energies

Article
Study of the Effect of Clay Particles on Low Salinity
Water Injection in Sandstone Reservoirs
Sina Rezaei Gomari * and Nikhil Joseph
Chemical Engineering and Chemistry Department, School of Science and Engineering, Teesside University,
Middlesbrough TS1 3BA, UK; nikhjoseph@gmail.com
* Correspondence: s.rezaei-gomari@tees.ac.uk

Academic Editor: Alireza Bahadori

Received: 22 December 2016; Accepted: 2 March 2017; Published: 7 March 2017

Abstract: The need for optimal recovery of crude oil from sandstone and carbonate reservoirs
around the world has never been greater for the petroleum industry. Water-flooding has been
applied to the supplement primary depletion process or as a separate secondary recovery method.
Low salinity water injection is a relatively new method that involves injecting low salinity brines
at high pressure similar to conventional water-flooding techniques, in order to recover crude oil.
The effectiveness of low salinity water injection in sandstone reservoirs depends on a number of
parameters such as reservoir temperature, pressure, type of clay particle and salinity of injected
brine. Clay particles present on reservoir rock surfaces adsorb polar components of oil and modify
wettability of sandstone rocks to the oil-wet state, which is accountable for the reduced recovery
rates by conventional water-flooding. The extent of wettability alteration caused by three low salinity
brines on oil-wet sandstone samples containing varying clay content (15% or 30%) and type of clay
(kaolinite/montmorillonite) were analyzed in the laboratory experiment. Contact angles of mica
powder and clay mixture (kaolinite/montmorillonite) modified with crude oil were measured before
and after injection with three low salinity sodium chloride brines. The effect of temperature was
also analyzed for each sample. The results of the experiment indicate that samples with kaolinite
clay tend to produce higher contact angles than samples with montmorillonite clay when modified
with crude oil. The highest degree or extent of wettability alteration from oil-wet to intermediate-wet
state upon injection with low salinity brines was observed for samples injected with brine having
salinity concentration of 2000 ppm. The increase in temperature tends to produce contact angles
values lying in the higher end of the intermediate-wet range (75◦ –115◦ ) for samples treated at 50 ◦ C,
while their corresponding samples treated at 25 ◦ C produced contact angle values lying in the lower
end of intermediate-wet range.

Keywords: clay particles; wettability; temperature’s effect; contact angle; sandstone reservoirs

1. Introduction
Low salinity water flooding (LSWF) is one such modified application of traditional water flooding
techniques. Field tests and core-flooding experiments have verified that LSWF improves the oil
recovery process by 5%–38% more than that by traditional water flooding techniques [1–4]. The usage
of brines with low salinity concentration and lower ionic strength plays a significant role in the
wettability alteration in both sandstone and carbonate reservoir rocks. Wettability alteration in the
case of sandstone reservoirs by LSWF is strongly influenced by the different type of clay particles
present in the reservoir. The uneven distribution of clays throughout the sandstone reservoir rocks
have also made it difficult to study the exact impact of each clay particle and that the amount of
clay content has on wettability alteration. The major clay particles involved in wettability alteration
mechanisms in sandstone reservoirs are montmorillonite, kaolinite and illite [5]. The clay particles

Energies 2017, 10, 322; doi:10.3390/en10030322 www.mdpi.com/journal/energies

Energies 2017, 10, 322 2 of 12

possess a net negative charge and they are able to adsorb polar components of crude oil (asphaltenes
and resins) and thereby alter the rock surface to an oil-wet state. During the process of LSWF, cations
are exchanged between the clay minerals and low salinity brines. The lower concentration of cations
present in injected brine causes the equilibrium established between connate water and reservoir rocks
to be disturbed, resulting in the cation exchange reactions. The cation exchange reactions result in
desorption of polar components of oil from negatively charged clay surfaces and they are replaced by
the cations from low salinity brine. The wettability of sandstone reservoir is found to be much more
water-wet after the cation exchange process [6].
Thus, the process of cation exchange is another important factor that determines the extent of
wettability alteration and thereby the amount of oil recovered from a sandstone reservoir. Different
clay particles have different cation exchange capacity (CEC) and, based on their value of CEC, they are
able to exert influence on the cation exchange process. Temperature and pressure have also been
observed to affect the extent of wettability alteration by LSWF.
In addition to above mentioned mechanisms of enhanced oil recovery by LSWF, the results of
experiments performed by Tang and Morrow [7] suggested that LSWF is able to cause the detachment
of mobile clay particles (fines) such as kaolinite from the pore walls and thereby also carry the oil
attached to pore walls through the clay particles, hence increasing the oil recovery, while high salinity
brines do not disturb the clay particles attached to the pore walls.
The laboratory experiment conducted in this research project is designed to provide
results that verify the main objective mentioned above and to also provide inferences to the
following sub-objectives:

• To evaluate the role of content (concentration) of individual clay particles such as montmorillonite
and kaolinite in modifying the wettability of sandstone rocks.
• To assess the role of reservoir temperature in the wettability alteration process of sandstone rocks.
• To determine the ideal low salinity concentration of injected brine required to obtain optimum oil
recovery in sandstone reservoirs, by measuring contact angles of Sandstone samples before and
after injection of three low salinity brines.
• To evaluate the pattern of variation in the values of contact angles measured for each sandstone
sample (having different clay content) that are injected with three brines of varying low
salinity concentrations.

