Article

pubs.acs.org/EF

Enhanced Oil Recovery (EOR) by Combined Low Salinity Water/

Polymer Flooding
Behruz Shaker Shiran* and Arne Skauge
Centre for Integrated Petroleum Research (Uni CIPR), University of Bergen, Allégaten 41, 5007 Bergen, Norway

ABSTRACT: Recently, low salinity brine injection has been given a great interest as a technique for enhanced oil recovery
(EOR) by waterflooding. Varying experimental results have been reported in the literature, from many promising results to
limited or no effects of low salinity. The application of low salinity water in combination with other established EOR processes
(e.g., surfactant flooding and polymer flooding) is of great interest. The combined processes involve dampening capillarity to
avoid trapping of mobilized oil, reducing residual oil saturation (Sor), and altering frontal stability and sweep. In this article, we
address the questions of timing of LS injection and the added benefit of polymer injection. Secondary-mode (at initial water
saturation) and tertiary-mode (after seawater residual oil saturation) low salinity waterflooding experiments were performed on
outcrop Berea sandstone core material. The main results are the oil recovery efficiencies of these two different flooding modes.
These results show an increase in oil recovery of about 13% of the original oil in place (OOIP) in secondary-mode compared to
tertiary-mode low salinity waterflooding. Moreover, the effect of polymer injection was found to be more positive when low
salinity was initialized from the start of water injection (secondary mode). In this case, the final recovery factor increased to about
90% OOIP. Possible mechanisms for low salinity and low salinity polymer injection are discussed.

■ INTRODUCTION
Increased oil recovery by substantially lowering the injection
brine salinity or modifying the brine composition of the injection
water has been reported in numerous experimental studies and
field trials for both tertiary (residual oil condition) and secondary
(initial water condition) modes of water flooding.1−11 The
mechanism or mechanisms behind the low salinity effect (LSE)
are not yet well understood and have been the subject of
extensive investigation and systematic research during the past
10−15 years. On the basis of many experiments, Tang and
Morrow3 concluded that mixed-wet porous media containing
clay and the presence of connate water are necessary conditions
for the LSE. They related the increased oil recovery to wettability
alteration toward more water-wet condition by fines migration
during low salinity water injection. In later studies, several other
mechanisms have been proposed by different researchers as reasons
for the LSE. The mechanisms often referred to as key factors in
sandstone include the following: (1) release and migration of mixed-
wet clay fines, which results in the alteration of wettability toward
a more water-wet state and, therefore, oil mobilization and
production3 and effective microscopic diversion;12,13 (2) mineral
dissolution and ion-exchange reactions, which increase the pH
through the formation of excess hydroxyl ions, OH¯, thereby
causing a reduction in interfacial tension (IFT);14 and (3)
multicomponent ionic exchange (MIE)15 between adsorbed
crude oil components, connate brine, and clay particles, which
leads to the development of a “self-freshening” zone within the
water-flooded region,16 double layer expansion17 that results in the
desorption of organic polar compounds from the rock surface, oil
layer destabilization, and microscopic diversion.12,13
Boussour et al.18 presented the different mechanisms
proposed in the literature as being responsible for the LSE and
provided experimental counterexamples, showing that the LSE is
very sensitive to a combination of different parameters inherent
in the crude oil−brine−rock system.
An increase in pH, for instance, has been reported in many
articles as the reason for the LSE. However, numerous
experimental studies have shown no correlation between the
LSE and changes in pH. That is, there are reports of a benefit to
low salinity with a slight change or even a decrease in pH,14,19,20
as well as evidence of significant increases in pH with no
corresponding increase in oil recovery.21
A local pH increase at the water−clay interface was proposed
as a factor by Austad et al.,22 who stated that, in a pH-buffered
system (e.g., reservoir conditions under which CO2 acts as pH
buffer), even though the effluent pH might not show any increase,
the LSE will be observed because acid−base reactions are very fast.
This is because a local pH increase close to the clay surface will
desorb the organic material from the clay surface and, because of the
dynamic nature of the flow conditions, the desorbed material will be
transported away from the adsorption sites and the clay surface will
become more water-wet. Austad et al.22 also attributed the
multicomponent ionic exchange (MIE) mechanism proposed by
Lager et al.15 to the precipitation of Mg(OH)2 as a result of a local
pH increase during low salinity water injection.
Recently, Aksulu et al.23 performed a study with the objective
of confirming that pH is a key parameter in the LSE and concluded
that effluent pH monitoring during successive flooding of a
sandstone reservoir core with appropriate high-salinity/low salinity/
high-salinity brines under reservoir temperature conditions might be
a valuable first approach to evaluate the possibility of achieving
increased oil recovery by using low salinity water.
In parallel with the ongoing discussions on the contribution of
pH to the LSE, other proposed mechanisms (e.g., wettability
alteration, fines migration) are also debated in the literature, and
Received: September 18, 2012
Revised: February 11, 2013
Published: February 12, 2013

© 2013 American Chemical Society 1223 dx.doi.org/10.1021/ef301538e | Energy Fuels 2013, 27, 1223−1235
Energy & Fuels Article

