Article

pubs.acs.org/EF

Enhanced Oil Recovery (EOR) by Combining Surfactant with Low

Salinity Injection
Annette Meland Johannessen* and Kristine Spildo
Centre for Integrated Petroleum Research (Uni CIPR), University of Bergen, Allegaten 41, 5007 Bergen, Norway
ABSTRACT: When injecting low salinity (LS) water, it is believed that destabilization of oil layers adhering to mineral surfaces
could be a contributing mechanism to enhanced oil recovery (EOR). Surfactant ooding is a proven EOR technique by
increasing the capillary number. The combination of LS water at reduced capillarity can avoid retrapping of destabilized oil and
exceed recoveries of either of the techniques applied alone. In this study, we have used an alcohol propoxy sulfate mixed with an
internal olen sulfonate to compare the oil recovery in a low salinity surfactant (LSS) ooding process at moderately low IFTs to
that of an optimal salinity surfactant (OSS) injection process at ultralow IFT. The surfactant formulation was selected on the
basis of an initial screening phase using a North Sea crude oil and diluted seawater. Its eect on oil recovery eciency in dierent
injection scenarios was investigated using crude oil aged Berea sandstone cores. The results showed comparable recoveries for
the LSS ooding at a capillary number 2 orders of magnitude lower than that for the surfactant ooding at ultralow IFT. In
addition, retention values in the latter case were around 60% higher than for the LS case. On the basis of this, it appears that the
LSS process may be more economically ecient than an OSS injection process at ultralow IFT.

1. INTRODUCTION
Low salinity (LS) water injection is an emerging enhanced oil
recovery (EOR) technique110 where it is believed that
destabilization of oil layers adhering to mineral surfaces could
be a contributing mechanism. Surfactant ooding is a proven
EOR technology where surfactant added to the injection water
improves recovery by increasing the capillary number.1113 The
capillary number, Nc, refers to the dimensionless ratio of
viscous to capillary forces, which commonly is dened as
u
Nc =
(1)

case, the process should not work on water-wet cores.

However, Ashraf el al.39 found that although the ultimate oil
recovery was largest for neutral wet Berea cores, the largest LSE
was found for water-wet conditions. Thus, at present, there is
no consistent correlation between wettability and LSE.
Spildo et al.9 showed that even though LS injection alone
gave negligible oil recovery, a combination of LS and surfactant
ooding on intermediate-wet cores gave higher recoveries than
what would be predicted by the relationship between capillary
number and residual oil saturation for Berea, published by
Garnes et al. 12 This was achieved at low surfactant
concentration with a moderate reduction in IFT showing low
retention values.
APS and IOS Surfactants. Alcohol propoxy sulfates (APS)
have previously been studied for EOR purposes. The propoxy
(PO) groups are weakly hydrophobic functional groups that
have anity for the interface and thus increase the width of the
ultralow IFT region.15 The degree of propoxylation can be used
to tailor the surfactant to a given crude oil, temperature, and
salinity, as the addition of PO groups lowers optimum salinity.
Further, the presence of PO groups also adds calcium tolerance
to the surfactant.1620 The use of PO groups, and branching of
such, also tends to decrease the order of micellar structures.
This again tends to reduce equilibration time and promotes the
formation of microemulsions instead of unwanted gel and other
viscous phases. Sulfate surfactants, however, have limited
temperature stability and are restricted to reservoirs up to
approximately 60 C. At higher temperatures, the sulfates tend
to hydrolyze.15
Ideally, one would like to limit the number of components in
a surfactant formulation, i.e. surfactant, cosurfactant, and

where u is the Darcy velocity, is the viscosity of the displacing

uid, and is the interfacial tension between the oil and the
displacing uid.
Increasing Nc reduces the amount of oil retained in the
formation by capillary forces and/or remobilizes oil that is
already capillary trapped. By combining these two techniques in
a low salinity surfactant (LSS) injection process, an increase in
recovery that exceeds that of either of the techniques applied
alone has been observed.8,9
Even though many studies have shown a negligible response
to LS injection, the most encouraging results show up to 25%
OOIP additional recovery.14 Compositions of LS injection
water used in eld tests range from 2 to 3000 ppm;14 however,
the low salinity eect (LSE) has been reported for brine
compositions of up to 5000 ppm.8 Despite growing interest in
low salinity brine injection for EOR purposes, a consistent
mechanistic explanation of the LSE has not yet emerged.14 As
noted by the authors, the various circumstances under which
LSE may or may not be observed indicates that there are
probably more than one contributing mechanism. The type and
amount of clays present has been suggested as important for
LSE. Nonetheless, wettability change from less to more waterwet conditions is the most frequently suggested cause of
increased recovery by low salinity brine injection. If that is the
XXXX American Chemical Society

Received: April 4, 2013

Revised: September 2, 2013

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anionic surfactants is complex. Healy et al.28 reported that S*

increases as WOR increases. On the other hand, Tien and
Bettahar26 found a decrease in S* with increasing WOR for
sodium dodecyl benzene sulfonate, while Flaaten et al.27 found
a slight decrease in S* with decreasing total surfactant
concentration for an APS-IOS surfactant system.
Surfactant concentrations during the phase behavior screening process are also usually higher than what is normally used in
a ooding process. However, lowering the surfactant
concentration may cause changes in the phase behavior system.
Salager et al.25 stated that the optimum surfactant solution,
obtained from minimum IFT at low surfactant concentration
and no detectable three-phase behavior, can be correlated to S*
that normally is found for high surfactant concentration from
three-phase behavior and minimum IFT. Wu et al.17 relied
solely on IFT measurements when searching for optimal
salinity for branched APS surfactants for improved oil recovery.
In this study, an APS and IOS1518 blend is used to compare
the oil recovery in a combined LSS ooding process at
moderately low IFTs to that of a surfactant injection process at
ultralow IFT. The surfactant formulation was selected on the
basis of an initial phase behavior screening process and IFT
measurements where variation in surfactant concentration and
WOR have been taken into consideration, using a North Sea
crude oil and diluted synthetic seawater (SW). The eect on oil
recovery eciency in dierent injection scenarios was
investigated using crude oil aged Berea sandstone cores.
Surfactant retention was also measured and compared in the
LS and the high salinity regimes to highlight the economic
benet from operating in a LS environment.

