Journal of Petroleum Science and Engineering 26 2000.

105119
www.elsevier.nlrlocaterjpetscieng

Improved oil recovery using alkaline solutions

in limestone medium
)
Ulas Turksoy
, Suat Bagci

Department of Petroleum and Natural Gas Engineering, Middle East Technical Uniersity, 06531 Ankara, Turkey
Received 12 December 1998; accepted 15 December 1999

Abstract
In this study, the effect of sodium hydroxide NaOH. and sodium silicate NaSiO4 . solutions for the improved oil
recovery of Garzan 26 API8. and Raman 17.2 API8. crude oils with variable salinity of the alkaline solutions, and the
effect of injection flow rate at the salinity values of the alkaline solutions that yielded maximum oil recovery for both crude
oils has been investigated using a one-dimensional unconsolidated limestone reservoir model. As the previous study, the
interfacial tension measurements of the given crude oils and alkaline solutions interface have been measured to find the
optimum concentrations of the alkaline that give the minimum interfacial tension at the crude oilralkaline solution interface,
at different salinity of the alkaline solutions. Using these optimum alkaline concentrations, 22 displacement runs have been
performed; 13 runs with the variable salinity of the alkaline solutions, six runs with the variable injection flow rate, and the
remaining three runs were the base floods, performed without oil to see the interaction of alkaline solutions with the porous
matrix. The results of the displacement tests showed that the NaOH solutions with increasing salinity, has given the most
significant incremental oil recovery, about 39% for Garzan crude oil, while the NaOH and NaSiO4 solutions with different
salinity did not produced any significant incremental oil recovery for Raman crude oil, when compared with the base
waterfloods performed for each crude oil types. Six displacement runs have been performed; three runs for Garzan crude oil
and three runs for Raman crude oil at injection flow rates of 400, 300, 200 and 100 cm3rh for each crude oil with the
salinity of the alkaline solution that yielded maximum oil recovery. The results of the displacement tests showed that
injection flow rate of alkaline solution has an important effect on Garzan crude oil and has less effect on Raman crude oil in
the scope of oil recovery achieved. The optimum injection flow rates for both Garzan and Raman crude oils have been
found, which was 200 cm3rh for Garzan crude oil and 300 cm3rh for Raman crude oil for our model. q 2000 Elsevier
Science B.V. All rights reserved.
Keywords: oil recovery; alkaline solutions; limestone medium

1. Introduction
Alkaline waterflooding is an enhanced oil recovery process in which the injection water pH is in-

Corresponding author.

creased by the addition of relatively inexpensive

chemicals, such as sodium hydroxide NaOH.,
sodium silicate NaSiO4 . and sodium carbonate
Na 2 CO 3 . of the injected water. The alkaline reacts
with certain crude oil constituents and can lower
waterrcrude oil interfacial tension, emulsify oil and
water, change rock wettability and solubilize interfacial films, all of which may lead to increased oil

0920-4105r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 4 1 0 5 0 0 . 0 0 0 2 5 - 5

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Journal of Petroleum Science and Engineering 26 (2000) 105119

recovery. The process is simple when compared to

other chemical floods, yet it is sufficiently complex
to require detailed lab evaluation and careful selection of a reservoir for application.
There are now several proposed mechanisms by
which caustic waterflooding may improve oil recovery. These include: 1. emulsification and entrainment; 2. wettability reversal water-wet to oil-wet.;
3. wettability reversal oil-wet to water-wet.; and
4. emulsification and entrapment. Each mechanism
requires somewhat different initial conditions with
respect to reservoir oil, rock and injection water
properties, and each process is designed to improve
oil recovery in a somewhat different manner.
Results of numerous laboratory experiments have
been reported in the literature, describing the processes that are taking place during alkaline waterflooding and the effect of many parameters such as
flow rate, salinity and adsorption of the alkaline. But
studies describing the alkaline waterflooding and
parameters influencing the processes that goes on
during alkaline flooding for limestone matrix as the
porous medium are very limited. From this point of
view, this study focused on an experimental investigation of alkaline waterflooding performance and
processes and parameter affecting the oil recovery
during alkaline waterflooding when the reservoir matrix is limestone. The main objectives of this study
were: i. to determine the optimum alkaline concentrations of both NaOH and NaSiO4 that will give
minimum interfacial tension when they are subjected
to Garzan and Raman crude oils at different salinity
of injection water; ii. to determine the recovery
performance of the alkaline solutions at different
salinity values of injection water with the determined
optimum alkaline concentrations; iii. to investigate
the effect of flow rate on recovery performance at
the conditions of maximum oil recovery achieved in
the second step; and iv. to determine the significance of the alkaline losses to the limestone rock
matrix.

