30 May – 2 June 2016 | Reed Messe Wien

Tu SBT2 11
Optimizing the Low Salinity Water for EOR Effects
in Sandstone Reservoirs - Composition vs Salinity
I.D. Piñerez Torrijos* (University of Stavanger), T. Puntervold (University of
Stavanger), S. Strand (University of Stavanger) & A. Rezaeidoust (Statoil
ASA)

SUMMARY
Particularly, even though a low salinity brine often is a successful EOR fluid, this paper shows that the
importance of specific salinity comes along with the brine composition. Water with salinities below 5000
ppm are generally accepted as LS EOR fluids, but in this work “smart water” EOR effects at higher
salinities than 5000 ppm have been observed. Improved oil recovery was observed in tertiary mode using a
40000 ppm NaCl brine and 25000 ppm NaCl brine, the results are in line with the suggested chemical
mechanism for wettability alteration due to a local pH increase triggered by calcium desorption. The speed
of oil production and ultimate recovery is influenced by the concentration of Ca2+ in the FW and salinity
(presence of NaCl) of the smart water brine.

78th EAGE Conference & Exhibition 2016

Vienna, Austria, 30 May – 2 June 2016
 30 May – 2 June 2016 | Reed Messe Wien

Introduction

Based on experimental data, we have previously showed that the low salinity (LS) enhanced oil
recovery (EOR) effect in sandstone is trigged by an increase in pH as the high salinity (HS) formation
water (FW) is displaced by the low salinity brine, sometimes referred to as “Smart Water”(Austad et
al. 2010a, RezaeiDoust et al. 2011). The initial pH of the FW, which should be in the acidic region,
and the clay content are very important in order to obtain mixed wet reservoir conditions, which
usually gives the best LS EOR response. A pH gradient of e.g. 2 pH units, when the LS brine
displaces the HS brine, is related to a large decrease in the concentration of H+, i.e. from 10-6 to 10-8
M, a variety of external factors can influence this pH gradient e.g. cation exchange capacity and
concentration of divalent ions. The reactivity of polar components in crude oil is sensitive to small pH
changes in a pH range from 6 to 8, these components act as anchor molecules towards the rock
surface, especially towards the clay minerals. Crude oil containing both basic, R3N:, and acidic,
RCOOH, functional groups, quantified as acid and base numbers (AN and BN, mgKOH/g of oil) are
surface active towards negatively charged clay minerals, and the concentration of the reactive form is
depending on the pH, as illustrated by the equations below, Eqs. (1) and (2):
Basic material: R3N: + H2O ↔ R3NH+ + OH- (1)
Acidic material: RCOOH ↔ RCOO- + H+ (2)

The most reactive forms are shown in bold (Austad et al. 2010b, RezaeiDoust et al. 2010, 2011,
Burgos et al. 2002, Madsen and Lind 1998). Protonated base, R3NH+ will adsorb onto negatively
charged clay by electrostatic interaction, and acidic material, RCOOH, can adsorb by hydrogen
bonding. It is extremely interesting to note that the pKa values of these active compounds are very
similar, pKa≈ 5.5, meaning that the concentrations change in the same way regarding pH. As the pH
increases, Eq. (1) is moved to the left and Eq. (2) is moved to the right. Thus, both the basic and
acidic material is transformed into species of low affinity towards the clay surface, and the water
wetness of the clay minerals is increased as indicated by the following equations:
Clay- R3NH+ + OH- = Clay + R3N: + H2O (3)
Clay-RCOOH + OH- = Clay + RCOO- + H2O (4)

Both clay minerals and sometimes Plagioclase/Albite (NaAlSi3O8) can influence pH as indicated by
the following reactions,(Friedman et al. 1992, Strand et al. 2014):
Clay-Ca2+ + H2O ↔ Clay-H+ + Ca2+ + OH- + heat (5)
NaAlSi3O8 + H2O ↔ HAlSi3O8 + OH- + Na+ (6)

Active cations, especially Ca2+ are desorbed from the clay surface as the formation water with high
Ca2+ concentration is displaced by the “smart water” with low Ca2+ concentration. The negatively sites
on the clay surface are, to some extent, balanced by protons from water, and the induced increase in
pH at the clay surface is suggested to promote desorption of organic material through ordinary acid-
base reactions, Eqs. (3) and (4). The adsorbed organic material is transformed to their alkaline
forms, i.e. R3N: and RCOO-, which have much lower affinity towards the clay surface (Burgos et al.
2002, Madsen and Lind 1998). The question then arises, “is the LS EOR effect mostly controlled by
salinity or are divalent ions also of interest?”

Experimental

Core material: Outcrop cores from the same block were used (B-01, B-21, B25), containing 10 wt%,
the major clay present is illite contributing to almost 8 wt%. The core material has also a significant
amount of reactive albite with approximately 30 wt%. All cores showed similar physical and chemical
properties.
Brines: The compositions of the brines used in this study is given in Table 1.

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 30 May – 2 June 2016 | Reed Messe Wien

Table 1 Composition and other properties of the brines used.

