SPE-171120-MS

Smart Water Injection for Heavy Oil Recovery from Naturally Fractured
Reservoirs
Heron Gachuz-Muro, Heriot Watt University/Pemex E&P; Mehran Sohrabi, Heriot Watt University

Copyright 2014, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Heavy and Extra Heavy Oil Conference - Latin Americaheld in Medellin, Colombia, 2426 September 2014.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract mus t contain conspicuous acknowledgment of SPE copyright.

Abstract
Enhanced Oil Recovery (EOR) from carbonate reservoirs can be a great challenge. Carbonate reservoirs are mostly oil-wet
and naturally fractured. For this type of reservoirs, primary production is derived mainly from the high permeability fracture
system which means that most of the oil will remain unrecovered in the low permeability matrix blocks after depletion.
Further difficulties arise under high pressure and high temperature conditions.
Oil recovery from carbonated rocks may be improved by designing the composition and salinity of flood water. The process
is sometimes referred to as smart water injection. The improvement of oil recovery by smart water injection is mainly
attributed to wettability modification in the presence of certain ions at high temperature. The resultant favourable wettability
modification is especially important for naturally fractured reservoirs where the spontaneous imbibition mechanism plays a
crucial role in oil recovery.
The objective of the work presented here was to experimentally investigate the performance of smart water injection for
heavy oil recovery from carbonate rocks under high reservoir temperature. A series of coreflood experiments were performed
using a group of carbonate cores in which smart water injection was tested under both secondary and tertiary injection
conditions. The experiments were conducted at 92 oC using an extra-heavy oil. Seawater from Gulf of Mexico (GOM) was
used in the seawater injection experiments and the smart water used in the tests was obtained by 10 times dilution of the
seawater. Although concentration of SO42- is lower in the smart water, the occurrence of SO42- as anhydrite in carbonates may
be sufficient to stimulate a similar reaction between the carbonated rock and the injected water with lower salinities at high
temperatures. Seawater injection resulted in oil recovery ranging between 30% and 40% whereas smart water injection
resulted in 60% oil recovery from the same system.
Additionally, analyses of brine composition before and after coreflood experiments confirmed that the effluent concentrations
of SO42-, Mg2+ and Ca2+ changed compared to its original values in the injected water. The results indicated that, for some
cases, the source of these ions was dissolution from the rock surface. The reactivity of the rock increased when lower salinity
water was used.

SPE-171120-MS

Introduction

Enhanced Oil Recovery (EOR) methods vary significantly from one type of reservoir to another. Heavy and extra heavy oil
reservoirs are amongst oil reservoirs that usually undergo EOR early in their production life. That is because these reservoirs
rarely produce under natural (primary) recovery mechanisms and sometimes even react inadequately to secondary recovery
methods. Thermal recovery methods (e.g., steam injection) are usually applied to heavy and extra heavy oil reservoirs.
However, steam injection cannot be successfully or economically applied to every heavy oil reservoir. There is therefore a
great interest in developing non-thermal methods for improving heavy oil recovery. Non-thermal methods such as gas
injection have been applied to light (conventional) oil reservoirs across the world with great success. The gas injection EOR
processes have shown good opportunities to revitalize mature oil fields and Naturally Fractured Reservoirs (NFR) around the
world. For instance, CO2 injection has been remarkably successful for improving light oil recovery and also for heavy oils
(Sohrabi et al). However, the cost of gas supply and injection can be prohibitive.
It is widely known that carbonates reservoirs are heterogeneous, essentially fractured, low porosity, with presence of vugs
and sometimes partially dolomitized. These characteristics along with oil-wet conditions result in low recovery factors from
these reservoirs. The initial oil production is produced from and by the fracture systems in the reservoir and the oil in the
matrix remains unaffected. In general, it is difficult to displace the oil located in the matrix blocks into the fractures. For this
kind of reservoirs, thermal EOR methods have been a common use (Manrique et al., 2007-2010). Gas injection has also been
popular in carbonates formations. Water injection in some carbonate reservoirs has led to good recoveries including in NFR.
Under these conditions, the spontaneous imbibition of water from fractures into the rock metrix is the main mechanism of oil
production. North Sea fields are good examples of successful water injection in carbonate reservoirs. Expulsion of the ligh oil
from the matrix as a natural process in presence of sulfates in the injection water has been cited as one of the reason for
change of wettability of carbonate rock to more water-wet enhancing the spontaneous imbibition phenomenon.
The complexity of NFR reservoirs are compounded by high pressure and high temperature conditions. NFR containing heavy
or extra heavy oils would be amongst the most difficult reservoirs to produce from and often leads to very poor reservoir
performance with low recovery factors.
The use of (smart) water injection as a natural wettability modifier has recently gained significant attention. The method is
considered relatively inexpensive and easy to inject even in hostile environments such as high pressure/high temperature or
deep reservoirs. It can also be implemented at any time during the reservoir life. Recent research has shown that ionic
composition (at times, in combination with high temperature above 90 oC), can play a vital role in oil recovery and may yield
up to 85 % of total oil under tertiary recovery mode (Austad et al., 2005-2007; RezaeiDoust et al., 2009; Shariatpahahi et al.,
2010-2011; Tweheyo et al., 2006; Yousef et al., 2010-2011-2012; Zhang et al., 2007-2012). Even though the alteration or
modification of the composition of the injection water has been mentioned by various research groups, the findings and
conclusions are not consistent. For instance, in carbonate reservoirs, smart water worked at high temperatures and about
33,000 ppm total salt content but affected the initial wettability in sandstones when was diluted to much a lower salinity <
5000 ppm. Clearly, other factors such as crude oil composition, rock mineralogy and formation and injected water
chemistries affect the wetting properties of oil reservoirs. Whilst some laboratory and field applications have had successful
outcomes, there are cases in which smart water did not make any significant difference.
Most of the laboratory tests on smart water injection have been conducted with light oils. The studies of smart water as
diluted water injection have been focused on sandstone reservoirs and more recently have been expanded to carbonate rocks
(Austad et al., 2012; Fathi et al., 2011; Romanuka et al., 2012; Strand el al., 2008; Yousef et al., 2010-2011-2012). However,
there are no published reports in the open literature on the application of smart water injection for heavy or extra heavy oils.
This paper is part of a study associated with improving heavy and extra-heavy oil recovery with a special emphasis on NFR
at high pressure and high temperature. Seawater was used as the injection fluid due to its favourable characteristics for oil
recovery in this system. Thus, this work focuses on investigating the implementation of smart (seawater and low salinity)
water injection for extra-heavy oil recovery from carbonates rocks at high temperature. Experiments including spontaneous
imbibiton and coreflood tests were carried out under both secondary and tertiary injection modes. Oil recovery, water
composition, and pH measurements before and after the experiments were all performed during the experiments.