2. Literature review
The use of alkaline waterflooding as an enhanced
oil recovery process has been studied in the laboratory by many investigators. Atkinson 1927. believed

that residual oil was held within the spaces between

sand grains by forces of capillary and adhesion in
conjunction with oil viscosity, and that alkaline solutions overcome these forces to release the oil. He
seems to be referring to a wettability change combined with oilwater interfacial tension reduction.
Mungan 1966. published additional laboratory work
on wettability effects and caustic flooding. He found
the process to be temperature dependent, working
well at 1608F but not at all at 708F for the particular
crude oil used. He also demonstrated that water
relative permeability was indeed lower after causticwettability reversal from oil-wet to water-wet, giving
a more favorable wateroil mobility ratio even
though water saturation reached higher values. Cooke
et al. 1974. reported a third mechanism by which
caustic NaOH could improve waterflood oil recovery. They observed that under proper conditions of
pH, salinity and temperature, some crude oils and
porous media are converted from water-wet to oilwet. If the composition of the crude oil is favorable,
wettability can be reversed and oilwater interfacial
tension can be simultaneously lowered to low values
by the right combination of caustic and salt.
Jennings et al. 1974. proposed yet a fourth mechanism by which caustic injection can improve oil
recovery. Their laboratory experiments showed that
if interfacial tension were low enough, residual oil in
a preferentially water-wet core could be emulsified
in situ, could move downstream with the flowing
caustic, and could be entrapped again by pore throats
too small for the oil emulsion droplets to penetrate.
This mechanism of emulsification and entrapment
results in a reduced water mobility that improves
both vertical and areal sweep efficiencies. This is
especially important in waterflooding viscous oil
where waterflood sweep efficiency is notoriously
poor. McAuliffe 1973a,b. has also provided sample
evidence that injection of oil-in-water emulsions can
improve waterflood oil recovery in much the same
way as emulsions generated in situ. Dranchuk et al.
1974., reporting on laboratory caustic floods of a
viscous Lloyminster crude oil, observed that stable
oil-in-water emulsions were produced in situ and that
there was evidence for reduced water mobility during displacement.
Symonds et al. 1991. studied caustic flooding for
heavy oil recovery. They performed experiments us-

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Journal of Petroleum Science and Engineering 26 (2000) 105119

ing NaOH as the alkaline agent, and Wainright 408

mPa s. and Horsfely 18 mPa s. as crude oils. They
compared the oil recovery that they had achieved by
alkaline flooding with those by waterflood. They
also examined the effect of injection rate and loss of
caustic to the porous medium and found that performance in all cases they had tried was sensitive to
injection rate, and loss of caustic to the rock and
fluids was significant.
Hornof et al. 1994. worked on the effect of
flooding sequence on the displacement of acidic oil
by alkaline solutions. Paraffin oil doped with linoleic
acid served as acidic oil while NaOH solutions of
different concentrations were used as the aqueous
flooding agents. They tried two different flooding
strategies; first, the injection of 5 PV alkaline flooding following injection of 1 PV water, and second,
the continuous alkaline flooding. They observed that
the oil recovery increased with increasing NaOH
concentration in the first strategy while the oil recovery decreased with increasing NaOH concentration
in the second one.
Chiwetelu et al. 1994. investigated the feasibility
of employing various alkaline agents NaOH, sodium
orthosilicate and sodium metasilicate. to enhance the
recovery of specific Saskatchewan heavy oil from
the Kindersley region. The dynamic interfacial tension of solutions of the alkali in contact with the
crude oil was measured for a range of concentrations
and temperatures, and the most interfacially active
formulations were then tested for their oil recovery
efficiencies by conducting oil displacement experiments in unconsolidated linear sand packs at 258C
and 658C. The most promising of the three alkali
tested was found to be NaOH, which was capable of
producing very significant enhancements in oil recovery relative to that obtained with pure waterflooding.
Mehdizadeh and Handy 1989. studied the effectiveness of alkaline, such as NaOH, sodium orthosilicate and Na 2 CO 3 , to recover residual oil during hot
waterfloods. They claimed that, though interfacial
tension and alkali consumption increase with an
increase in temperature, recovery efficiencies obtained at high temperatures were comparable with
those obtained at lower temperatures. Hawkins et al.
1994. tried to identify mechanisms responsible for
the observed synergism between alkali and polymer

