread flow).[7]
A typical polymer flood is shown in Figure 2.
Regarding conventional PF, there are two main types of poly-
mers commonly used in EOR: synthetic and biopolymers. Ac-
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cording to Sheng,[7] a polymer suitable for oil displacement must
follow these essential criteria:
1) The carbon chain in the backbone must not contain oxygen
atoms to guarantee thermal stability;
2) The backbone must contain negative ionic hydrophilic
groups, such as –COO−, to reduce adsorption on the sand-
stone’s surface due to the repulsion between chain links. This
structure also guarantees good viscosity behavior (thickening
agent). On the other hand, less chemical stability.
3) The backbone must contain nonionic hydrophilic groups,
such as –OH or –CONH2 , to guarantee chemical stability but
no repulsion between chain links. Thus, less viscosity behav-
ior and high adsorption are due to the hydrogen bond between
the polymer solution and the sandstone rocks.
Polyacrylamide (PAM) is the reference synthetic polymer used
to reduce mobility, increasing the corresponding solution viscos-
ity in PF.[9] It is a high molecular weight (>106 g mol−1 ) polymer
formed from acrylamide and its derivate with chemical formula
-[CH2 CH]x (CONH2 )-. Also, it is a nonionic, water-soluble, and
biocompatible polymer due to the strong hydrogen bond between
amide groups and water molecules.[10]
Partially hydrolyzed polyacrylamide (HPAM), a copolymer of
acrylamide and acrylic acid, is the most used polymer in EOR
applications. With the chemical formula -[CH2 CH]x (CONH2 )-
[CH2 CH]y (COO− )-, it is obtained by partial hydrolysis of PAM.
Some amide groups (CONH2 ) convert to carboxyl groups (COO− )
with a hydrolysis degree between 15% and 35%.[11] However,
there is a limit to the degree of hydrolysis, as it increases the
brine’s sensitivity to salinity.[9] HPAM has a coil conformation
making it extremely sensitive to ionic environments.
In freshwater, this process creates electrostatic charges along
the polymer backbone due to the charge repulsion of the car-
boxylic group. The electrum repulsion can promote the stretch-
ing of the polymer chains in water and increase viscosity.
In contrast, in saline water, when adding an electrolyte to a
polymer solution, the repulsive forces are shielded or neutralized
by a double layer of electrolytes; so, HPAM flexible chains are
compressed, resulting in low viscosity.[7,9]
Low hydrolysis and more CONH2 increase chemical stability,
but adsorption rises too. However, there is a limit in the hydrol-
ysis degree because when it is higher, COO− increases so that
the adsorption reduces and the viscosity increases. Still, chemi-
cal stability reduces owing to less CONH2 .
The viscosity reduces when hydrolysis is above 40% because
the flexible chains are seriously compressed and distorted. A
higher hydrolysis degree causes precipitation in the presence of
divalent cations such as Ca2+ and Mg2+ . Strong interactions be-
tween COO- and cations can reduce viscosity in HPAM even
without polymer precipitation.
2.2. Polymer Screening Criteria and Requirements for PF
The polymer screening criteria go beyond good rheological, ther-
mal, and adsorption properties. The polymer should also have
compatibility with reservoir brine, chemical stability, biological
stability, shear stability, good injectivity, and low cost.
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There are advantages and disadvantages to each polymer. For
example, suitable viscosity is obtained with PAMs in freshwa-
ter with its adsorption on the rock surface. The result is a long-
duration permeability reduction. However, its disadvantages are
at high-flow rates, where shear degradation occurs, and high-
salinity water (HSW) retention. Good viscosity behavior and re-
sistance to shear degradation are observed in biopolymers in
HSW. The temperature limit for reservoir applications is the fast
thermal degradation of biopolymers and PAMs at a temperature
above 93 °C, in the presence of calcium.[12]
In some cases, achieving more viscosity is not a good choice
to increase the polymer concentration. Consequently, there is an
increased cost and injectivity problem because an increased in-
jection pressure will be necessary.[13] Otherwise, for a given con-
centration, a high molecular weight polymer will produce higher
viscosity polymer solutions, higher resistance factors (the resis-
tance to flow by a polymer solution compared to the flow of wa-
ter), higher permeability reductions, and higher oil recoveries.
On the other hand, a higher tendency for share degradation will
be observed, reducing the molecular weight. Also, by increasing
molecular weight, the polymer molecule size may be larger than
the pore size and will cause reduced injectivity. Thus, the polymer
may plug the pore space as it flows through.[12,13]
This summary includes the parameters that contribute to the
success or failure of a PF project, including oil gravity and viscos-
ity, porosity, oil saturation (start and end), permeability, depth,
and temperature.[14] Other essential parameters in designing
polymer flood are: American Petroleum Institute (API) gravity
should be higher than 13, low salinity of injected and formation
water is preferred less than 40 g L−1 (divalent more critical), and
low clay content in the reservoir.[4,15]
The PF technique often applies for oil recovery in sandstone
reservoirs. However, it is restricted in carbonate reservoirs due to
harsh conditions: the high salinity formation water, the high tem-
perature, and the low permeability (poor injectivity).[16] The type
and nature of the porosity affect the oil recovery by PF. The pore
surface and volume strongly influence reservoir rock’s retention
characteristics and flow. Also, clay content should be low since it
strongly affects the pore throats in the reservoir, the flow behav-
ior, and permeability. This phenomenon occurs because certain
minerals swell when contacted with nonequilibrium waters.[4]
Salinity and water hardness are key parameters in PF. Its qual-
ity and quantity exert a favorable or unfavorable effect depending
on the total salt concentration and the concentration of monova-
lent and divalent salts. According to Shakeel et al.,[5] the best con-
ditions in formation water are: salinity must be <100 000 ppm,
chlorides must be <20 000 ppm, Ca2+ and Mg2+ divalent ions
must be <500 ppm, low salinity (LS) is preferred to avoid polymer
degradation.
Polymer adsorption can reduce permeability. The reservoir
permeability and heterogeneity influence the success of PF and
dominate the water injection rate. Due to its high viscosity and
reduced mobility, the polymer solutions used for flooding have
lower injectivity than the solvent brine. The polymer solution’s
injectivity decreases with the polymer’s molecular weight, and
the injection rate directly affects the efficacy of the PF. Because
of the lower injectivity of the polymer solution, it is necessary to
increase its volumetric displacement efficiency so that flood life
does not extend. The injectivity decreases in shallow, low perme-
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ability reservoirs under pressure-limited conditions, which may
be an economic problem.[12] Technically, the permeability of the
rock should preferably be up to 5500 mD. It must be above 10
mD, especially when the polymer weight is high, so the molecu-
lar size is larger than the pore throat.[14]
As pH affects hydrolysis, HPAM viscosity is pH dependent,
and the carboxyl groups mainly control its pH-sensitive rheo-
logical properties. At high pH values, the carboxyl groups dis-
sociate and are negatively charged. Consequently, a strong elec-
trostatic repulsion develops between them, with polymer chains
stretched, increasing solution viscosity. At pH = 6, the polymer
molecules reach their maximum extension, resulting in the max-
imum viscosity. At low pH, no charges on the polymer chain
result, and the polymer molecules are tightly coiled, decreasing
viscosity.[17]
2.3. Challenges Associated with PF
Polymer retention due to mechanical trapping and adsorption
can reduce the polymer flow efficiency. Minimum adsorption is
the process target. Polymer retention causes economic problems
since reducing the available polymer to flooding flow with a favor-
able mobility ratio will require a higher polymer concentration.
Polymer chemistry and its composition in the brine solution,
reservoir rock composition, and temperature influence polymer
retention. The polymer adsorption is heavily affected by electro-
static attraction between the reservoir rock surface and the ionic
polymer. In the sandstone reservoir, the HPAM adsorption de-
creases due to the reservoir surface’s negative charge and the
polymer structure’s high carboxylic group. However, high adsorp-
tion of HPAM in sandstone reservoir occurs with a high salt con-
centration, allowing interaction between this rock and polymer.
On the other hand, in a carbonate reservoir, the HPAM adsorp-
tion is very high. This retention process is due to the strong inter-
action between Ca2+ in the carbonate reservoir and the negative
carboxylic groups in the polymer structure. There is a relation-
ship between polymer retention and permeability. As the perme-
ability decreases, mechanical entrapment and polymer retention
increase. The instability and degradation of polymers under high
temperatures and high salinity are a great challenge in PF due to
the resulting viscosity reduction and precipitation in the presence
of high-salinity reservoir brine. It is known that pH and temper-
ature affect the rate of hydrolysis. It is low at neutral pH and in-
creases in acid or basic environments. There are divalent cations
concentrations and temperature restrictions for reservoir brine:
when the concentration is less than 200 ppm, HPAM is safe to
use up to 100 °C. If divalent concentrations exceed 200 ppm, the
temperature application limits to 70 °C.[18]
In PF, it is imperative to evaluate the polymer stability crite-
ria to avoid polymer degradation (a process that breaks down the
molecular structure and, consequently, partial or complete vis-
cosity loss). Polymer stability throughout polymer propagation
is vital since the EOR process is lengthy. For example, hydroly-
sis should be less than 40% after 3 months.[7] In reservoirs with
high well-spacing, this is a major challenge. For example, the res-
idence time could be in years in offshore fields.[16]
High temperature and low permeability are the main chal-
lenges for PF with biopolymers, and for synthetic polymers, high
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salinity/hardness is the primary concern. Understanding that
these challenges vary from reservoir to reservoir is essential.[16]
Regarding oil recovery, to evaluate the primary degradation
sources, the following stability criteria must be analyzed: chemi-
cal, mechanical, and biological.
Two approaches must be considered when analyzing chemi-
cal stability: the presence of contaminants, such as oxygen and
iron (oxidation–reduction), and attack to the molecular backbone
(hydrolysis). The first source of polymer degradation for HPAM
solution is temperature. At low temperatures, this effect is not
significant. However, as the temperature increases, it becomes
stronger.
Regarding hydrolysis, the temperature and the divalent effects
are relevant. The amide groups in HPAM hydrolyze in an aque-
ous solution depending on pH and temperature. The degree and
rate of hydrolysis increase with temperature, a linear function of
pH. If the hydrolysis is greater than 30 mol%, the solution has
a sufficient degree of hydrolysis, and in the presence of divalent
cations, HPAM precipitates.[16,19]
Mechanical degradation refers to the breakdown of molecules
in the high-flow rate region and the result of high mechani-
cal stresses on polymer molecules. This degradation occurs at
chokes and perforations in a porous medium, especially in the
near wellbore area. Mechanical degradation is more pronounced
in low permeability formations where small pore throats exert
more stress on the molecules. A tiny pore throat diameter low-
ers the polymer’s molecular weight, viscosity loss, and pore plug-
ging. The mechanical degradation represents a severe economic
limitation in the polymer solution injected in low permeability
reservoirs.[16]
Biological degradation refers to the bacterial breakdown of
polymer molecules during storage in the reservoir. Synthetic and
natural polymers are subjected to this degradation, but the prob-
lem is more prevalent for biopolymers.[7]
3. LSW Flooding
Water injection is an oil recovery method used when the reser-
voir’s natural energy is insufficient to promote the oil flow to the
surface.
The most common practice in waterflooding is the reinjection
of produced water. Several problems arise from this procedure:
the produced water volumes are insufficient to restore the sys-
tem pressure, and more complex surface conditions are not read-
ily available on site. On the other hand, we can highlight some
economic and technical advantages of seawater injection, such
as abundance, lower cost convenience for offshore use, and im-
proved oil recovery.[20]
LSW flooding, also known as modified salinity waterflood-
ing or smart waterflooding, is a method to improve oil recovery
wherein the injected water has very low salinity compared to sea-
water or formation water.[21]
The injected LSW interacts with crude oil and reservoir rock,
disturbs the initial thermodynamic equilibrium, and reaches a
new equilibrium, which modifies the wetting properties toward
a more desirable condition and releases the trapped or adsorbed
oil. This behavior depends on the characteristics of the crude oil,
the reservoir condition, and the properties of the formation brine
(FB).[22]
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LSW is widely used due to its high efficiency. It can produce up
to 10% extra crude oil compared to simple waterflooding. Lower
capital cost, ease of injection, availability of water, and environ-
mental friendly are the main advantages of this technique.[23]
LSW injection also has the benefit of using chemical processes
instead of seawater in PF. This process can decrease polymer con-
sumption considerably.[24] The injected LSW interacts with crude
oil and reservoir rock, improving final oil recovery.
In positively charged carbonate surfaces, the adsorption of
negatively charged carboxylic materials (–COO− ), present in the
heavy end fractions of crude oil, such as resin and asphaltene
fractions, occurs. An increase in the concentration of divalent an-
ions, in particular, SO4 2− , in carbonates surface, originally oil-wet
and positively charged, plays a critical role in decreasing the rock
surface potential. Therefore, the divalent cations Ca2+ and Mg2+
can be conjoined to the oil.[25] However, the industrial applica-
tion of LSW is limited because its mechanisms are still a topic of
much debate.
Due to the chemical interactions between the carbonate
rock/brine/oil system and the complexity of carbonate reservoirs,
there has not been a consensus on the underlying mechanisms.
Nonetheless, wettability modification from oil to water-wet by
chemical treatment has been a commonly accepted mechanism
for LSW.
Among the mechanisms suggested to promote additional oil
recovery in carbonate reservoirs are multicomponent ion ex-
change (MIE), mineral dissolution, fluid–fluid interactions, elec-
tric double layer (EDL) expansion, and fine migration. Pressure,
temperature, water, and crude oil chemistry affect the wettability
alteration and is a mechanism that involves the physical and
chemical interactions between fluid and rock surface, especially
interactions across the film between oil and rock.[26] A summary
of the advantages and limitations of the main mechanisms
related to the injection of LSW into carbonates is presented in
Table 1.
MIE, as the main drive for wettability change in carbonate,
was first proposed by Austad et al.[36] According to these authors,
PDIs (SO4 2− , Ca2+ , and Mg2+ ) must be present in the injection
brine for this mechanism. MIE, presented in the schematic of
Figure 3, occurs due to the exchange of anions, including the
adsorption of SO4 2− . This process leads to the co-adsorption of
Ca2+ and Mg2+ onto the rock surface resulting in desorption and
release of negatively charged acid components of crude oil from
the surface. The role of sulfate is as a catalytic agent. Calcium
and magnesium react with the adsorbed surface-active compo-
nent from the oil phase bonded to the rock surface, breaking the
attractive interaction between the oil and rock surface, releasing
some of them, and diminishing the oil-wet nature of the rock
surface.
Another suggested mechanism, elaborated by Hiorth et al.[37]
and Yousef et al.,[38] is the dissolution of calcite (collapsing some
of the pore space and hence the oil is expelled) as a mechanism
for wettability alteration. They observed an increased anhydrite
(CaSO4 ) precipitated due to the increase of SO4 2− ions in the
system owing to the LSW injection. The chemical dissolution of
calcite minerals increases to restore the equilibrium caused by
the loss of Ca2+ concentration in the brine solution. This disso-
lution enhances pore size and the connectivity between micro-
pores and macropores.[38] This process improves water wetness
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Table 1. Summary of the advantages and limitations of the main mechanisms related to the injection of LSW into carbonates.