so far, no single proposed mechanism is conclusive from the Table 2. Properties of Fluids Used in Experimental Work
point of view of experimental observations. Therefore, more
viscosity density AN (mg of BN (mg of
studies and investigations are needed to further understand the fluid (cP) (g/mL) KOH/g) KOH/g) pH
mechanisms involved in increased oil recovery upon low salinity
diluted crude oil 2.40 0.88 1.71 0.57 −
water injection.
SSW 1.07 1.03 − − 8.45
The goal of this article is to contribute to the understanding of
LS 1.03 1.00 − − 7.50
mechanisms involved in the low salinity effect and to investigate the
polymer (300 ppm) 2.60 − − − −
synergy of low salinity waterflooding and polymer injection. In our
polymer (1000 ppm) 7.50 − − − −
previous work,24 we studied the effects of different initial wettability
LPS (300 ppm) 2.20 − − − −
states on oil recovery by tertiary-mode low salinity waterflooding on
Berea and Bentheimer outcrop sandstones. The results showed no
increased oil recovery by the LSE in strongly water-wet Bentheimer Porous Media. Core plugs from outcrop Berea sandstone were used
cores and limited oil recovery (∼2% OOIP) in oil-wet samples. The in this study. Mineralogy measurements by X-ray diffraction (XRD)
oil recovery from intermediate-wet Berea cores was marginal. In the showed that the Berea samples contained 7.9% clay minerals, including
3.2% kaolinite (Table 3). The core plugs were cut from whole cores and
current study, the aim was to investigate the efficiency of secondary-
versus tertiary-mode LS injection on strongly water-wet and
intermediate-wet Berea sandstone cores. After the LS injection Table 3. Mineralogical Composition of Berea Samples
experiments, the cores were subjected to polymer flooding to content content content
examine further enhanced oil recovery by combined low salinity component (wt % bulk) component (wt % bulk) component (wt % bulk)
water/polymer injection. illite/mica 3.0 quartz 87.5 calcite trace

■ EXPERIMENTAL SECTION
Brines. Synthetic seawater (SSW) was used primarily for saturating
kaolinite
chlorite
3.2
1.7
feldspar
plagioclase
1.9
0.9
dolomite
siderite
0.9
0.9

and establishing connate water in core plugs and also as the injection
fluid in tertiary-mode low salinity experiments. The SSW was prepared
by dissolving different salts in distilled water such that the total dissolved
solids (TDS) was about 36000 ppm (mg/kg). Table 1 lists the
Table 1. Composition of Synthetic Seawater (SSW)
ion concentration (ppm, mg/kg)
Na+ 11156
Ca2+ 471
Mg2+ 1330
Cl− 20129
HCO3− 139
SO42− 2743
K+ 350
TDS 36318
composition of the synthetic seawater used in this study. This SSW also
was diluted by a factor of 10 to prepare low salinity water (LS) with a
salinity of about 3600 ppm (mg/kg), which was used as the injection
fluid during low salinity waterflooding experiments. The ionic strengths
of the SSW and LS were 0.69 and 0.069, respectively.
Polymer Solution. Polymer solutions were prepared by addition of
the required amount of Flopaam 3630S (SNF Floerger) polyacrylamide
with a hydrolysis degree of 25−30% and a molecular weight of 20 million
Da to low salinity water. Polymer solutions were prepared in con-
centrations of 300 and 1000 ppm.
Linked Polymer Solution. Linked polymer solution (LPS) was
prepared by adding aluminum citrate (AlCit) cross-linker to polymer
solution at a polymer-to-aluminum ratio of 30:1.
Oils. The initial water saturation (Swi) of the core plugs was attained
by injection of a high-viscosity mineral oil called Marcol 152. After Swi
had been established in all core plugs, Marcol 152 was replaced by
another mineral oil, n-decane. This mineral oil was also used to measure
the oil permeability of the core plugs at initial water saturation. A North
Sea stock tank oil (filtered) was used as a crude oil for aging of the core
plugs and as the oil phase in flow experiments. The viscosity of this crude
oil was in the range of 50−80 cP (from different production wells).
Compared to seawater and low salinity water, which have a viscosity of
only 1 cP, the mobility ratio was highly unfavorable. To achieve a more
effective displacement in flow experiments, the crude oil was diluted by
addition of xylene to reach a favorable viscosity. Table 2 lists some
properties of the injection fluids used in this experimental work at 22 °C.
placed in oven at 70 °C for about 48 h. The dried cores were then
mounted individually in an Exxon-type core holder, and the overburden
pressure was set at 20 bar. A vacuum pump was used to evacuate air from
the core samples. Then, the cores were saturated with synthetic
seawater, and their porosity and permeability were measured. After
permeability measurements, the synthetic seawater was displaced by
high-viscosity Marcol 152 to attain initial water saturation (Swi)
conditions in the core plugs. Then, several pore volumes of n-decane
mineral oil were injected at different flow rates to displace the Marcol
152 and measure the oil permeability at Swi. The physical properties of
the core plugs used in this study are reported in Table 4.
Aging with Crude Oil. Core plugs mounted in a core holder were
placed in heat cabinet at 110 °C and were aged by injection of crude oil for
4 weeks to obtain wettability states other than strongly water-wet. As
reported in a previous work,24 the unaged Berea cores were strongly water-
wet, and wettability studies for cores S1−S4 showed wettability changes
toward the intermediate-wet state after aging with crude oil (Figure 1).
Core Flooding Experiments. A pair of core plugs was mounted
together in a longer core holder, and a confining pressure of 20 bar was
applied. Five displacement experiments were performed in this study.
Intermediate-wet cores S6−S7 and S3−S4 were selected to examine LS
injection at intermediate wettability in secondary and tertiary modes,
respectively. Also, strongly water-wet core S11 and composite core
S9−S10 were used to perform low salinity tests under water-wet condi-
tions in secondary and tertiary modes, respectively. The intermediate-wet
core S12 was used to examine the reproducibility of increased oil recovery
by combined low salinity water/polymer flooding. The experiments were
performed at room temperature (22 °C). All flow experiments started at a
flow rate of 0.1 cm3/min, and then the flow rate increased to 0.2, 0.5, and
1.0 cm3/min to eliminate capillary end effects. For each flow rate, water
was injected until no more oil was produced and the pressure difference
across the cores was stabilized. The differential pressure across the core
plugs was continuously recorded by a data gathering system during the
flooding experiments.
Estimation of Capillary Pressure (Pc) and Relative Perme-
ability Curves. To obtain the capillary pressure and relative
permeability curves, the experimental data (differential pressure,
production data, and end-point data) were imported into the core
flood simulator Sendra.25 This simulator is a one-dimensional fully
explicit black oil simulator and was used to history match the core flood
experiments and estimation of Pc and Kr curves. To obtain the best
estimation of these curves from experimental data, the Corey26
correlation was used for relative permeability, and the Skjaeveland
et al.27 correlation was used for the capillary pressure.