107

in combined chemical floods. They performed coreflood tests to assess alkalirpolymerrsurfactant

flooding as a tertiary recovery process for the Wainwright field of east central Alberta and found that
alkalirpolymerrsurfactant flooding could be a suitable tertiary recovery process for the Wainwright
field. Lieu et al. 1985. studied the chemical reactions with reservoir matrix in the recovery of
petroleum by alkaline flooding. They observed an
important initial combination of rapid reversible adsorption and chemical reactions followed by slower
non-reversible chemical reactions that can later assume great importance because of the long contact
time that may prevail in flooding a petroleum reservoir.

3. Experimental equipment
This study was conducted in two parts. In the first
part, the interfacial tension of NaOH and NaSiO4
solutions at different salinity of injection water with
Garzan and Raman crude oils were determined to get
the optimum alkaline concentrations. In the second
part, using these optimum alkaline concentrations,
displacement tests were performed to investigate the
recovery performance of the NaOH and NaSiO4
solutions and the effect of flow rate on oil recovery
and adsorption of the alkaline used.
The interfacial tension measurements were done
by Fisher Surface Tensiometer Model 20. The experimental apparatus for the displacement tests conducted consists of a positive displacement pump
ISCO., a cylindrical one-dimensional model, pressure gauges, differential pressure transducer and indicator, digital temperature controller and indicator,
air bath, and a back pressure regulator. Fig. 1 shows
the schematic diagram of the experimental set-up for
the displacement tests. The inside diameter of the
one-dimensional model was 6.1 cm, outside diameter
was 7.3 cm, and the length was 50 cm. Screens and
filters were installed at both ends of the model to
minimize the end effects. Air bath and temperature
controller were used to raise the model temperature
to the desired level and adjust the model temperature, respectively. Two pressure gauges were used to
measure the pressure at the inlet and outlet of the
model and a differential pressure transducer was

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Journal of Petroleum Science and Engineering 26 (2000) 105119

Fig. 1. Schematic diagram of the experimental set-up.

connected to the inlet and outlet of the model to

measure the differential pressure. A back pressure
regulator was used to adjust the pressure inside the
model and the produced flow rate. A vacuum pump
with a vacuum gauge was used to evacuate the sand
pack prior to each run. The fluid injection system
consists of a constant rate, positive displacement
ISCO pump, two graduated glass containers and
three different inlet lines for the injection of alkaline
solution, brine and oil.

4. Experimental procedure
Garzan and Raman crude oils were used during
the displacement tests. Crude oil properties are given
in Table 1. Clean crushed limestone samples were
used as the packing material. Limestone samples
between y14 and q35 mesh sizes gave a porosity
of 38%. The properties of limestone packing data for
all displacement tests are given in Table 2.
After the preparation of the packed model, the
model was fixed to the inlet line coming from the
displacement pump and to the outlet line going to the
production end. Then, the heater was started to reach
the desired temperature. After completing the evacuation procedure, the saturation procedure was started

with the prepared brine having salt concentration of

40 000 ppm at a low injection flow rate. A Raman or
a Garzan crude oil was then injected to displace the
brine water to irreducible water saturation. After the
model was prepared for the displacement tests, 500
cm3 of alkaline solution was injected by ISCO pump
and the rate of injection was adjusted on the ISCO
pump. All chemical solutions were freshly prepared
just before use to avoid any effect of air exposure or
precipitation. The injection rate was maintained constant at 200 cm3rh, which is equivalent to a frontal
velocity of about 1.65 mrday 5.4 ftrday. for all
runs. Then, the injection of the alkaline solution was
started. The injection and production pressures were
recorded at regular time intervals. The experiments
were terminated after the injection of approximately
1400 cm3 about 2.5 pore volumes. of the alkaline

Table 1
Properties of crude oils

Oil gravity 8API.