Mechanism Advantages Limitations

Mineral dissolution
Multicomponent-ion-exchange
Electric double-layer
expansion
Mineral dissolution can remove the oil-wet layer on the
carbonate surface and expose a water-wet layer that has not
been aged by oil contact.[ 27 ]
Oil release can occur when dissolution takes place on the
mineral surface that has adsorbed oil.[ 28 ]
Mineral dissolution can connect macro- and micropores,
allowing access to regions that would otherwise not be
reached and increasing oil recovery.[ 29 ]
MIE is the most accepted mechanism in the literature when
discussing the injection of low-salinity water in carbonates.
EDL expansion is widely mentioned as a mechanism for
wettability alteration in carbonates and MIE.
The expansion of the layer between the mineral interface and
the oil occurs with the repulsive forces increase, which
favors the oil release.[ 35 ]
Mineral dissolution is not considered the main mechanism
that alone results in increased oil recovery through LSW
injection.[ 21,28,30]
Disagreements are mentioned regarding this mechanism,
mainly because recovery improvements were not observed
in tests with the injection of brines that could promote
mineral dissolution.[ 31–33]
MIE mechanism is favored at high temperatures (>70 °C).[ 34 ]
Sulfate is considered an ion exchange process catalyst, but
increasing its concentration too much can be detrimental
for oil recovery.[ 34 ]

Figure 3. Schematic of the multicomponent ion exchange mechanism.

because the oil molecules move from the rock surface due to cal-
cite dissolution.[32] The schematic of this mechanism is shown
in Figure 4.
A mechanism of EDL expansion, schematized in Figure 5, was
first suggested by Ligthelm et al.[39] EDL describes double-layer
ordered ions appearing on rock minerals exposed to pore fluid.
It occurs due to an unequal distribution of ions when a surface
electrically charged gets in touch with an aqueous solution. Con-
sequently, a potential will develop at the interface between this
surface and the solution. The first layer of EDL (a compact layer)