cosolvent, as much as possible. This gives the system added

robustness and eliminates possible challenges related to
chromatographic separation of the components. However, in
many cases, mixtures are needed to avoid the formation of
highly viscous phases and obtain clear, stable surfactant
solutions that are suitable for injection. Earlier studies have
shown that mixed surfactant systems of APS with dierent
carbon chain cuts of internal olen sulfonate (IOS) ranging
from C15 to C28 provide advantages in matching a system to
specic conditions,2123 in addition to showing no measurable
chromatographic separation during core oods.37 The mixed
surfactant systems can improve microemulsion phase behavior
with a wider salinity window in the Winsor III region, improve
aqueous solubility, show good tolerance of divalent ions, and
require low cosolvent concentrations, or even no cosolvent.
It should also be noted that APSs have previously been
reported to give low IFT and high oil mobilization without the
addition of cosurfactants or cosolvents.22,23
Phase Behavior. In the following, we classify microemulsion systems as Winsor I, Winsor II, or Winsor III.24
Winsor I and II refer to two phase equilibrium between a
microemulsion and an excess phase: in a Winsor I system, the
equilibrium is between oil-in-water microemulsion and an
upper excess oil phase, whereas in the Winsor II system the
equilibrium is between a water-in-oil microemulsion and a
lower excess water phase. The Winsor III system has a middle
microemulsion phase in equilibrium with an upper excess oil
phase and a lower excess water phase. At optimal salinity (S*)
or OS, the middle microemulsion phase solubilizes equal
volumes of oil and water. The volume of oil or water per
volume of surfactant at S* is referred to as the solubilization
parameter at optimum SP*:

SP* =

Vo
V
= w
Vs
Vs

2. EXPERIMENTAL SECTION
2.1. Fluids. The compositions of the brines used in the ooding
experiments are listed in Table 1.

(2)

Table 1. Concentration [ppm] and Ionic Strength [mol/kg]

of SW and Dilutions of SW

where Vi is the volume of oil (o), water (w), and surfactant (s).
The middle microemulsion phase has been reported to show
very low IFTs against oil and water,2830 with a minimum when
the microemulsion phase contains equal amounts of oil and
water. The interfacial tension between oil and water () at an
optimum can be calculated using the Chun Huh relation:30
C
=
(SP*)2

0.43 SW (OS
brine)

SW

(3)

C is an empirical constant, usually 0.3 mN/m.

Changing variables such as salinity, type of oil, cosolvent,
surfactant concentration, and wateroil ratio (WOR) will lead
to a shift in phase behavior. For example, for anionic surfactants
the phase behavior changes from Winsor I Winsor III
Winsor II as the salinity increases. The opposite is observed
when the alkane carbon number (ACN) of the oil phase
increases, i.e., the phase behavior changes from Winsor II
Winsor III Winsor I as S* increases.25
Standard procedures, like using NaCl brines, high surfactant
concentration, alkanes as an oil phase, and 1:1 WOR, are
usually used when performing phase behavior experiments in
order to quickly screen surfactants and obtain comparable data
sets across dierent studies. However, a phase behavior study
with 1:1 WOR may not be representative of a surfactant
ooding experiment, which is conducted at residual oil
saturation, Sor. Salager et al.25 claimed that the eect of varying
surfactant concentration and WOR on the system type for

0.07 SW (LS
brine)

ions

[ppm]

I
[mol/kg]

[ppm]

I
[mol/kg]

[ppm]

I
[mol/kg]

Na+
Ca2+
Mg2+
K+
Cl
SO42
HCO3
SUM

11185
474
1332
359
20186
2749
145
36431

0.243
0.024
0.110
0.005
0.285
0.057
0.001
0.724

4760
202
567
153
8590
1170
62
15503

0.103
0.010
0.047
0.002
0.121
0.024
0.0
0.308

793
34
94
25
1432
195
10
2584

0.017
0.002
0.008
0.0
0.020
0.004
0.0
0.051

Ionic strength, I, is dened as

I=

1
2

cizi2
i=1

(4)

where c is molality [mol/kg] and z is the valence of the ion.

The 0.43 SW brine is the concentration where ultralow IFTs were
obtained and will be referred to as the optimal salinity (OS) brine in
the following. The 0.07 SW one is the low salinity (LS) brine.
In static phase behavior tests, dierent dilutions of SW than those
mentioned in Table 1 were used, as well as dierent concentrations of
pure sodium chloride (NaCl) brines.
Surfactant Solutions. A series of branched C1213 alcoholxPO
sulfates (x = 7, 9, and 13) with purities of 32%, 27%, and 28%,
B

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respectively, were evaluated through phase behavior experiments. They

were tested in mixtures with an internal olen sulfonate cosurfactant
with a C1518 hydrocarbon chain length (IOS1518) with a purity of
33%. Secondary butanol (SBA) was used as a cosolvent. All of the
surfactants used in this study were supplied by Shell.
Oils. The oils used in this study and their physical properties at 50
C are listed in Table 2.