Oil viscosity at 258C cP.
Oil viscosity at 508C cP.
Oil density grcm3 .

Garzan

Raman

26
185
45
0.8984

17.2
365
125
0.9516

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Journal of Petroleum Science and Engineering 26 (2000) 105119

109

Table 2
Properties of packing data for displacement tests
Lithology

Limestone

Porosity %.
Permeability Darcy.
Pore volume cm3 .
Rock density grcm3 .
Weight of rock g.
Formation water salinity ppm.

38
10
555
2.65
2365
40 000

solution. After each experiment, the volumes of produced oil and alkaline water were read directly from
the graduated glass cylinders. The samples of alkaline water produced were analyzed for their pH and
density values. At the end of all runs, injection and
production line connections of the model were dismantled and the model was removed from the air
bath. The sand was removed from the model and the
model was completely cleaned to make it ready for
the next run.

5. Experimental results and discussion

In this section, the results of the interfacial tension measurements are presented. This is to determine the optimum alkaline concentrations of Garzan
and Raman crude oils with NaOH and NaSiO4 solutions at different salinity values. The results of displacement tests for recovery performance of the
NaOH and NaSiO4 solutions at their optimum concentrations are then presented. The effect of flow
rate and adsorption losses of the alkaline at the
conditions of maximum recovery for each crude oil
and alkaline solutions are also discussed.

Fig. 2. Interfacial tension measurements for Garzan oilrNaOH

interface at different salinity values.

ity for Garzan crude oil. The concentration of NaOH

for getting minimum interfacial tension has a tendency to increase with increasing salinity. Fig. 3
shows similar result for Raman crude oilrNaOH
interface. The minimum interfacial tensions for the
given salinity values were observed to be increasing
with increasing salinity for Raman crude oil. The
concentration of NaOH for getting minimum interfacial tension has a tendency to decrease with increasing salinity. Fig. 4 shows the results of the interfacial
tension measurements for Garzan crude oilrNaSiO4
interface. The minimum interfacial tensions for the
given salinity values were observed to be increasing
with increasing salinity for Garzan crude oil. The
concentration of NaSiO4 for getting minimum interfacial tension has a tendency to decrease with in-

5.1. Interfacial tension measurements

The interfacial tension between the Garzan and
Raman crude oils and the NaOH and NaSiO4 are
measured at different salinity values. Fig. 2 shows
the results of the interfacial tension measurements
for the Garzan crude oilrNaOH interface. The minimum interfacial tensions for the given salinity values
were observed to be decreasing with increasing salin-

Fig. 3. Interfacial tension measurements for Raman oilrNaOH

interface at different salinity values.

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Journal of Petroleum Science and Engineering 26 (2000) 105119

Fig. 4. Interfacial tension measurements for Garzan oilrNaSiO4

interface at different salinity values.

creasing salinity. Fig. 5 shows the results of the

interfacial tension measurements for Raman crude
oilrNaSiO4 interface. There was no significant difference between minimum interfacial tensions of different salinity values. But, the concentration of
NaSiO4 for getting minimum interfacial tension has
a tendency to increase with increasing salinity. Table
3 displays the optimum concentrations of the alkaline solutions to get the minimum interfacial tension
with Garzan and Raman crude oils at different alkaline solution salinity. The interfacial tensions measured for Raman crude oil were noticed to be less
than the interfacial tensions measured for Garzan
crude oil for each salinity values. These optimum
concentrations determined from the interfacial tension measurements were used for the displacement
tests.