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Figure 4. Schematic of the Mineral dissolution mechanism.
comprises oppositely charged ions adsorbed onto the surface and
is closed to the charged surface. The second layer includes ions
loosely attracted to the surface charge and varying thicknesses.
The thickness of the EDL is dependent (inversely correlated) with
the ion strength of the solution. As a result, EDL expands in
LSW because the electrolyte concentration of the bulk water solu-
tion decreases, so suppressive force from the ions in the solution
decreases.[23] The EDL expansion increases the electrostatic re-
pulsive force between oil-brine and rock-brine interfaces, creates
a more stable water film on the rock surface, and causes the oil
complexes to desorb from the surface, thus altering the wettabil-
ity by increasing the water-wet condition.[25]
Different variables involved in LSW belong to reservoir param-
eters and injected brine parameters.
3.1. Reservoir Parameters
The PDIs present in the formation water and its pH can affect oil
recovery efficiency due to the interactions between the injected
brine and formation water (usually extremely saline) that change
wettability.
According to Derkani et al.,[25] pH variation is a temporary
mechanism to change wettability in carbonate oil reservoirs.
Among the PDI, we should highlight SO4 2− since it is the most
active anion that affects carbonate rock’s wettability. Even its
small concentration in formation water can influence the initial
wetting condition, therefore, the oil recovery efficiency.[40]
The correlation between initial water saturation and improved
oil recovery from limestone cores was studied by Strand et al.[41]
The experimental results showed increased oil recovery by in-
creasing the initial water saturation. However, for chalk cores,
Puntervold et al.[42] showed that depending on the range of ini-
tial water saturation, there is a positive or no correlation.
Estimating crude oil composition is one of the critical steps for
any LSW process. To create conditions of wettability alteration,
polar components in oil are essential. Asphaltene and resins are
the most polar fractions of crude oil, and their potent interfacial
activity can alter wettability. Functional groups of acidic and basic
organic molecules are related to the crude oil polarity. One way
of quantifying their presence in crude oil is through the total acid
number (TAN) and total base number (TBN).
The TAN and TBN are crucial in understanding the extent
of oil adsorption on the rock surface as well as the initial wet-
ting characteristics of rocks.[20] The effect of oil composition on
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carbonate wettability alteration was discussed by Takeya et al.[43]
Their results showed that an increase in TAN is related to a de-
cline of water moisture of carbonate rocks due to the strong bond
between the positive carbonate surface and negatively charged
acidic oil components. Standnes and Austad[44] similarly ob-
served that the oil recovery was about 70% when the oil had no
acidic polar components, while the oil recovery decreased dra-
matically with a TAN increase. Regarding the action of TAN, on
the chalk surface, the formation of an acid–base complex in the
crude oil was responsible for an increase in the water-wetting
state by increasing the TAN for a given base number. On the other
hand, a decrease in oil recovery was observed with an increase in
high TAN and an intermediate-wet state modified by increasing
the base number.[25]
The rock–water and oil–water interfaces are temperature de-
pendent, affecting the wettability in carbonate reservoirs by LSW.
This temperature dependence is related to the behavior of the
ionic species activity in brine and the interaction of the polar
compounds in crude oil with the surface across the activation en-
ergy required for these chemical reactions.[32] Several experimen-
tal studies agreed that the wettability changes to water wet from
oil wet with increasing temperature.[45,46] For example, Tweheyo
et al.[47] detached that a temperature variation from 70 to 100 °C
activated sulfate adsorption, removing the oil from the rock sur-
face. Zhang et al.[48] argued that Mg2+ substitutes Ca2+ at the rock
surface at high temperatures, while this substitution does not oc-
cur at low temperatures. This effect attributed to the higher activ-
ity of Mg2+ was more pronounced as the temperature increased.
However, there is limited understanding to identify the tempera-
ture threshold at which a shift in this change occurs.
There is no general rule to understand the role of rock min-
eralogy in LSW flooding. This conclusion is based on different
mineral compositions directly impacting the nature of the sur-
face charges of the rock, and so the initial wetting state of the
reservoir. Besides calcite, carbonate reservoirs often contain other
minerals such as chalk, limestone, anhydrite, and dolomite. They
can affect the rock/brine/oil interactions, leading to wettability al-
teration and improved oil recovery.[32] The reactivity of limestone
cores toward PDIs tends to change wettability depending on the
chemical treatment carried out, as well as the salinity sequence of
the injection. In some cases, wettability does not change even if
the crude oil has a small acid number. Different sources of lime-
stone lead to diverse behaviors. For instance, outcrop and reser-
voir limestone differ significantly in their grain structure and de-
gree of crystallinity, which affects their properties.[25]
The role of carbonate mineralogy on LSW flooding using chalk
core and limestone cores investigated by Qiao et al.[49] showed dif-
ferent results. Seawater can change the limestone wettability due
to the presence of anhydrite. However, only the injection of spe-
cific ions can change the wettability of chalks. A similar study of
oil recovery assessment from fractured limestone was performed
by Strand et al.[41] because chalk is known to have higher reactiv-
ity toward PDIs than limestone. A comparison between dolomite,
chalk and limestone cores was conducted by Shariatpanahi
et al.[50] They concluded that the presence of sulfate ions is critical
to observing wettability alteration and increasing oil recovery. The
sulfate ions source may be the injected brine or the result of anhy-
drite dissolution. Chalk and limestone cores presented a greater
extent of adsorption of sulfate ions than the dolomite surface.
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Figure 5. Schematic of the electric double-layer expansion mechanism.
3.2. Injected Brine Parameters
LSW injection is responsible for wettability alteration in carbon-
ates by changing the salinity and ionic strength with the dilution
of the injected brine or altering the concentration of PDI while
keeping the ionic strength constant by tuning the ionic composi-
tion of seawater.
Ionic composition and temperature are injection brine param-
eters that have been extensively studied in the LSW process with
the target of improving oil recovery. Increasing oil recovery in
LSW process depends on favorable conditions for wettability al-
teration. These conditions can be achieved with PDIs that af-
fect crude oil/rock/brine interactions. The primary PDIs for LSW
flooding in carbonate surfaces are SO4 2− , Ca2+ , and Mg2+ , which
tend to impact oil recovery depending on their concentration and
temperature positively.[21]
The ionic strength (overall salinity) influences the activity of
the PDI. Therefore, composition and salinity are critical parame-
ters for determining the optimum injection brine. Improved oil
recovery from a chalk core has been reported with SO4 2− and Ca2+
due to their adsorption with increasing temperature. At temper-
atures beyond 100 °C due to anhydrite’s precipitation, surface
adsorption decreases as the ratio Ca2+ /SO4 2− increases.[51] An
extensive study involving PDI as wettability modifiers of chalk
and limestone cores showed that Mg2+ could substitute Ca2+
above 70 °C for the first core. This substitution occurred at high
temperatures (130 °C) for limestone, but the reactivity was less
than for chalk. Despite SO4 2− playing a significant role as PDI,
it alone cannot improve oil recovery without divalent cations
Ca2+ and Mg2+ . It occurs due to SO4 2− adsorption onto the pos-
itively charged carbonate surface, thus reducing the electrostatic
attraction between carboxylic groups and rock surfaces.[25] By re-
ducing water salinity in fractured carbonate rocks, Gupta and
Mohanty[52] reported that sulfate ions are only active when Mg2+
and Ca2+ are present. An appropriate balance between tempera-
ture and sulfate ions concentrations is critical since experimental
results show increased oil recovery even at ambient temperature.
Depending on a specific type of rock, the elevated temperature
does not always lead to an increase.[46]
Gupta et al.[53] performed core flood experiments and nu-
merical simulations for LSW injection on several limestone and
dolomite cores. They investigated the influence of polyatomic an-
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ions replacing sulfate ions with phosphate and borate anions.
Their results showed that replacing sulfate ions with borate ions
increases oil recovery and that replacing them with phosphate
ions led to even higher oil recovery. Detaching the risk of reser-
voir souring and scaling is essential when water injection has a
high SO4 2− ion concentration.[51]
4. Hybrid LSWPF
4.1. Fundamental Concepts to Develop a Hybrid Method to
Enhance Oil Recovery by a Possible Combination of LSW and PF
The viscosity contrast between the oil and the injected LSW leads
to an unfavorable mobility ratio and poor microscopic sweep ef-
ficiency as with conventional water flooding. This contrast could
be a reason for unsuccessful cases of low salinity injection when
an incremental oil recovery does not happen. Also, formation
water salinity, hardness, reservoir temperature, and high chem-
ical degradation of polymers are some constraints in the PF
applicability.[54]
The oil recovery increase by PF occurs by improving fractional
sweep flow, the displacement mobility ratio, and delay break-
through of injected water. However, high-salinity brines cause
polymer viscosity degradation in reservoirs. In this way, inject-
ing LSW can also improve pore-scale displacement efficiency by
changing the wettability of the reservoir rock from oil-wet to more
water-wet. Addressing these constraints is necessary to accom-
plish oil recovery objectives. The mutual benefits occur by com-
bining both techniques, i.e., injecting a low-salinity polymer solu-
tion. LSWPF improves the efficiency of oil production by combin-
ing the effect of a favorable mobility ratio by adding polymers and
altering carbonate rock surface wettability by using LSW in the
polymer solution. The synergistic impact also allows using small
quantities of polymer to obtain the target viscosity and significant
cost reduction, higher oil recovery over conventional PF, better
polymer stability (especially at high temperatures), reduced sen-
sitivity to polymer shear degradation, lower polymer adsorption,
and lower scaling and souring tendency. LSWPF allows oppor-
tunities to apply PF in high-salinity and high-temperature reser-
voirs, for which PF with produced or formation water would be
impossible or uneconomic.[54]
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Based on various experimental and modeling studies on ap- conventional water flooding to LSWPF. In water flooding, more
plying LSWPF in carbonates, Shakeel et al.[5] show an average of adsorption sites are available on the rock reservoir. Therefore, the
10% incremental oil recovery and equal to or more than the sum polymer retention is higher; thus, the oil recovery is not observed.
of the recovery from each process. Alterations in types and ion concentrations influence the poly-
To maximize the EOR efficiency of LSWPF, it is essential to mer solution properties. For example, active sulfate ions affect
appropriately design the composition of LSW while considering the polymer solution viscosity, which must be considered.[55]
polymer properties.
4.3.1. Wettability Modification using LSW
4.2. Effect of Hybrid LSWPF on Residual Oil Saturation: Capillary
LSWPF has a synergistic effect that improves the efficiency of oil
Desaturation
production by adding polymers, which provide a favorable mobil-
ity ratio while also altering the wettability of carbonate rock sur-
It is necessary to overcome high capillary or interfacial forces by
faces by using LSW in the polymer solution.[56] Reservoir rock
viscous or gravity forces to recover the microscopically trapped
wettability indicates the rock’s affinity to water or oil and primar-
oil held in place. Generally, a capillary desaturation curve (CDC),
ily depends on the oil/brine/rock interactions.[32] This method in-
which depicts releasing and producing the trapped residual oil,
volves combined and complementary mechanisms of both LSW
is required. It is one of the essential curves of any improved oil
and polymer, so a description is necessary to understand both,
recovery as it allows examining the flow conditions for good oil
detailed in Sections 2 and 3.
displacement efficiency. CDC depends on the pore structure, ar-
Understanding the mechanism that governs the incremental
rangement within the porous media, and fluid distribution inside
oil recovery using hybrid methods is essential to evaluate the
the pores.[22]
physical–chemical aspects that promote these interactions, such
The performance of an EOR method is determined by measur-
as the MIE, the EDL expansion, and the mineral dissolution. Wet-
ing the Sor, which is the oil amount left behind in a reservoir. The
tability change by the MIE process proposed by Austad et al.[36]
CDC depicts the relationship between the residual oil saturation
designates the adsorption of SO4 −2 onto the positively charged
(Sor and the capillary number Nc (the ratio between viscous and
carbonate surface, thus reducing the carbonate’s surface positive
capillary forces). It is constructed by plotting Sor against the cap-
charge. Consequently, Ca2+ and Mg2+ adhere to the rock surface
illary number, which is inversely proportional. A CDC requires
due to the lower electrostatic repulsion. These cations react with
carrying out core flooding runs at different rates and examining
the adsorbed surface-active components from the oil phase, re-
the microscopic sweep efficiency. Nc is directly proportional to
leasing some and changing from oil to water wettability.
the pressure gradient and inversely proportional to the oil–water
Al-Shalabi et al.[30] proposed the wettability modification due to
interfacial tension (IFT).
calcite dissolution to show the loss of Ca2+ in the aqueous phase
There is no change in the residual oil saturation until reaching
due to increased CaSO4 precipitation. First, they disturbed the
a critical Nc. The critical value is usually in the range of 10−4 to
initial equilibrium of carbonate rock, formation water, and crude
10−3 ; however, for polymer and water flooding (WF), the typical
oil by injecting LSW. The injected brine had more SO4 −2 ions
Nc is between 10−7 and 10−5 .[5] Since this lower Nc range for PF
than the formation water. Consequently, the dissolution of cal-
and WF corresponds to a higher Sor, it is not sufficient to cause
cite minerals increases to compensate for the loss of Ca2+ and
any reduction in capillary-trapped residual oil. Therefore, achiev-
the areas where the oil molecules adsorb detach from the rock
ing an acceptable range of Nc with conventional water flooding
surface.
and PF is impossible since the pressure gradient should be high
The EDL expansion occurs when the pH of the brine solution
enough, or the IFT should be extremely low.
exceeds the point of charge zero. Then, the rock surface charge
Shakeel et al.[5] compiled experimental data from different
changes, and the rock wettability alters with increased oil recov-
sources to compare PF and LSWPF capillary desaturation ten-
ery. Thus, these three mechanisms lead to a wettability change by
dencies. The results show that the LSWPF curve falls below the
LSW. The other mechanism involves adding water-soluble poly-
PF curve for almost all points, indicating a significant Sor reduc-
mer in LSW, improving mobility control.[30] Therefore, reduced
tion, even at smaller values of Nc. This performance comes from
trapping and formation of an oil bank lead to stable front ad-
the synergistic effects of wettability modification and efficient oil
vances so efficiently that oil displacement by LSWPF is achieved.
bank displacement using LSW and polymer.
Usually, conventional PF only affects the volumetric sweep ef-
ficiency and conventional LSW can only improve the microscopic 4.3.2. Role of PDIs and pH
sweep efficiency. So, understanding this hybrid process’s details
is vital to discuss the dominant recovery mechanisms for LSWPF. When analyzing LSWPF performance, it is essential to properly
assess the composition of LSW and consider the polymer proper-
ties. The PDIs are a key factor of wettability alteration in the LSW
4.3. Recovery Mechanisms injection method. However, few studies show how the PDIs in
LSWP solution affect polymer adsorption and oil recovery. SO4 2−
At the design stage, LSWPF process requires different opera- ions present in high concentrations in LSW alter the wettability
tional parameters: initial rock wettability, which is a critical factor of the carbonate surface such that it attains water-wet conditions.
that affects LSWPF performance, LSW design (salinity concen- The first point to be detached is related to the stability of the poly-
tration and composition), and appropriate time to change from mer to improve oil recovery. The negative charge of sulfate anion