Table 4. Core Properties, Aging Oil, and Time for Each

Core

Table 2. Oil Density () and Viscosity () at 50 C

oil
C8
C10
crude
crude
crude
crude

A
A mod (25% xylene)
B
B mod (23% xylene)

(g/cm3)

(mPas)

0.68
0.71
0.85
0.87
0.906
0.893

0.39
0.63
20
3.3

core

Swi

Kw [mD]

aging oil

aging time

L1
L2
L3
H1
H2

0.33
0.32
0.30
0.26
0.34

100
100
85
330
320

crude A

crude B

2 weeks

4 weeks

The dimensions of the cores are similar with core lengths around 10
cm, cross-sectional areas around 11 cm2, PVs around 22 mL, and
porosity around 20%.
Dry core samples were mounted in Hassler core holders with an
overburden pressure of 20 bar, and saturated with SW under vacuum
to determine pore volumes (PVs) and porosities. Absolute
permeabilities to water were measured at 100% SW saturation before
the cores were drained with ltered crude oil to establish initial water
saturation, Swi. The cores were aged at 110 C in order to get a
wettability state other than strongly water-wet. L1L3 were aged for
two weeks, while H1 and H2 were aged for four weeks due to delayed
initialization of the core ooding experiments. It should be noted,
however, that equal amounts of oil were ushed through each of the
cores during the aging process. After aging, crude oil was displaced by
four PVs of crude A mod or crude B mod, which were used for relative
permeability measurements and otherwise throughout the experiments.
Figure 1 shows an illustration of the core displacement setup. The
displacement experiments were carried out at 50 C at an injection
rate of 0.1 mL/min followed by increased injection rates of 0.5 and 1
mL/min, after each injection step to minimize capillary end eects.
Relative permeabilities were measured after each injection step. The
coreooding tests were either performed in tertiary (cores L1L3) or
secondary mode (cores H1 and H2). Tertiary mode refers to a
ooding sequence starting with an initial SW ood to establish residual
oil saturation, Sorw, followed by a waterood at reduced salinity, and
nally surfactant injection at reduced salinity. In secondary mode, the
SW ooding step is omitted, and brine with reduced salinity was
injected directly at Swi, followed by surfactant injection at reduced
salinity.
The process of combining LS brine injection with a reduced
capillarity environment is referred to as LSS injection. The LSS
injection was evaluated using cores L1, L3, and H1. Cores L2 and H2,
on the other hand, were ooded with a surfactant solution at OS (0.43
SW). This salinity is associated with a minimum in IFT for the
selected surfactant system, but it is too high for a low salinity eect14
and will be referred to as optimal salinity surfactant (OSS) in the
following. Thus, these experiments are representative of classical
surfactant injection experiments.
2.4. Dispersion Measurements. To gain better understanding of
the uid ow in the core material, both with and without laminations,
dispersion measurements were conducted at Sor and at 100% water
saturation. Dispersion proles for all the cores at Sor and at 100% water
saturation after cleaning were obtained by measuring the euent
resistance when brine with a dierent salinity from the connate brine
(i.e., dierent resistance) was injected.
2.5. Retention Measurements. In addition to measuring the
euent surfactant concentration after the core ooding experiments,
surfactant retention experiments with retention proles were
performed on two cores, R1 and R2, at 100% water saturation. The

3.3

The alkanes, n-octane (C8) and n-decane (C10), were only used in
static phase behavior experiments for initial screening of surfactants.
Crudes A and B are North Sea crude oils coming from the same
reservoir, only from dierent batches. Crude B was the oil supplied
when the supply of crude A ran out. Crude A was used for aging three
cores with permeabilities around 100 mD, cores L1L3, and crude B
was used for aging two cores with permeabilities around 300 mD,
cores H1 and H2. Before the ooding experiments started, the crudes
were modied with the addition of xylene to obtain a more
representative viscosity ratio under typical North Sea reservoir
conditions. The amount added was a trade-o between achieving a
low viscosity and a low dilution factor. After the aging procedure,
crude A mod and crude B mod were used to ush through cores L1
L3 and cores H1 and H2, respectively, to replace the aging oil.
2.2. Static Phase Behavior Screening and IFT Measurements. Test samples were prepared by adding a xed amount of
surfactant, cosurfactant, and cosolvent to NaCl brines or diluted SW
brines of varying salinities and mixed with the appropriate oil. The
samples were prepared in specially designed, graduated pressure tubes,
placed in mixing rigs, and stored in heating cabinets at 50 C.
Solubilization parameters (SPi) were obtained by measuring the phase
heights in the samples after equilibrium was reached. S* was
determined by the intersection point when SPw and SPo were plotted
as a function of salinity. IFTs were measured at a total surfactant
concentration of 0.2 wt % (3:1 surfactant, cosurfactant ratio) with 0.2
wt % SBA for various diluted SW brines at 50 C. The surfactant
solutions were measured against crude A mod and crude B mod using
a spinning drop tensiometer (SITE100 from KRU SS).
2.3. Core Material and Core Preparation. Berea sandstone was
used as the core material in this study. Table 3 shows the Berea core
mineralogy, clay type, and content for a typical core from the batch of
Berea used.
The cores designated L1L3 come from a heterogeneous core
material containing visual deformation bands/lamina. The host rock
which represents the largest part of the rock was characterized as
homogeneous. The deformation bands stretch along the core with a
lower porosity and permeability than the host rock, giving absolute
permeabilites to water (Kw) of around 100 mD. The cores designated
H1H2 had a Kw around 300 mD and did not contain visible
laminations. Core properties and aging procedures are summarized in
Table 4.