conducted displacement tests. Run 1 was the base

water flooding for Garzan crude oil. In the Runs
27, the variable was the salinity of the alkaline
solution for the displacement of the Garzan crude oil
with NaOH and NaSiO4 alkaline solutions at an
injection rate of 200 cm3rh. Run 8 was the base
water flooding performed for Raman crude oil. In
Runs 913, the variable was again the salinity of the
alkaline solution injected to displace the Raman crude
oil with NaOH and NaSiO4 alkaline solutions. In
Runs 1419, injection flow rate was varied in order
to see the effect of flow rate on the incremental oil
recovery for Garzan and Raman crude oils. The
alkaline solution and the salinity of this solution
were selected from the previous group of displacement tests that gave the best result of incremental oil
recovery. In Runs 2022, base flood tests were
performed without oil, for both NaOH and NaSiO4
solutions that gave the maximum oil recovery for
Garzan and Raman crude oils. Because of the precipitation problem of the NaSiO4 , the base flood of
NaSiO4 solution for Raman crude oil could not be
done. The reason of the displacement test that was
not performed in the group Runs 1213 was infected
the same precipitation problem of NaSiO4 in the
40 000 ppm brine. Run 5 was done by the filtrated
part of the NaSiO4 solution as a trial.
Figs. 6 and 7 show the results of the oil recovery
and effluent NaOH concentrations of alkaline flooding of Garzan, respectively. It can be clearly seen
from Fig. 6 that the salinity of the alkaline solution

5.2. Displacement runs

After determination of the optimum alkaline concentrations for each Garzan and Raman crude oils,
the displacement runs were done in order to see the
performance of alkaline flooding on the incremental
oil recovery using a one-dimensional unconsolidated
limestone model. Twenty two displacement runs were
performed having the variables as crude oil type,
alkaline solution used to displace the crude oil,
salinity of the alkaline solution, injection flow rate
and base floods that were done with brine. Table 4
shows the experimental conditions and results of

Fig. 5. Interfacial tension measurements for Raman oilrNaSiO4

interface at different salinity values.

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Journal of Petroleum Science and Engineering 26 (2000) 105119

111

Table 3
Optimum concentrations of the alkaline solutions for the minimum interfacial tension
Crude oilralkaline
combination

Salinity of alkaline
solution ppm.

Minimum interfacial
tension dynercm.

Optimum concentration
of alkaline solution wt.%.

GarzanNaOH
GarzanNaOH
GarzanNaOH
RamanNaOH
RamanNaOH
RamanNaOH
GarzanNaSiO4
GarzanNaSiO4
GarzanNaSiO4
RamanNaSiO4
RamanNaSiO4
RamanNaSiO4

Distilled water
20 000
40 000
Distilled water
20 000
40 000
Distilled water
20 000
40 000
Distilled water
20 000
40 000

17.0
13.3
11.3
4.9
5.7
6.8
6.7
8.4
15.0
7.1
8.3
7.6

0.4
0.4
0.6
0.3
0.3
0.2
5.0
1.0
0.5
1.0
2.0
4.0

has a significant effect on the Garzan crude oil

recovery. The oil recovery for 40 000 ppm brine q
0.6% NaOH gave the highest oil recovery for Garzan
crude oil. As the salinity of the alkaline solution
decreased, the oil recovery achieved declined. At 1.8

pore volume of injection, 63% of the OOIP with

40 000 ppm brine q 0.6% NaOH solution, 61% of
the OOIP with 20 000 ppm brine q 0.4% NaOH
solution and 46% of the OOIP with distilled water
q0.4% NaOH solution was recovered. In Fig. 7,

Table 4
Experimental conditions and results of conducted displacement runs
Run No.

Oil

Displacing phase

So %.

S wi %.

Injection
rate cm3rh.

Sor %.

