Article

pubs.acs.org/EF

Experimental Study of the Response Time of the Low-Salinity

Enhanced Oil Recovery Effect during Secondary and Tertiary Low-
Salinity Waterflooding
Iván D. Piñerez Torrijos,* Tina Puntervold, Skule Strand, Tor Austad, Hakar I. Abdullah, and Kaia Olsen
University of Stavanger, 4036 Stavanger, Norway

ABSTRACT: Despite it more than 500 papers being published on low-salinity (LS) water injection into sandstone oil reservoirs
to enhance oil recovery, very few field applications of this enhanced oil recovery (EOR) technique are known. Laboratory
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investigations of LS water floods under tertiary conditions have shown varying results, and especially, the response time for
establishing a new bank of oil in the porous medium has been too slow for application in the field. Usually, many pore volumes
(PVs) of LS brine must be injected to obtain an increase in recovery of 5−10% of original oil in place (OOIP). Provided that the
initial reservoir conditions for observing LS EOR effects are present, a close connection between the imposed pH gradient and
additional oil recovery has been experimentally verified. To improve the chemical understanding of the LS EOR mechanism, it
appeared important to study the development of the pH gradient because the HS brine is displaced by the LS brine. Therefore,
the relationship between the LS EOR effect, pH gradient development, and heterogeneity in the pore size distribution of the
porous medium was addressed in this paper. The experimental work covered both tertiary and secondary LS core flooding. The
outcrop core material used had consistent composition and contained 8.2 wt % illite and 32.0 wt % albite, which both can
contribute to the pH gradient under LS flooding conditions. In comparison to secondary oil recovery by injection of formation
water (FW), ∼40% of OOIP, the secondary oil recovery using LS brine produced an additional 24% of OOIP. Tertiary injection
of LS brine increased the recovery by about 10% of OOIP, after a secondary flood by FW. Injection of a tertiary low-salinity
polymer (LSP) solution after secondary flooding with LS brine increased the ultimate recovery from 65 to about 86% of OOIP.
In both cases, the response time for the LS EOR effect was discussed in terms of imposed pH gradient and heterogeneity in the
pore size distribution. The results showed that oil recovery was closely linked to an increasing pH gradient. The response time to
develop the pH gradient and a new bank of oil that could be produced seemed to be related to the pore size distribution; i.e., it
took a longer time to develop a pH gradient and to displace the oil from the smaller pores than from the larger pores.

■ INTRODUCTION
Recently, Hamon presented a paper where he reviewed
published work by addressing the low-salinity (LS) enhanced
oil recovery (EOR) response time, especially focusing on
tertiary LS effects after first flooding with a high-salinity (HS)
brine.1 In the same paper, he also modeled the LS EOR effects
after establishing residual oil saturation with the HS fluid,
(Sorw)HS. According to Hamon,1 “conditions of existence of a
double saturation shock, effects of dispersion in water phase at
(Sorw)HS, and the direction of wettability modification” were
discussed as hypotheses for the great differences in tertiary LS
response time for establishing a new oil bank. It appeared that
the response time to generate a tertiary LS oil bank could be
related to the value of the viscosity ratio, μo/μw. At low values
of ≈2, the oil bank could be created after injecting 0.5−0.6 pore
volumes (PVs) of LS brine, while at a viscosity ratio of ≈7, the
oil bank vanished. Furthermore, strong dispersion at (Sorw)HS
might totally suppress positive LS EOR effects. As pointed out
by the author, it was always possible to find contradictions to
these observations, meaning that the observations were not
general.
The LS fluid will change the mixed-wet sandstone to a more
water-wet state, which, in turn, will improve the microscopic
sweep efficiency as a result of increased capillary forces.
According to the suggested chemical mechanism, the
wettability alteration is triggered by an increase in pH as the
HS formation water (FW) is displaced by the LS smart water,
as illustrated by the following chemical equations using Ca2+ as
the active cation toward the clay surface:2−4
slow reaction
clay−Ca 2 + + H 2O = clay−H+ + Ca 2 + + OH− + heat
(1)
fast reaction
clay−R 3NH+ + OH− = clay + R3N:+H 2O (2)
fast reaction
clay−RCOOH + OH− = clay + RCOO− + H 2O (3)
It is believed to be a two-step process: (1) desorption/exchange
of Ca2+ by H+ at the clay surface creating alkaline conditions
(eq 1) and (2) ordinary acid−base reactions between OH− and
the protonated form of the organic anchor molecules adsorbed
on the clay surface (eqs 2 and 3). It should be noticed that
desorption of active cations from the clay minerals (eq 1) is
believed to be the rate-determining step in the wettability-
modifying process. It is also an exothermic process, meaning
Received: March 18, 2016
Revised: May 18, 2016
Published: May 18, 2016