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Table 4. Physical Properties of Core Samples

core ID L (cm) D (cm) PV (mL) porosity (%) Swi (%PV) Kw (mD) Ko at Swi (mD) Ko at Swia (mD)
S0 5.82 3.78 12.69 19.55 19 98.98 − −
S1 6.0 3.7 12.35 19.14 25 103.86 128.92 78.69
S2 6.23 3.76 13.28 19.19 23 90.23 110.86 78.68
S3 6.17 3.73 13.18 19.55 20 109.17 133.02 83.68
S4 6.17 3.73 12.63 18.73 21 90.96 118.43 70.72
S6 6.26 3.72 12.54 18.43 22 84.61 109.43
93.93
S7 6.17 3.73 12.85 19.04 22 117.43 146.02
S9b 5.92 3.71 12.35 19.31 22 95.06 118.40 −
S10b 5.98 3.74 12.65 19.25 22 101.70 122.12 −
S11b 8.82 3.76 17.77 18.11 22 75.14 89.20 −
S12 6.90 3.76 15.18 19.81 25 108.90 − −
a
Oil permeability after aging. bUnaged cores.

Figure 1. Amott/Harvey-USBM wettability plot, showing intermediate-wet state for aged cores S1−S4 (red) and strongly water-wet state for unaged
core S0 (blue).24.

Figure 2. Oil recovery factor, differential pressure, and injection rate as functions of volume injected for strongly water-wet composite core S9−S10
(tertiary-mode LS injection).

■ EXPERIMENTAL RESULTS
In this section, first, the experimental results obtained during low
salinity waterflooding in tertiary and secondary modes are presented,
and then the results from combined low salinity water/polymer
injection are displayed. In all experiments, injection continued until
1225
production ceased and/or a stable pressure profile was attained.
Throughout this article, the oil saturation at the end of each process
refers to remaining oil saturation, but because almost all of the literature
mixes remaining and residual oil saturation, residual oil saturation (Sor)
was used for experimental process end points in this article.
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Figure 3. Oil recovery factor, differential pressure, and injection rate as functions of volume injected for intermediate-wet composite core S3−S4
(tertiary-mode LS injection).
Figure 4. Oil recovery factor, differential pressure, and injection rate as functions of volume injected for strongly water-wet core S11 (secondary-mode
LS injection).
Tertiary-Mode Low Salinity Waterflooding. Strongly
water-wet composite core S9−S10 and intermediate-wet
composite core S3−S4 were chosen to perform tertiary-mode
low salinity water injection.
The oil recovery profile for this composite core is a typical
profile for water-wet systems, with almost no oil being produced
(no two-phase production) after breakthrough even when the
injection rate was increased (Figure 2). The oil recovery factor at
the end of SSW flooding was 51% OOIP, and injection of low
salinity water did not change the recovery factor. The relative
permeability of the injection water was 0.11 at the end of both
SSW and LS flooding, confirming the water-wet conditions of the
porous media.
The intermediate-wet composite core S3−S4 was flooded with
synthetic seawater to establish residual oil saturation conditions,
and then tertiary-mode low salinity water was injected to examine
the LSE on oil mobilization. The oil recovery factor for this core
at SSW breakthrough was about 45% OOIP, and after a long tail
(two-phase) production, which is typical for nonwater-wet
porous media, the oil recovery factor reached about 64.4% OOIP
at the end of SSW flooding. Tertiary-mode LS injection started
after SSW injection. No oil production was observed for lower
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injection rates. However, marginal oil production (about 0.4%
OOIP) was observed at rate of 1 cm3/min (Figure 3), where the
final recovery factor reached 64.8% OOIP. The water relative
permeabilities at the end of SSW and LS injections were 0.33 and
0.37, respectively, reflecting a less water-wet system than in the
previous experiment.
The higher recovery factor for core S3−S4 compared to that
for strongly water-wet core S9−S10 is in line with previously
reported results28 that intermediate-wettability conditions give
more oil recovery than strongly water-wet conditions because of
low capillary forces. This is because the Amott index for the cores
used in this study was very close to zero (Figure 1), and therefore,
the contact angle was close to 90° (θ = 90°). Under such
conditions, cos θ will have a very low value close to zero, and
based on capillary pressure formula, Pc = (2σ cos θ)/r, the
capillary forces will be lower than in strongly water-wet porous
media, where the contact angle is close to zero and, as a result, the
capillary forces reach the highest possible values.
For the crude oil−brine−rock system of this study, the
obtained results showed no potential for increased oil recovery
by tertiary-mode LS flooding under strongly water-wet
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Figure 5. Comparison of oil recovery factor, differential pressure, and injection rate as functions of volume injected for core S11 (secondary-mode LS
injection) and core S9−S10 (secondary-mode SSW injection).

Figure 6. Experimental and simulation data for recovery factor and differential pressure of water-wet cores S11 (secondary LS injection, left) and
S9−S10 (secondary SSW injection, right).

Figure 7. Estimated (A) capillary pressure and (B) relative permeability curves for cores S11 (secondary-mode LS injection) and S9−S10 (secondary-
mode SSW injection). (C) Expanded plot for capillary pressure.