2. Material and Methods

2.1. Materials

2.1.1. Solids
The solid materials used in the experiment include mica powder, two clays and a salt. Mica
powder is chosen to be the representative sandstone rock sample in order to diminish rock
heterogeneity and hysteresis on readings taken from Drop Shape Analyser, DSA 100, machine (KRÜSS,
Hamburg, Germany) that indicate the contact angle of each sample. Mica powder was supplied by
CEMCRAFT (Bromsgrove, UK). The two clays used in this study are kaolinite and montmorillonite.
Both kaolinite and montmorillonite were supplied by Sigma Aldrich (Irvine, UK). The salt used in this
experiment to produce low salinity brine was sodium chloride (NaCl). Sodium chloride was provided
by Fisher Chemicals (Loughborough, UK) with purity of 99.5%.

Kaolinite
Kaolinite is 1:1 type clay and contains a tetrahedral sheet of silicon (SiO4 ) and an octahedral sheet
of aluminium in one layer and the layers are placed sequentially one above the other [8]. The layers
are bound to each other by hydrogen bonds that exist between oxygen atoms in tetrahedral sheets and
hydroxyl groups in octahedral sheets [9]. Kaolinite is not chemically inert and does possess a small
Energies 2017, 10, 322 3 of 12

net negative charge due to broken bonds at the edges of the kaolinite particles. These small negative
charges are stabilised by minor cationic substitutions. The least reactive clay particle in sandstone
reservoirs is kaolinite, and it is also classified as a non-swelling type of clay particle. Due to less surface
area and less substitutions occurring, they have low CEC and hence low reactivity [10].

Montmorillonite
Montmorillonite clay belongs to the Smectite category of clays and is a 2:1 type of clay. Two sheets
of tetrahedral silicon atoms surround a central octahedral sheet of aluminium atom [8]. Polar molecules
such as water can occupy the space in between the tetrahedral and octahedral sheets in between the
layers, leading to expansion of the overall clay particle [8]. Montmorillonite clay is also referred to as a
swelling clay. Substitution of Si4+ by Al3+ in tetrahedral layers and Al3+ by Mg2+ in the octahedral layer
results in a strong net negative charge for montmorillonite clays. The negative charge so developed
is balanced by adsorbing exchangeable cations such as Ca2+ or Na2+ from the connate water [9].
Montmorillonite also possesses the highest CEC among all the clay particles found in sandstone
reservoirs and montmorillonite is classified as a swelling type of clay.

2.1.2. Liquid
Crude oil and distilled water are the two liquids that were used to study the wettability alteration
process in mica powder mixed with clays (representing a sandstone sample). Crude oil was supplied
by Statoil (Stavanger, Norway) and the source of the crude oil is the North Sea. The crude oil has an
API gravity of 37.50. The distilled water was used in the preparation of low salinity brines. In this
study, three types of low salinity brines with salinity content of 500 ppm, 1000 ppm and 2000 ppm
were used to study the wettability alteration characteristic in sandstone samples.

2.2. Methods

2.2.1. Clay Content and Sandstone Reservoir Rocks

In this experiment, mica powder was employed to represent sandstone reservoir rock as it is one
of the major components found in sedimentary rocks. It was used as the mean solid concentration
and mixed with different amounts of kaolinite and montmorillonite separately. The preparation of
samples by mixing mica powder and a single clay component (kaolinite/montmorillonite) was carried
out to analyze the effect of that individual clay component on wettability alteration of sandstone rocks.
Firstly, a total of eight samples were prepared by varying different concentrations of mica powder and
the two clays. The first four samples contained either 15% or 30% clay content of one particular type of
clay (kaolinite/montmorillonite) and was prepared at 25 ◦ C. The remaining four also contained 15%
or 30% clay content of one particular type of clay (kaolinite/montmorillonite) and was mixed at 50 ◦ C.
Then, the mixture of mica powder (sandstone samples) and clays that are naturally water-wet need to
be altered to the oil-wet state by using crude oil. Finally, the contact angles of all eight samples were
measured. The composition of all eight samples with varying clay content (15% or 30%) and type of
clay are illustrated below in the table below (Table 1).

Table 1. Composition of eight samples with different concentrations of mica, kaolinite

and monotmorillonite.

Sample No. S1 S2 S3 S4 S5 S6 S7 S8
Temperature (◦ C) 25 25 25 25 50 50 50 50
Clay Content (%) 15 30 15 30 15 30 15 30
Mica (g) 42.5 35 42.5 35 42.5 35 42.5 35
Components Kaolinite (g) 7.5 15 0 0 7.5 15 0 0
Montmorillonite (g) 0 0 7.5 15 0 0 7.5 15
Energies 2017, 10, 322 4 of 12

2.2.2. Oil-Wet Sample Restoration

Following procedure was applied to prepare oil-wet samples:

