PETROLEUM EXPLORATION AND DEVELOPMENT

Volume 45, Issue 5, October 2018

Online English edition of the Chinese language journal

Cite this article as: PETROL. EXPLOR. DEVELOP., 2018, 45(5): 927–931. RESEARCH PAPER

Enhanced oil recovery of low salinity water flooding in

sandstone and the role of clay
Al-SAEDI Hasan N.1, 2, *, FLORI Ralph E.1
1. Missouri University of Science and Technology, Rolla, MO 65401, USA
2. Missan Oil Company, Missan, Amara 62001, Iraq

Abstract: Sandstone core and free-clay sandstone core were prepared in chromatography columns, and core flooding experiments were
performed to determine the EOR mechanisms of low salinity (LS) water flooding and analyze the effect of clay on recovery factor. First,
brine with a high salinity (HS) of 100 000 mg/L was injected to simulate formation water. Then, LS water of 1 000 mg/L was then in-
jected at different temperatures. Concentrations of Ca2+ and CH3COO and pH of the fluid flowing out of the chromatography column
were recorded. The results showed that during flooding the free-clay core with LS water, the carboxylic acid detached from the sand, as
great as that of the clay-containing cores. It showed a noteworthy desorption of Ca2+ from the free-clay core surface, which indicated that
LS water flooding resulted in a high recovery in sandstone without clay. Compared with HS water flooding, in the LS water flooding, the
pH of produced fluid increased significantly; also, as the temperature increased, the pH and Ca2+ concentration of the produced fluid de-
creased; and the hydrophilic property of the sandstone was stronger. The results of oil recovery tests using the same columns were in line
with the chemical analyses. The oil recovery from the free-clay columns was as great as from the column clay-containing column. The
results of wettability measurements supported our theory.

Key words: sandstone reservoir; low salinity water flooding; enhanced oil recovery; water-rock reaction; wettability alteration; clay

Introduction in natural porous media are typically distributed unevenly

The wettability alteration mechanisms during LS water
flooding are less understood than other EOR techniques. The
mechanisms of LS water flooding are still a topic of debate. The
incremental oil recovery from sandstone using LS water include
several proposed mechanisms: mineral dissolution[1], multi-com-
ponent ion exchange[2], double-layer expansion[3], desorption
of organic material from clay surface[4], reduction in interfacial
tension[5], and fines migration[6]. The presence of clay in the
reservoir[26] has a significant impact on oil recovery. The
chemical composition of the injected water is another major
factor affecting additional oil production[4,78]. However, there
is no consensus on the dominant mechanism of enhancing re-
covery in sandstone reservoirs[4,89]. This may be because sev-
eral simultaneous processes contribute to the overall process.
To our knowledge, no systematic experimental and numerical
studies have been carried out that consider the most important
water-rock interactions in sandstones simultaneously.
Reservoir chemical heterogeneity may also play a role. Ex-
perimental and field scale projects indicate that incremental
oil recovery by LS water flooding varies significantly case-
by-case in both carbonates[1011] and sandstones[512]. Minerals
with random spatial patterns, ranging from uniform distribu-
tion to clustered minerals[1314]. On one hand, physical hetero-
geneity changes flow fields and therefore the spatial distribu-
tion of ions[15]. On the other hand, chemical heterogeneity
significantly changes dissolution rate[1617] and adsorption/de-
sorption[18]. Combination of physical and chemical hetero-
geneity can significantly impact water-rock interaction and
wettability alteration. However, the effect of spatial distribu-
tion of reservoir physical and chemical properties on wa-
ter-rock interaction and wettability alteration during LS water
flooding has not been fully considered.
In this study, we quantify the effect of mineral composition
and water chemical properties on the water-rock reaction and
wettability alteration. The mechanisms of LS waterflooding in
sandstone with and without clay under different temperatures
are examined by using two chromatographic columns con-
taining free-clay quartz and quartz with clay, and the effect of
clay on recovery enhancement is analyzed.
1. Methodology
1.1. Column packing
A chromatography column was packed with minerals to

Received date: 24 Feb. 2018; Revised date: 02 Jul. 2018.