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and the same polymer charge result in a repulsive interaction,
so the polymer stability is maintained. Lee et al.[56] investigated
PDI (SO4 2− , Ca2+ ) and pH effects on a carbonate oil reservoir
during LSWP injection. They analyzed the mobility of polymer
solution, the degradation and adsorption of polymer molecules,
and the mineral dissolution. In their analysis, they selected six
types of injection water, with pH between 4 and 7, total dissolved
solids (TDS) set equal to 6000 ppm, SO4 2− concentration set be-
tween 1000 and 40 000 ppm, and Ca2+ concentration in the 100
and 1000 ppm range. The polymer (HPAM) concentration was
300 ppm, so the mobility ratio with oil was closer to one with in-
jection water pH 7. The experimental results show that the poly-
mer solution viscosity increased slightly when the sulfate concen-
tration in the injection water was high. This behavior was due to
the repulsive force between sulfate ions and polymer molecules
since they have a negative charge; therefore, avoiding polymer
degradation. Regarding Ca2+ concentrations, the result indicated
a viscosity reduction with higher Ca2+ concentration due to more
precipitation with polymer molecules.
At pH 7, comparing polymer solutions containing SO4 2− and
Ca2+ , the results indicated higher viscosity for the first ion. The
same behavior was observed in the SO4 2− -containing polymer so-
lution regardless of the pH level.
With a larger zeta (𝜁) potential value, its absolute value cor-
responds to a stronger electrostatic repulsion and the polymer
solution becomes more stable. Zeta-potential measurements in-
dicated that in injection water containing sulfate, regardless of
the pH level and sulfate anion concentration, the polymer solu-
tion was more stable than the polymer solution containing cal-
cium ions. The results of the injection water with neutral pH and
acidic condition (pH 4) indicated that the instability increased
with Ca2+ concentration. The change in residual oil saturation be-
tween after-LSW and after-LSWP injections was used to analyze
wettability alteration. Under a neutral polymer solution contain-
ing SO4 2− ion, the saturation change was more remarkable with
higher SO4 2− concentration because sulfate ions interfered with
the adsorption of polymer molecules. Due to more significant
polymer adsorption in the acidic condition (pH 4), this change
was smaller than in the neutral case. Regarding Ca2+ in a neutral
polymer solution, this injection resulted in a more minor change
since Ca2+ was involved in precipitation and adsorption. In acidic
conditions, this change was greater than in the neutral case.
4.3.3. Favorable Mobility Ratio from PF
The chemical reaction involving oil–rock–water interaction due
to the injection of LSW into carbonate cores causes the degrada-
tion of polymer molecules and, consequently, viscosity change.
This change affects the pressure difference between the core inlet
and outlet and the ability of the polymer to improve the mobility
ratio characterized by the resistance factor. The resistance factor,
also known as the mobility reduction factor, is defined by the poly-
mer solution to the injected water mobility ratio. The constant
flow rates of the two different injections and single-phase flow
are expressed as stabilized pressure drop relation. The polymer
adsorption can reduce permeability. The residual resistance fac-
tor defines the permeability reduction due to the PF, indicating
the permeability change before and after the polymer injection.
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A decrease in salinity water polymer injection corresponds to an
increase in the pressure drop due to the higher resistance expe-
rienced by the polymer solution. Comparing LSWPF and high
salinity water-polymer flooding (HSWPF) reduces the repulsion
between the polymer backbone, which helps in the polymer so-
lution’s swelling. Swelling of the polymer causes higher viscosity
and a higher pressure drop across the core flooding. The resis-
tance factor (mobility reduction) increases with an increase in
flow rate. Two properties are related to this behavior: viscosity and
permeability. The shear rate grows at a higher flow rate, and the
viscosity and permeability decrease due to the polymer’s induced
adsorption. Thus, a reduction in water salinity injection results
in the swelling of the polymer solution and reduces the polymer
adsorption on the core surface.[57]
This analysis is helpful for the improved fractional flow re-
sulting from using the polymer. The mobility ratio is inversely
proportional to the fractional flow curve. If the mobility ratio de-
creases, the fractional flow curve shows a piston-like flow. As a
result, a stable front movement forms, and a residual oil bank
shifts more quickly.
4.3.4. Enhanced Polymer Stability using LSW
PF is based on improved sweep efficiency by increasing water
viscosity.[54] A higher polymer concentration is needed to achieve
a chosen viscosity if it dissolves in a higher salinity brine, mainly
for hydrolyzed HPAM. Combining processes such as low salin-
ity polymer solution must preserve viscosity stability through the
flooding. On the other hand, polymer degradation results in a par-
tial or complete loss of viscosity. An advantage of using LSWPF is
applying PF in high salinity and/or high-temperature reservoirs
since these severe conditions are the main concern for synthetic
polymers. Without this synergistic effect, injecting polymer flood
in reservoirs with these characteristics would be uneconomic or
impossible.
HPAM is the most widely used type of polymer in EOR ap-
plications due to its low cost and high molecular weight. HPAM
is susceptible to water composition (salinity, hardness, pH, and
ionic composition) due to its chemical structure (long chains
with a negatively charged backbone), resulting in a viscosify-
ing power. Under high-temperature and high-salinity conditions,
HPAM has poor viscosity and stability characteristics since these
harsh conditions affect polymer degradation and chemical, ther-
mal, and mechanical stability.
4.3.5. LSW Effect on Polymer Retention
Polymer propagation is a crucial control parameter to evaluate
its delayed arrival in PF. Polymer acceleration and retention are
the two main factors determining polymer front propagation.
The polymer acceleration, which the wall exclusion volume can-
not reach, is caused by the pore volume. As a result, polymer
molecules flow through the pore channel center and the polymer
is carried to the brine. Polymer retention refers to losses from the
flowing aqueous solution that effectively slows down the polymer
front. Polymer depletion due to mechanical and hydrodynamic
entrapment and polymer adsorption onto the rock surface are the
dominant causes.[58]
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LSW/polymer synergy highlights the possible impact of LSW
on polymer floods, specifically polymer injectivity. AlSofi et al.[59]
investigated the retention and acceleration. Two polymer solu-
tions were used with different concentrations: conventional wa-
ter (3000 mg L−1 ) and LSW (2000 mg L−1 ). Two single-phase dis-
placement experiments were conducted at a constant low flow
rate to assess polymer retention and acceleration, and collected
effluents were analyzed to determine polymer back production.
The results indicated lower polymer retention levels ranged from
0.084 to 0.102 mg g-rock−1 for LSW compared with 0.133 to
0.230 mg g-rock−1 for injection water solutions. This lower reten-
tion translates into reduced chemical consumption. Two factors
may explain the decrease in polymer retention: better solvency of
LSW that decreases the effects of polymer–solid interactions and
the expansion of the size of polymer molecules due to repulsion
results. Consequently, smaller molecules are required to satisfy
the adsorption sites.[58]
4.3.6. Impact of Polymer on LSW Performance
AlSofi et al.[59,60] carried out a series of experiments to assess the
impact of polymer on LSW performance. They investigated the
rheological and electrophoretic mobility, electrokinetic (zeta) po-
tential, contact angle, IFT, and oil recovery. A brine with a total
salinity ten times lower than injection water was used as LSW,
an anionic sulfonated PAM polymer with dead oil, and carbonate
plugs with LSW, polymer, and LSWP. The results show additional
oil recovery for the hybrid LSWPF process.
Rheological tests demonstrated the possibility of achieving the
same target viscosity at lower polymer concentrations with LSW.
By comparison, to achieve the same target viscosity, the polymer
concentration for the LSW was found to be one-third less than
the typical height salinity water injection.
A change in zeta potential and electrophoretic mobility from
positive to negative values means LSW leads to additional oil re-
covery by wettability alteration. The results show that the impact
in electrophoretic mobilities and zeta potential are relatively com-
parable with and without the polymer, only slightly higher with
the polymer. The contact angle measurement results showed
that the polymer had a negligible to somewhat favorable impact
on wettability alteration induced by LSW. A comparison of IFT
oil/brine with and without polymer in the LSW resulted in a neg-
ligible effect. These experiments confirmed the potential synergy
between these two EOR methods for a realistic scenario, and the
polymer can enhance LSW effects.
4.4. Potential Risks Associated with LSWPF
The viscosity variation with the salinity curve for a polymer so-
lution has two plateaus. The highest corresponds to a very low
salinity of less than 10 ppm. The lower plateau is related to the
high salinity. The polymer concentration in the low salinity range
is on the steep curve between these plateaus. For this reason, the
viscosity of an LSWP solution is more sensitive to minor com-
position variations and adsorption. A slight increase in the brine
salinity can reduce the polymer viscosity significantly. Also, it af-
fects the adsorption onto pore walls, which increases as a func-
tion of water salinity.
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It is essential to evaluate the risk of cation exchange at the pore
scale, which requires the analysis of rock and fluid interactions.
As LSW moves through the reservoir, equilibrium between the
LSW and the reservoir rock is necessary. This equilibrium in-
volves the charged molecule polymer, the reservoir rock, and the
changing brine injected. So, it leads to reduced injectivity or min-
eral dissolution due to the cation exchange and affects the poly-
mer viscosity between the brine and porous media.
Mixing the low salinity injection slug with the reservoir brine
would result in a lower polymer slug viscosity and, consequently,
lower oil recovery. However, due to the polymer adsorption, the
polymer slug will not be in contact with the high-salinity brine.
This behavior is because the low salinity slug without polymer
will form between the two fluids as a buffer against mixing
and will not affect the polymer viscosity. On the other hand,
this positive aspect of polymer adsorption causes a delay in oil
recovery, negatively affecting economic viability. Because of the
polymer adsorption, a reduced polymer concentration occurs,
requiring a significant slug volume and a larger volume to
inject before achieving polymer breakthrough and a delay in oil
recovery.[54,61]
AlSofi et al.[59] conducted two experiments at variable high flow
rates to investigate synergistic aspects of LSWPF, focusing on the
possible impact of LSW on polymer floods, specifically the poly-
mer injectivity. The polymer solutions were prepared using con-
ventional injection water and LSW with this target. Based on sta-
bilized pressure drops at each flow rate, the results showed that,
at high injection rates, polymer and residual resistance factors
were only slightly higher for LSW than for injection water. These
results indicate a slightly negative impact of LSW on polymer in-
jectivity. AlSofi et al.[59] attributed the higher residual resistance
with LSW to the more extensive expansion of polymer molecules
at the low salinity concentration due to the higher repulsion be-
tween the polymer backbone charges. This expansion increases
the adsorbed layer’s thickness and further reduces the effective
permeability.
4.5. Lab-Scale Studies
This study focuses on the experimental work to evaluate the syn-
ergy between LSW and PF: oil, brine, and polymer preparation;
rock properties; the effect of salinity on polymer rheology, vis-
cosity, density, and 𝜁-potential; contact angle measurement; the
effect of salinity on polymer retention; and the oil recovery effi-
ciency of low salinity polymer flooding.
Most of the polymer injection EOR in the world has been ap-
plied in sandstone rocks. However, anionic polymers (such as
HPAM) adsorb in carbonate rocks. Thus, nowadays, many field
projects are implemented in different types of rocks, including
carbonates.[3,62]
It is crucial to avoid polymer degradation and loss of viscos-
ity during an injection procedure. The rheology of the polymeric
solution injected into the porous media is directly affected by
the reservoir conditions and may suffer from salinity and ther-
mal or biological degradation. Temperature also hydrolyzes the
polymer solution, which causes a decrease in viscosity. For ex-
ample, HPAM hydrolyzes at 25–90 °C in most polymer injection
applications.[13]
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It is essential to select appropriate rock samples for laboratory After cleaning, the rock samples are dried using one of the fol-
studies to determine the capabilities of a polymer during flood- lowing methods: conventional oven, vacuum oven, or humidity
ing, as lithology differences affect the performance of the poly- oven. Method selection is based on rock lithology and clay con-
mer. Reservoir fluids must be available or the information neces- tent, among other properties. A traditional oven is the most com-
sary to reproduce them in the laboratory.[63] monly applied drying method, where the plugs are placed in the
oven at a constant temperature (typically 40 to 100 °C) until no
change in sample weight is observed. A vacuum can be used to
4.5.1. Oil, Brine, and Polymer Preparation
speed up the drying process.[64]
Afterward, the properties of the rock samples, such as porosity,
“Live oil” is reservoir oil with all hydrocarbon components un-
wettability, and permeability, are measured. Mineralogical analy-
der reservoir temperature and pressure,[64] and the quality and
sis of the plug is also recommended, as it directly affects cleaning
availability of reservoir oil samples limit its use. “Dead oil” is
and saturation procedures. It is also suggested to use core sam-
the oil sample from the stock tank (or separator) that can be
ples at least 7 in. long. Using more extended plugs minimizes
used directly or recombined with gas, taking into account the
the influence of capillary end effects that can add uncertainty to
pressure–volume–temperature data of the live oil to simulate
flow properties.[63,64]
its conditions properly.[63] Oil properties such as viscosity, den-
Rock sample porosity, a measure of the space available for
sity, TAN, TBN, and SARA (content of saturates, aromatic resins,
fluid storage in the rock, usually involves determining the re-
and asphaltenes) must be obtained using appropriate methods.
saturation porosity, which requires the samples to be saturated
A suitable oil can also be prepared by mixing the solvent with a
in brine. The pore volume (PV) is calculated based on the mass
dead oil, reducing its viscosity and density to suit the reservoir
of the rock sample. First, the dry plug weight is measured using
conditions.[63] The oil must be filtered to remove contaminants
a balance. Then the plug is placed in a pressure vessel and
(such as sand particles and asphaltenes) to minimize the risk of
saturated in formation water at 2000 psi for 2 to 3 days to full
core clogging during testing.[64]
saturation. Afterward, the mass of the saturated plug is mea-
Brine preparation follows the reservoir formation water and
sured using a balance. The dry and saturated plug mass and the
injection water composition. They also consider the brine’s ionic
density of the formation water are used to calculate the PV of the
composition using reagent-grade salts and ultrapure water. If FB
plug.[64]
is used with carbonate rocks, additional calcium carbonate must
be added to ensure supersaturation.[64] After preparation, brine
properties such as density, pH, TDS, and conductivity are mea-
4.5.3. Effect of Salinity on the Polymer Rheology, Viscosity, Density,
sured using standard protocols.[63]
and 𝜁 -Potential
The polymer solution (e.g., HPAM or PAM) is prepared at a
concentration of 5000 ppm. The polymer is introduced slowly
Polymer viscosity and density must be evaluated as a function
into the brine under agitation to avoid the formation of fish eyes.
of concentration and temperature using high-precision instru-
The polymer solution is then filtered through a 5 μm polycar-
ments. Density measurements should be performed at reser-
bonate filter to remove aggregates. The desired polymer concen-
voir temperature, while viscosity analysis should be performed at
tration is achieved by diluting the prepared and filtered polymer
shear rates ranging from 0.1 to 500 s−1 for concentrations rang-
solution with brine, which is gradually added to the polymer
ing from 0 to 5000 ppm. An increase in salinity is expected to de-
solution under continuous stirring until complete homogeniza-
crease the viscosity of the solution. Thus, the effect of brine salin-
tion of the solution. Polymer-brine compatibility (formation and
ity and pH on viscosity should also be evaluated. Viscosity moni-
injection) is evaluated at the reservoir temperature and fixed con-
toring can also be used to assess polymer mechanical degradation
centration. Then, the polymer solution is stored in a temperature-
by shearing polymer solutions at constant temperature and high
controlled oven. The solution viscosity is measured daily and the
velocity for different time intervals.[63,65]
solution appearance is observed for solubility analysis. The most
To improve oil recovery, the injection brine (IB) must cause a
stable solution is the slightest viscosity change measured over
measurable change in the brine/rock 𝜁 -potential, either positive
21 days.[63]
or negative, which increases electrostatic repulsion. This change
indicates the injection brine’s ability to change wettability.[66]
4.5.2. Rock Properties For a negatively charged brine–oil interface, the injection brine
composition must be changed to produce a more negative
Due to reservoir heterogeneity, it is essential to select different 𝜁-potential at the mineral surface, which improves recovery.
rock samples to ensure they are representative. After selection, On the other hand, for a positively charged oil–brine interface,
core samples (usually plugs) are cleaned to remove oil, mud fil- the injection brine composition must be changed to produce a
trates, salts, and connate water.[63] The most common cleaning more positive 𝜁-potential at the mineral surface.[67] A core plug
methods are Soxhlet extraction, total immersion Soxhlet extrac- is usually crushed to provide powdered rock samples for these
tion, and solvent cleaning. At least two solvents are required tests. Any changes in the measured 𝜁-potentials are treated only
to clean rock samples effectively: a nonpolar solvent (such as as potential qualitative indicators of the ability of a given solution
toluene), which is used to dissolve petroleum components, and to change wettability, as well as to assess possible side effects of
a polar solvent (such as methanol), used to dissolve water and the presence of the polymer on the performance of the injection
precipitated salts.[64] brine.[66]