© 2016 American Chemical Society 4733 DOI: 10.1021/acs.energyfuels.6b00641

Energy Fuels 2016, 30, 4733−4739
Energy & Fuels Article

that the induced pH gradient, when switching from HS to LS Table 3. Crude Oil Properties
brine, will be smaller as the reservoir temperature is
crude AN BN densitya viscositya
increased.5,6 Therefore, it can be difficult to observe LS EOR oil (mg of KOH/g) (mg of KOH/g) (g/cm3) (cP)
effects at high temperatures, especially when Tres > 100 °C. The
total oil 0.10 1.80 0.846 17.6
combination of high Tres and very high salinity of FW will a
decrease the adsorption of organic material onto the clay Measured at room temperature.
minerals. The rock will become too water-wet to obtain a
significant LS EOR response.7 Brines. FW and LS water were prepared using chemicals purchased
from Merck Laboratories. Deionized water (DI) was used for the brine
The presence of reactive plagioclase, such as albite, can preparation, having a total organic content (TOC) of <5 ppb and
contribute to increasing the pH as the HS brine is displaced by resistivity of 18.2 MΩ cm. The brine compositions are provided in
the LS brine, even at high temperatures.5 The hydrolysis of Table 4.
albite is hardly affected by the temperature.
NaAlSi3O8 + H 2O ↔ HAlSi3O8 + OH− + Na + (4) Table 4. Brine Compositions and Properties

In the present study, we will demonstrate experimentally that parameter units FW LS LSP
+
there is a very close connection between the response time for [Na ] mM 1540 17.1 17.1
tertiary LS EOR effects and the development of the pH [Ca2+] mM 90
gradient as the HS brine is displaced by the LS brine. Outcrop [Mg2+] mM
sandstone core material with consistent composition, contain- [Cl−] mM 1720 17.1 17.1
ing mainly illite as clay material (8.2 wt %) and a lot of albite ionic strength mM 1810 17.1 17.1
(32 wt %) was used in the experiments. salinity ppm 100000 1000 1000
In 1990, Buckley and Morrow8 tested adhesion properties of density g/cm3 1.067 0.999 0.999
22 crude oils onto silica surfaces as a function of the brine pH 5.5 5.7 7.8
composition and pH and noticed remarkable similarities. In the
adhesion map, they observed characteristic pH values, in the
range of 6−7, above which adhesion did not occur at different Polymer. The polymer used was hydrolyzed polyacrylamide
salinities. They concluded that the pH was the dominant factor (HPAM) Flopaam 3630S from SNF Floerger. It had a hydrolysis
for this behavior. Additionally, it was observed that deasphalted degree of 25−30% and a molecular weight of 20 × 106 Da. The low-
crude oil did not exhibit adhesion in the low pH range, salinity polymer (LSP) solution used in this study was prepared by
confirming that the pH effect on adhesion was primarily linked dissolving 1000 ppm of HPAM in 1000 ppm of NaCl brine. The
to surface-active components in the crude oil. Similar viscosity of the LSP solution at 25 °C was 13.3 cP at a shear rate of
100 s−1.
observations were recently made by Didier et al.9 for two
Methods. Core Flooding Setup. The flooding setup consisted of a
different sands. They also observed that, at lower salinity and computer-controlled system, a Gilson high-performance liquid
acidic pH (pH < 7), oil adhesion increased, meaning that oil chromatography (HPLC) pump, stainless-steel piston cells, a Hassler
wetness increased as the salinity decreased.