(1) The powdered mix were measured in a digital weighing balance and the amount of powdered
mix after the process of filtration recovered was noted as shown in the table below (Table 2).
(2) The Crude oil and powdered mix of each sample was mixed in a fixed ratio. The ratio taken is for
every 10 g of powdered mix, and 40 mL of crude oil was added. Based on this ratio, the amount
of crude oil required for each sample is illustrated in the table below (Table 3).
(3) The samples and required crude oil were mixed in 400 mL beakers and were stirred using a
magnetic hot plate stirrer and magnetic beads. The stirring and heating (at 25 ◦ C/50 ◦ C) of each
sample were as per specifications of the table above. The stirring was done to ensure proper
mixing in order to obtain oil-wet samples. The mixture was allowed to stir at a medium rotation
speed (45 rpm) and the stirring process was continued overnight for a duration of 24 h.
(4) Two days of decantation time was required for all samples after the agitation process.
(5) The mixture of crude oil and samples were then filtered using a vacuum pump, 1.5 L Erlenmeyer,
a funnel and filter paper. All equipment mentioned here was cleaned and sterilized. The process
of filtration for each sample took about two hours each. The solid phase of mixture was collected
and then placed onto a watch glass.
(6) The solid mixtures of samples obtained from the vacuum filtration process were then allowed to
dry off in an oven preheated to 100 ◦ C. The samples were allowed to dry in the oven for a time
period of 24 h.
(7) The dried samples were then removed from the oven and placed outside to cool off for 30 min.
Finally, the solid mixtures of each sample were then crushed in a mortar to obtain powdered mix
in order to measure contact angle of each sample.

Table 2. The powdered mix of each sample recovered after filtration process.

Sample No. S1 S2 S3 S4 S5 S6 S7 S8
Temperature (◦ C) 25 25 25 25 50 50 50 50
Clay Content (%) 15 30 15 30 15 30 15 30
Powdered Mix
38.5 36.3 37.7 25 47.2 47.2 41.3 27
Recovered (g)

Table 3. Quantity of crude oil required for each sample.

Sample No. S1 S2 S3 S4 S5 S6 S7 S8
Temperature (◦ C) 25 25 25 25 50 50 50 50
Clay Content (%) 15 30 15 30 15 30 15 30
Powdered Mix (g) 38.5 36.3 37.7 25 47.2 47.2 41.3 27
Crude oil Required (mL) 160 145 150 100 189 189 165 108

2.2.3. Wettability Study of Oil Wetted Samples with Low Salinity Brines
(1) The prepared oil-wet samples from the above procedure were then used to study effect and extent
of LSWF in the presence of clay on their wetting state.
(2) The oil-wet powder mix was weighed in a digital weighing machine having a capacity of 250 g
and minimum value of 0.01 g. The oil-wet powder mix of each sample was then equally divided
into three different sets that are to be injected with the three brines. The mass of each sample to
be mixed with each brine was determined using a fixed ratio. The ratio was fixed, as for every 4 g
of oil-wet sample, 20 mL of brine was required. Based on this ratio, a total of 24 samples were
prepared by mixing the required amount of the original eight oil-wet samples (S1–S8) and the
Energies 2017, 10, 322 5 of 12

three brines (B1–B3) individually. For example, 20 g of oil-wet sample S1 was mixed with 100 mL
of brine B1. The amount of brine required per sample was calculated and the required amount of
oil-wet sample/brine is shown in the tables below (Table 4).
Energies 2017, 10, 322 5 of 12
Table 4. Quantity of sample and each brine required for the tests.
Table 4. Quantity of sample and each brine required for the tests.
Sample No. S1 S2 S3 S4 S5 S6 S7 S8
Sample No. S1 S2 S3 S4 S5 S6 S7 S8
Temperature ◦
( C) 25 25 25
Temperature (°C) 25 25 25 25 50 25 50 50 50 50 50 50
50
Clay Content (%)
Clay Content 15
(%) 30 15
15 30 30 15 15 30 15 30 30 15 15 30
30
Oil-wet Powder
Oil-wet Powder Available/Sample
20 20 (g) 20 20 15 20 15
25 25 25 25 22
22 15
15
Available/Sample (g)
B1 Required
B1 Required (mL) (mL)
100 100 100
100 100 75 100 75
125 125 125125 125
125 75
75
B2(mL)
B2 Required Required (mL)
100 100 100
100 10075 100 125 75 125125125 125 125 75
75
B3(mL)
B3 Required Required (mL)
100 100 100
100 10075 100 125 75 125125125 125 125 75
75

(3) The beakers containing the required amount of oil-wet sample and brine were then placed on
(3) The beakers containing the required amount of oil-wet sample and brine were then placed on
magnetic hot plate stirrers. A magnetic bead was placed in each beaker for stirring the mixture
magnetic hot plate stirrers. A magnetic bead was placed in each beaker for stirring the mixture
and stirring was done at medium speed of rotation (45 rpm). Heat was also provided at ◦25 °C
and stirring was done at medium speed of rotation (45 rpm). Heat was also provided at 25 C for
for brines mixed with samples S1–S4, and brines mixed with samples S5–S8 were heated at 50
brines mixed with samples S1–S4, and brines mixed with samples S5–S8 were heated at 50 ◦ C.
°C.
(4) After stirring the samples for a time period of 2 h, they were removed from the hot plate stirrers
(4) After stirring the samples for a time period of 2 h, they were removed from the hot plate stirrers
and kept for two days for the process of decantation to occur.
and kept for two days for the process of decantation to occur.
(5) After two days, the samples were filtered using a simple conical flask, funnel and filter paper.
(5) After two days, the samples were filtered using a simple conical flask, funnel and filter paper.
The flasks and funnels were thoroughly cleansed before being used for the filtration process.
The flasks and funnels were thoroughly cleansed before being used for the filtration process.
The filtration process takes about 1 h for each sample. The solid phase of each sample was then
The filtration process takes about 1 h for each sample. The solid phase of each sample was then
collected onto a watch glass.
collected onto a watch glass.
(6) The oven
oven was
was preheated
preheated to to 100 ◦ C and the samples placed on the watch glass were kept in the
100 °C
(6) The and the samples placed on the watch glass were kept in the
oven and allowed to dry for
oven and allowed to dry for 24 h. 24 h.
(7) The samples
(7) The samples were
were then
then removed
removed from from the
the oven
oven and
and placed
placed outside
outside to
to cool
cool for
for aa time
time period
period of
of
30 min.
30 min. The
The solid
solid mix
mix ofof each
each sample
sample was
was then
then crushed
crushed in
in aa mortar
mortar to
to obtain
obtain the
the powder
powder mix.
mix.
(8) The powdered
(8) The powdered mixes
mixes of of all
all 24
24 samples
samples obtained
obtained were
were then
then used
used to
to make
make pellets
pellets and
and measure
measure
their contact
their contact angle
angle as
as per
per the
the same
same procedure
procedure mentioned in the earlier section. Two Two examples of
pellet discs
pellet discs made
made for
for contact
contact angle
angle measurement are presented in Figure 1.