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Figure 6. Brine/sandstone 𝜁 -potential as a function of brine salinity at dif-
ferent temperatures.
Figure 7. Examples of contact angle measurements on calcite disks for a)
high salinity brine (69 000 mg L−1 ) and b) low salinity polymer solution
(2000 mg L−1 of polymer in a brine containing 6900 mg L−1 of dissolved
salts).
Typical results of brine/sandstone 𝜁-potential as a function of
brine salinity at different temperatures are shown in Figure 6.
Low salinity brine has the lowest 𝜁-potential, indicating that this
solution may have the ability to change wettability.
4.5.4. Contact Angle Measurement
Since the 𝜁 -potential only indicates wettability alteration due to
changes in brine composition, contact angle measurements be-
tween oil/brine/rock should be performed. The contact angle is a
more direct and accurate measurement of wettability alteration.
In this technique, a drop-shape analyzer can measure the static
contact angle of captive-oil droplets below a rock disk in the pres-
ence of different polymer solutions (brine) at reservoir tempera-
ture. The rock disks are usually prepared by cutting and sanding
the already characterized plugs.[66]
Disks are soaked in FB at reservoir temperature for 2 to 3 days
before measurement. The disks are then aged in oil for over 40
days at reservoir temperature.[64] Contact angle measurements
complement the analysis of surface potentials and provide more
accurate information about possible polymer side effects on the
brine’s ability to change wettability.[66]
Figure 7 shows examples of contact angle measurements on
calcite disks.[66] In Figure 7a, the calcite disk shows a more oil-wet
condition when exposed to high salinity brine (69 000 mg L−1 ).
When the low salinity polymer solution (2000 mg L−1 of polymer
in a brine containing 6900 mg L−1 of dissolved salts) is applied
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(Figure 7b), the contact angle reduces the calcite wettability to a
more water-wet condition, which favors oil recovery.
4.5.5. Effect of Salinity on Polymer Retention
One of the main parameters of PF in EOR activities is the loss
of polymers due to adsorption on the reservoir rock. Polymer re-
tention during injection into the porous medium can hinder oil
movement, which affects recovery.[58,68]
Polymer retention is a property that informs the degree of
polymer propagation through the core sample. Polymer retention
can be determined using static and dynamic measurements.[69,70]
Several factors can affect polymer retention, such as the type of
polymer used in the solution (anionic, cationic, and amphoteric),
the polymer concentration, brine salinity, wettability, oil satura-
tion, as well as lithology and permeability.[65] An increase in pres-
sure differential across the core sample during PF may indicate
increased polymer retention. A retention level close to 20 μg of
polymer cm−3 of bulk volume is considered acceptable.[58]
4.5.6. Oil Recovery Efficiency of Low Salinity PF
Core flooding tests allow comparing the flow behavior of selected
polymer solutions in the porous media, including evaluating rela-
tive retention, permeability reduction, and the impact on steady-
state pressure differential. These property data are used to de-
velop applied models to simulate EOR projects and field tests.[63]
PF studies are generally performed in core flooding systems
(CFS) as illustrated in Figure 8. A CFS consists of an injection
pump, some floating piston accumulators for fluid storage, a core
holder, a backpressure system, a confinement system, a differ-
ential pressure transducer, and a computer used for data acqui-
sition. The system is set up inside an oven which controls the
temperature.[71]
The characterized rock sample (plug) is mounted on a core
holder and confined within a rubber sleeve. Simulating reservoir
conditions such as temperature and pressure is crucial, so a con-
finement pump is used to compress the plug.[71] The system is
heated to the desired temperature. Then, FB is injected into the
core until the system pressure reaches 2000 psi and remains sat-
urated for 48 h. The next step consists of determining the per-
meability of the plug by injecting FB at different flow rates. An
actuating backpressure valve keeps the pressure at the core out-
let constant at 2000 psi. For each flowrate studied, the pressure
differential across the core sample during the injection is used to
calculate the permeability of the plug by applying Darcy’s law.[64]
After the permeability determination, a saturation of the core
with FB is complete. The backpressure valve is then adjusted to
the reservoir pressure, and oil saturation is initiated. Oil is in-
jected into the core, and the fluid volume is analyzed. Ideally, oil
should be injected until no brine is observed in the liquid col-
lector. The brine volume produced during the oil injection step
determines the core’s irreducible water and initial oil saturation.
Then, the core is allowed to age for 5 to 40 days to restore the
wettability of the reservoir.[64,73] During the aging period, the sys-
tem’s pressure and temperature are kept constant.
Then, the polymer solution is injected into the core. The num-
ber of PV’s injected, the injection flow rate and the possibility of
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Figure 8. Scheme of an experimental core flooding system. Reproduced with permission.[72] Copyright 2019, American Chemical Society.
alternating with other brine depend on the properties of the fluid
and the rock. The produced fluids are collected and analyzed to
determine the amount of oil recovered, which, together with the
initial oil saturation and the oil formation volume factor (Bo ), al-
lows the calculation of the oil recovery factor.
Shiran and Skauge[24] evaluated PF experiments in Berea sand-
stones. The polymer solution was prepared using HPAM at a
concentration of 300 ppm. According to the authors, the water
flood/low salinity polymer combination leads to higher oil recov-
ery due to the synergy effects of this hybrid EOR process: the poly-
mer increases the stability of the low salinity flood by improving
the sweeping efficiency and, therefore, oil recovery.
Bennetzen et al.[74] performed laboratory core flooding tests
on strongly oil-wet limestone samples using polymeric solutions
prepared with HPAM at concentrations ranging from 500 to
1000 ppm in the formation of brine and seawater. The polymer
decreased the mobility and permeability of the brine, but no clog-
ging was observed. The authors attribute the low adsorption to
the rock being strongly oil-wet. Therefore, the oil film on the rock
surface prevents polymer adsorption.
Vermolen et al.[54] studied the low-salinity PF in aged sam-
ples from reservoir cores. They confirmed that using low-salinity
brine in the preparation of polymers reduces costs, as it allows
cheaper polymers to increase oil recovery. The polymer increases
the viscosity of the injection fluid, improving the sweeping effi-
ciency. At the same time, the low salinity can favor a modification
of the wettability of the core to a more water-wet condition. Al-
sofi et al.[66] and Wang et al.[75] obtained similar results in their
experiments. Similar results of the total oil recovered due to the
subsequent injection of brines of different salinities are given by
Vermolen et al.[54]
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5. Final Remarks
This review critically discusses the synergistic effects of hybrid
LSW and PF (LSWPF) on oil recovery in carbonate reservoirs.
First, it focuses separately on LSW and PF fundamentals. Sec-
ond, it presents the effects and advantages of hybrid LSWPF on
recovering residual oil saturation. LSWPF recovery mechanisms,
such as wettability alteration, PDIs and pH, mobility ratio, poly-
mer stability and retention, were appropriately addressed. Poten-
tial risks associated with LSWPF and some lab-scale studies were
also stressed. As a result, this critical analysis of LSWPF as an al-
ternative to PF using seawater has filled an essential gap in the lit-
erature regarding carbonate reservoirs, which complements pre-
vious studies involving only sandstone reservoirs.
Acknowledgements
The authors acknowledge the support by ANP – Agência Nacional de
Petróleo, Gás Natural e Biocombustíveis and by Petrogal Brasil S.A., re-
lated to the grant from R&D investment rule.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
carbonates, enhanced oil recovery, low-salinity water, polymer flooding
Received: January 13, 2023
Revised: February 23, 2023
Published online:
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[35] E. W. Al-Shalabi, K. Sepehrnoori, M. Delshad, presented at SPE Reser-