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Figure 8. Oil recovery factor, differential pressure, and injection rate as functions of volume injected for intermediate-wet composite core S6−S7
(secondary-mode LS injection).
Figure 9. Comparison of oil recovery factor, differential pressure, and injection rate as functions of volume injected for cores S6−S7 (secondary-mode
LS injection) and S3−S4 (secondary-mode SSW injection) .
conditions and very limited potential for intermediate-wet
porous media.
Secondary-Mode Low Salinity Waterflooding. Strongly
water-wet core S11 and intermediate-wet composite core S6−S7
were used to investigate the LSE in secondary-mode LS flooding.
Figure 4 shows the oil recovery, pressure drop across the core,
and injection rate as functions of injected pore volume for
strongly water-wet core S11 during secondary-mode LS
injection. The oil recovery factor for this core at breakthrough
was 52.9% OOIP compared to 50.5% OOIP for water-wet core
S9−S10, where SSW was injected under initial water conditions.
Also, the final oil recovery by secondary LS injection reached
54.3% OOIP, about 3% more than oil recovery in core S9−S10
after SSW flooding. As for core S9−S10, almost no oil production
(no two-phase production) was observed after breakthrough,
even when the injection rate was increased, a typical behavior
for water-wet cores. Figure 5 shows a comparison of the
experimental results obtained during secondary-mode LS and
secondary-mode SSW injection in strongly water-wet cores S11
and S9−S10, respectively.
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The capillary pressure (Pc) and water−oil relative permeability
curves for core S11 and composite core S9−S10 were estimated
by history matching the experimental pressure and production
data using the core flood simulator Sendra. The history match of
pressure and production data for these cores is presented in
Figure 6. Figure 7 shows the estimated capillary pressures and
relative permeabilities based on the history match obtained for
these cores. This figure indicates that LS injection shifted the
wettability of the rock to a more oil-wet state. The Pc curve
(Figure 6) shows that, in core S11, both spontaneous and forced
imbibition of water are responsible for oil recovery whereas, in
core S9−S10, oil is recovered through spontaneous oil
imbibition. The relative permeability curves also show more oil
wetness for core S11.
Composite core S6−S7 under intermediate-wet conditions
was used to investigate the LSE in secondary mode. The physical
properties and initial saturation conditions of this core were very
similar to those of core S3−S4 (Table 4). Low salinity water was
injected into this core at initial water saturation (Swi) conditions
using the same procedure as before. The oil recovery factor for
this core at breakthrough was 51.5% OOIP, compared to 45.2%
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Energy & Fuels
Figure 10. Experimental and simulation data for recovery factor and differential pressure of intermediate-wet cores S6−S7 (secondary-mode LS
injection, left) and S3−S4 (secondary-mode SSW injection, right).
Figure 11. Estimated (A) capillary pressure and (B) relative permeability curves for intermediate-wet cores S6−S7 (secondary-mode LS injection) and
S3−S4 (secondary-mode SSW injection).
OOIP for core S3−S4 where synthetic seawater was injected
under initial water conditions. Also, the final oil recovery reached
more than 78% OOIP (Figure 8), leaving a residual oil saturation
of 17% PV, whereas the residual oil saturation in core S3−S4 was
28% PV after SSW flooding. The additional oil recovery by LS
was about 13% OOIP (10% saturation units) compared to
seawater injection. The water relative permeability at the end of
LS injection was 0.4 (at Sor = 0.17% PV).
Figure 9 shows a comparison of pressure drop and recovery
profile for secondary-mode LS and secondary-mode SSW injections
for intermediate-wet cores. During the early period of the injection
(before breakthrough), the pressure increase in core S6−S7 was
greater than that in core S3−S4, which could be related to strong oil
mobilization and two-phase flow in porous media. In the later part of
the experiments, the higher differential pressure in core S3−S4
compared to that in core S6−S7 was due to the higher residual oil
saturation in this core (0.28% PV compared to 0.17% PV).
Later breakthrough, which is an indication of improved
displacement stability (shock front), and higher oil recovery
at breakthrough, were the characteristics of the secondary LS
injection in core S6−S7 compared to the secondary SSW
injection in core S3−S4.
A positive response to direct LS flooding has been observed
and reported by others (references have been included) and can
now be regarded as a general trend. The explanation of secondary
versus tertiary LSE is still not conclusive, but a tertiary LS flood
might encounter already trapped oil that might be hard to
remobilize, whereas direct LS injection will meet continuous oil
and avoid trapping/remobilization of oil. This seems to be a
plausible reason for higher oil recovery from direct LS flooding
compared to tertiary LS flooding. Comparing secondary high-
salinity to secondary low salinity waterflooding in our results, no
fines migration was observed, but other mechanisms as discussed