(a) (b)

Figure 1. Example of discs made from powder mix for contract angle measure. (a) mica mixed with
Figure 1. Example of discs made from powder mix for contract angle measure. (a) mica mixed with
kaolinite; and (b) mica mixed with kaolinite and aged in crude oil.
kaolinite; and (b) mica mixed with kaolinite and aged in crude oil.

2.2.4. Contact Angle Measurements

2.2.4. Contact Angle Measurements
The measurement of contact angle of each sample of oil-wet mica powder and clay mix was
Theout
carried measurement of contact
using a Kruss angle analyser
drop shape of each sample
(DSA of oil-wet
100, mica
KRÜSS, powder and
Hamburg, clay mix The
Germany). was contact
carried
out
angleusing a Krusswas
of sample dropmeasured
shape analyser (DSA 100,
on a system withKRÜSS, Hamburg,i.e.,
three interfaces, Germany). Theand
air, water contact angle
surface of
powdered sample. The DSA 100 machine is regarded as the finest machine available to measure
contact angle of samples with maximum accuracy. The final reported contact angle is the average of
three contact angle measurements on the same surface. All contact angles were measured after 10
min of the releasing of droplets on the surface. Figure 2 below illustrates the type of images recorded
by the DSA 100 machine for each sample.
Energies 2017, 10, 322 6 of 12

of sample was measured on a system with three interfaces, i.e., air, water and surface of powdered
sample. The DSA 100 machine is regarded as the finest machine available to measure contact angle of
samples with maximum accuracy. The final reported contact angle is the average of three contact angle
measurements on the same surface. All contact angles were measured after 10 min of the releasing of
droplets on the surface. Figure 2 below illustrates the type of images recorded by the DSA 100 machine
for each sample.
Energies 2017, 10, 322 6 of 12

Figure 2. Example of images of water droplets recorded by Drop Shape Analyser, DSA 100, on the
Figure 2. Example of images of water droplets recorded by Drop Shape Analyser, DSA 100, on the
rock sample.
rock sample.

3. Results and Discussion

3. Results and Discussion
3.1. Role
3.1. Role of
of Clay
Clay Content
Content in
in Modifying Wettability of
Modifying Wettability of Sandstone
Sandstone Rocks
Rocks to
to Oil-Wet
Oil-Wet
The influence
The influence ofof clay
clay particles
particles montmorillonite
montmorillonite andand kaolinite
kaolinite in
in modifying
modifying the
the wettability
wettability of
of
naturally water-wet mica powder (representing sandstone reservoir) to the oil-wet state
naturally water-wet mica powder (representing sandstone reservoir) to the oil-wet state was analyzed was
analyzed
by measuringby measuring
the contactthe contact
angles angles
of the ofsamples.
eight the eightEach
samples. Eachcontact
sample’s sample’s contact
angles angles
were were
measured
after they had been altered with crude oil. Table 5 provides the composition of each sample andeach
measured after they had been altered with crude oil. Table 5 provides the composition of the
sample and the result of the average value of contact
result of the average value of contact angle obtained. angle obtained.

Table 5. Contact
Table 5. Contact angle
angle values
values of
of oil-wet
oil-wet sandstone
sandstone samples.
samples.