voir Characterization and Simulation Conf. Exhibition, Abu Dhabi,
[1] A. Gbadamosi, X. Zhou, M. Murtaza, M. S. Kamal, S. Patil, D. Al
UAE, September 2013.
Shehri, A. Barri, Polymers 2022, 14, 4621.
[36] T. Austad, S. Strand, E. J. Høgnesen, P. Zhang, presented at SPE Int.
[2] L. Zhang, X.’A.n Yue, F. Guo, Pet. Sci. 2008, 5, 56.
Symp. Oilfield Chemistry, Houston, TX, February 2005, SPE-93000-
[3] R. B. Needham, P. H. Doe, J. Pet. Technol. 1987, 39, 1503.
ms.
[4] V. Vishnyakov, B. Suleimanov, A. Salmanov, E. Zeynalov, in Primer
[37] A. Hiorth, L. M. Cathles, M. V. Madland, Transp. Porous Media 2010,
on Enhanced Oil Recovery, Gulf Professional Elsevier Inc., Houston,
85, 1.
TX 2020, pp. 141–159, https://doi.org/10.1016/B978-0-12-817632-
[38] A. A. Yousef, S. Al-Saleh, M. Al-Jawfi, SPE Middle East Oil Gas Show
0.00011-6.
Conf. MEOS, Proc. 2011, 1, 632.
[5] M. Shakeel, P. Pourafshary, M. R. Hashmet, Appl. Sci. 2020, 10, 6087.
[39] D. J. Ligthelm, J. Gronsveld, J. P. Hofman, N. J. Brussee, F. Marcelis,
[6] H. H. Al-Sharji, C. A. Grattoni, R. A. Dawe, R. W. Zimmerman, pre-
H. A. van der Lin, presented at SPE European Annual Conf. Exhibition,
sented at SPE European Formation Damage Conf., Hague, Nether-
Amsterdam, Netherlands, June 2009, SPE 119835.
lands, May 2001, SPE-68972-MS.
[40] S. F. Shariatpanahi, S. Strand, T. Austad, Energy Fuels 2011, 25, 3021.
[7] J. J. Sheng, in Modern Chemical Enhanced Oil Recovery: Theory and
[41] S. Strand, T. Austad, T. Puntervold, E. J. Høgnesen, M. Olsen, S. M.
Practice, Gulf Professional Elsevier Inc., Houston, TX 2011, pp. 101–
F. Barstad, Energy Fuels 2008, 22, 3126.
206, https://doi.org/10.1016/B978-1-85617-745-0.00005-X.
[8] D. Wang, H. Xia, Z. Liu, Q. Y. Anda, presented at SPE – Asia Pacific [42] T. Puntervold, S. Strand, T. Austad, Energy Fuels 2007, 21, 1606.
Oil and Gas Conf. Exhibition, Jakarta, Indonesia, April 2001. [43] M. Takeya, M. Shimokawara, Y. Elakneswaran, T. Nawa, S. Takahashi,
[9] D. A. Z. Wever, F. Picchioni, A. A. Broekhuis, Prog. Polym. Sci. 2011, Fuel 2019, 235, 822.
36, 1558. [44] D. C. Standnes, T. Austad, J. Pet. Sci. Eng. 2000, 28, 123.
[10] Y. Carolina Araujo, M. Araujo, Fuentes, Reventon Energ. 2018, [45] A. A. Hamouda, K. A. R. Gomari, Proc. – SPE Symp. Improv. Oil Recover
2006, 2, 848.
16, 55.
[46] H. Mahani, R. Menezes, S. Berg, A. Fadili, R. Nasralla, D. Voskov, V.
[11] L. W. Lake, Enhanced Oil Recovery, Prentice Hall, Englewood Cliffs, NJ
Joekar-Niasar, Energy Fuels 2017, 31, 7839.
1989.
[47] M. T. Tweheyo, P. Zhang, T. Austad, Proc. – SPE Symp. Improv. Oil
[12] Y. Du, L. Guan, presented at SPE Int. Petroleum Conf. in Mexico,
Recover. 2006, 1, 200.
Puebla, Mexico, November 2004, SPE 91787.
[48] P. Zhang, M. T. Tweheyo, T. Austad, Colloids Surf., A 2007, 301, 199.
[13] A. Mohsenatabar Firozjaii, H. R. Saghafi, Petroleum 2020, 6, 115.
[49] C. Qiao, R. Johns, L. Li, J. Xu, presented at SPE Annual Technical Conf.
[14] L. D. Saleh, M. Wei, B. Bai, Soc. Pet. Eng. 2014, 17, 15.
Exhibition, Houston, TX, September 2015.
[15] G. Bourdarot, S. Ghedan, presented at SPE Reservoir Characterisa-
[50] S. F. Shariatpanahi, P. Hopkins, H. Aksulu, S. Strand, T. Puntervold,
tion and Simulation Conf. Exhibition, Abu Dhabi, UAE, October 2011,
T. Austad, Energy Fuels 2016, 30, 180.
SPE 148323.
[51] S. Strand, E. J. Høgnesen, T. Austad, Colloids Surf. A 2006, 275, 1.
[16] W. N. Diab, E. W. Al-Shalabi, presented at Offshore Technology Conf.
Brasil, Rio de Janeiro, Brazil, October 2019, OTC-29739-MS. [52] R. Gupta, K. K. Mohanty, presented at SPE Symp. Improved Oil Re-
[17] T. Q. C. Dang, Z. Chen, T. B. N. Nguyen, W. Bae, Energy Sources, Part covery, Tulsa, Oklahoma, USA, April 2008, SPE-113407-ms.
A 2015, 37, 2189. [53] R. Gupta, P. G. Smith, L. Hu, T. W. Willingham, M. Lo Cascio, J. J.
[18] M. S. Kamal, A. S. Sultan, U. A. Al-Mubaiyedh, I. A. Hussein, Polym. Shyeh, C. R. Harris, presented at SPE Middle East Oil and Gas Show
Rev. 2015, 55, 491. and Conf., Manama, Bahrain, September 2011, SPE-142668-ms.
[54] E. C. M. Vermolen, M. Pingo Almada, B. M. Wassing, D. J. Ligthelm,
[19] A. Moradi-Araghi, P. H. Doe, SPE Reservoir Eng. 1987, 2, 189.
S. K. Masalmeh, presented at Int. Petroleum Technology Conf., Doha,
[20] P. Purswani, M. S. Tawfik, Z. T. Karpyn, Energy Fuels 2017, 31, 7734.
Qatar, January 2014.
[21] S. B. Nande, S. D. Patwardhan, J. Pet. Explor. Prod. Technol. 2022, 12,
[55] P. Pourafshary, N. Moradpour, in Enhanced Oil Recovery Processes –
1037.
[22] M. Shakeel, A. Samanova, P. Pourafshary, M. R. Hashmet, Energies New Technologies (Ed: A. Samsuri), IntechOpen, London 2019, Ch. 1.
2021, 14, 4368. [56] Y. Lee, W. Lee, Y. Jang, W. Sung, J. Pet. Sci. Eng. 2019, 181, 106211.
[23] A. Namaee-Ghasemi, H. S.-.Z. Behbahani, S. Kord, A. Sharifi, J. Mol. [57] A. Kakati, G. Kumar, J. S. Sangwai, Energy Fuels 2020, 34, 5715.
Liq. 2021, 326, 114854. [58] K. S. Sorbie, Polymer-Improved Oil Recovery, Springer Sci. Media, New
[24] B. Shaker Shiran, A. Skauge, Energy Fuels 2013, 27, 1223. York 1991.
[59] A. M. Alsofi, J. Wang, Z. F. Kaidar, J. Pet. Sci. Eng. 2018, 166, 274.
[25] M. Derkani, A. Fletcher, W. Abdallah, B. Sauerer, J. Anderson, Z.
[60] A. M. AlSofi, J. Wang, A. M. AlBoqmi, M. B. AlOtaibi, S. C. Ayirala,
Zhang, Colloids Interfaces 2018, 2, 20.
A. A. AlYousef, presented at SPE Heavy Oil Conf. Exhibition, Kuwait
[26] F. Liu, M. Wang, Fuel 2020, 267, 117112.
City, Kuwait, December 2016, SPE-184163-MS.
[27] Y. A. Hadi, F. Hussain, F. Othman, IOP Conf. Ser.: Mater. Sci. Eng.
[61] M. Shakeel, P. Pourafshary, M. R. Hashmet, ACS Omega 2022, 7,
2019, 579, 012029.
14961.
[28] L. Opoku Boampong, R. Rafati, A. Sharifi Haddad, Fuel 2023, 331,
[62] Z. Jiang, J. Zhu, Asian J. Chem. 2014, 26, 629.
125856.
[63] Y. Araujo, M. Araujo, in Enhanced Oil Recovery – Selected Topics (Eds:
[29] B. Bourbiaux, Oil Gas Sci. Technol. 2020, 75, 37.
B. I. Morsi, H. O. Baled), IntechOpen, London 2022, Ch. 8.
[30] E. W. Al-Shalabi, K. Sepehrnoori, G. Pope, SPE J. 2015, 20, 1212.
[64] C. McPhee, J. Reed, I. Zubizarreta, Core Analysis: A Best Practice Guide,
[31] H. Mahani, A. L. Keya, S. Berg, W.-B. Bartels, R. Nasralla, W. Rossen,
1st ed., Developments in Petroleum Science, Vol. 64, Elsevier B.V., New
presented at EUROPEC 2015, Madrid, Spain, June 2015, https://doi.
York 2015.
org/10.2118/174300-MS.
[65] Y. C. Araujo de Itriago, M. A. Fresky, presented at Offshore Technology
[32] P. I. Sagbana, K. Sarkodie, W. A. Nkrumah, Petroleum 2022, https:
Conf. Houston, Texas, USA, May 2019.
//doi.org/10.1016/j.petlm.2022.01.006
[66] A. M. Alsofi, J. Wang, A. M. Alboqmi, M. B. Alotaibi, S. C. Ayirala, A.
[33] M. F. Snosy, M. Abu El Ela, A. El-Banbi, H. Sayyouh, J. Pet. Explor.
A. Alyousef, SPE Reservoir Eval. Eng. 2018, 22, 61.
Prod. Technol. 2022, 12, 701.
[67] M. D. Jackson, D. Al-Mahrouqi, J. Vinogradov, Sci. Rep. 2016, 6,
[34] R. K. Saw, A. Mandal, RSC Adv. 2020, 10, 42570.
37363.