SPE-171120-MS

Material
Crude oil- An extra heavy oil was used in the experiments. Table 1 shows the basic properties of the crude oil. The total acid
and base number are also presented. The results of the analysis of metal and sulphur content of this crude oil are shown in
Table 2. The crude oil was centrifuged before being used to ensure it was free from solid particles or emulsions.
Table 1. Crude Oil Properties.
Crude
Oil
A

Density
@ 22 oC
(0API)
12.55

Viscosity
@ 22 oC
(cp)
32, 537.99

Asphaltenes
Content ( %wt)

Resins
Content (%wt)

Acid Number
(mg KOH/g)

Base Number
(mg KOH/g)

13.20

31.70

1.00

3.50

Table 2.The metal element contents in the crude oil (mg/kg).

Crude
Oil

Al

Ca

Cu

Fe

Mg

Na

Ni

Pb

Si

Sr

3.84

5.13

<0.05

0.69

0.85

0.95

4.98

47.42

<1.00

2.31

<1.00

<0.05

217.40

Brine- Systematic experimental results have shown that seawater tends to be an effective type of water for improving the oil
recovery factor in fractured carbonates reservoirs. The existing literature points out that the reservoir temperature and some
specific components of the seawater are essential with regard to weetability changes. Based on these results, five different
brines were used in this study. Brine 1 was synthetic formation water, Brine 2 was synthetic seawater from Gulf of Mexico
whilst Brine 3 and 4 were diluted versions of that seawater, 10 and 50 times dilution, respectively. Brine 5 was a solution of
sodium and calcium chloride (NW). The compositions of the brines used in this study are given in Table 3.
Table 3. Brine compositions.
FW

SW

LSSW10

LSSW50

NW

(mg/L)

(mg/L)

(mg/L)

(mg/L)

(mg/L)

Na+

9,614.97

11,429.38

1,142.93

228.58

3,147.00

Ca2+

320.36

429.60

42.96

8.59

365.00

Mg2+

218.94

1361.60

136.16

27.23

K+

351.10

35.11

7.02

Ba2+

0.01

Sr2+

8.37

0.83

0.16

Cl-

15,117.25

20,040.00

2,004.00

400.80

5,498.73

SO42-

550.63

3,500.00

350.00

70.00

HCO3-

1,135.9

47.58

4.75

0.95

pH

8.01

7.80

7.20

6.75

5.35

Viscosity (cp)

1.03

1.07

1.00

0.99

1.01

Ion

SPE-171120-MS

Cores- Table 4 shows a list of both limestone and dolomite cores used for coreflood experiments at 92 oC. Dimensions were
measured and porosity and brine permeability was also determined by measuring the differential pressure across each core at
different flow rates in a special core holder designed for high pressure and high temperature. Environmental Scanning
Electron Micrscopic (ESEM) revealed that the cores obtained from dolomite rocks contain carbon, oxigen, magnesium,
calcium and small amounts of iron and silicon. Meanwhile, limestone cores contain carbon, oxygen, calcium, and also small
magnesium and silicon concentrations were noted. Figure 1 exhibits the mineralogy of the rocks.
Table 4. Properties of cores used for laboratory experiments.
Core
Limestone 1
Limestone 2
Limestone 3
Dolomite 1
Dolomite 2
Limestone 4