Sample No. S1 S2 S3 S4 S5 S6 S7 S8
Sample
Temperature No.
(°C) 25 S1 25 S2 25 S3 25S4 50S5 S6
50 S7
50 S8 50
Clay Type
Temperature ◦
( C) Kaolinite
25 25 Montmorillonite
25 25 Kaolinite
50 50 Montmorillonite
50 50
Clay Content (%)
Clay Type 15 30
Kaolinite 15 30
Montmorillonite 15 30
Kaolinite 15 30
Montmorillonite
Contact Angle
Clay Content (%) 120.4°15 120.3°30 119.7°
15 119.7°
30 120.5°
15 123.6°
30 117.3°
15 111.0°
30
Measured—Average Value
Contact Angle
120.4◦ 120.3◦ 119.7◦ 119.7◦ 120.5◦ 123.6◦ 117.3◦ 111.0◦
Measured—Average Value
The measured contact angle values of sandstone samples containing both types of clays, i.e.,
kaolinite (S1, S2, S5 and S6) and montmorillonite (S3, S4, S7 and S8), indicate the successful alteration
The measured
of wettability contact from
of sandstone anglea values of sandstone
naturally water-wet samples
state to acontaining
more oil-wet both types
state. Theofinteraction
clays, i.e.,
kaolinite
of crude (S1,
oil S2,
andS5clay
and particle
S6) and montmorillonite
montmorillonite(S3, in S4, S7 andS3,
samples S8),S4,
indicate
S7 andtheS8 successful
has ledalteration
to polar
of wettabilityof
components of crude
sandstone fromasa naturally
oil such asphalteneswater-wet statebeing
and resins to a more oil-wet
adsorbed state.
onto theThe
clayinteraction
surface and of
crude oil and
modifying clay particle
wettability to montmorillonite
an oil-wet state in samples
[11]. In theS3, S4, of
case S7 sandstone
and S8 has samples
led to polarS1, components
S2, S5 and S6 of
crude oil such
containing as asphaltenes
kaolinite and resins
clay particle, being adsorbed
interaction between onto the clay
crude oil surface and modifying
and kaolinite wettability
again led to the
to an oil-wet
adsorption ofstate
polar[11]. In the case
components of of sandstone
crude oil and samples S1, S2, S5 of
thereby alteration and S6 containing
wettability to ankaolinite clay
oil-wet state.
particle,
Kaoliniteinteraction
is rich inbetween
hydroxyl crude oil and
groups onkaolinite againand
its surface led thus
to theisadsorption
susceptibleof polar components
to adsorption of
of crude oil [12].
asphaltenes and thereby alteration
The adsorption of of wettability
heavy to an of
components oil-wet
crudestate.
oil suchKaolinite is rich inand
as asphaltenes hydroxyl
resins
tend to impart a more hydrophobic nature to the clay particles [13].
It is also observed that all four oil-wet samples having kaolinite clay content (S1, S2, S5 and S6)
have higher contact angle values than their corresponding four oil-wet samples containing
montmorillonite clay content (S3, S4, S7 and S8). Higher contact angle values of samples with
kaolinite clays are due to the fact that kaolinite clay is hydrophobic in nature and shows more
Energies 2017, 10, 322 7 of 12

groups on its surface and thus is susceptible to adsorption of asphaltenes [12]. The adsorption of heavy
components of crude oil such as asphaltenes and resins tend to impart a more hydrophobic nature to
the clay particles [13].
It is also observed that all four oil-wet samples having kaolinite clay content (S1, S2, S5 and
S6) have higher contact angle values than their corresponding four oil-wet samples containing
montmorillonite clay content (S3, S4, S7 and S8). Higher contact angle values of samples with kaolinite
clays are due to the fact that kaolinite clay is hydrophobic in nature and shows more attraction
towards asphaltenes and resins than montmorillonite clays [14]. Montmorillonite, on the other hand,
Energies 2017, 10, 322 7 of 12
is hydrophilic in nature and hence samples with montmorillonite have lower contact angle values
Energies 2017, 10, 322 to samples with kaolinite content as shown in Figure 3 below.
when compared 7 of 12
130
(degree)

128
126
130 120.5 123.66
(degree)

124 120.47
128 119.7
122
126 120.3 119.73 120.5 123.66
117.3 118
angleangle

120 120.47
124 119.7
118
122 120.3 119.73
116
120 117.3 118
Contact

114
118
112
116
Contact

110
114
112 S1 S2 S3 S4 S5 S6 S7 S8
110
S1 S2 S3 Sample
S4 number
S5 S6 S7 S8
Sample number
Figure 3. Contact angle values of samples S1–S8.
Figure 3. Contact angle values of samples S1–S8.
Figure 3. Contact angle values of samples S1–S8.
3.2. Effect of Temperature
3.2.Effect
3.2. EffectofofTemperature
Temperature
As shown in Figure 3 above, the contact angle values obtained do not show a significant
variation
As in thein
As shown
shown case
in of samples
Figure
Figure 3 above,
3 above, S1, S2,
thethe S3
contactand S4angle
angle
contact prepared
values at 25
obtained
values °C.
do Samples
obtained notdo shownotS1 and S2a contain
a show
significant 15%
variation
significant
and
in the30%
case ofof kaolinite
samples clay.
S1, S2,S3S3 and
and S4
S4 contain
prepared 15%
at 25 ◦ C. 30%
and of
Samples montmorillonite
S1 and S2 contain clay,
15% respectively.
and 30% of
variation in the case of samples S1, S2, S3 and S4 prepared at 25 °C. Samples S1 and S2 contain 15%
However,
kaolinite in
clay. the
S3 case
and of
S4 samples
contain S5,
15% S6,
andS7 and
30% S8
of (blended at
montmorillonite 50 °C),
clay,
and 30% of kaolinite clay. S3 and S4 contain 15% and 30% of montmorillonite clay, respectively. we observe
respectively. variation
However, in contact
in the
angles measured. Samples S1 S8
and S5 ◦ kaolinite
case
However,of samples
in the S5,caseS6,
ofS7 and
samples S5, S6,contain
(blended at 5015%
S7 and S8C), atclay,
we observe
(blended whereas
50 variation
°C), insamples
we observe contact S2 and in
angles
variation S6 contain
measured.
contact
30%
Sampleskaolinite
S1 andclay.
S5 Though
contain all
15% four samples
kaolinite contain
clay, whereas kaolinite
samples clay,
S2 the
and
angles measured. Samples S1 and S5 contain 15% kaolinite clay, whereas samples S2 and S6 contain increased
S6 contain temperature
30% kaolinite (50clay.
°C)
in the
Though case
all of
fourS5 and
samples S6 has resulted
contain in
kaolinite increased
clay, the value of
increased contact angles
temperature (50 ◦ C) in the
measured when
case compared
of S5 and
30% kaolinite clay. Though all four samples contain kaolinite clay, the increased temperature (50 °C)
tothe
S6
in samples
hascase ofS1S5and
resulted in S2.
S6The
haseffect
increased
and valueofofincreased
resulted contact
in temperature
angles
increased measured
value resulted
when
of contact incompared
angles decreased
measured tocontact
whenangle
samples S1 andvalues
compared S2.
in
The the case
effect of of samples
increased S5 and
temperatureS6 (blended
resulted at
in 50 °C)
decreasedthat contain
contact 15%
angle and
values
to samples S1 and S2. The effect of increased temperature resulted in decreased contact angle values 30%in montmorillonite
the case of samples clay
S5
when
and compared to50 ◦
samples S3S6and S4 15%
(blended at 25that
°C).contain
Figures15%
4–6clayillustrate the increasetoinsamples
contact
in theS6case
(blended at
of samples C)and
S5 that contain
(blended and
at 50 30%
°C) montmorillonite and when compared
30% montmorillonite clay
angle
S3 and measured.
S4 (blended at 25 ◦ C). Figures 4–6 illustrate the increase in contact angle measured.
when compared to samples S3 and S4 (blended at 25 °C). Figures 4–6 illustrate the increase in contact
angle measured.