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Article
are possible either as single effects or as combined effects of
different mechanisms.
As for the water-wet cores in this study, the capillary pressure
(Pc) and water−oil relative permeability curves for intermediate-
wet cores S3−S4 and S6−S7 were estimated by history matching
of the experimental pressure and production data. The results are
shown in Figures 10 and 11. As for the water-wet cores, in this
case, the estimated capillary pressure and relative permeability
curve also indicated a more oil-wet state when the core was
flooded with secondary-mode low salinity water, whereas the
end-point permeability (most often reported in the literature)
indicated a shift toward more water-wet conditions. The
estimated capillary pressure suggests that spontaneous water
imbibition was absent during the oil production, as spontaneous
water imbibition is responsible for more oil trapping by snap-off
events during water flooding. The absence of spontaneous water
imbibition and, therefore, the lack or weakness of snap-off events
indicates the weakness of trapping mechanisms during
secondary-mode LS flooding, where, as a consequence, the oil
is produced over the longer period before water breakthrough.
Combined LS/Polymer/Linked-Polymer Injection. The
goal of this part of experiment was to investigate the possible
positive interaction of low salinity water and polymer/linked-
polymer injection as a hybrid EOR process on final oil recovery
efficiency. It has been previously reported that high tertiary oil
recovery could be obtained by surfactant injection after stabilizing
a low salinity environment as surfactant adsorption is reduced in low
salinity environments.12 This might also be applicable for anionic
polymers, such as hydrolyzed polyacrylamide (HPAM), where the
adsorption is strongly dependent on salinity29 and decreases at
lower salinities. This could result in a lower loss of polymer from the
bulk solution, a longer-lasting favorable mobility ratio, and an
improved sweep efficiency. In this study, polymer injection was
initiated after low salinity residual oil saturation in both secondary
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Figure 12. Oil recovery profile, differential pressure, and injection rate as functions of volume injected during secondary-mode low salinity-polymer/
LPS injection for intermediate-wet core S6−S7.
Figure 13. Comparison of oil recovery and differential pressure as functions of volume injected during secondary-mode low salinity-polymer injection
for cores S6−S7 and S12.
and tertiary modes to investigate the possibility of further
reductions in Sor.
In strongly water-wet core S9−S10 after tertiary LS injection,
300 ppm linked polymer solution (LPS) was injected when the
residual oil saturation was 0.38 PV. No more oil production was
observed with LPS injection, even though the core experienced a
considerably higher pressure differential than during LS
injection.
Injection of 300 ppm polymer was performed in strongly
water-wet core S11 at a residual oil saturation of 0.36 PV after a
low salinity environment had been established by secondary-
mode LS injection. Similarly to core S9−S10, even though the
core experienced higher differential pressure during polymer
flooding, no reduction in Sor was observed.
After tertiary-mode LS injection in intermediate-wet core
S3−S4, where the residual oil saturation was 0.28 PV, the core
was subjected first to 300 ppm LPS injection and then to 1000 ppm
polymer flooding to examine the effect of a highly viscous force in
reducing the residual oil saturation. The increased recovery factor
from this sequence was about 5% OOIP, and the Sor reduced to
0.24% PV. The increase in oil recovery upon injection of 1000 ppm
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polymer was only 1% OOIP, showing that a favorable mobility ratio
is a necessary but not sufficient condition for oil recovery
improvement.
In intermediate-wet core S6−S7, which was used for
secondary-mode LS flooding, after LS injection at initial water
saturation (Swi), the core, with a considerably low residual oil
saturation of 0.17% PV, was injected with 300 ppm polymer and
then 300 ppm LPS at a constant injection rate of 0.1 cm3/min. In
this case, the core showed a very encouraging response to
polymer flood as is shown in Figure 12. The increased oil
recovery was about 12% OOIP. The residual oil saturation was
reduced to a very low value of 0.08 PV (9 saturation units
reduction in Sor due to polymer injection).
Examining the Reproducibility of Increased Oil
Recovery by Combined Low Salinity Water/Polymer
Flooding. To confirm the reproducibility of increased oil recovery
by combined secondary-mode LS/polymer flooding, the experiment
was repeated by a second flooding. The intermediate-wet core S12,
which previously was used for a wettability test at an oil saturation of
0.5% PV, was flooded with low salinity water to establish residual oil
saturation conditions. Then, the core at a residual oil saturation of
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Figure 14. Comparison of oil recovery and residual oil saturation as functions of volume injected during secondary-mode low salinity-polymer injection
for cores S6−S7 and S12.