Table 3. Berea Core Mineralogy

mineral
content
clay type
content

quartz
87.5

K feldspar
1.9
smectite
0.0

plagioclase

calcite

dolomite

siderite

pyrite

0.9

TR

0.9

0.9

0.0

clay
7.9

mica

kaolinite

chlorite

3.0

3.2

1.7

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Figure 1. Illustration of the experimental setup for dynamic core displacements.

cores are from the laminated material and have similar core properties
to those of L1L3. Surfactant concentration was measured by a
potentiometric autotitrator from Metrohm. The euent surfactant
samples were titrated against a cationic surfactant supplied by
Metrohm, a dialkyl methylimidazolium chloride called TEGOtrant
A100.
The pHs in the euent fractions were measured using a standard
pH electrode.

3. RESULTS AND DISCUSSION

3.1. Phase Behavior and Interfacial Tension. The goal
of the phase behavior studies was to nd a surfactant
formulation which could show ultralow IFT at a salinity too
high for a LS eect to be expected and at the same time show
low, but not ultralow, IFT at a salinity considered to be in the
LS region. That way, we can compare the eciency of the two
processes of low salinity surfactant (LSS) injection and
surfactant injection at optimal salinity (OSS) in terms of
increased oil recovery and surfactant retention.
In order to be used in coreood experiments, the surfactant
formulation has to fulll certain requirements. The aqueous
surfactant solution should be stable with no precipitation or
phase separation at the given temperature and salinity. A
further requirement is a low tendency to form viscous phases.
Such phases tend to form outside the three phase region,18
which is important to prevent, especially since the LSS ooding
experiments takes place here. The surfactant formulation
should also have as short of an equilibration time as possible.
Ideally, one would like to limit the number of components in
a surfactant formulation to increase the systems robustness and
get simpler logistics for an o-shore operation. Therefore,
phase behavior studies were initially performed without the
addition of cosurfactant or cosolvent to the NaCl brine.
However, the results showed poor phase behavior characteristics; highly viscous phases formed over a wide salinity range
with no visible three phase region. Adding cosolvent, SBA, and
a small amount of IOS1518 as a cosurfactant improved the
phase behavior. However, at salinities outside the three phase
region, viscous phases still remained (see Figure 2).
Equilibration times were on the order of three weeks.
Since some of the ooding experiments will take place at LS
conditions in the Winsor I region, it is important to eliminate
viscous behavior here. To achieve this, the surfactant to
cosurfactant ratio was further reduced due to viscous behavior
outside the Winsor III region. A 3:1 ratio of APS to IOS1518
has proven successful in other studies15,19,27 and was thus
selected. In this case, the total surfactant concentration was
kept at 3.33 wt % with 3 wt % SBA added as the cosolvent in
NaCl brine. Results of the phase behavior tests are summarized

Figure 2. Phase behavior for 2 wt % total surfactant concentration (7:1

ratio of C1213PO9-to-IOS1518) and 2 wt % SBA with n-decane
(WOR = 1:1) as a function of NaCl concentration. Salinity is given as
% NaCl at the base of the tubes and increases from left to right. Note
the viscous phases outside the III phase region.

in Table 5. Compared to the formulation with a 7:1 ratio, this

formulation showed reduced equilibration time (<24 h) and no
Table 5. Phase Behavior Results for 3.33 wt % APS and
IOS1518 with a 3:1 Ratio, and 3 wt % SBA
surfactant (C12
13POx)

oil

SP*

S* [wt %
NaCl]

S [wt %
NaCl]

7
9
13
7
9

C10
C10
C10
C8
C8

10
12.5
13.5
12
18

4.9
4.1
3
3.8
3

1.6
1.4
1.6
1.6
1.4

viscous phase formation. The salinity window, i.e., the range of

salinity giving rise to Winsor III behavior, and optimal salinity
were increased. The latter is likely due to the 3:1 system
containing a larger amount of the more hydrophilic IOS1518
surfactant, which shows an optimal salinity of 10 wt % NaCl
with decane at 50 C.31
As expected, SP* decreases and S* increases with increasing
ACN from octane to decane. Further, as the hydrophobic
character of the surfactant increases with an increasing number
of PO groups, SP* increases, and S* decreases, consistent with
results obtained by Barnes et al.19 If the aim of the phase
behavior studies was to nd a surfactant solution showing low
IFT under LS conditions, the surfactant choice would probably
be the 9 or 13 PO system due to high SP* at low S*, Table 5.
However, in this study we have to consider the surfactants
ability to show both low IFT under low salinity conditions and
ultralow IFT at a higher salinity, which must be outside what is
considered the LS region.
D

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to live crude oil; i.e., the equivalent ACN decreases.38 Crude B

is a dierent batch of crude oil from the same North Sea eld.
When Crude B diluted with xylene, crude B mod, is used in the
experiments, a further decrease in S* is found. Also, SP*
increases from 8 to 12.5 going from crude A mod to crude B
mod. Thus, crude B mod seems to have a lower equivalent
ACN than crude A mod.
When the total surfactant concentration is reduced to 2 wt %
using crude B mod, S* decreases to 1.5 wt % NaCl, and SP*
increases to 15. Further, the salinity window, i.e., the region
where three phase behavior is seen, is roughly halved. When the
total surfactant concentration was further reduced to 1 wt %,
only one of the test tubes showed three phase behavior (S*
around 1 wt % NaCl), while no clear indication of the optimal
salinity was seen in the phase behavior tests performed at the
target concentration for the ooding experiments (0.2 wt %
total surfactant). Nonetheless, the salinity screening at low total
surfactant concentrations showed that there was no viscous
phase formation. The decrease in S* with decreasing surfactant
concentration is in accordance with the results obtained by
Flaaten et al.27 on similar systems.
By extrapolation, the trend of decreasing S* with decreasing
surfactant concentration for the C1213PO7 formulation
would show S* below 1 wt % NaCl (0.24 SW) for a total
surfactant concentration of 0.2 wt %. However, this may only
be true when the wateroil ratio is 1 for this system. Phase
behavior experiments were therefore conducted when the
surfactant formulation (3.33 wt % C1213PO7 IOS1518, 3 wt
% SBA) and the diluted SW concentration (0.38 SW) were
held constant, with the WOR as the variable. WOR started at 1
and was gradually increased to observe the eect on phase
behavior.