Figure 4.
Figure 4. Contact
Contact angle
angle variation
variation in
in eight
eight samples
samples with
with increase
increase in
in temperature
temperature for
for brine
brineB1.
B1.

Figure 4. Contact angle variation in eight samples with increase in temperature for brine B1.
Energies 2017, 10, 322 8 of 12
Figure 4. Contact angle variation in eight samples with increase in temperature for brine B1.

Figure 5. Contact angle variation in eight samples with increase in temperature for brine B2.
Figure
Energies 2017, 5. Contact angle variation in eight samples with increase in temperature for brine B2.
10, 322 8 of 12

Figure 6. Contact angle variation in eight samples with increase in temperature for brine B2.
Figure 6. Contact angle variation in eight samples with increase in temperature for brine B2.

In the case of brine B1, the average difference in contact angle measured was about seven
degreesthe
In forcase of brine
samples B1, the average
containing same typedifference
of clayinand
contact angle
similar measured
content wasand
(i.e., S1 about
S5, seven
S2 anddegrees
S6, S3
for samples containing same type of clay and similar content (i.e., S1 and
and S7 and S4 and S8), as shown in Figure 4 above. In the case of brine B2, the average differenceS5, S2 and S6, S3 and S7 in
and S4 and S8), as shown in Figure 4 above. In the case of brine B2, the average
contact angle measured was about three degrees again for samples with the same type of clay and difference in contact
angle
similar measured was about
clay content, three in
whereas degrees againofforbrine
the case samplesB3, with the same difference
the average type of clayinand similarangle
contact clay
content, whereas in the case of brine B3, the average difference
measured was about three to four degrees as shown in Figures 5 and 6 above. in contact angle measured was about
threeThe
to four degrees
higher as shown
contact angleinvalues
Figuresindicate
5 and 6 above.
that the wettability alteration process at higher
temperatures results in weakly water-wet state. that
The higher contact angle values indicate Lower thereservoir
wettability alteration on
temperatures, process at higher
the other hand,
temperatures results in weakly water-wet state. Lower reservoir temperatures,
seem to encourage a higher degree of wettability alteration from an oil-wet state to a strongly on the other hand, seem
to encourage
water-wet a higher
state degree
[15]. The of wettability
increase alteration
in temperature andfrom an oil-wet
decrease stateof
in degree to wettability
a strongly water-wet
alteration,
state [15]. The increase in temperature and decrease in degree of wettability
observed in all cases except for the case of sample S8 injected with brine B2, demonstrates alteration, observed in
that the
all cases except for the case of sample S8 injected with brine B2, demonstrates
results of this experiment confirm the correlation between reservoir temperature and modification of that the results of this
experiment confirm the correlation between reservoir temperature and modification of wettability state.
wettability state.
3.3. Role of Low Salinity Brines in Wettability Alteration of Oil-Wet Samples
3.3. Role of Low Salinity Brines in Wettability Alteration of Oil-Wet Samples
The eight oil-wet samples (S1–S8) were separately injected with three low salinity brines—B1,
The eight oil-wet samples (S1–S8) were separately injected with three low salinity brines—B1,
B2 and B3, respectively. Three contact angle measurements were taken and their average value was
B2 and B3, respectively. Three contact angle measurements were taken and their average value was
calculated and selected as the final contact angle value of each sample. The primary aim of this part of
calculated and selected as the final contact angle value of each sample. The primary aim of this part
the experiment was to analyze the extent of wettability alteration to the water-wet state by measuring
of the experiment was to analyze the extent of wettability alteration to the water-wet state by
reduction in contact angle values for each sample when they were subjected to treatment with three
measuring reduction in contact angle values for each sample when they were subjected to treatment
brines having different salinity concentrations. The results also help to identify the ideal salinity range
with three brines having different salinity concentrations. The results also help to identify the ideal
for LSWF operations. Table 6 provides the contact angle values obtained after low salinity water
salinity range for LSWF operations. Table 6 provides the contact angle values obtained after low
treatment for each brine. Treating oil-wet sandstone samples with the low salinity brines resulted
salinity water treatment for each brine. Treating oil-wet sandstone samples with the low salinity
brines resulted in reduction of contact angle values in the case of each sample (S1–S8). The values of
contact angles obtained as shown in Table 6 lies in the intermediate-wet state [16]. The results
indicate that the low salinity brines successfully altered the wettability of sandstone from an oil-wet
state to a more water-wet state.
Energies 2017, 10, 322 9 of 12

in reduction of contact angle values in the case of each sample (S1–S8). The values of contact angles
obtained as shown in Table 6 lies in the intermediate-wet state [16]. The results indicate that the
low salinity brines successfully altered the wettability of sandstone from an oil-wet state to a more
water-wet state.

