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Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
34
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Effects of Low Salinity Water Ion Composition on Wettability
Alteration in Sandstone Reservoir Rock: A Laboratory
Investigation
Abdolmohsen Shabib-Asl* Mohammed Abdalla Ayoub Mohammed Massoud Kermanioryani
Pedro Paulo Jose Valentim
Department of Petroleum Engineering, Faculty of Geoscience and Petroleum Engineering, Universiti Teknologi
PETRONAS (UTP), Bandar Seri Iskandar, 31750, Tronoh, Perak, MALAYSIA.
*Email address of corresponding author: msn.shabib@gmail.com
Abstract
For various decades, water-flooding mechanisms have been playing important role for improving oil recovery. It
was not until recently that researchers discovered that the ionic strength of the brine was substantial. With regard
to this, many studies started being published which focused more on the comparison of effects of having high
ionic strength and low ionic strength for brine during flooding processes. Low salinity water comprises brine
concentration below 5000ppm. At optimum concentration, low salinity water (LSW) when injected into the
reservoir enhances the oil recovery considerably. This is attributed to the change of reservoir rock wettability.
The process governing these changes are not well understood thus requiring a scrupulous investigation.
Moreover there is no a certain fixed salinity range. This study investigates wettability alteration of Berea
sandstone rock with brine of different ion composition (NaCl, KCl, MgCl2, CaCl2, and formation water-mostly
Mg2+
and Ca2+
ions) and strength (500ppm-6500ppm with exception of formation water which consisted of
13000ppm). For the study, (31) core slabs were extracted from the core plug then saturated with formation water
(FW). Next, the slabs underwent aging process in crude oil at ambient pressure and a temperature of 800
c. Later,
the slabs were removed and immersed in containers with low salinity water at different ionic composition and
strength, which is mentioned. The wettability was measured by applying the sessile drop method in certain range
of time. According to the results, there have been significantly great change of wettability at Low salinity water
in case of KCl was observed.
Keywords: ionic strength, wettability, low salinity water, saturation, brine composition
1. Introduction
In the last two decades, the level of investigation into low salinity water flooding has sharply increased. Nasralla
et al. 2011, by conducting injection studies with deionized water and seawater, demonstrated that former
improved oil recovery significantly rather than later. With the purpose of enhancing oil recovery, low salinity
water (LSW) with adequate composition and salinity is injected into the reservoir, which changes the wetting
properties of the reservoir rock into that favoring oil recovery (Tang and Morrow (1999) and McGuire et al.
(2005)). Lager et al. (2007) in their studies, demonstrated that the effects of low salinity water are linearly
proportional to the amount of clay minerals in the rock. There are many theories regarding the mechanisms of
wettability alteration in presence of low salinity water. Ligthelm et al. (2009) proposed the double layer effect.
They suggested that the application of low salinity water results in an expansion of the ionic electrical double
layer between the clay and the oil interfaces. This causes the oil to be desorbed from the rock surface thus
increasing the water wetness. Another mechanism is that proposed by Tang and Morrow (1996) which attributes
wettability changes by decrease in ion binding as microscopic mechanism.
The wettability of the reservoir rock plays an important role in the determination of residual oil saturation and
recovery efficiency during the Low salinity water flooding process. Rock wettability can be indicated by using
contact angle technique which is measured by several methods such as sessile drop method and Zeta potential.
Fanchi et al.,2010 classified the wettability, in terms of contact angle, as per below.
Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
35
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Table 1. wettability classification according to Fanchi et al.,2010
Wetting conditions for a water-oil system
Wetting Condition Contact Angle [degrees]
Strongly water-wet 0-30
Moderately water-wet 30-75
Neutrally wet 75-105
Moderately oil-wet 105-150
Strongly oil-wet 150-180
The injection of low salinity water(<1500ppm) has revealed to improve oil recovery up to 16% of Reserves
initially in Place (OOIP) (Zhang et al. 2007). Many Researchers have been more focused on comparative studies
between the low and high salinity water, It has been verified that most of them were effective at brine
concentration below 5000ppm (Tang and Morrow (1999), Mc Guire et al. (2005), Wideroee et al. (2010), Ramez
et al, (2011)).