about 0.16% PV was flooded with a 300 ppm polymer solution at Table 5. Summary of the Experimental Results
an injection rate of 0.1 cm3/min. As for core S6−S7, a significant
PV Soi RFLS SorLS RFf Sorf ΔRFP Krow at
increase in oil recovery of about 17% OOIP was recorded, and core ID (mL) (% PV) (%OOIP) (% PV) (% OOIP) (% PV) (% OOIP) SorLS
the residual oil saturation decreased to about 0.07% PV. Figures S9−S10 25.01 78 51.0 38 51.0 38 0 0.11
13 and 14 present a comparison of the differential pressure, S11 17.77 78 54.3 36 54.3 36 0 0.09
recovery factor, and residual oil saturations observed during S3−S4 25.80 79 64.8 28 70.1 24 5 0.37
polymer flooding in cores S6−S7 and S12. S6−S7 25.39 78 78.1 17 89.8 8 12 0.40
The results from these experiments confirm that the increased S12 15.18 50 68.7 16 85.8 7 17 0.36
oil recovery by combined secondary-mode LS/polymer flooding
was reproducible under the experimental conditions of this
especially during polymer flooding, were below the critical
study. desaturation number.

As Figure 12 shows, the injection rate was increased stepwise
during LS flooding to eliminate or further reduce capillary end
effects. Generally, if the differential pressure becomes high during
polymer flooding but is lower than the pressure during the bump
rate, end effects are unlikely. If the pressure during polymer
injection exceeds the bump rate pressure, end effects are possible,
but the increase in pressure could also be due to additional oil
production (relative permeability effect).
Considering the pressure differential during different rate
increases and the corresponding oil recovery at each bump in the
rate, it was possible to produce some oil from the region affected by
capillary end effects. However, according to the differential pressure
during polymer flooding, which increased by less than a factor of 2
compared to that during LS flooding at a rate of 1 cm3/min, and
comparing the oil recovery during polymer flooding with oil
recovery by the LSE when the injection rate was increased, we
believe that the majority of oil is produced from better sweep
efficiency throughout the core. Furthermore, in other experiments
in this study, for example, for core S9−S10, a considerable increase
in pressure gave no significant change in residual oil saturation.
Therefore, it seems that pressure accumulation is not a necessary
condition for increased oil recovery in this study.
A summary of the results obtained from different flooding
experiments is presented in Table 5. Also, the capillary numbers
(Nc) for all experiments at different flow rates and during
injection of different fluids are reported in Table 6. The capillary
number at which residual oil saturation tends to drop with
increasing capillary number is known as the critical desaturation
number or critical capillary number (Ncc) and is dependent on
wettability states of the porous media. From the literature,30 the
critical capillary numbers for water-wet and intermediate-wet
Berea sandstone are ∼10−5 and ∼10−4, respectively. Therefore,
Table 6 shows that the capillary numbers during all experiments,
1231
■
DISCUSSION
Secondary- versus Tertiary-Mode LS Flooding. The
design of an LS flooding process might be influenced by when the
injection was started. Previous studies have been mostly focused
on examining increased oil recovery by LS injection in tertiary
mode, where the invading low salinity fluid is injected at residual
oil saturation left behind after high-salinity water flooding. Some
researchers have investigated the oil recovery efficiency of low
salinity water as an invading fluid in secondary mode (at initial
water saturation). Zhang and Morrow6 compared the oil
recovery obtained by LS flooding in secondary and tertiary
modes upon changing the injection brine composition and
concluded that, in the case of a positive response, injection of LS
improves oil recovery for both secondary and tertiary modes but
sometimes for only one or the other. Secondary-mode LS
injection and the effect of wettability on oil recovery was
investigated by Ashraf et al.7 They reported a higher oil recovery
for secondary-mode LS injection than for high-salinity brine
injection under different initial wettability states. They also found
the highest reduction in residual oil saturation by LS injection
under water-wet conditions. In research performed by Rivet et
al.,8 tertiary-mode LS did not produce incremental oil recovery.
They observed improved ultimate oil recovery by secondary-
mode LS injection only in intermediate-wet systems, whereas
water-wet systems did not show any recovery by secondary LS
flooding. Other researchers also reported better recovery
response for secondary- compared to tertiary-mode LS
injection.9,31
The results of this experimental work indicate that an early
start to LS injection is beneficial for oil recovery. Under the
reported experimental conditions of this study, during tertiary-
mode LS injection, no oil recovery was observed for strongly
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Energy & Fuels Article

Table 6. Capillary Numbers (Nc) for Different Experiments at Different Flow Rates of Different Displacing Fluids
injection rate (cm3/min) S3−S4 S6−S7 S9−S10 S11 S12
SSW
0.1 1.02 × 10−7 − 1.02 × 10−7 − −
0.2 2.04 × 10−7 − 2.05 × 10−7 − −
0.5 5.10 × 10−7 − 5.11 × 10−7 − −
1.0 1.02 × 10−6 − 1.02 × 10−6 − −
LS
0.1 6.28 × 10−8 6.27 × 10−8 6.30 × 10−8 6.18 × 10−8 6.18 × 10−8
0.2 1.26 × 10−7 1.25 × 10−7 1.26 × 10−7 1.24 × 10−7 −
0.5 3.14 × 10−7 3.13 × 10−7 3.15 × 10−7 3.09 × 10−7 3.09 × 10−7
1.0 6.28 × 10−7 6.27 × 10−7 6.30 × 10−7 6.18 × 10−7 6.18 × 10−7
polymer/LPS
0.1 1.34 × 10−7 1.58 × 10−7 1.35 × 10−7 1.56 × 10−7 1.56 × 10−7
0.2 2.68 × 10−7 − − − −
0.3 4.03 × 10−7 − − − −
0.4 5.37 × 10−7 − − − −