Diameter
(cm)
2.55
2.50
2.64
2.62
2.60
2.63

Length
(cm)
15.30
9.70
15.20
15.20
15.30
15.20

PV
(ml)
16.58
17.91
20.11
17.04
21.42
18.55

(%)
21.21
37.42
24.17
20.79
26.37
22.36

Sw
(%)
31,17
28.78
31.57
36.89
34.30
33.95

Kbrine
(mD)
6.90
19.51
51.80
194.32
345.49
62.77

2.52
2.52
2.52
2.52

15.2
15.2
15.2
15.2

18.34
15.55
15.55
15.55

24.25
20.64
20.64
20.64

28.30
32.13
32.13
32.13

146.51
19.40
19.40
19.40

Limestone 5
Limestone 6

1-2

Ca

3-3

Ca

O
Fe

Mg

C
Ca
Ca
C
Ca
Ca

Ca

Si

Fe

Fe
0

Ca

Mg

Fe
1

10

11

12

13

14

15

16

Full Scale 2526 cts Cursor: 0.000

17

18

19

20
keV

Si

10

Full Scale 11382 cts Cursor: 9.905 (17 cts)

11

12

13

14

15

16

17

18

19

20
keV

Figure 1. Mineral composition of cores, dolomite (right) and limestone (left).

Factors Affecting Wettability Conditions

In carbonates, wettability state is principally controlled by: a) polar components in the crude oil such as asphaltene and resin,
b) nature of the rock (mineralogy), c) chemistry of the brine, d) core treatment/preparation and e) aging time.

Polar components in the crude oil- Experiments have shown that the polar components from the crude oil can be adsorbed
by the core surfaces bringing about oil-wet conditions. Several researchers have reported contact angle measurements
indicating that carbonate reservoirs are usually more oil wet than reservoirs with silica (Chilingar et al., 1983; Treiber et al.,
1972).
Mineralogy- Carbonates reservoirs such as dolomite, limestone or chalk (Lucia, 2007; Puntevold et al., 2007) generally
include traces of sulphate in the rock. The presence of sulphate in the rock would have an influence on the initial state of
wettability of the rock (Shariatpanahi et al, 2010) making the rock more water-wet.

SPE-171120-MS

Core treatment- Several researchers have published techniques for generating different initial wettability conditions in the
laboratory. A large range of combinations of solvents have been proposed to restore the reservoir conditions. For instance,
Puntevold (2007) reported that special care should be taken with the preparation of carbonate cores. The carbonate cores
cleaned with kerosene and heptanes tend to be preferentially water wet but when toluene and methanol were used, the cores
were more oil wet.
Aging- Aging period for cores with crude oil and formation water has extensively been studied due to its importance. It is
believed that aging cores can result in wetting conditions that are more representative of reservoir conditions (compared to
using chemicals). A rise in aging time results in decrease in water wetness (Zhou et al., 2000). Moreover, the restoration of
wettability could begin since the start of the crude oil injection into the core and this could occur faster at high temperature
(Al-Mahrooqi et al., 2005).
Moreover, Chilingar and Yen in their extensive wok found (1983) that principally, carbonate reservoirs are more oil-wet and
intermediate wet systems. In our experiments, the cores were cleaned with toluene and methanol and then were aged for 20
days at 92 oC to restore the original wetting conditions.

Experimental Work
During core flood experiments, complex rock/fluid and fluid/fluid interactions take place which are difficult to interpret. In
this work, we begin by evaluating each element of the parameters affecting the experiments, Figure 2. Core, brine and crude
oil were individually analysed. The details of the interactions between reservoir fluids/injected fluids or injected fluids/rock
can vary widely depending on the composition of such elements. For this reason, interactions between theses elements were
meticulously evaluated before and after each experiment. The outcomes of these simple and practical analyses put in
evidence the level of complexity. The complete evaluation of the fluids/rock interactions led to a better picture of such
indications. Then, the next important parameter that had to be considered was to correctly interprete such results. More
detailed information on interactions, spontaneous imbibition and coreflood tests will be provided below.

Crude Oil

Rock
Injected
Water

Formation
Water

Figure 2. Variables dictating or affecting original reservoir conditions.

Effects of Fluids/Rock Interactions- One important consideration in the selection of a water composition for EOR in
carbonates reservoirs, is the compatibility between the injection and formation brine. Formation water of carbonates
reservoirs contains high concentrations of calcium and magnesium, even SO 42-, potential determining ions for wettability
changes (Austad et al., 2005-2007; Puntervold et al., 2009; RezaeiDoust et al., 2009; Shariatpanahi et al., 2010; Tweheyo et
al., 2006; Zhang et al., 2007). Seawater, in contact with formation water, may cause damage to the formation; even more, in
contact with the rock surface this damage can also happen. Recently, we (Gachuz et al. 2013) examined brines in contact with
crude oils. The study revealed that the viscosity of the crude oils changed in contact with brine when crude oils/brines were
shaken or simply by static contact. Therefore, an evaluation of the extent of interactions between crude oil and brine was
performed before starting a coreflood experiment.