Table 6. Contact angle values of eight samples before and after injection with brines B1, B2 and B3.

Contact Angle Average Value (◦ )

Sample No. Temperature (◦ C)
Oil-Wet State Brine B1 500 ppm Brine B2 1000 ppm Brine B3 2000 2000 ppm
S1 25 120.467 91.3 89.8 88.5
S2 25 120.30 91.6 89.7 86.6
S3 25 119.70 98.47 88.2 87.567
S4 25 119.73 96.53 94.67 91.3
S5 50 120.50 99.53 92.35 90.075
S6 50 123.66 98.16 91.267 90.5
S7 50 117.30 105.63 91.26 91.38
S8 50 111.0 103.54 88.45 94.375
Energies 2017, 10, 322 9 of 12

3.4. Effect
3.4. Effect of
of Type
Type and
and Content
Content of
of Clay
Clay Particle
Particle in
in Wettability
Wettability Alteration
Alteration
The results
The results clearly
clearly indicate
indicate that
that samples
samples containing
containing clay clay particle
particle kaolinite
kaolinite (S1,
(S1, S2,S2, S5
S5 and
and S6)
S6)
produced lower values of contact angle after treatment with brines B1, B2
produced lower values of contact angle after treatment with brines B1, B2 and B3 as compared to the and B3 as compared to the
values obtained
values obtained byby samples
samples containing
containing montmorillonite
montmorillonite clay clay (S3,
(S3, S4,
S4, S7
S7 and
and S8).
S8). The
The increase
increase in in clay
clay
content from 15% to 30% did not produce much variation in the values
content from 15% to 30% did not produce much variation in the values of contact angle measured forof contact angle measured for
samples containing kaolinite clay (S1, S2, S5 and S6) in case of the three brines.
samples containing kaolinite clay (S1, S2, S5 and S6) in case of the three brines. However, in the case However, in the case
of samples
of samples containing
containing montmorillonite
montmorillonite clay clay (S3,
(S3, S4,
S4, S7
S7 andand S8),
S8), the
the increase
increase inin concentration
concentration of of clay
clay
content from 15% to 30% resulted in variation of contact angle values
content from 15% to 30% resulted in variation of contact angle values measured in the case of eachmeasured in the case of each
brine as
brine as illustrated
illustrated inin Table
Table 5. There is
5. There is aa difference
difference of of three
three degrees
degrees on on average
average between
between measured
measured
contact angle values of samples S3 and S4 (mixed at 25 ◦ C) containing 15% and 30% of Montmorillonite
contact angle values of samples S3 and S4 (mixed at 25 °C) containing 15% and 30% of
clay in the case ofclay
Montmorillonite the in
three
the brines
case ofB1,theB2 threeandbrines
B3. Similarly,
B1, B2 and there
B3.isSimilarly,
a difference of is
there three degrees on
a difference of
average between measured contact angle values of samples S7 and S8 (mixed at 50 ◦ C) containing 15%
three degrees on average between measured contact angle values of samples S7 and S8 (mixed at 50
andcontaining
°C) 30% of montmorillonite
15% and 30% clay in the case of the
of montmorillonite three
clay in thebrines
caseB1,
of B2
theand
threeB3.brines B1, B2 and B3.
Figures 77 and
Figures and 8 8 further
further illustrate
illustrate the the variation
variation in in contact
contact angle
angle observed
observed for for samples
samples withwith
varying concentration of clay content when treated with different brines.
varying concentration of clay content when treated with different brines. The values of contact angle The values of contact
angle measured
measured for allforthree
all three
brinesbrines lie the
lie in in the intermediate-wet
intermediate-wet range,i.e.,
range, 75◦ –115◦[17].
i.e.,75°–115° [17]. The
The highest
highest
recovery factors
recovery factors have
have been
been observed
observed for for reservoirs
reservoirs having
having intermediate-wet
intermediate-wet state state of
of wettability
wettability [18].
[18].
The wettability modification of samples to the intermediate-wet state
The wettability modification of samples to the intermediate-wet state by low salinity brines in theby low salinity brines in the
experiment conducted here indicates that low salinity brines are able to
experiment conducted here indicates that low salinity brines are able to yield the highest recovery yield the highest recovery
factors when
factors when applied
applied as as aa secondary
secondary recovery
recovery method.
method.

Figure 7. Variation in contact angle of samples containing kaolinite clay with each brine.
Figure 7. Variation in contact angle of samples containing kaolinite clay with each brine.
Energies 2017, 10, 322 10 of 12
Figure 7. Variation in contact angle of samples containing kaolinite clay with each brine.

Figure 8. Variation
Figure 8. in contact
Variation in contact angle
angle of
of samples
samples containing
containing montmorillonite
montmorillonite clay
clay with
with each
each brine.
brine.