After phase behavior screening using model oils and pure

NaCl brines, phase behavior experiments with various oils and
diluted SW were performed for the APS with 7 PO mixed with
IOS1518 and SBA. The background for choosing this surfactant
formulation will be discussed later in this section. The results
are shown in Table 6, with the salt scan for crude B mod in
Figure 3.
Table 6. Phase Behavior Results for 3.33 wt % Total
Surfactant Concentration in a 3:1 C1213PO7:IOS1518
Blend with 3 wt % SBA Added
oil

SP*

S* [x SW]

S* [wt % NaCl]

C10
crude A
crude A mod
crude B mod

7.5
7.5
8
12.6

1.14
1.09
0.50
0.43

4.9
4.6
2.1
1.8

Going from NaCl brine to diluted SW makes the water phase

more polar and thus less compatible with oil. This signicantly
reduces SP*. S* is also slightly reduced, which is expected as
divalent ions are more eective in packing the surfactant
molecules together, which results in a faster phase transition.32
A further reduction in S* is seen when the oil phase is
changed from decane to crude A, while there is no signicant
eect on SP*. When crude A is diluted with xylene to crude A
mod, however, S* decreases while SP* increases slightly. This is
consistent with the trend seen for a decrease in ACN of the oil
phase on going from decane to octane (see Table 5); i.e., the
equivalent ACN of the crude decreases when it is diluted with
xylene, and consequently it becomes easier to solubilize. The
same trend is observed when going from stock-tank oil (STO)

Figure 3. Solubilization parameters (upper left), phase ratio (upper right), and phase behavior tubes (WOR = 1:1) for the crude B mod scan, as a
function of salinity. Salinity is given as fractions of SW salinity at the base of the tubes and increases from left to right.
E

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Figure 4. SP for water and oil at increasing WOR (left). Phase behavior tubes with increasing WOR (right).

The graph in Figure 4 shows increasing SPw and decreasing

SPo with increasing WOR; i.e., as the WOR is increased,
solubilization of oil in water increases, indicating the phase
transition Winsor II Winsor III Winsor I for this system.
Visual observation of the phase behavior tubes photographed in
Figure 4 shows that the rst four tubes from the left display a
clear excess water phase, an excess oil phase, and a middle
microemulsion phase, i.e., Winsor III. With a further increase in
WOR, in tube 5 from the left, an upper microemulsion phase
with a yellow colored water phase is observed. The color
change in the water phase from clear to yellow indicates small
amounts of solubilized oil, and the system moves toward
Winsor II. In the tube to the far right, i.e., the largest WOR, all
of the oil is solubilized in the water phase. Thus moving from
left to right, i.e., increasing WOR, a phase transition of Winsor
II Winsor III Winsor I occurs. This result is in line with
that reported by Healy et al.28
Spinning drop tensiometry was used to measure IFT at a
total surfactant concentration of 0.2 wt % at 50 C, as this was
the chosen concentration and temperature for the core ooding
experiments. Measurements were performed over a salinity
range of diluted SW for the three APS surfactants (7, 9, and 13
PO groups). Each sample was allowed to spin until the drop
was stable, usually taking around 1 h.
Building on previous LS experiments with pure NaCl brines,9
it was decided to use a SW dilution with an ionic strength equal
to that of a 3000 ppm NaCl solution, which corresponds to
0.07 SW. For the surfactant blend with 7 PO, the IFT at this
SW dilution is 0.018 mN/m. A minimum in IFT was found at a
salinity of 0.43 SW, i.e., OS, with a value in the ultralow
region (IFT = 3 104 mN/m), see Figure 5. At a total
surfactant concentration of 0.2 wt %, the volume of the middlephase microemulsion is too small to be visually detected or
sampled for IFT measurements due to the low total surfactant
concentration. Consequently, the spinning drop measurements
were conducted on phases that were not equilibrated in
advance. However, the phases were allowed to equilibrate in the
tensiometer while spinning. The IFTs in Figure 5 were
measured against crude A mod. Equivalent IFTs were measured
for crude B mod at the ooding salinities. There should be a
good distance in terms of salinity between the OS and LS
region to make sure that there is no eect of reduced salinity on
oil recovery in the OS case. The other two surfactants with 9
and 13 PO have a more hydrophobic character due to a larger
number of PO groups and, thus, displayed the ultralow region

Figure 5. IFT as a function of salinity for the 0.2 wt % APS 7PO blend
and crude A mod.

at a lower SW concentration, hence closer to the LS region

than what was observed for the 7 PO blend.
The mismatch between the optimum formulation found by
IFT measurements and that found by phase behavior
experiments may be due to the large WOR dierence in
phase behavior experiments compared with IFT measurements.
According to Healy et al.,33 interfacial tensions observed will
depend on the specic ratios of water to oil used in the
experiment as well as on the surfactant concentration.
On the basis of the phase behavior studies and IFT
measurements, the surfactant system with C1213PO7 showed
suitable behavior for this studys purpose and was selected for
core ooding experiments.
3.2. Core Flooding Results. This section will discuss the
ve core ooding experiments beginning with the cores
subjected to low salinity surfactant (LSS) injection, followed
by the cores subjected to optimal salinity surfactant (OSS)
injection at ultralow IFT.
LSS Flooding. Figure 6 shows the oil recovery and the
dierential pressure (dP) as a function of injected PVs for core
L1. Initial SW ooding, with a ooding rate of 0.1 mL/min,
resulted in a recovery of 73.0% OOIP. Thus, a signicant part
of the total volume in place was recovered in this rst step. Two
phase production continued after water breakthrough (WBT)
at 0.39 PVs. To eliminate end eects, the injection rate was
increased in steps at the end of each ooding sequence. This
gave a nal oil recovery by SW injection of 76.0% OOIP.
Injection of the LS brine gave an additional recovery of 0.7%
OOIP. Injection of LSS gave a small oil bank with a
F

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Figure 6. Oil recovery [% OOIP], WBT, and dP prole as a function

of PV injected for core L1. Injection rate is increased from 0.1 mL/min
to 0.5 and 1 mL/min after each ooding sequence.