SPE-171120-MS

a) Formation Water/ Injection Water Interaction- As we know, some salts show an uncommon bahaviour and
become less soluble in water as the temperature increases (Carlberg et al., 1973; Li et al., 1995). Figure 3 presents a
case where seawater was mixed with formation water resulting in salt precipitation (CaSO4). For our experiments,
we verified the compatibility between formation brine and injected or imbibing brine. There was no precipitation
under different volume fractions neither at 20 oC nor 92 oC. We concluded that the low salinity waters and seawater
would not cause any precipitation in contact with the formation brine.

Figure 3. Salt crystals formation at high temperature.

b) Crude Oil/Injection Water Interaction.- The procedure described by Gachuz et al. (2013) was used at tests
temperature. The crude oil showed changes in its viscosity, density, water content and pH values. For instance, the
crude oil viscosity decreased when it came in contact with the NW brine at dynamic conditions (samples were
shaken) but when the conditions were static, the viscosity increased (up to 68, 377 cp), see Table 5. For this last
case, the water content is considerably higher in comparison with the original crude oils water content. The
analyses of the water also indicated variations of its pH showing more acidic conditions and its effluents also
reported variations of the ions. In addition, the metal and sulphur content analysis revealed that some metals content
were lower for the crude oil contacted by NW brine. Na+, K+ and S2- turned out to be more active. It was evident that
crude oil was undergoing alteration in its structure when was put in contact with injection brines. Although this
simple evaluation has not revealed a pattern in the results, we presume that temperature had a large effect on the
interactions between crude oil and brine even when the fluids were in static conditions. Similar observations were
made when LSSW10 brine was in contact with the crude oil at tests temperature. The oil viscosity increased; pH and
oil density dropped and water content increased dramatically. When crude oils and brines were shaken together, a lot
of small droplets of water would form and remain suspended in the crude oil. These droplets would last for some
time but eventually would go back to the state of two separate phases. Nevertheless, some water droplets stayed
suspended in the crude oil (high amount of water). The water was retained by two main mechanisms described by
Fingas and Fieldhouse (2012): 1) chemically by asphaltenes and resins and 2) by viscous retention of water droplets.
The phenomenon of ions exchange between the crude oil and brines is not completely clear, however, on the basis of
these analyses; the crude oil/brine interactions have a large effect even no movement of the fluids.

Table 5. Oil viscosity values for crude oil A in contact with two brines.
Viscosity
Oil Viscosity
System

Oil Density
Reduction

(cp)

( API)

Water Content
pH
(ppm)

(%)
Crude oil A

53,484.31

14.12

208.40

Crude oil A/NW*

36,314.00

32.10

12.36

6.6

10,795.10

Crude oil A/NW**

68,377.13

11.81

4.7

1,151.57

Crude oil A/LSSW10*

66,660.54

11.76

3.7

51,218.2

*Shaking.
**Static condition.

SPE-171120-MS

c) Injected Water/ Rock Interaction.-The process of solid precipitation is not limited to water/water interactions; it
can also be caused by incompatibility between injected water and rock mineralogy. The precipitation may reduce the
permeability considerably; therefore, injectivity may be reduced. Before running an experiment, cores were first
fully saturated with formation brine. Then the brine permeability was obtained. Later, the cores were cleaned with
toluene and methanol and then once again they were saturated with either seawater or low salinity brine and
permeability was measured. In general, there were no changes in the cores permeability. The variations were not
significant. The results determined that mixing seawater and low salinity brines would not cause any major damage
to the rock. The effluents samples were analised for all ions and some results are present in the Figures 4 and 5. The
solid lines are the original concentrations in the prepared brine.

Figure 4. Variations of potential determining ions at laboratory conditions.

Figure 5. Variations of secondary ions at laboratory conditions.