3.5. Effect
Energies of Salinity
2017, Concentration of Brine in Wettability Alteration
3.5. Effect of 10, 322
Salinity Concentration of Brine in Wettability Alteration 10 of 12

All
All three brines (B1,
three brines (B1, B2
B2and
andB3)
B3)managed
managedtotoalter
alterthe
thewettability
wettabilityofof each
each sample
sample (S1–S8)
(S1–S8) fromfrom
an
an oil-wet state to a more water-wet state as shown by the measured contact angle
oil-wet state to a more water-wet state as shown by the measured contact angle values in Table 6. values in Table 6.
The lowest value of contact angle of six samples (S1, S2, S3, S4, S5 and S6) was measured
The lowest value of contact angle of six samples (S1, S2, S3, S4, S5 and S6) was measured in the case in the case of
brine B3,B3,
of brine having
havinga salinity concentration
a salinity concentration ofof2000
2000ppm.
ppm.TheThelowest
lowestvalue
valueofofcontact
contactangle
angle measured
measured
for samples S7 S7 and
andS8 S8was
wasfor
forthe
thecase
case
of brine B2, having a salinity concentration of 1000 ppm.ppm.
of brine B2, having a salinity concentration of 1000 The
The highest
highest values
values of contact
of contact angleangle measured
measured for sample
for each each sample
was inwas
thein theofcase
case of B1.
brine brine B1. Figure
Figure 9 below 9
below illustrates
illustrates the variation
the variation in contact
in contact angle ofangle
eachofsample
each sample with
with the the brines.
three three brines.

Figure 9. Contact angle value of each sample for brines B1, B2 and B3.
Figure 9. Contact angle value of each sample for brines B1, B2 and B3.

The ideal salinity range of brines to be injected for low salinity water injection operations was
The ideal
identified in thesalinity rangereview
literature of brines to beasinjected
section forthe
lying in lowrange
salinity waterand
of 1000 injection operations
2000 ppm. was
This ideal
identified in thewas
salinity range literature
first review
mentioned section
as as
a lying in the range
pre-requisite of 1000 in
condition andorder
2000 ppm. This ideal
to observe salinity
wettability
range was first mentioned as a pre-requisite condition in order to observe wettability
alteration caused by the low salinity brines by the same researchers who proposed a chemical alteration caused
by the low salinity brines by the same researchers who proposed a chemical mechanism
mechanism to explain low salinity effect [19]. The results of the experiment conducted here clearly to explain low
salinity effect [19].
demonstrate that The results of
the lowest the experiment
contact angle valuesconducted here clearly
and hence demonstrate
the highest degree that the lowest
of wettability
contact angle values and hence the highest degree of wettability alteration were observed
alteration were observed when salinity concentration of injected brine was in the range of 1000–2000 when salinity
concentration
ppm (B2 and B3). of injected
Thus, thebrine was obtained
results in the range of 1000–2000
in this experimentppm (B2 and
provided B3). evidence
further Thus, thethat
results
the
obtained in this experiment provided further evidence that the ideal
ideal salinity range for improved oil recovery by LSWF is between 1000 and 2000 ppm. salinity range for improved oil
recovery by LSWF is between 1000 and 2000 ppm.
4. Conclusions
(1) The results of the laboratory experiment conducted in this work provides further insight and
confirmation that the influence that clay particles, temperature and salinity concentration has
on wettability of sandstone rocks when treated with low salinity brines. The experiment
involved the use of samples containing mica powder, different type of clay particles
(kaolinite/montmorillonite) and varying clay content (15%/30%) that represented sandstone
Energies 2017, 10, 322 11 of 12

4. Conclusions
(1) The results of the laboratory experiment conducted in this work provides further insight and
confirmation that the influence that clay particles, temperature and salinity concentration has
on wettability of sandstone rocks when treated with low salinity brines. The experiment
involved the use of samples containing mica powder, different type of clay particles
(kaolinite/montmorillonite) and varying clay content (15%/30%) that represented sandstone
reservoir rock samples. These samples were modified with crude oil from the North Sea and then
treated with three brines of sodium chloride having varying low salinity concentration (500, 1000
and 2000 ppm). The main conclusions that can be drawn from the results of the experiment
conducted are listed below.
(2) The modification of mica powder and clay mix with crude oil proved that the type of clay and
clay content do play a significant role. Samples containing kaolinite clay produced higher contact
angle values when compared to samples with montmorillonite clay.
(3) The contact angle values measured indicate wettability alteration of oil-wet samples to
intermediate-wet state as the contact angle values lie in the range of 75◦ –115◦ . Thus, low salinity
brines when applied as injection brine are able to modify wettability to the intermediate-wet
range and thereby produce the highest oil recovery rates, as reservoirs with a wettability state of
intermediate-wet have the highest recovery factors.
(4) The salinity range established for observing the highest degree of wettability alteration from the
oil-wet state to a more water-wet state in the experiment conducted here is 1000–2000 ppm. Thus,
the ideal salinity concentration for low salinity brine lies in the range 1000–2000 ppm.
(5) The results of the experiment further verify the established correlation between reservoir
temperature and the extent of wettability alteration, i.e., the higher the reservoir temperature, the
lower the degree of wettability alteration from an oil-wet state to a more water-wet state.

Acknowledgments: The authors wish to acknowledge Teesside University for providing the materials and
facilities to perform the experiments. The authors also feel grateful to Statoil and Kristian Sandengen for providing
crude oil.
Author Contributions: Each author has made contribution to the present paper. Sina Rezaei Gomari was director
of the research project and designed the experiments. Nikhil Joseph performed the experiments and collected
the data.
Conflicts of Interest: The authors declare no conflict of interest.

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