■
core holder, an oven, and a glass buret. The experiments were
performed with a confining pressure of 20 bar and a back pressure of
EXPERIMENTAL SECTION 10 bar.
Material. Outcrop Cores. The terminology and properties of the Core Restoration. Mild Core Cleaning. The core was mildly
outcrop sandstone cores are listed in Table 1. The core material and cleaned by flooding with (1) kerosene until a clear effluent is observed,
the mineral composition given in Table 2 were provided by TOTAL. (2) heptane to displace kerosene, and (3) 4 PVs of LS brine to
displace FW and easily dissolvable salts. Each flood was carried out at a
rate of 0.1 mL/min.
Table 1. Outcrop Core Plug Data Initial Water Saturation. Initial FW saturation (Swi = 0.2) was
property B-21 B-24 B-26 established using the desiccator technique in line with the procedure
described by Springer et al.10 Once the target weight of the core was
dry weight (g) 235.1 236.2 235.8
reached, it was left to equilibrate for 72 h. The core was then placed in
length (cm) 10.0 10.0 10.0 a core holder and shortly evacuated prior to oil saturation.
diameter (cm) 3.8 3.8 3.8 Crude Oil Saturation. The core was first saturated with crude oil
bulk volume (cm3) 112.2 112.8 113.0 and then flooded with 2 PVs of crude oil in each direction at 50 °C.
pore volume (cm3) 23.3 22.5 22.5 Afterward, it was aged in a steel aging cell at the respective test
porosity (%) 20.8 19.9 19.9 temperature (60 °C) for 14 days.
permeability (md) 48.4 22.3 34.6 Oil Recovery Test. The restored core was mounted in the core
BET (m2/g) 1.81 ± 0.02 holder with a back pressure and confining pressure of 10 and 20 bar,
respectively, and left overnight to achieve thermal stability at the actual
test temperature prior to the initialization of the experiment. The core
Table 2. Mineralogical Properties of the Outcrop Cores, was flooded with various brines, and in all cases, the cumulative oil
Given as Weight Percent produced was monitored as well as pH and salinity of the produced
quartz albite chlorite illite anatase apatite calcite pyrite water.
pH Screening Test. The mildly cleaned core was used to evaluate
57.0 32.0 1.7 8.2 0.5 0.2 0.3 0.1 the interaction of minerals and injected brines by performing a test
without the presence of crude oil (pH screening test). Effluent samples
were collected, and pH and density were plotted against PV injected.
Crude Oil. Stabilized crude oil was supplied by TOTAL. Prior to Analyses. pH Measurement. The pH was measured using the pH
use, the oil was centrifuged for 1 h at a high rotation speed and then meter S20 from the SevenEasy range of products of Mettler Toledo.
filtered with a 5 μm Millipore filter. The crude oil properties are listed The reference Semi micro-pH was used. The relative accuracy of the
in Table 3. measurement was ±0.01 pH units at room temperature.