For limestones cores, samples from effluent were taken when the core was saturated with formation water. The
analyses of the effluents revealed that some ions were released such as sulphur and also small amounts of chloride
and sodium. The Ca2+ decreased its concentration in the brine. In addition, Al 3+ and Fe3+ ions were also present in
the effluent. Although the mineralogy analyses did not show presence of ions cited before, effluent water samples
collected and analysed mainly detected that the concentrations exceed the original values in the original water; this
indicated that the source of these ions was dissolution or release from the rock surface. Later, it was confirmed that
all the limestone cores had traces of anhydrite. For the dolomite cores, they turned out to be more active with
potassium and chloride; even these elements were not present in the mineralogy evaluation. The concentration levels
for sulphur and magnesium sometimes stayed constant. Sulphur or magnesium did not show a pattern, for instance, a

SPE-171120-MS

dolomite core exposed to formation brine did reveal a significant loss of calcium and at the same time a considerable
amount of S2- and Mg2+ was produced. Note that every experiment was evaluated separately in function of each
element. Therefore, the chemical analyses of the effluent confirmed the presence of S 2-.
d) pH Changes.-the pH of a solution can change due to some factors that could mainly affect its value such as ionic
strength of solution or temperature changes. There are some chemical that can rise or lower pH. Lime, sodium
bicarbonate, calcium hypochlorite, sodium hypochloride or others increase the pH of the solution. Sulfuric acid,
carbon dioxide and sodium hydroxide are examples of chemicals decreasing pH. The pH of various effluents was
also analysed. The pH of the produced water for the cores when they were saturated with formation water remained
close to 8.0 indicating a chemical equilibrium between the injected formation water and the core surface. The
effect of bicarbonate into the brine was also tested. When the brine permeability was measured with formation
water, some cores were newly saturated with formation water without bicarbonate, pH= 6.3. For these cases, the pH
from the effluents rose to ~ 7.12 (limestone cores). Similar results were for dolomite cores from an initial value of
~6.3 to ~7.6 also saturated with formation brine without bicarbonate. It appears to be that the pH change is
presumably because of rock dissolution. Thus, the jump of the pH values is a result of dissolution of the core. It is
important to mention that it was not possible to detect the bicarbonate concentration coming from the cores
throughout the ion chromatographs analysis.
Spontaneous Imbibition Tests-As we know, the recovery of oil by spontaneous imbibition (SI) from fractured reservoirs is
of relevant importance, especially when the matrix has low permeability and can relatively be a slow process and then timedependent. Spontaneous imbibition experiments were performed using both limestone and dolomite cores with initial water
saturation. The cores were initially saturated with synthetic formation water. A water saturation (Sw) was stablished and then
the cores were aged and flooded with fresh crude oil at different times for 20 days. The cores were placed in a typical Amott
Cell using two different imbibing fluids, seawater and normal brine at 92 oC. The oil production by spontaneous imbibition
was constantly monitored. Expelled oil that was still attached to the cores was removed as much as possible by gently
shaking the cell. After a while, oil recovery was measured. Once the production stopped, oil and brine were taken out and
centrifuged. Brines samples were then taken to be analysed. Tests are listed in Table 6.
Coreflood Experiments-In this serie of coreflood experiments, the working temperature was kept and a high overburden
pressure was applied. In addition, a back pressure was used to maintain the pressure of the core outlet and deliver the
produced liquids at atmospheric pressure. The orientation of the cores was horizontal. Effluents and oil were first collected
and centrifuged and then the separated water analysed for ion concentrations. The pH of the effluents was also measured. As
the SI experiments, coreflood tests followed the same procedure for getting similar conditions up to get aging time. All
coreflood experiments are also indicated in Table 6.
Table 6. Summary of Tests.
Injected Smart
Fluid
(Secondary
Process)

Injected Smart
Fluid
(Tertiary
Process)

Coreflood

Seawater

32.13

Coreflood

Seawater

Normal Brine
Low Salinity
Seawater 10

32.13

Coreflood

32.13

Coreflood

Sw
(%)

Experiment

Used
Smart Fluid

Limestone 1
Limestone 2
Limestone 3
Dolomite 1
Dolomite 2
Limestone 4

41.17
28.78
41.57
36.89
34.30
33.95

Spontaneous Imbibition
Spontaneous Imbibition
Spontaneous Imbibition
Spontaneous Imbibition
Spontaneous Imbibition
Spontaneous Imbibition

Seawater
Seawater
Seawater
Seawater
Seawater
Normal Brine

Limestone 5

28.30

Core

Limestone 6

Low Salinity
Seawater 10
Low Salinity
Seawater 10

Seawater
Low Salinity
Seawater 50

SPE-171120-MS

Results and Discussions

SI Experiments
Five SI tests were performed. The results are shown in Figure 6. Limestones core surrounded by brines showed rises of
15.38, 16.47 and 15.31 %. In general, these cores indicated the same oil recovery roughly. It seems to be that the highest
permeability cores yielded the fastest recovery at early time. The experiment with lower permeability core was stopped due to
unexpected problems but oil was still slowly produced from the core at that point so we could have expected additional oil
volume. It was of great interest to check the impact of smart fluids against other possible carbonate cores. The fourth and
fifth experiments were conducted using dolomites cores. Seawater was used as smart water (imbibing fluid). The fourth
experiment recovered around 14 % of OOIP, however, the oil recovery was lower than that obtained from the fifth
experiment. This core recovered around 30 %. It seemed that the oil recovery was governed by the permeability when the
dolomite rock was used, hovewer, in the case of limestones the trend was different. The best oil recovery was observed at the
highest permeabilities and not at the lowest values.
When the limestones and dolomites cases for almost the same dimensions are compared, it was observed that faster
recoveries were obtained with dolomite samples. For limestone cores, the process of imbibition took more time than
expected. It is evident that oil production at early stages is better. Figure 7 ilustrates the picture of the imbibition experiments
with both types of rock. The upper faces of the cores revealed accumulation of oil in larger drops, as well as that oil was
expelled from the sides of the cores. In general, the oil drops covered the whole core except for the areas where the surface
was more compact.