* Corresponding author. E-mail: hnav36@mst.edu
Copyright © 2018, Research Institute of Petroleum Exploration & Development, PetroChina. Publishing Services provided by Elsevier B.V. on behalf of KeAi Com-
munications Co., Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 Al-SAEDI Hasan N. et al. / Petroleum Exploration and Development, 2018, 45(5): 927–931
imitate sandstone cores. Using such a column allows us to
control the mineralogy of the porous media. The sandstone
core without clay was made up of pure quartz, while the
sandstone core with clay was composed of 5% illite, 5%
kaolinite and 90% quartz. The cores are all 6.3 cm long and 1.5
cm in diameter. In order to avoid air bubbles in the column,
which can change the hydraulic conductivity, the columns
were packed using wet packing method[19]. The connections to
the column ports were supplied with a fine filter to prevent
mineral grains from moving out of the column.
1.2. Water flooding
The column was flushed with HS water and then aged for a
week at 70 °C with the same HS water containing 10 mmole
sodium acetate. This was done to maximize adsorption of
carboxylic material to the surface of the rock so as to simulate
bonding of carboxylic material to reservoir rock. The impor-
tance of the carboxylic acid is shown in Fig. 1. The system
was then flooded with HS water until the pH of the fluid out
of the column stabilized. Water samples were collected at the
column outlet for later analysis of ionic concentrations. After
each experiment, the column was aged in the same condition
for a week to restore the sample to the initial state. The whole
experiment was done inside an oven set to the temperature of
interest.
1.3. Chemical analysis
The Ca+2 concentration of produced fluid was measured
using (2000D ICP-OES). The acetate concentration was
measured using a Dionex DX-120 ion chromatography setup.
1.4. Preparation of brines
HS brine was prepared by dissolving reagent CaCl2 and
NaCl in Deionized water, and LS water was prepared by dis-
solving reagent NaCl only in deionized water. Compositions
of the brines are listed in Table 1.
1.5. Oil recovery test
Another column was flushed with HS water and saturated
with oil and aged for a week at 70 °C. HS water and then LS
water were injected into the column, and oil recovery was
measured from the produced fluid.
1.6. Wettability measurement
We utilized the new method described in our work[20] to
measure wettability in this study.
Fig. 1. Carboxylic acid on the clay surface during LS water
flooding[4].
 928 
Table 1. Composition of HS and LS brines (mg/l).
Element HS LS
Na+ 35 000 350
Cl- 60 000 600
Ca2+ 4 500 0
Acetate (aging) 820 0
TDS 98.32 1.182
Salinity ~100 000 ~1 000
2. Results and discussion
2.1. Sand column without clay
2.1.1. Chemical analysis results of the effluent
This column containing quartz only, no clay was presented
in this column. The permeability of Sand Column is 602×103
μm2 and the porosity measured by HS water is 33.64 %. At 25
C, the pH was 7.26 when flooded with HS water. Upon
switching to LS water, the pH rose to pH 9.77. When the in-
jected water was transferred to the original HS water, the pH
fell back to 7.29. There was about a 2.5 pH difference be-
tween HS water effluent pH and LS water effluent pH.
At 70 C, the pH for the HS water effluent was 7.28. The
water then switched to the LS water and pH for the LS water
effluent was 9.72. After that, switching the flooding to the
original HS water stabilized the pH back to its original value.
An important variance ~2.44 in pH between HS water and LS
water effluents was observed.
The pH trend is about the same at 90 C. The pH stabilized
at 7.23 while flooding the column by HS water, after switch-
ing to LS water the pH increased directly and stabilized at
9.32. The injected fluid switched again to the original HS
water and pH return to its original value.
At 120 C, the pH initially was 7.15 when flooded Column
1 by HS water. The pH suddenly rose and stabilized at 9.20
pH unit when switching the flooding to LS water. The in-
jected fluid then switched again to the same HS water, and the
pH fluctuated until fell again to its original value.
Traditionally, it is believed that the rise of pH value during
LS water flooding is caused by the replacement of Ca2+ ad-
sorbed on the surface of clay by H+ (ion exchange). Flooding
the free-clay column with LS water, the same trend was observ-
ed (pH upward shift). We attributed that to the exchange of Ca2+
and Na+ absorbed on negatively charged site of quartz by H+.
As can be noticed from Table 1 that LS water contains no
Ca2+, but the collected fluid after LS water flooding contains
Ca2+ (Fig. 2), verifying the desorption of Ca2+ from quartz
surface. The desorption of Ca2+ is the result of ion exchange
between Ca2+ and H+ and Na+ on the surface of negatively
charged quartz.
The core was aged in HS water containing 10 mmole so-
dium acetate for a week at 70 C, then it was flooded by HS
water and then LS water at different temperatures, the con-
centration of acetate in the produced fluid from the flooding
was measured, and its variations under different temperatures
 Al-SAEDI Hasan N. et al. / Petroleum Exploration and Development, 2018, 45(5): 927–931

are shown in Fig. 3. It needs to be noted that the injected fluid
volume under all temperatures were 40 times of pore volume.
It can be seen from the Fig. 3 that when the sandstone core
without clay is flooded by HS and LS water, the desorption of
carboxylic materials has no correlation with the rise of tem-
perature. As can be noticed, the detachment of CH3COO was
higher at 25 C than at 70 C, but that at 70 C was lower than
that at 90 C, and that at 120 C is the lowest.
In conclusion, because quartz surface and carboxylic ma-
terials are both negatively charged, they are repelled from
each other. Indeed, the carboxylic material bonded with diva-
lent cation Ca2+ [–COOCa+] [>Si-O2-] in form of electrostatic
bridging with quartz surface. When LS water invades into the
porous media, ion exchange takes place, then organic com-
plexes are removed and replaced with uncomplexed cations,
providing a more water wet environment and in turn enhanc-
ing recovery. At 25 C, 70 C, 90 C, and 120 C, the differ-
ences of pH values of the effluents from flooding by HS water
and LS water are 2.5, 2.44, 2.09, and 2.04 respectively. It can
be seen with the rise of temperature the difference of pH be-
comes smaller. It can be seen from Fig. 2 that when the core
without clay was flooded with LS water at 25 C,
70 C, 90 C, and 120 C, about 0.32, 0.37, 0.32, and 0.16
mmole of Ca2+ desorbed from the quartz surface respectively.
When the HS water was changed to LS water, a large amount
of CH3COO was detached from quartz surface. It can be seen
from Fig. 3 that the acetate released was 10.60%, 8.35%, and
3.80% at 25, 70, and 90 C, respectively, while the concentra-