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[68] Developments in Soil Science, Vol. 9 (Ed: B. K. G. Theng), Elsevier, New
York 1979, pp. 37.
[69] L. Chiappa, A. Mennella, T. P. Lockhart, G. Burrafato, J. Pet. Sci. Eng.
1999, 24, 113.
[70] R. N. N. Manichand, R. S. S. Seright, SPE Reservoir Eval. Eng. 2014,
17, 314.
[71] H. Hematpour, M. Parvazdavani, S. Abbasi, S. M. Mahmood, J.
Teknol. Lab. 2016, 78, 93.
[72] H. N. Al-Saedi, Y. Long, R. E. Flori, B. Bai, Energy Fuels 2019, 33, 9644.
[73] M. Ahkami, K. H. Chakravarty, I. Xiarchos, K. Thomsen, P. L. Fosbøl,
presented at SPE Bergen One Day Seminar, Bergen, Norway, April
2016.
[74] M. V. Bennetzen, S. F. Gilani, K. Mogensen, M. Ghozali, N. Bounoua,
presented at Abu Dhabi Int. Petroleum Exhibition and Conf., Abu
Dhabi, UAE, November 2014.
[75] J. Wang, S. C. Ayirala, A. M. AlSofi, A. A. Al-Yousef, S. Aramco, pre-
sented at SPE EOR Conf. Oil and Gas West Asia, Muscat, Oman,
March 2018.