4734 DOI: 10.1021/acs.energyfuels.6b00641

Energy Fuels 2016, 30, 4733−4739
Energy & Fuels
Density Measurement. To follow the displacement front, when
switching from one fluid to another, the density of the eluted water
was analyzed using a density meter DMA-4500 from Anton Paar.
Rheology/Viscosity. Brine and crude oil viscosities were determined
using the rotational rheometer Physica MCR 302 from Anton Paar.
The shear rates ranged from 0.1 to 1000 s−1.
Surface Area. Brunauer−Emmett−Teller (BET) surface area
measurements were carried out in a TriStar II PLUS instrument
from Metromeritics, using small pieces of outcrop material from the
same sample block as the core material used in this study.
■ RESULTS AND DISCUSSION
The outcrop core material used, consistent in composition, has
probably been exposed to fresh water for many years. Mineral
analysis showed that illite (8.2 wt %) was the main clay mineral
and that a large amount of albite (32 wt %) was present (Table
2). In such a case, some of the clay and albite minerals will be in
their protonated form, as shown by eqs 1 and 4. In the presence
of HS FW, protons will be exchanged by other cations, and the
FW becomes acidic, as shown by eqs 5 and 6.
clay−H+ + Ca 2 + ↔ clay−Ca 2 + + H+ (5)
HAlSi3O8 + Na + ↔ NaAlSi3O8 + H+ (6)
Acidic conditions increase the adsorption of acidic and basic
anchor molecules onto the clay surface, and the rock becomes
mixed-wet.5,11 Therefore, the present outcrop core material is
excellent for doing parametric studies on LS EOR effects.2,3,5,12
Tertiary LS EOR Effect. The first tertiary LS EOR test on
core B-21 at 60 °C is shown in Figure 1. The secondary oil
Figure 1. Oil recovery test from core B-21 at 60 °C. The core was
successively flooded with FW−LS at 4 PVs/D, and at the end, the
injection rate was increased to 16 PVs/D.
recovery using FW was about 40.1% of original oil in place
(OOIP). No wettability modification will take place because the
formation was initially in equilibrium with the FW. After about
4 PVs, the flooding fluid was switched to the LS brine, and after
12 PVs, the oil recovery increased to 49.3% of OOIP,
corresponding to a LS EOR effect of 9.2% of OOIP. The
response time was about 8 PVs, which appeared unacceptable
for field applications. After increasing the flooding rate 4 times,
some possible end effects were noticed. The pH of the first
produced water was 6.1, and it stabilized close to 6.5 before
injecting the LS brine. The increase in pH during injection of
the LS brine was very well synchronized with the increase in oil
recovery. Both oil recovery and pH increased the most between
4 and 8 PVs. Thereafter, the increase in oil recovery and pH
4735
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was much smaller. A steady-state equilibrium was obtained at a
pH close to 9, corresponding to a total pH gradient of ΔpH =
2.3.
The pH development may look different in the absence of
crude oil as a result of buffering effects from acidic and basic
organic components present in the crude oil. Therefore, the B-
21 core was mildly cleaned, and a pH scan was performed by
flooding the core with FW−LS−FW at 60 °C to study the
rock−brine interactions without oil present (Figure 2). A fast
Figure 2. pH scan at 60 °C for core B-21. Flooding sequence, FW−
LS−FW; flooding rate, 4 PVs/D.
increase in pH was observed from pH 6 to 7. Then, there was a
break in the pH curve, and the increase in pH from 7 to 8 was
significantly slower, indicating two different mechanisms for the
pH change. A possible explanation is that both reactions
described by eqs 1 and 4 will contribute to the pH gradient by
the exchange of easily accessible cations on the clay and albite
surfaces, with protons (H+) from water. The slow increase in
pH after pH 8 may be linked to the exchange cations from less
accessible minerals in smaller pores or from the clay, i.e.,
cations in between the layers of illite. A steady-state situation/
equilibrium was established as the pH reached 9. It was noticed
that the salinity gradients were very sharp and that the
desorption of H+ from the minerals as the flooding fluid was
switched from LS to HS was much faster than the adsorption of
H+ by changing flooding fluid from FW to LS brine.
Because the response time for the tertiary LS EOR effect
appeared to be synchronized with the pH gradient, it was
interesting to ask the following question: “Is it possible to
decrease the response time for the tertiary LS EOR effect by
alternating injection of LS and HS brine?” When switching
from LS to HS brine, there will be a fast decrease in pH,
according to eqs 5 and 6 and Figure 2, because the adsorption
of cations onto the minerals is a much faster reaction compared
to desorption. Core B-24 was prepared for oil recovery at 60 °C
in the same way as core B-21 (Figure 3). The secondary oil
recovery with FW was 39.0% of OOIP, i.e., quite similar to the
test with core B-21. After injection of 8 PVs of FW, a slug of 2
PVs of LS brine was injected and the oil recovery increased to
44.2% of OOIP, corresponding to a LS EOR effect of 5.2% of
OOIP. In this case, the initial pH was 6.8 and the pH increased
rapidly by 2 pH units to 8.8. The oil recovery stopped
immediately when injecting FW, and the pH dropped to the
initial value. After the pH was stabilized at 16 PVs, LS brine was
DOI: 10.1021/acs.energyfuels.6b00641
Energy Fuels 2016, 30, 4733−4739
Energy & Fuels Article