Oil recovery
% OOIP.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22

Garzan
Garzan
Garzan
Garzan
Garzan
Garzan
Garzan
Raman
Raman
Raman
Raman
Raman
Raman
Garzan
Garzan
Raman
Garzan
Garzan
Garzan
Raman
Raman
Raman

40 000 ppm brine

40 000 ppm brineq 0.6% NaOH
20 000 ppm brineq 0.4% NaOH
Distilled water q 0.4% NaOH
40 000 ppm brineq 0.5% NaSiO4
20 000 ppm brineq 1.0% NaSiO4
Distilled water q 5.0% NaSiO4
40 000 ppm brine
40 000 ppm brineq 0.2% NaOH
20 000 ppm brine q 0.3% NaOH
Distilled water q 0.3% NaOH
20 000 ppm q 2.0% NaSiO4
Distilled water q 0.3% NaOH
40 000 ppm brine q 0.6% NaOH
20 000 ppm brine q 1.0% NaOH
Distilled water q 0.3% NaOH
40 000 ppm brine q 0.6% NaOH
40 000 ppm brine q 0.6% NaOH
40 000 ppm brine q 0.6% NaOH
Distilled water q 0.3% NaOH
Distilled water q 0.3% NaOH
Distilled water q 0.3% NaOH

76.5
80.5
88.4
62.5
85.5
81.0
86.1
87.5
83.7
85.9
79.2
79.8
81.9
0.0
0.0
0.0
86.4
74.7
78.5
94.4
86.4
92.0

23.5
19.5
11.6
37.5
14.5
19.0
13.9
12.5
16.3
14.1
20.8
20.2
18.1
100.0
100.0
100.0
13.6
25.3
21.5
5.6
13.6
8.0

200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
400
300
100
400
300
100

18.9
13.9
40.9
1.4
38.0
29.2
38.8
42.9
39.6
46.9
32.8
33.3
34.4
0.0
0.0
0.0
36.2
20.0
21.9
48.0
37.2
44.3

55.8
66.6
47.5
61.1
47.5
51.8
47.3
44.7
44.1
39.0
46.4
46.5
47.5
0.0
0.0
0.0
50.2
54.7
56.7
46.4
49.2
47.8

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Journal of Petroleum Science and Engineering 26 (2000) 105119

Fig. 6. Oil recovery curves for Garzan oil NaOH..

from the concentration profiles of NaOH at the

effluent, 40 000 ppm brine q 0.6% NaOH concentration curve shows that the front of the solution was
stable. The stability of the front shows a decrease as

the salinity of the injected alkaline solution decreases, yielding less oil recovery. The distilled water q 0.4% NaOH alkaline solution gave less oil
recovery while the others gave incremental oil recov-

Fig. 7. NaOH concentration profiles of produced water Garzan oil..

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Journal of Petroleum Science and Engineering 26 (2000) 105119

ery when compared with the base flood. The cause

of the less recovery for the distilled water q 0.4%
NaOH alkaline solution was the problem of the
mobility control of the displacing front in the porous
matrix. Fig. 8 shows the comparison of the NaOH
concentration profiles for the displacement of the
Garzan crude oil with 40 000 ppm brine q 0.6%
NaOH solution and the base flood performed without
oil. The effluent concentration of NaOH for the
displacement of Garzan crude oil was higher than the
concentrations of the base flood performed for the
same solution without oil showing that the consumption of the NaOH solution was significantly reduced
in the presence of crude oil in limestone matrix.
Figs. 9 and 10 show the results of the oil recovery
curves for Raman crude oil and the effluent concentration profiles for the NaOH solutions, respectively.
From Fig. 9, it can be seen that the presence of
NaOH solution did not significantly increase the
incremental oil recovery of the Raman crude oil.
40 000 ppm brine q 0.2% NaOH solution and distilled water q 0.3% NaOH solution showed the same
performance as the base water flooding done for the
Raman crude oil and yielded oil recovery of about
45% of OOIP. The oil recovery for 20 000 ppm