Spontaneous Imbibition Experiments

92 oC
40

Oil Recovery (%)

35
30
25
20
15

10
5
0
0

10

15

20

25

30

35

40

45

50

Time (Days)
Limestone 1 (6 mD)

Limestone 2 (19.51 mD)

Limestone 3 (51.80 mD)

Dolomite 1 (194.32 mD)

Dolomite 2(345 mD)

Figure 6. Effect of seawater as smart water on spontaneous imbibiton test with different cores at high temperature.

The cores showed a favourable response to seawater and the recovery difference between limestone and dolomite samples
can be attributed to their structures and heterogeneities. It was also conducted an additional imbibition experiment (limestone
core) by directly using NW removing from the brine the active ions, especially sulphate and magnesium. After 15 days, its
recovery was 16.5 % which is slightly higher that the oil recovery by seawater in limestones.

10

SPE-171120-MS

Figure 7. Cores producing oil in contact with seawater. Limestone core (left side) and dolomite core (right side).

To monitor a possible interchange of ions during the SI tests, samples of the brines were collected and analysed before and
after the contact with the cores. Original composition and composition at the end of the tests for limestones cores are
presented in Figure 8. Some ions suffered variations such as calcium, sulphur, chloride and sodium. For the experiments
using seawater as smart fluid, the variation of the concentrations was unremarkable for magnesium and chloride, except the
calcium where a rise was more notorious. These variations may be related to the imbibing fluid/rock interaction. The analysis
also reported small variations of sulphur and sodium. Previously, in the effects of fluid/rock interactions section, a rise of the
sulphur during the saturation with formation water was detected and turned out to be important for the anhydrite detection.
This firstly meant that there possibly was dissolution of the rock, removing with the water saturation part of the rock
components. Now, the concentration profile has also changed but in a different scenario for the sulphur at least with seawater
as an imbibing fluid, which could be viewed as almost contradictory. Previous experiments (Austad et al., 2005-2007; Fathi
et al., 2011; RezaeiDoust et al., 2009; Tweheyo et al., 2006) have indicated that the sulphur, calcium and magnesium have
been more active at high temperatures. Those systematic observations have allowed us to confirm that the cores released
additional amounts of calcium but the sulphur remained more reactive with the cores at 92 oC. When NW was used as an
imbibing fluid, small concentrations of sulphur were detected for the imbibing fluid after the imbibition process.

Figure 8. Changes in concentrations of ions when two different waters were used through limestone cores.

As a part of the project of research, a new spontaneous imbibition cell was manufactured in-house to facilitate more
experiments. The objectives of this whole setup are to measure, collect, monitor and record the oil production by spontaneous
imbibition tests from a core at reservoir conditions (up to 200 oC and 10,000 psi). A new series of experiments are being
developed using this setup in order to validate and observe changes concerning pressure, temperature and different imbibing
fluids. The results and more details of this new apparatus will be published soon.