Figure 8. Oil recovery [% OOIP], WBT, and dP prole as a function

of PV injected for core H1. Injection rate is increased from 0.1 mL/
min to 0.5 and 1 mL/min after LS injection.

corresponding increase in pressure drop over the core as seen

in Figure 6. The last percentages of oil were produced as
alternating pure oil and emulsion, hence the moderate slope in
the oil recovery curve over the last injected PV in Figure 6.
Final recovery was 84% OOIP. It should be noted that since the
SW recovery was high, we may not see the full potential of the
LSS process in this experiment.
The experiment in core L1 was duplicated in core L3, Figure
7. In this case, the SW ooding resulted in a recovery of 60%

60% OOIP. After 1.7 PV, the injection uid was changed to
LSS, which mobilized oil to a total recovery of 90% OOIP.
OSS Flooding. A surfactant ooding process outside the LS
region and in the ultralow IFT region for the given surfactant
system was performed in core L2, to compare the eciency of a
more conventional surfactant ooding process to that of a LSS
process. The results are shown in Figure 9. Injection of SW

Figure 9. Oil recovery [% OOIP], WBT, and dP prole as a function

of PV injected for core L2. Injection rate is increased from 0.1 mL/min
to 0.5 and 1 mL/min after each ooding sequence.
Figure 7. Oil recovery [% OOIP], WBT, and dP prole as a function
of PV injected for core L3. Injection rate is increased from 0.1 mL/min
to 0.5 and 1 mL/min after each ooding sequence.

resulted in an oil recovery of 62.0% OOIP. WBT was observed

after 0.43 PV. Two phase production continued for 12 PV
after breakthrough. The sequence continued with the injection
of OS brine, to replace the SW. No oil was produced during
this step, nor during the increased injection rates. Increased
pressure over the core was observed due to the formation of an
oil bank after injecting the surfactant solution. A total of 23.2%
OOIP additional oil was recovered, giving a nal oil recovery of
85.2% OOIP.
In core H2, OS brine was injected directly without a
preceding SW ood. This gave a recovery of 55% OOIP, which
is 7% lower than for the LS secondary mode approach. WBT
was observed after 0.37 PV. Injection of OSS resulted in an oil
bank which contributed to a total recovery of 92% OOIP. A
high recovery was expected in this experiment as the surfactant
ooding took place at ultralow IFT between the surfactant

OOIP, which is 16% lower than after the injection of SW for

L1. Neither increased injection rates nor LS ooding gave
additional recovery. This time a pure oil bank was produced
during the LSS injection step with a corresponding increase in
pressure drop over the core, resulting in a nal recovery of 85%
OOIP.
Core H1 is a dierent core material from cores (L1 and L3)
used in the previous experiments, with a Kw around 300 mD,
and no visible laminations.
A direct LS water injection, without a preceding SW ood,
gave a WBT at 0.46 PV in core H1, Figure 8. Two phase
production followed by increased rates gave a total recovery of
G

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presence of isolated pores that do not contribute to ow.

The dispersion curve for core L2 (blue curve) at Sor shows
signicant tailing of the tracer prole, indicating mass exchange
with dead-end pores. After cleaning, at 100% water saturation,
the prole shifts toward the right, showing a more symmetrical
and ideal dispersion, right in Figure 11. One possible
explanation for the observed shift is that residual oil is blocking
pores, especially in the laminations since the porosity and
permeability are lower here, giving rise to both isolated and
dead-end pores. By cleaning the core, previously isolated and
dead-end pores become accessible and contribute to the uid
ow; i.e., a more ideal dispersion is displayed.
Dierences between the proles at Sor and at 100% Sw are
also observed for L1. At Sor, L1 is the core showing the highest
degree of isolated pores as the prole breaks through earliest;
however it is relatively symmetrical, indicating few dead-end
pores. After cleaning L1, the tracer prole still breaks through
early, indicating that the core contains isolated pores both at Sor
and at 100% Sw. After cleaning L1, the prole shifts to having a
long tailing. It may be that removing residual oil opens up deadend pores causing tailing of the prole due to mass exchange
with these pores. On the basis of dispersion measurements, L1
seems to be the most heterogeneous core used in this study.
With the core ooding experiments in mind, the heterogeneous
properties of L1 may have contributed to the dierent behavior
in secondary mode in this core compared to the other cores.
And it may explain the dierent behavior that was observed in
the duplicate experiment in L3. H1 and H2 do not display large
variations in Sor compared to at 100% Sw, indicating a more
homogeneous material.
The lowest graph in Figure 11 illustrates the dierence for a
homogeneous core relative to a heterogeneous core at 100%
water saturation and at Sor.
3.4. Summary Core Flooding Results. Table 7
summarizes oil recoveries, Sor, after various ooding stages,
the Nc during ooding stages, as well as relative permeability
measurements.

solution and the oil. The results are shown graphically in Figure
10.

Figure 10. Oil recovery [% OOIP], WBT, and dP prole as a function

of PV injected for core H2. Injection rate is increased from 0.1 mL/
min to 0.5 and 1 mL/min after OS injection.