113

brine q 0.3% NaOH solution was less when compared with the base water flooding yielding oil recovery of about 39% OOIP. From Fig. 10, the
20 000 ppm brine q 0.2% NaOH solution was recovered at 98% of the original concentration while the
other solutions were recovered at about 50% of the
original concentration. Fig. 11 shows the comparison
of the NaOH concentration profiles for the displacement of the Raman crude oil with distilled water q
0.3% NaOH solution and the alkaline flooding performed without oil. At the base alkaline flooding, the
movement of the front was stable, while at the
alkaline flooding displacement of the Raman crude
oil, the front was not stable. Almost 50% concentration of the original alkaline solution was lost during
base alkaline flooding performed without oil. The
alkaline seems to be effective on Raman crude oil
after 2 pore volumes of injection as the concentration
of the displacement with the solution becomes higher
than the base alkaline flooding concentration.
Figs. 12 and 13 show the results of the oil recovery curves for Raman crude oil and the effluent
concentration profiles for the NaSiO4 solutions, respectively. From Fig. 12, it can be seen that the
NaSiO4 alkaline solution did not have significant

Fig. 8. Comparison of the NaOH concentration profiles Garzan oil..

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Journal of Petroleum Science and Engineering 26 (2000) 105119

Fig. 9. Oil recovery curves for Raman oil NaOH..

effect on the incremental oil recovery of Raman

crude oil. The oil recoveries were all around 45%
OOIP, including the base flood performed for Raman
crude oil. Looking at the concentration profiles at
Fig. 13, 83% of the original concentration of the
distilled water q 1% NaSiO4 solution and 91% of
the original concentration of the 20 000 ppm brine q

2% NaSiO4 solution were produced during the displacement tests. The displacement test with 40 000
ppm brine could not be performed because of the
precipitation problem of the NaSiO4 in this solution.
Fig. 14 shows the oil recovery curves for Garzan
crude oil and the concentration profiles for the displacing phase at different injection rates of 40 000

Fig. 10. NaOH concentration profiles of produced water Raman oil..

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Journal of Petroleum Science and Engineering 26 (2000) 105119

115

Fig. 11. Comparison of the NaOH concentration profiles Raman oil..

ppm brine q 0.6% NaOH solution. The cause of the

selection of the 40 000 ppm brine q 0.6% NaOH
solution was that this solution yielded the maximum
incremental oil recovery for Garzan crude oil in the
previous study. The maximum Garzan oil recovered

was about 63% OOIP at an injection rate of 200

cm3rh with 40 000 ppm brine q 0.6% NaOH solution. The oil recovery obtained from 100 cm3rh was
about 53% of OOIP, for 200 cm3rh, about 63% of
OOIP, for 300 cm3rh, about 51% of OOIP and for

Fig. 12. Oil recovery curves for Raman oil NaSiO4 ..

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Journal of Petroleum Science and Engineering 26 (2000) 105119

Fig. 13. NaSiO4 concentration profiles of produced water Raman oil..

400 cm3rh, about 47% of OOIP at 2 pore volume of

injection. At slow rates, the differential pressure
through the pore throats in the porous matrix is not
enough to overcome the capillary pressure. As the

rate is increased, this differential pressure increases,

and overcomes the capillary pressure, yielding more
oil recovery. But when the injection rate is further
increased, mobility control of the displacing front

Fig. 14. Effect of injection rates on oil recovery curves for Garzan oil NaOH..

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Journal of Petroleum Science and Engineering 26 (2000) 105119

117

Fig. 15. Effect of injection rates on oil recovery curves for Raman oil NaOH..

decreases, and due to this effect, the volumetric

sweep efficiency decreases yielding less oil recovery.
Fig. 15 shows the oil recovery for Raman crude oil
at different injection rates of distilled water q 0.3%

NaOH solution. From this figure, the injection flow

rate seems to have no important effect on the recovery of Raman crude oil with distilled water q 0.3%
NaOH solution. For the injection rate of 100 cm3rh,

Fig. 16. Residual oil saturation vs. capillary number.