Figure 3. Oil recovery test for core B-24 at 60 °C. The core was
successively flooded with FW−LS (2 PVs)−FW−LS at 4 PVs/D, and
at the end, the injection rate was increased to 16 PVs/D.

reinjected. As in the first injection of the LS slug, the pH

increased rapidly to about 8.8 but the response time for the
observed LS EOR effect was much longer compared to the first
LS slug. After a fast increase in pH to about 8.8, the pH
increased slowly to 9.3, and at that stage, the oil recovery also
stopped. Thus, in the second LS injection, the increase in pH
up to 8.8 was fast and comparable to the first injected LS slug
but the response time for the LS EOR effect was significantly
longer, as illustrated by the slope of the oil recovery curves in
Figure 3. Therefore, the LS EOR response time is not
necessarily directly related to the response time of the pH
gradient, but the oil recovery stopped when a steady-state
equilibrium in the pH was achieved.
A possible explanation for this behavior is schematically
illustrated in Figure 4, and it is explained in the following way:
(1) During the secondary flood with HS brine, at slightly acidic
pH, the oil present in the larger pores will be mobilized and the
oil saturation becomes (Sorw)HS (Figure 4a). No wettability
alteration takes place. (2) The first slug of the LS brine, with Figure 4. Mobilization of oil from a porous medium, controlled by
lower viscosity compared to the HS brine, will surely follow the surface wetting and pore size distribution. (a) Large pores are flooded
same pore path as the HS brine, and wettability modification by HS brine to (Sorw)HS without wettability alteration. (b) The LS slug
will take place mostly in the larger pores, decreasing the oil brine will mostly displace the HS from the larger pores and decrease
saturation from (Sorw)HS to (Sorw)LS1 (Figure 4b). This will give oil saturation to (Sorw)LS1 by wettability alteration. (c) Reinjection of
HS brine will displace the LS brine without displacing oil, leaving the
a fast LS EOR response. In addition, some oil will be mobilized
oil saturation at (Sorw)LS1. (d) Reinjection of LS brine will displace oil
by some spontaneous imbibition of LS brine into bypassed from the bypassed smaller pores by spontaneous imbibition as a result
pores, which is a slower process. (3) A new injection of HS of wettability modification in a slower process, resulting in a final
brine will of course follow the pore path with the highest water residual oil saturation of (Sorw)LS2.
saturation, i.e., the larger pores, and the pH will decrease as the
LS brine is displaced. No oil is produced, and the oil saturation
remains the same, (Sorw)LS1 (Figure 4c). (4) Injection of a new According to Figure 5, the pH gradients corresponded well
slug of LS brine will give a fast pH response in the larger pores, to the density gradients by switching injection fluids.
similar to the first LS slug injection. The oil saturation in these In both oil recovery experiments, about half of the tertiary LS
pores is, however, at residual saturation, and a negligible EOR effect was produced after injecting 2 PVs of LS brine and,
amount of oil will be produced from these pores. The LS EOR additionally, 6 PVs must be injected to arrive at the plateau for
effect in the second LS slug will mainly be produced by further the oil recovery (Figures 1 and 3). According to the discussion
spontaneous imbibition into bypassed pores as a result of above, a fast tertiary LS EOR response can only be obtained if
wettability modification, i.e., increased water wetness. The oil the LS brine can mobilize oil from the pores preflooded with
saturation will decrease to the final residual oil saturation HS brine and if this oil can be displaced by viscous forces after
(Sorw)LS2 (Figure 4d). The extra oil produced by spontaneous wettability modification. The response time for oil recovery
imbibition of LS brine into bypassed smaller pores appeared to from bypassed pores by spontaneous imbibition and improved
be a relatively slow process. microscopic sweep efficiency is a much slower process, but it
Note that the residual oil saturations for this experiment can contribute to a large fraction of the total EOR effect. For
changed in the following way: (Sorw)HS > (Sorw)LS1 > (Sorw)LS2. the present crude oil−brine−rock system, it appeared that
4736 DOI: 10.1021/acs.energyfuels.6b00641
Energy Fuels 2016, 30, 4733−4739
Energy & Fuels
Figure 5. pH and density gradients of the eluted brine during the oil
recovery test for core B-24 at 60 °C by LS slug injection. Flooding
sequence: FW−LS (2 PVs)−FW−LS−LS high rate.
about 50% of the extra oil was produced with a short response
time (2 PVs) and the remaining 50% was produced with a long
response time (6 PVs). It therefore appears that the pore
structure of the porous medium can have a great impact on the