3.3. Dispersion. Dispersion proles for all the cores L1L3

and H1 and H2 are shown in Figure 11. The dispersion
measurements are carried out at Sor and at 100% Sw after the
cores have been washed with toluene and methanol. In a
homogeneous core displaying ideal dispersion, half of the
injected concentration breaks through after 1 PV with the
prole being symmetrical around this point.36 Earlier breakthrough is associated with the presence of isolated pores that
are not participating in ow, meaning that the eective PV
during ow is less than the total PV. Tailing of the tracer
prole, i.e. deviation from symmetry, is due to mass exchange
with dead-end pores.
The dispersion proles at Sor, left in Figure 11, show a
distinction between the two homogeneous cores (H1 and H2)
from the three heterogeneous cores (L1L3). The homogeneous cores display close to ideal dispersion behavior, while the
heterogeneous cores break through earlier, indicating the

Figure 11. Dispersion proles for L1L3 and H1 and H2 at Sor (left) and Sw = 1 (right) and dispersion proles for L1 and H1 at both Sor and Sw =1
(bottom). The fractional ow of water is plotted against the eective PV, i.e., PV corrected for the presence of residual oil.
H

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Table 7. Summary of Relative Permeabilities, Nc, Recoveries and Sor at Dierent Injection Stagesa
LS brine
core
Soi
ko(Swi) (before aging) [mD]

L1
0.67
135

OS brine

L3

H1

0.70
105

0.74
600
300

ko(Swi) (after aging) [mD]

60

50

Nc(SW)
SW recovery [% OOIP]
Sor(SW)
So(SW)
Nc(LS)
LS/OS recovery [% OOIP]
Sor (LS/OS)
So(LS/OS)
Nc(LSS/OSS)
LSS/OSS recovery [% OOIP]
Sor(LSS/OSS)
So(LSS/OSS)
Sor(LSS/OSS) /Sor(LS/OS)
kw (Sor(LSS/OSS)) [mD]

2.0 107
76
0.16
0.51
7.2 107
76.7
0.16
0.00
2.4 104
84.0
0.10
0.06
0.63
40

2.0 x107
59.9
0.27
0.43
7.3 107
59.9
0.27
0.00
2.4 104
85.9
0.10
0.17
0.37
30

L2

H2

0.68
131

0.66
700

85

300

2.0 107
62
0.26
0.42
6.1 107
62.7
0.28
0.46
2.0 104
90.3
0.07
0.21
0.25
80

62.0
0.26
0.00
1.5 102
85.2
0.10
0.16
0.38
2

55.0
0.30
0.36
1.3 102
92.4
0.05
0.25
0.17
50

LS brine is used in L1, L3, and H1. OS brine is used in L2 and H2.

The relative permeability to oil after aging at 110 C

decreases to around half of the measured value before aging for
all of the cores, indicating a shift in wettability to a less waterwet state.
Sor for core L1 is 0.16 after waterooding, as opposed to
close to 0.30 for the other cores, thus the low potential for the
LSS process. The oil mobilized by the LSS process in this core
may not have been enough to form a continuous oil bank;
instead an alternating oil and emulsion was produced. The
nature of the heterogeneity in L1 may have aected the core
ooding result and thereby explains the dierence in recovery
and Sor after waterooding compared to the other cores.
The core material in H1 and H2 is more homogeneous
without visible laminations. The change in oil saturation, So,
after direct LS injection in H1 is 10 saturation units higher than
after direct OS injection in H2. This is in line with previous
results reported by, for example, Zhang and Morrow.5 LS
injection in tertiary mode, i.e., after an initial SW ood, in L1
and L3 gave a negligible increase in oil recovery.
Sor after surfactant oods reaches values 0.1 in all cores
independent of ooding procedure. The lowest Sor was
obtained in core H2, which was ooded at optimal salinity
with minimum IFT.
The surfactant oods in L1, L3, and H1 were all in the LS
regime with a moderate reduction in IFT (0.02 mN/m).
Normalized Sor, i.e. Sor(LSS)/Sor(LS), for L3 and H1 were 0.37 and
0.25, respectively. In both cases, the oil recoveries are
signicantly higher than what would be predicted from capillary
desaturation curves (CDC) measured on Berea cores.12 This
increase in recovery above what is expected from a CDC is
attributed to the combined eect of low salinity and surfactant
(LSS). Even though oil production during LS injection is
marginal, oil may nonetheless be redistributed and/or oil layers
may be destabilized due to changes in crude oilbrinerock
interactions taking place during LS injection. Redistribution of
oil is expected to result in uctuations in the dierential
pressure measured across the cores during LS injection. Thus,
signicant redistribution of oil is less likely to occur in cores L1,
L3, and H1 as there is little response on the dierential

pressures during LS injection. Still, even with a moderate

reduction in IFT, such as in the LSS ooding experiments in
this study, oil layer destabilization coupled with reduced
capillarity may give rise to added recovery beyond what would
be expected by the action of the surfactant alone.
The Ncs during the OSS ood in L2 and H2 are around 2
orders of magnitude higher than during the LSS ood in L1,
L3, and H1. However, the nal recoveries and Sor are more or
less equal, highlighting the combined eect of LSS.
Identical core preparations and ooding sequences were
performed on cores L1 and L3, yet the production proles in
these experiments show large variations. This may be a result of
the laminations in the cores and address the problem of
reproducibility in heterogeneous core material.
3.5. Dynamic Retention. During a surfactant ooding
process in an oil containing core, retention mechanisms include
adsorption on the mineral surface, precipitation of surfactant,
and surfactant partitioning into the oil phase.34 In a dynamic
retention experiment in an oil free core, such as in cores R1 and
R2, the last mechanism above is excluded.
Dynamic retention experiments were performed in two
heterogeneous Berea cores named R1 and R2, with
permeabilities around 100 mD, at 100% Sw. R1 and R2 were
saturated with LS and OS brine, respectively. Retention
proles, Figure 12, were obtained by injecting a surfactant
slug (R1 = 5 PV and R2 = 6 PV) into the core which had a
salinity corresponding to the surfactant solution salinity. The
slugs contained the same components and concentrations as in
the ooding experiments and were followed by a continuous
injection of chase water with the appropriate salinity. The
euent was collected in fractions at dierent cumulative
injection volumes to be analyzed for total surfactant content by
potentiometric titration.
Comparing the two graphs in Figure 12, it is seen that the
LSS solution injected into core R1 saturated with LS brine
breaks through nearly 1 PV before the OSS solution injected
into core R2 saturated with OS brine, indicating higher
retention in R2. Another indication of higher retention is the
smaller area under the graph for R2 despite the larger slug size
I