Fig. 2. Effluent concentrations of Ca2+ from Sand Column at 25, 70, 90, and 120 C.

Fig. 3. Concentrations of RCOO in first HS and LS water effluent at 25, 70, 90, and 120 C.
 929 
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tion curve of CH3COO was not stable at 120 C. The ob-
served results of Ca2+ desorption and CH3COO detachment
was in line with our expectations, verifying LS water flooding
can facilitate the detachment of carboxylic acid from sand-
stone without clay, and thus improve recovery.

2.1.2. Oil Recovery Test

The sandstone core without clay was initially flooded by

HS water at 25 C until no additional oil recovery was observed
the oil recovery factor was 41% OOIP. The injected fluid
then was switched to LS water and the oil recovery increased
by 4% to 45.0% OOIP. At 70 C, 90 C, and 120 C, the in-
cremental oil recovery was 2%, 1.5% and 1% OOIP respec-
tively.
2.1.3. Wettability alteration
Figs. 4 and 5 show the wettability alteration when HS and
LS water were used to flood the sand column without clay, the
areas (Ao) between Ca2+ and Br curves were 0.14 and 0.185
respectively. It can be known from Fig. 6 that when the core is
totally water-wet, the area between Ca2+ and Br- curves (AH) is
0.22 (Fully saturated with heptane). The wettability index of
the porous media can be calculated by dividing Ao by AH. The
wettability index ranges from 0 for strongly oil-wet to 1 for
strongly water-wet and 0.5 for intermediate wettability[20].
Wettability index of the sandstone core without clay when
flooded by HS water was 0.63, while it was 0.84 when
flooded by LS water, meaning that the wettability of the core
becomes more water-wet when flooded with LS water.
Fig. 6. Concentrations of Ca2+ and Br for the water-wet core.
2.2. Sand column with clay
This column contains 5% illite + 5% kaolinite + 90%
quartz. The column was packed and prepared the same way as
the sand column. When flooded with HS water at 25 C, the
core had a recovery factor of 41.85% OOIP and pH value of
the produced fluid from the core was 7.14. At the same tem-
perature, flooding the column with LS water, the recovery
factor increased by 3.7% OOIP%, for the core without clay,
the recovery increment was 4.0%; and the pH of the produced
fluid was 8.90. The core was flooded with LS water at tem-
peratures of 70 °C, 90 °C and 120 successively, and the in-
cremental oil recoveries were 2.45%, 1%, and 0.70%, and the
pH of produced fluids were 8.78, 8.10 and 8.00 respectively.
It can be seen that the recovery factors of core without clay
and core with clay flooded by LS water differ little, suggest-
ing the existence of clay has little effect on recovery factor.
The experimental observations of Tang and Morrow[6] for
LS water flooding set out conditions for how LS water works.
The conditions were: (1) the crude oil must contain acid and
base numbers and (2) sandstone should contain clay such as
illite and kaolinite. After several years, McGuire[21] and Lager
and Webb[2] added another condition, which was that divalent
cations must be present in the FW. In this study, we examined
the role of clay during LS water and the results revealed that
the clay role is weak. This study provides insights into the
mechanisms that control LS EOR.

3. Conclusions
2+ 
Fig. 4. Concentrations (C) of Ca and Br while injecting HS
When the core without clay was flooded with LS water, the
water.
amount of CH3COO and Ca2+ released were large, indicating
ion exchange on the surface of quartz, and LS water can fa-
cilitate the detachment of carboxylate from the core, and thus
improving oil recovery. In the flooding of sandstone with LS
water, clay has little effect on recovery, even with no clay in
the sandstone, the flooding can improve recovery factor.
The approach of this work is that it allows us to isolate the
interplay between ion exchange, pH, and carboxylate release,
which should allow us to better decode the chemical mecha-
nisms that control LS water EOR flooding in sandstones. The
following conclusions were established:
Fig. 5. Concentrations of Ca2+ and Br while injecting LS (1) Clays are not essential for sandstone during LS water
water. flooding.
 930 
 Al-SAEDI Hasan N. et al. / Petroleum Exploration and Development, 2018, 45(5): 927–931
(2) Oil recovery increased during LS water flooding even
though there was no clay in the porous media.
(3) Ca2+ desorption and acetate released from quartz were
as high as when clay exists, meaning that an ion exchange and
carboxylic detachment occurred on the quartz surface.
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