Parameter Units FW LS nSW NaCl25 FW (40 000 ppm
(25 000 ppm CaCl2) NaCl)
[Na+] (mM) 1540 17.1 402 427.8 - 684.5
[K+] (mM) - - 10 - - -
[Ca2+] (mM) 90 - 0.1 - 225.3 -
[Mg2+] (mM) - - 0.2 - - -
[Cl-] (mM) 1720 17.1 411 427.8 450.5 684.5
pH - 5.5 5.7 8.0 5.7 7.1 5.8
Total (ppm) 100000 1000 24350 25000 25000 40000
salinity

Crude oil: A crude oil with an acid and base number of 0.1 and 1.8 mg KOH/g respectively was used.
The oil viscosity was 17.6 cP at 20°C.
Core preparation: For all oil recovery tests an initial water saturation of 20% was established using the
desiccator technique(Springer et al. 2003). The core was air evacuated, saturated and flooded with
crude oil (2 PV from each direction), and aged in ageing steel cells at 60°C for 14 days.
Oil recovery tests: The oil recovery test for core B-21 was performed following the flooding sequence
FW-LS. The oil recovery test for core B-25 was performed by successively flooding FW-NaCl25. The
oil recovery tests for core B-01 was performed by successively flooding FW (25000 ppm CaCl2)-
(40000 ppm NaCl). The produced oil, pH and density of the produced water were measured at
ambient conditions in all experiments.
pH screening test: After the oil recovery test of core B-21, the core was mildly cleaned with Kerosene
and Heptane. The pH screening (Aksulu et al. 2012) test was performed in a Hassler core holder, the
core was initially 100% saturated with formation water, FW. The core was successively flooded with
FW-LS-FW-nSW-FW. Effluent samples were collected and pH was measured to investigate rock-
brine interactions.

Results and discussion

In the experiments performed, the effect of smart water composition in tertiary mode have been
evaluated.

Oil recovery test with low salinity brine in tertiary mode

The oil recovery test performed on core B-21 (Figure 1a) represents a typical smart water EOR test
using LS brine, 1000ppm. The flooding sequence was FW-LS. The oil production with FW was
approximately 40% of OOIP. The tertiary EOR effect with the LS was 9 % of OOIP, this incremental
oil was produced after 8 PV of LS injection, pH of first produced formation water is 6.1 but a further
increment to pH 9 is observed during the LS injection.

Oil recovery test with 25 000 ppm salinity brine in tertiary mode
In the oil recovery with the core B-25, the flooding sequence was FW-NaCl25 (Figure 1b), the
production with FW was approximately 35% of OOIP and the tertiary EOR effect with NaCl25 was
10 % of OOIP. This incremental oil was produced after 16 PV of LS injection, the initial pH with
formation water is 6.5 but a further increased until pH 7.2 is observed during the NaCl25 flood.

In both oil recovery tests an increased recovery of ~10% OOIP was observed, even though the salinity
of the smart water brines were significantly different, 1000 ppm and 25 000 ppm respectively, the
recovery plateaus were also different, it was needed to inject 8 PV when using LS (1000 ppm) and 16

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PV with the NaCl25 brine. In addition, a smaller pH gradient was also observed when the NaCl25 was
injected ~0,5 pH units in comparison with ~3 pH units observed in the core B-21 with the LS.

Figure 1 a) Oil recovery test performed on core B-21 at 60°C, injection sequence FW(100 000 ppm)-
LS(1000 ppm), injection rate 4PV/D b) Oil recovery test with outcrop B-25, injection sequence
FW(100 000 ppm)-NaCl25(25 000 ppm) at 60 °C, injection rate 4 PV/D.

pH screening test
The core was successively flooded with FW-LS-FW-nSW-FW (Figure 2a) as explained before. The
initial pH established with FW was 6, the LS brine was injected and an increment of 3 pH units was
observed, after that FW water was injected again and the pH dropped. Then a brine of 24 350 ppm
was injected and a pH increment of 1.5 pH units was observed confirming a pH increase for both
fluids; however, the LS showed a higher reactivity towards the surface. The low reactivity of the
25 000 ppm brine could be caused due to the high sodium concentration, which shifts partially the
equilibrium of Eq. (6) to the left, reducing the contribution in alkalinity of the reactive plagioclase
(Strand, 2012).

Figure 2 a) pH screening test performed on core B-21 at 60°C injection sequence FW-LS-FW-nSW-
FW, flooding rate of 4PV/D. b) Oil recovery test performed with the outcrop B-01 at 40 °C, injection
sequence FW(25 000ppm CaCl2)-Smart water(40 000 ppm NaCl), flooding rate of 4PV/D.
(RezaeiDoust et al. 2011).

EOR effect at 40 000 ppm salinity in tertiary mode

The smart water EOR potential for a brine of 40 000 ppm of NaCl has previously been tested in core
B-01 at 40°C (Figure 2b) (RezaeiDoust et al. 2011). The oil production plateau with formation water,
FW(25 000 ppm CaCl2), was 35% OOIP, after that the high salinity smart water was injected, 40 000
NaCl, and the production increased approximately 3% OOIP was observed. The first oil in tertiary
mode was not observed before 2 PV of smart water injected. The delayed production could be
explained by the initial high concentration of Ca2+ in the formation water that need to be displaced
before that the smart water effect could be observed.

78th EAGE Conference & Exhibition 2016

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 30 May – 2 June 2016 | Reed Messe Wien

Conclusions

Water with salinities below 5000 ppm are generally accepted as LS EOR fluids, but in this work
“smart water” EOR effects at higher salinities than 5000 ppm have been observed. Improved oil
recovery was observed in tertiary mode when injecting a 25 000 ppm NaCl brine. A previous
experiment had even showed tertiary increased recovery when injecting a 40 000 ppm NaCl brine as
EOR fluid.
The experimental results indicate that it is not the salinity of the EOR fluid that is important, but
rather the composition, and more explicitly the Ca2+ concentration. These results agree well with the
suggested pH induced chemical mechanism for wettability alteration. The speed of oil production and
ultimate oil recovery are both influenced by the concentration of Ca2+ in the FW and by the salinity
(presence of NaCl) of the smart water brine and by the resulting pH gradient during the waterflooding.

Acknowledgements

The authors acknowledge TOTAL E&P Norge AS and Talisman for financial support and for
permission to publish this paper.

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78th EAGE Conference & Exhibition 2016

Vienna, Austria, 30 May – 2 June 2016