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The surfactant retention values are lower in a LS environment (average of 0.24 mg surfactant/g rock) than in an OS
environment (average of 0.39 mg surfactant/g rock) both at
100% water saturation, and when oil is present.

AUTHOR INFORMATION

Corresponding Author

*Telephone: +4755583691. Fax: +4755588265. E-mail:

annette.johannessen@uni.no.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors acknowledge the Norwegian Research Council,
NFR, for nancial support.

Figure 12. Retention proles showing normalized produced surfactant

concentration as a function of PVs for core R1, red curve, and R2, blue
curve.

injected in this core. Adsorption equilibrium, C/C0 = 1, is

obtained for a larger number of fractions in R1 than R2, despite
the larger slug injected in R2.
Retention data for cores L1L3 and H1 and H2 were
obtained as a supplement to the core displacement experiments. The surfactant solutions were continuously injected in
all cores, Figures 610.
R2, L2, and H2 are ooded with the OSS solution, whereas
R1, L1, L3, and L1 are ooded with the LSS solution. Table 8
shows the retention data for the cores where all of the OS core
oods display a higher retention than the LS core oods.
Average retention is 0.39 mg surfactant/g rock for the OS
oods and 0.24 mg surfactant/g rock for the LS oods. This
veries that retention increases with increasing salinity.35
Surfactant retention is higher during ow through a 100%
water saturated core than during ow at Sor in all experiments.
One possible explanation for the lower retention values during
ow at Sor could be oil occupying adsorption sites on the rock
surface and thus making less sites available for surfactant
adsorption.

4. CONCLUSIONS
A 3:1 ratio of an APS 7 PO and IOS1518 blend show good
aqueous solubility and microemulsion phase behavior over a
wide range of salinities containing divalent ions.
The tested Berea cores, both homogeneous and heterogeneous, show insignicant response to LS injection alone.
A moderate reduction in IFT under LS conditions gives
similar oil recoveries as ultralow IFT at higher salinity. The LSS
oods give higher oil recovery than what would be predicted by
the Nc relationship. The OSS oods give oil recoveries in line
with what would be expected by the Nc relationship.
Heterogeneity in core material can aect the ooding
behavior and cause diculties with respect to reproducibility.
However, dispersion measurements at various Sors can help
reveal heterogeneities and help interpret the results.

NOMENCLATURE
ACN = alkane carbon number
APS = alcohol propoxy sulfate surfactant
c = molality
C = empirical constant
C8 = octane
C10 = decane
CDC = capillary desaturation curve
dP = dierential pressure
EOR = enhanced oil recovery
IFT = interfacial tension
IOS = internal olen sulfonate surfactant
I = ionoic strength
LS = low salinity brine
LSS = low salinity surfactant solution
ko(Swi) = permeability to oil at initial water saturation
Kw = absolute permeability
kw(Sor)(LSS) = relative permeability to water at residual oil
saturation after LSS injection
kw(Sor)(OSS) = relative permeability to water at residual oil
saturation after OSS injection
NaCl = sodium chloride
Nc(SW) = capillary number for seawater ood
Nc(LS) = capillary number for low salinity water ood
Nc(LSS) = capillary number for the low salinity surfactant
ood
Nc(OSS) = capillary number for the optimal salinity surfactant
ood
OOIP = originally oil in place
OS = optimal salinity brine
OSS = optimal salinity surfactant solution
PO = propylene oxide group
PV = pore volume
ppm = parts per million
S = salinity window
S* = optimal salinity

Table 8. Retention Data for Cores R1, R2, L1, L2, L3, H1, and H2
LSS
core
surfactant
surfactant
surfactant
retention

injected [g]
recovered [g]
retention [g]
[mg/g]

OSS

R1

L1

L3

H1

R2

L2

H2

0.206
0.143
0.063
0.28

0.129
0.088
0.041
0.17

0.165
0.109
0.056
0.24

0.164
0.104
0.06
0.26

0.269
0.161
0.108
0.45

0.189
0.106
0.082
0.35

0.161
0.076
0.085
0.36

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SBA = secondary butanol alcohol

SP = solubilization parameter
Soi = initial oil saturation
Sor(LS) = residual oil saturation after the low salinity ood
Sor(LSS) = residual oil saturation after combined low salinity
surfactant ood
Sor(OS) = residual oil saturation after the optimal salinity ood
Sor(OSS) = residual oil saturation after the optimal salinity
surfactant ood
Sor(SW) = residual oil saturation after seawater ood
STO = stock-tank oil
SW = synthetic seawater
Sw = water saturation
Swi = initial water saturation
u = Darcy velocity
Vo = volume oil
Vs = volume surfactant
Vw = volume water
WBT = water breakthrough
WOR = wateroil ratio
z = valence of ion
= viscosity
= density
= interfacial tension

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