water-wet cores, and only very limited oil was recovered from
intermediate-wet cores. Low salinity water injection as a
secondary recovery mode was promising. Both water-wet and
intermediate-wet cores showed positive response for this
flooding mode. Unlike the observations by Rivet et al.,8 this
study showed increased oil recovery of about 3.3% OOIP in
strongly water-wet cores by secondary-mode LS injection
compared to secondary-mode SSW injection (Table 5).
However, a substantial increase in oil recovery by secondary
LS injection was obtained in intermediate-wet cores, where the
oil recovery was 13% OOIP more than that of secondary SSW
injection in intermediate-wet cores. The results showed that the
reduction in residual oil saturation by secondary LS injection is
higher for intermediate-wet cores than for strongly water-wet
cores. This contrasts with the observations by Ashraf et al.,7 who
found a higher reduction in Sor under water-wet conditions.
The pressure profiles during all experiments, especially during
LS flooding, were stable, and no fines production was observed.
This indicates that microscopic flow diversion by fines migration
was not a key contributing mechanism to the increased oil
recovery by LS injection in our cases. This is in accordance with
other observations in the literature, among them those of
Boussour et al.18 and Cissokho et al.32
The reason for high oil recovery in secondary-mode compared
to tertiary-mode LS flooding might be effective trapping31 of oil
clusters during high-salinity water injection before initiation
of tertiary-mode LS flooding. Referring to Figure 1, the
wettability of the cores during aging with crude oil was changed
to an intermediate-wet state, where possibly the larger pores were
oil-wet and the smaller pores remained water-wet.33 During high-
salinity water injection, the invading fluid first occupies smaller
pores through film flow, which might lead to snap-off oil clusters
in the larger pores. This might limit the continuity of oil through
porous media and increase the chance of oil trapping. Tertiary-
mode LS would pass through “open-to-flow” channels and pores,
in which case the pores with trapped oil would be bypassed by
low salinity water. No contact with low salinity water would
prevent any reaction of low salinity water with pore elements
(pore throats and pore walls) to mobilize trapped oil. Oil
mobilization in secondary-mode LS is possible by maintaining
film continuity and allowing for fewer snap-off events in a weaker
water-wet state for direct LS injection. Also, multicomponent ion
exchange together with expanding double layer (due to the
1232
difference in ionic strength of LS and connate water) is likely and
could lead to destabilized oil layers (movable oil).
The results obtained in this study show that the initial
wettability state of a porous medium is a key factor in the
waterflooding efficiency of LS injection and that more
intermediate-wet cores give a better response; however, this
factor alone cannot explain the mechanism(s) behind the success or
failure of LS injection. It is commonly believed that wettability
alteration toward a more water-wet state is the reason for oil
mobilization and production. However, there are also some reports
of shifting to a more oil-wet state (this study and article by Fjelde
et al.34). The discussion here is that, if the wettability alteration is a
mechanism for the LSE, it is not always toward a more water-wet
state (as most researchers have reported), but it could also be toward
a more oil-wet (less water-wet) state as well. The mechanism leading
to this effect is an increase in the adsorption of organic components
with salinity reduction, because of the competition between the
different active species toward the negative sites of the clay. Thus, a
negative salinity gradient will increase the adsorption of organic
material onto the clay. This will shift the wettability to lower water
wetness.22
Adhesion mapping studies by Buckley et al.35 also showed that
there are regions of stability and instability of water films, where
nonadhesion or adhesion of crude oil components onto the rock
surface could be observed, depending on brine salinity. This
adhesion mapping shows that, under low salinity conditions,
water films are unstable and, therefore, adhesion of crude oil
components could alter the wettability to a less water-wet state.
Combined Low Salinity Water/Polymer Injection. The
results of this study indicate that combined LS/polymer flooding
containing a low polymer concentration of 300 ppm could
mobilize residual oil in porous media and further increase the oil
recovery factor. The concentration of polymer solutions used in
this hybrid EOR process (300 ppm) is low enough from the
point of view of their practical applicability (injectivity), because
the viscosity of such solutions is only 2.6 cP compared to a water
viscosity of 1 cP at room temperature. The increased oil recovery
by LS/polymer flooding was examined for reproduc-
ibility by a second flood, and the results were in line with those
of the primary experiments. The results also suggest that,
although polymer injection could mobilize residual oil after
tertiary-mode LS flooding, higher oil recovery by polymer
injection occurs when the low salinity environment is established
at initial water saturation (Swi) rather than Sor (i.e., when the
dx.doi.org/10.1021/ef301538e | Energy Fuels 2013, 27, 1223−1235
Energy & Fuels
Figure 15. Comparison of propagation of 300-ppm polymer/LPS solution through water-wet and intermediate-wet sandstone cores based on the
differential pressure at each wettability state.
polymer solution is injected after residual oil saturation
established by secondary-mode LS flooding).
The reason why combined LS/polymer injection produces
more oil can be attributed to an improvement of the stability of
the LS flood by addition of polymer,36 which improves the
efficient banking of oil through a favorable mobility ratio and/or
inaccessible pore volumes, thereby increasing the displacement
efficiency. The inaccessible pore volume (IPV) indicates the
portion of the pore volume for which the entrance radii of the
pore elements are smaller than the polymer particles (especially
when a high-molecular-weight polymer is used). This volume
is mostly occupied by the irreducible or connate water.
Inaccessibility of this volume to the polymer would result in
the absence of a highly mobile connate water bank, and therefore,
the polymer solution would not displace the connate water.37
The consequence is a better sweep efficiency of the polymer
solution and increased oil recovery.
Moreover, the results of this study show that the initial
wettability state of a porous medium is important for the
combined LS/polymer effect, where the strongly water-wet cores
did not display any reduction in residual oil saturation as a result
of this combined process, despite the considerably high
differential pressure experienced in the system. The differential
pressure in intermediate-wet cores was much lower than that in
water-wet cores, as presented in Figure 15. This figure shows the
differential pressure across water-wet and intermediate-wet cores
during first three pore volumes of polymer flooding.
The higher pressure buildup in water-wet cores could possibly
be related to higher adsorption/retention of polymer on water-
wet rock surfaces compared to intermediate-wet media. During a
polymer flood in an intermediate-wet reservoir, the injected
polymer will interact with significant portions of oil-wet rock. In
this case, it is possible that rock wettability will have a considerable
effect on polymer adsorption.38 The adsorption of crude oil
components reduces the adsorption sites on rock surface, and
therefore, the tendency of polymer molecules to interact with the
rock surface is decreased. Higher polymer adsorption on water-wet
rock surfaces results in a poor sweep efficiency of polymer solution
as a result of retention in porous media and intensification of the
trapping of oil in the blocked pores.
The increased oil recovery from combined low salinity water/
polymer flooding in this study is in line with the simulation study
of the benefit of combining polymer with low salinity water for
1233
Article
enhanced oil recovery reported by Mohammadi and Jerauld,39 as
well as the experimental studies by Kozaki.40 Mohammadi and
Jerauld39 demonstrated that addition of polymer to a low salinity
aqueous base fluid enhances recovery efficiency in both
secondary and tertiary modes, but secondary mode gives better
timing of oil recovery. They attributed most of the benefit of the
polymer to an improvement in fractional flow behavior. The
difference between this experimental work and the simulation
study by Mohammadi and Jerauld39 is that they injected a low
salinity polymer solution at Swi (in secondary mode) or after
high-salinity residual oil saturation, whereas in the current work,
first low salinity water was flooded in secondary or tertiary mode
to establish a low salinity environment in the porous media and
then polymer solution was injected.
■ CONCLUSIONS
Injection of low salinity water (LS) was found to increase oil
recovery compared to injection of seawater even in the water-wet
state, but injection of LS after high-salinity water gave no change
in Sor in the water-wet state. This behavior can be explained by
effective trapping (snap-off of oil clusters in larger pores) during
seawater injection.
The initial wettability state of a porous medium seems to be a
key factor in the waterflooding efficiency of LS injection as more
intermediate-wet cores give a better response.
Wettability alteration by low salinity can be interpreted as a
shift toward either more water-wet or more oil-wet conditions,
possibly depending on the wettability indicator detected. The
derived capillary pressure and relative permeability in our
experiments indicate a shift toward a more oil-wet state.
Wettability shift in our experiment is very uncertain, and other
possible factors such as clay swelling, internal fines migration, and
residual oil distribution might all affect the differential pressure
and production in a manner to be interpreted as an alteration in
wettability.
A stable pressure profile during LS flooding and the lack of
fines production indicate that, in our cases, microscopic flow
diversion by fines migration is not a key mechanism and
multicomponent ion exchange together with an expanding
double layer is likely and could lead to destabilized oil layers
(movable oil).
Combined low salinity water/polymer flooding was found to
lead to very high total oil recovery, probably because of the
dx.doi.org/10.1021/ef301538e | Energy Fuels 2013, 27, 1223−1235
Energy & Fuels Article