response time of the LS EOR effect.
The pore size distribution of the outcrop core material used
in the oil recovery tests appeared to be quite heterogeneous, as
shown by Figure 6. The pore distribution has a peak at about
Figure 6. Pore size distribution of a core from the same block as the
tested core material. Data were submitted by TOTAL E&P. The core
material has a heterogeneous pore size distribution, with pores ranging
from ∼0.01 to 100 μm. The majority of the pores are in the range of
10 μm.
10 μm but with a significant distribution of pores, even down to
0.01 μm. Therefore, the actual pore distribution of the rock
matched very well with the above discussion. A heterogeneous
pore structure will also increase the dispersion in the water
phase at (Sorw)HS, which can delay the effect of the LS response,
as proposed by Hamon.1
Viscosity ratios between the oil and FW or LS brine are
shown in Table 5 at different temperatures of 25, 60, and 120
°C. At the present flooding condition (60 °C), the viscosity
ratio between the oil and the LS brine was 7.65, which
according to Hamon1 could give unfavorable conditions,
meaning that the incremental oil should be delayed and
produced very slowly. In the present experiments, however,
about 50% of the extra oil was produced relatively fast, within 2
PVs, but the remaining 50% was produced rather slowly.
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Table 5. Viscosities of Crude Oil and Brines at Different
Temperaturesa
temperature total crude FW LS viscosity ratio viscosity ratio
(°C) oil (cP) (cP) (cP) (μo/μwFW) (μo/μwLS)
25 17.6 1.18 1.01 14.92 17.43
60 4.5 0.63 0.60 7.29 7.65
a
The percent error for this data set is below 1%.
The suggested LS EOR mechanism for mixed-wet core
material containing low swelling clay minerals was based on
wettability modification toward more water-wet conditions.
Therefore, some of the mobilized oil by the LS EOR effect
could be trapped as a result of increased capillary forces in the
porous system. If, however, the mobilized oil bank is larger than
the amount of oil trapped because of increased capillary forces,
a positive LS EOR effect will be observed. This retrapping of oil
from the created oil bank may also have an impact on the
response time for the observed tertiary LS EOR effect.
It is important to note that acidic initial conditions of the FW
must be present to obtain mixed-wet conditions, because it is
the protonated acidic and basic polar components that act as
anchor molecules. Initial alkaline conditions will make the rock
too water wet, and a negligible LS EOR response will be the
result, as was the case for the Snorre pilot in the North Sea.13,14
Secondary LS EOR Effect. As summarized by Hamon,1
there is a large number of studies showing that injection of LS
brine in a secondary mode will increase oil recovery compared
to that by injection of a HS brine. Additional oil recovery could
be observed at water breakthrough or shortly afterward using
LS compared to HS injection fluid. We have also observed that
secondary water flood with LS resulted in higher oil recovery
than that obtained by injecting the same LS brine under tertiary
conditions. The number of studies comparing EOR effects in
secondary and tertiary modes are limited probably as a result of
the lack of homogeneous core material showing reasonably
good LS EOR effects. The consistent composition outcrop core
material used in this work allowed us to compare secondary and
tertiary LS oil recovery effects.
Core B-26 was prepared in the same way as the two previous
cores used for tertiary LS studies. The first restoration
secondary LS oil recovery test is shown in Figure 7a, and the
second restoration after mild cleaning oil recovery test is shown
in Figure 7b. In both cases, the oil recovery reached about 59%
of OOIP after injecting 2 PVs of LS, and this was about 10% of
OOIP higher compared to the recovery results obtained under
tertiary LS injection conditions, after injecting many PVs. It was
noticed that the gradient/fluctuation in the pH of the produced
water was much smaller compared to those of the previous tests
at tertiary conditions. The water saturation was, however, quite
different when the LS injection started in the two cases. In the
first test (Figure 7a), the pH of the produced water continued
to increase a little after injecting 2−8 PVs and an additional oil
production of 8% of OOIP was noticed in the same interval.
The oil recovery stopped when the pH started to decrease. In
the second test (Figure 7b), after mild cleaning, the pH
stabilized close to 7 after 2 PVs and only traces of oil were
produced afterward. Also, in this case, the oil recovery reached
approximately 60% of OOIP after injecting only 2 PVs of LS
brine. In both cases, there was a small increase in the pH of the
first produced water as long as the oil recovery increased.