SPE-171120-MS

11

Coreflood Tests
Four tests were carried out. In all of them when the oil production stopped, a change of the injection rate was applied to make
sure that there was no more mobile oil. The oil volume (expressed as a percentage of the original oil in place) was measured
as a function of pore volume injected. The experiments confirmed additional oil recovery when smarts fluids were injected in
both secondary and tertiary mode. Each test had an additional coreflood experiment in order to evaluate repeatability of the
results. They were consistent with the first estimations.
First Coreflood Experiment.-In the first injection cycle, the core was flooded with seawater. In this case, the total amount
of oil was 37.65 % OOIP (Figure 9). The effluents were completely analysed for calcium, magnesium, sulphur, chloride,
sodium, and potassium and possible traces of strontium, iron, silicon and aluminium. The results exhibited that the
concentration of Ca2+ increased whilst the Mg2+ and S2- dropped in the effluents. Chloride, potassium and sodium remained
stable. Minimum traces of others ions were not relevant. These outcomes are in line with studies in SI tests. The recovery
factor with normal brine was lower. 1.83 % of oil was recovered under this method. It appeared that the core was not affected
anymore by normal brine. We analysed the impact of the oil recovery based on the pH and the variation of the effluents.
Nevertheless, the pH did not show a perceptible change. In general, the calcium remained stable in its rise during the whole
experiment. Both effluents and pH for the tertiary program were not analysed.
Second Coreflood Experiment.-For the second coreflood experiment, synthetic seawater first was also injected as a
secondary process and low salinity seawater for a tertiary process. The total recovery factor was 52.09 %, 36.81 % using
seawater and 15.28 % with LSSW10. It appeared that LSSW10 worked much better in comparison with NW for the first
coreflood experiment. The pH of the effluent also was measured at regular intervals after the effluents were collected. The
values are indicated in the Figure 9. The pH values stayed constant during the rest of the injection with seawater. It is also
interesting to observe that for the tertiary program, the pH values increased gradually up to 7.4. The increase of oil recovery
by LSSW can not be attributed to this perceptible change in pH.
The concentration profiles of S2-, Mg2+ and Ca2+in the effluent suffered variations. For instance, S2-and Mg2+ decreased its
concentrations a little, however, there was a constant production of Ca2+ during all the experimental seawater injection, see
Figure 10. Mg2+ and S2- decreased as Ca2+ increased. The broken lines are the ions analysed from the effluent. This result is
consistent with previous coreflood test (first experiment) where the same ions had similar trends. Zhang et al. reported (2007)
an increase in the effluent calcium concentration during seawater experiment at high temperatures. This reaction was
interpreted as a result of substitution of certain ions on the internal rock surface. In such a case, our results may confirm this
kind of substitution of ions as well. When the cores were saturated with FW at 20 oC, sulphur was gained and calcium was
retained, see Figure 4. Either injecting or imbibing SW at high temperature, the influence becomes more pronounced (Figures
8 and 10) and this represents one explanation to the effect attributed to the reactivity of key ions that have the capability of
improving oil recovery. Therefore, S2-, Mg2+and Ca2+ turned out to be more reactive with cores at high temperature.

Figure 9. Oil Recovery and pH versus pore volumes of injected fluids during both secondary and tertiary programs.

12

SPE-171120-MS

Figure 10. Changes in concentrations of ions when flooding seawater through the limestone core 6 at 92 oC.

For the second part of the experiment, the behaviour of the concentrations changed (tertiary injection). The ions
concentrations in the beginning of the LSSW injection were higher than injected and this meant that effluents of the first pore
volumes appeared to have a mix of brines, seawater and low salinity seawater. Later, calcium and sulphur was slightly higher
than injected concentrations (Figure 11), in contrast, the magnesium, chloride and sodium concentrations stayed constant.
The potassium was without changes throughout the whole experiment. As we have described; during the course of the
injection pH was monitored in the effluents. In this experiment a pH increase occurred for the tertiary process.

Figure 11. Changes in concentrations of ions when flooding low salinity seawater through the limestone core 6 at 92 oC.

Third Corflood Experiment.-Another coreflood experiment was conducted at 92 oC reusing the previous core. For this
experiment, a diluted version of seawater was also flooded as a secondary process. The LSSW injection resulted in the final
recovery of 62.91 % OOIP. After the LSSW10 injection, seawater was injected but did not result in significant production,
Figure 12. Once again, the pH had variations for both processes. On the one hand, the pH increased from ~7.2 to ~7.7 for the
first period. Oil was not observed when the injection rate was increased. After switching to seawater, pH kept about 7.6 due
to the difference in the concentration of ions between LSSW10 and SW. No extra oil was recovered after SW injection. In
both experiments with the same core, the response in the growth in pH during the secondary processes may be caused by the
reaction between the rock and the composition of the injected brine. Effluents were collected for ion analysis. The
equilibrium was assumed to be reached when the effluents pH and ionic composition got at least 5 pore volumes. When no
more oil was produced by LSSW injection, pH stabilised whereas ions concentrations had curious variations composed of
irregular increases and decreases.
Flooding the core with low salinity seawater concentrations of the potential determining ions indicated possibly liberation of
such ions. Figure 13 depicts results where certain ions suffered variations in the concentrations with the same core injecting
low salinity seawater as a secondary process. Magnesium became constant and sulphur became slightly higher that the
original value. Calcium increased at least two more times its concentrations in the effluent. Potassium concentration kept
more or less stable up to 13 pore volumes injected but then made a significant recovery, Figure 13b. The variation continued
for more than 5 pore volumes and could indicate for this case with low salinity seawater that these two ions is being released
by the core and specially the potassium is active for LSSW10 as secondary water. From 13 to 20.6 pore volume injected no
more oil production was gained for this experiment under secondary method, however, important ion changes were detected.

SPE-171120-MS

13

One could generalize that such a variation of ions concentrations in the effluents did not yield extra oil under low salinity
injection. This generalization may be adapted as a working hypothesis for coming experiments.

Figure 12. Cumulative oil recovery at two stages of injection with smart waters.

Figure 13. Variations in ions concentrations during low salinitiy water injection.