combined effects of this hybrid EOR process. The polymer
concentration was low and gave only a small change in mobility
ratio. The oil recovery by polymer injection was improved
significantly in the case where the low salinity environment was
established at initial water saturation (Swi) rather than Sor.
(5) Webb, K. J.; Black, C. J. J.; Edmonds, I. J. Low salinity oil recovery:
The role of reservoir condition corefloods. Presented at the 13th
European Symposium on Improved Oil Recovery, Budapest, Hungary, Apr
25−27 2005.
(6) Zhang, Y.; Morrow, N. R. Comparison of secondary and tertiary

■
recovery with change in brine composition for crude oil/sandstone
combinations. Presented at the 2006 SPE/DOE Symposium on Improved
AUTHOR INFORMATION Oil Recovery, Tulsa, OK, Apr 22−26, 2006; Paper SPE 99757.
Corresponding Author (7) Ashraf, A.; Hadia, N. J.; Torsæter, O.; Tweheyo, M. T. Laboratory
*E-mail: behruz.shaker@uni.no. investigation of low salinity water flooding as secondary recovery
process: effect of wettability. Presented at the SPE Oil and Gas India
Notes Conference and Exhibition, Mumbai, India, Jan 20−22, 2010; Paper SPE
The authors declare no competing financial interest. 129012.

■ ACKNOWLEDGMENTS
The authors acknowledge the Norwegian Research Council
(8) Rivet, S. M.; Lake, L. W.; Pope, G. A. A core flooding investigation
of low salinity enhanced oil recovery. Presented at the SPE Annual
Technical Conference and Exhibition, Florence, Italy, Sep 19−22, 2010;
Paper SPE 134297.
(NFR) for financial support.

■
(9) Gamage, P.; Thyne, G. Comparison of oil recovery by low salinity
water flooding in secondary and tertiary recovery modes. Presented at
ABBREVIATIONS the SPE Annual Technical Conference and Exhibition, Denver, CO, Oct
D = core diameter (cm) 30−Nov 2, 2011; Paper SPE 147375.
(10) Mahani, H.; Sorop, T. G.; Ligthelm, D.; Brooks, A. D.; Vledder, P.;
EOR = enhanced oil recovery
Mozahem, F.; Ali, Y. Analysis of field responses to low salinity water
HPAM = hydrolyzed polyacrylamide flooding in secondary and tertiary mode in Syria. Presented at the SPE
IFT = interfacial tension (mN/m) EUROPEC/EAGE Annual Conference and Exhibition, Vienna, Austria,
Ko = permeability to oil (mD) May 23−26, 2011; Paper SPE 142960.
Kr = relative permeability (11) Winoto, W.; Loahardjo, N.; Xie, X.; Yin, P.; Morrow, N. R.
Krow = oil relative permeability to water Secondary and tertiary recovery of crude oil from outcrop and reservoir
Kw = permeability to water (mD) rocks by low salinity water flooding. Presented at the Eighteenth SPE
L = core length (cm) Improved Oil Recovery Symposium, Tulsa, OK, Apr 14−18, 2012; Paper
LPS = linked polymer solution SPE 154209.
LS = low salinity water (12) Alagic, E.; Skauge, A. Combined low salinity brine injection and
LSE = low salinity effect surfactant flooding in mixed-wet sandstone cores. Energy Fuels 2010, 24
Nc = capillary number (6), 3551−3559.
Ncc = critical capillary number (13) Skauge, A. Microscopic diversion: A new EOR technique.
OOIP = original oil in place (mL) Presented at the 29th IEA Workshop & Symposium, Beijing, China, 2008.
(14) McGuire, P. L.; Chatham, J. R.; Paskvan, F. K.; Sommer, D. M.,
ppm = parts per million (mg/kg)
Carini, F. H. Low salinity oil recovery: an exciting new EOR opportunity
PV = pore volume (mL) for Alaska’s North Slope. Presented at the 2005 SPE Western Regional
RF = recovery factor (%OOIP) Meeting, Irvine, CA, Mar 30−Apr 1, 2005; Paper SPE 93903.
RFf = final recovery factor (%OOIP) (15) Lager, A.; Webb, K. J.; Black, C. J. J.; Singleton, M.; Sorbie, K. S.
RFLS = recovery factor at the end of low salinity water injection Low salinity oil recoveryAn experimental investigation. Presented at
(%OOIP) the International Symposium of the Society of Core Analysts, Trondheim,
Soi = initial oil saturation (%) Norway, Sep 12−16 2006.
Sor = residual oil saturation (%) (16) Sorbie, K. S.; Collins, I. R. A proposed pore-scale mechanism for
Sorf = final residual oil saturation (%) how low salinity water flooding works. Presented at the 2010 SPE
SorLS = residual oil saturation at the end of low salinity water Improved Oil Recovery Symposium, Tulsa, OK, Apr 24−28, 2010; Paper
injection (%) SPE 129833.
Swi = initial water saturation (%) (17) Liegthelm, D. J.; Gronsveld, J.; Hofman, J. P.; Brussee, N.;
SSW = synthetic seawater Marcelis, F.; van der Linde, H. A. Novel waterflooding strategy by
manipulation of injection brine composition. Presented at the
TDS = total dissolved solids
EUROPEC/EAGE Annual Conference and Exhibition, Amsterdam, Jun
XRD = X-ray diffraction 8−11, 2009; Paper SPE 119835.
ΔRFP = incremental recovery factor by polymer injection

■
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