Contrary to the tertiary LS flooding, the heterogeneity in the
pore size distribution of the core material appeared to play a
DOI: 10.1021/acs.energyfuels.6b00641
Energy Fuels 2016, 30, 4733−4739
Energy & Fuels
Figure 7. Oil recovery test from core B-26 at 60 °C by secondary injection of LS brine: (a) first restoration and (b) second restoration of core B-26
after mild cleaning with LS in secondary mode followed by a LSP flood.
minor effect on the LS response time under secondary flooding
conditions.
After the plateau in oil production was reached, 1000 ppm of
HPAM polymer was added to the LS brine, making up the LS
polymer solution termed LSP. From injection of LSP, a fast
response in oil recovery was observed, reaching a recovery of
86% of OOIP. This “hybrid EOR” response combining two
EOR techniques, LS and polymer flooding, was very efficient.
However, a fast response in oil production by LSP injection was
only observed in previously published work by Shaker Shiran
and Skauge15 when the core had been preflooded with LS
brine. A possible explanation is that the residual oil saturation is
distributed differently in the porous system when flooding the
oil to Sor with HS and LS brine, because the final wetting
conditions will be different. A relatively large fraction of residual
oil may be trapped in the larger pores in the presence of LS
brine as a result of higher water wetness. This trapped oil is
easily contacted by the injected LSP solution.
In the experiment in Figure 7b, the pressure drop was logged
manually to possibly observe pressure changes of the different
flooding stages (Figure 8). The initial value during the LS flood
in secondary mode was 46 mbar, and it went down
progressively to approximately 17 mbar, where it became
relatively stable at 8 PVs injected. Once the polymer solution
Figure 8. Pressure drop during oil recovery test of core B-26 (second
restoration) after mild cleaning with LS in secondary mode followed
by a LSP flood. Pressure drop values collected were average values
during 10 s of observation. Data were registered simultaneously as
effluent samples were taken for analysis.
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was injected, the pressure drop increased rapidly up to 50 mbar
and continued to rise to 200 mbar for 4 PVs. As the LSP flood
progressed, the pressure drop became relatively stable at
around 205 mbar.
On the basis of the results from this study, there is no doubt
that the best benefit of LS water injection is obtained by
performing a secondary LS water injection. A tertiary LSP flood
may be a good investment and should be evaluated.
■ CONCLUSION
The response time for observing the LS EOR effect by injecting
the LS brine in tertiary and secondary modes was addressed in
this paper. Very homogeneous outcrop sandstone core material,
containing both illite (8.2 wt %) and reactive albite (32.0 wt %)
was used for oil recovery tests at 60 °C. The pore distribution
was heterogeneous with a peak around 10 μm and with a
significant tail down to 0.01 μm. A stabilized crude oil with an
acid number (AN) = 0.10 mg of KOH/g and a base number
(BN) = 1.80 mg of KOH/g was used. The salinity of FW was
100 000 ppm (containing 90 mM CaCl2 and NaCl), and the
salinity of the LS brine was 1000 ppm (containing only NaCl).
The results from the study are summarized below.
Tertiary LS EOR Results. (1) A pH scan by flooding a core
successively with FW−LS−FW at 60 °C showed a pH gradient
with three distinct slopes when FW was displaced by LS brine:
two steeper slopes, which were linked to cation exchange at
easily accessible albite and illite surfaces, and one more
moderate gradient, which was related to the contact of the
LS brine with micropores. (2) In the first oil recovery test, core
B-21, the secondary oil recovery with FW was 40.1% of OOIP.
The LS EOR effect was 9.2% of OOIP, and plateau recovery
was obtained by injecting 8 PVs of LS brine. The observed pH
gradient was very well synchronized with the recovery of extra
oil. (3) In the second oil recovery test, core B-24, the secondary
oil recovery with FW was 39.0% of OOIP. A LS slug of 2 PVs
was injected followed by FW. The pH increased from 6.8 to
8.8, and the LS EOR effect was 5.2% of OOIP. The pH
dropped to the initial value, and oil recovery stopped
immediately as the FW was being reinjected. (4) Reinjection
of LS brine resulted in a fast increase in pH at the start, during
2 PVs, but later on, the pH increased slowly for 4 PVs. During
the injection of 6 PVs, extra oil was recovered slowly, 4.7% of
OOIP in total. The oil recovery stopped as the steady-state
equilibrium in the pH value was reached at pH 9.3. (5) The
results from the LS slug injection were discussed in terms of the
heterogeneity in the pore size of the core material used.
DOI: 10.1021/acs.energyfuels.6b00641
Energy Fuels 2016, 30, 4733−4739
Energy & Fuels Article