118

U. Turksoy,
S. Bagcir

Journal of Petroleum Science and Engineering 26 (2000) 105119

42% of OOIP were obtained at 2.3 pore volume

injection, for 200 cm3rh, it was 45%, for 300 cm3rh,
48% and for 400 cm3rh, 45%. The optimum injection rate was found to be 300 cm3rh for Raman
crude oil. This value is higher than the value found
for the Garzan crude oil in Section 5.1. Because the
capillary forces are much more effective for the
Raman crude oil and to overcome these capillary
forces, higher flow rate was needed when compared
to the Garzan crude oil. From these results, the
effectiveness of an alkaline flooding can depend on
injection rate. For some systems, there is a minimum
rate at which the emulsion or lamellae zone will
form. At rates greatly in excess of this minimum
rate, the amount of oil recovered decreases, although
the displacement mechanism still operates and oil
bank is formed. The minimum rate, at which an
emulsion bank will form, also depends on oil saturation when alkaline injection has begun. The emulsion
bank will form at a lower rate when oil saturation is
higher Cooke et al., 1974.. Fluid flow at reservoir
rates 0.3 mrdayf 1 ftrday. has no effect on the
chemical reaction of alkali with limestone matrix.
From this point of view, the frontal displacement
velocities were chosen between 0.82 2.7 ftrday.
and 3.29 mrday 10.8 ftrday.. The higher rate was
used to minimize mineral dissolution caused by the
alkali.
Taber 1969., Melrose and Brandner 1974.,
Lefebure du Prey 1973., Bardon and Longeron
1980., and Taylor et al. 1990. have studied the
effect of capillary number Nc . on residual oil saturation. Laboratory tests have shown a correlation between the residual oil saturation, Sor , and the capillary number, Nc . In those studies, higher values of
Nc were achieved by increasing either the velocity or
the viscosity of the displacing phase, or by reducing
the IFT. The capillary number is defined as:
Nc s Vm . rs
where V is the Darcy velocity of the displacing
wetting phase, m is the effective viscosity of the
displacing phase, and s is the interfacial tension
between the displaced and displacing phases. The
correlation generally found is that for increasing Nc ,
the residual oil saturation decreases roughly logarithmically. Sometimes, a porosity term is included in

the denominator to convert the fictitious Darcy velocity to real velocity in the pore channels. Conventional waterfloods generally operate at or near a
capillary number of 10y6 . In order to achieve an
improvement in the level of oil recovery, the capillary number must be increased to more than 10y4 . In
Fig. 16, residual oil saturation vs. capillary number
is plotted. In order to obtain a significant reduction
in the residual oil saturation, i.e. to achieve an
improvement in the level of oil recovery, the capillary number must be increased. Furthermore, viscosity and porosity are fixed, leaving interfacial tension
as the only parameter that can be modified to increase the capillary number.

6. Conclusions
Based on the experimental results presented in
this study, the following conclusions can be drawn.
1. Increasing the salinity of the alkaline solution
yields less interfacial tension at the Garzan crude
oilralkaline solution interface and the optimum alkaline concentration needed to give minimum interfacial tension decreases as the salinity of the alkaline
solution is increased for Garzan crude oil for both
NaOH and NaSiO4 solutions. For Raman crude oil,
the interfacial tensions at Raman crude oilralkaline
solution interface are lower than the Garzan crude oil
and the optimum alkaline concentration to give minimum interfacial tension at the interface for Raman
crude oil shows slight increase as the salinity of the
NaOH solution increases and decrease as the salinity
of the NaSiO4 solution increases.
2. The NaOH solutions with 20 000 and 40 000
ppm salinity have given the most significant incremental oil recovery of about 9% and 7%, respectively, for Garzan crude oil, while NaSiO4 solutions
have been not effective on the incremental oil recovery, when compared with the base waterflood performed for Garzan crude oil.
3. Both NaOH and NaSiO4 solutions at different
salinity values, have been not effective on the incremental oil recovery of the Raman crude oil, when
compared with the base waterflood performed for
Raman crude oil.
4. The injection flow rate of alkaline solution has
an important effect on Garzan crude oil and less

U. Turksoy,
S. Bagcir

Journal of Petroleum Science and Engineering 26 (2000) 105119

effect on Raman crude oil, in the scope of oil

recovery achieved.
5. The consumption of the alkaline from the
alkaline solutions in limestone porous medium and
to the oil was significant and the concentration loss
reached about up to 50% of the original concentration during some displacement tests.

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