Fourth Coreflood Experiment.-In order to validate the outcomings, the third experiment was repetead. The LSSW10
injection was turning out to be as the previous behaviour. During the injection, we had to stop the injection for a while
because of problems with pumps. We had a soak period that lasted 24 hours approximately (at 13.5 injected pore volume).
Later, the injection continued. Unexpected volume of oil was recovered during this time. This event is more clearly illustred
in Figure 14. We did not expect to get this change. This close could have created a new oil bank. Oil production increased
from 61.72 to 67.98 % of OOIP. A rise of the rate was applied to make sure that there was more mobile oil. A new close was
applied in order to validate the new findings. No extra oil was recovered. The pH of the LSSW10 started around 7 and
increased gradually to stabilize at approximately 7.8. Effluents were also taken and they were analysed. Based on Middle
East results (Yousef et al., 2010-2011-2012), a second diluted version of seawater was considered for the tertiary program.
This new version had 50 times less salt concentrations. It did not result in significant production. Once again, the pH had
variations. On the one hand, the pH increased from ~6.7 to ~7.9. The pH did not increase when we modified the rate of

14

SPE-171120-MS

injection. Oil was not observed during these variations. On the other hand, after switching to LSSW diluted 50 times, some
extra oil was recovered after injection of this new brine, ~1 % of OOIP.

Figure 14. Recovery oil vs pore volume for the fourth experiment.

Figure 15. Presence of more ion concentrations in effluents for limestone 6.

SPE-171120-MS

15

Figures 15 describe the variations in ions concentrations for this experiment. For magnesium and sulphur, no major variations
on the concentrations occurred. Calcium rose at 2 times the original concentration and then maintained stable at those values.
It may be seen that potassium rose from 5 to 20 pore volume injected then dropped off and reached low values. The core
exposed to LSSW50 injection did indicate loss of potassium from the brine at the same time an amount of calcium was
produced by the core, Figure 16.

Figure 16.Chemical analysis results for Ca2+ and K+ in effluents for limestone6 flooded with LSSW50.

Remarks
Three experiments performed at 92 oC using the same core, confirmed additional oil recovery when low salinity water was
injected in both secondary and tertiary modes, Figure 17. An additional recovery of 15.28 % was obtained when low salinity
seawater was injected after seawater. pH and specific ions (calcium and potassium) concentration were higher than the
original values during secondary LSSW injection. A summary of the results is presented in the Table 7.

Figure 17. Final recovery factors for the limestone 6 with different scenarios of injection.

16

SPE-171120-MS

Table 7. Results for smart water injection program in the limestone core 6.

Process

Fluid

First
Experiment

Fluid

Second
Experiment

Secondary Process

Seawater

36.81 %

Low Salinity
Seawater

62.91 %

Tertiary Process

Low Salinity
Seawater

15.28 %

Seawater

0.74 %

Fluid
Low Salinity
Seawater
Low Salinity
Seawater (50)

Third
Experiment
67.98 %
1.10 %

The most significant observations from this work are that injection of diluted seawater into carbonate rocks brought about
significant additional oil recovery up to 65 % of OOIP in secondary mode. This result clearly demonstrates the substantial
potential of a properly designed low salinity seawater and seawater injection in recovering significant additional oil from
heavy oil carbonate reservoirs. This result is significant as it indicates that low salinity water injection can potentially be a
lower cost alternative for other oil recovery processes used for heavy oil recovery such as thermal methods, gas injection or
variations of them (Adibhatla et al., 2006; Gupta et al., 2007-2009; Han et al., 2011; Weiss et al., 2007).

Conclusions
The explotation of heavy and extra-heavy oil resources has so far been minimal and more work still need to be done. Our
goal in this work is to motivate further research into exploring potentials of smart water injection for as a cost effective
alternative oil recovery technique for heavy and extra-heavy oil recovery. The following conclusions can be drawn from this
study:

Smart water injection has so far been mainly considered for light oil reservoirs, but our results reveal that it may also
have significant potential for improving recovery from extra-heavy and heavy oil carbonate reservoirs.
The results of the experiments performed in this work with smart water have demonstrated that substantial
additional amount of oil can be obtained under secondary as well as tertiary injection.
An important observation to be highlighted is the additional oil recovery reported from a soak period which
represented around 8 %. The shut-in period led to bigger contact time between the injected fluid and the core
allowing the water to act through unswept zones for longer time expelling oil from the rock matrix into the channels.
Fluid analysis showed changes occurred in the concentrations of certain ions which caused a possible change of
wettability producing more oil.
Rock/fluids interaction evaluations revealed that there was no a direct relationship between pH increase and
additional recovery as it had been pointed out for low salinity water injection. For carbonate rocks, an increase of pH
is originated by the brine/rock interaction not by brine/rock/oil interaction.

Acknowledgements
The authors acknowledge the financial support for this project provided by the National Council for Science and Technology
and the Ministry of Energy of Mexico (Conacyt-SENER-Hidrocarburos). Acknowledgement is extended to Lorraine Boak
and Wendy Mcewan for their support and help with ICP analysis. Special thanks to Amir Farzaneh for helpful discussions.

SPE-171120-MS

17

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