Fabio Pedro Nascimento completed his D.Sc. in chemical engineering at the Universidade do Estado
do Rio de Janeiro (UERJ, Brazil) under the joint supervision of Prof. Márcio Paredes and Prof. Fernando
Pessoa. He currently works as a researcher at the Universidade Federal da Bahia (UFBA, Brazil) with
Prof. Silvio Vieira de Melo and Prof. Gloria Costa, where they investigate the effect of water salinity
on recovery mechanisms of enhanced oil recovery methods. His research interests include applied
thermodynamics focused on phase equilibrium measurements and model development.

Verônica de Jesus Pereira is a chemical engineer with a Ph.D. in industrial engineering from the Federal
University of Bahia. She is a researcher in the Post Graduate Program in Industrial Engineering at
UFBA. Her research interests include petroleum characterization, high-pressure phase behavior, and
enhanced oil recovery techniques.

Ladislane dos Santos Bastos got her B.Sc. and M.Sc. in chemical and industrial engineering from the
Federal University of Bahia (UFBA) in Brazil. She is currently a Ph.D. student at UFBA, working un-
der the joint supervision of Prof. Silvio Vieira de Melo and Prof. Gloria Costa. Her research interests
include evaluating enhanced oil recovery methods mechanisms through CO2 and brine injection,
considering the experimental and numerical simulation approaches.

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www.advancedsciencenews.com www.mre-journal.de

Gloria Meyberg Nunes Costa holds a Ph.D. in industrial engineering from the Federal University of
Bahia, Brazil. She is a retired professor at the Department of Chemical Engineering at the Federal
University of Bahia. Her academic experience of more than 45 years includes teaching and research
activities in Phase Equilibria Model Development.

Silvio Alexandre Beisl Vieira de Melo holds a Ph.D. in chemical engineering from the Federal Univer-
sity of Rio de Janeiro, Brazil. He is a full professor at the Department of Chemical Engineering at the
Federal University of Bahia. His academic experience of more than 25 years includes teaching and
mentoring in undergraduate and graduate programs and research activities in energy and sustainable
chemical processes to provide solutions to the world´s complex problems.

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