Secondary LS EOR Results. (1) Secondary LS injection
into the B-26 core resulted in a fast oil recovery of
approximately 59% of OOIP after injecting 2 PVs, which was
about 10% of OOIP higher than the total recovery at tertiary LS
flooding conditions. (2) The change in pH of the produced
water in a secondary LS recovery test was much smaller
compared to those of the previous LS tests at tertiary
conditions. The pH increased to a maximum value (pH ∼
7.5) at 8 PVs, and the oil recovery was about 65% of OOIP. (3)
Mild cleaning of the core material during core restoration
resulted in reproducible results. (4) The secondary LS response
time for oil recovery was very fast, and it appeared to be little
affected by the heterogeneity of the pore size distribution in the
core material. (5) A tertiary LSP flood was performed after the
plateau in oil recovery was established. A fast response in oil
recovery was observed, and the ultimate recovery was 86% of
OOIP.
International Symposium of the Society of Core Analysts; Pau, France,
Sept 21−24, 2003; DOI: 10.2118/78059-pa.
(11) Burgos, W. D.; Pisutpaisal, N.; Mazzarese, M. C.; Chorover, J.
Environ. Eng. Sci. 2002, 19 (2), 59−68.
(12) Cissokho, M.; Boussour, S.; Cordier, P.; Bertin, H.; Hamon, G.
Petrophysics 2010, 51 (5), 305−313.
(13) Reinholdtsen, A. J.; RezaeiDoust, A.; Strand, S.; Austad, T. Why
such a small low salinity EORPotential from the Snorre formation?.
Proceedings of the 16th European Symposium on Improved Oil Recovery;
Cambridge, U.K., April 12−14, 2011; DOI: 10.3997/
22144609.201404796.
(14) Skrettingland, K.; Holt, T.; Tweheyo, M. T.; Skjevrak, I. SPE
Res. Eval. Eng. 2011, 14 (2), 182−192.
(15) Shaker Shiran, B.; Skauge, A. Energy Fuels 2013, 27, 1223−1235.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: ivan.d.pinereztorrijos@uis.no.
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
The authors acknowledge TOTAL E&P Norge AS for financial
support and for submitting core material and crude oil.

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4739 DOI: 10.1021/acs.energyfuels.6b00641

Energy Fuels 2016, 30, 4733−4739