Wang and Gupta (1995) when investigating the effect of temperature and pressure on wettability, made
important observation in that contact angle was not sensitive to pressure changes whereas remarkable changes in
wettability were experienced with temperature for the crude-oil/brine/quartz system. Another study that supports
change in wettability due to change in temperature was presented by Ramez et al, (2011) who noticed that low
salinity water decreased significantly the contact angle as compared to high salinity water. Furthermore, they
also concluded that temperature changes affected greatly on contact angle alteration. In addition, the authors
suggested that low salinity water injection is potential for improving oil recovery in various ranges of reservoir
temperature.
This study investigates the wettability alteration of Berea sandstone rock with brine of different ion composition
and salinity in order to understand which ion composition is more effective during LSW flooding.
2. Materials and Methods
2.1 Materials
2.1.1 Cores
In this experiment Berea sandstone core was used. The core was received from the KOCUREK Company (USA)
with the properties that are shown in the table 2. It is around 50 years ago that the Berea sandstone rock has been
employed for experimental work due to its homogeneity and petro-physical properties. The mineralogy of the
rock is presented in the table3.
Tale 2: Properties of core
Product ID A-101
Formation Kipton
Permeability 100mD- Brine permeability
Porosity 20%
UCS 6,500-8,000 psi
Dimension 1.5 inch D * 12 inch L
Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
36
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Table 3: Mineralogy of Sandstone Rock
Properties SiO2
(Silica)
Al2O3
(Alumina)
FeO/Fe2O3
(Iron Oxide)
TiO2
(Titanium Oxide)
CaO
(Calcium Oxide)
MgO
(Magnesium Oxide)
Alkalies H2O
(water)
Undetermined Total
% 86.47 7.31 1.14 0.70 1.21 0.11 1.65 1.20 0.21 100
Figure 1: Sandstone Rock before and after cutting
2.1.3 Crude Oil
The oil must contain polar components, which are naturally occurring surface-active agents, like acids, and
bases, which can change the wettability. No effect has been observed by the use of oil free from polar
components. The acid number (AN) is another important component. It is defined as the amount of potassium
hydroxide (KOH) in milligrams, required for neutralizing 1 g of the petroleum acid in the crude oil, and
reversely, the base number (BN) is defined as the amount of KOH in milligrams, required neutralizing 1 g of the
petroleum base (Green & Willhite, 1998). When water is present, the oil and rock surfaces become charged.
Their polar components behave as acids and bases by giving up a proton and becoming negatively charged, and
gaining a proton and becoming positively charged, respectively (Buckley and Liu, 1998). These surface charges
influence the adsorption behavior and thus wettability during injection of smart water.
In this, research the crude oil with the following properties used
Table 4: properties of the crude oil
TAN (mgKOH/g) TBN (mgKOH/g) Density (g/cm3
)
0.667 0.146 0.821
2.1.2 Brine
In this research, two types of brine were employed
o Formation Water termed “FW” was used for establishing initial and connate water saturations. It was
composed of the following ions (Ca2+
, Na+
, Mg2+
, Cl-
, K+
, HCO3
-
,SO4
2-
).
o Low Salinity Water abbreviated “LSW” was prepared with distilled water that contained the (Ca2+
, Na+
,
Mg2+
, Cl-
) with different TDS and concentration.
All Salts were received from the AVANTIS Company (Ipoh, Malaysia). Properties and concentration of all
brines shown in table 5.
Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
37
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Table 5: brine composition and concentration
Composition Na+
Ca2+
Mg2+
K+
HCO3
-
SO4
2-
Cl-
TDS
Name (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
LSW-1 196.7 0 0 0 0 0 303.3 500
LSW-2 393.4 0 0 0 0 0 606.6 1000
LSW-3 983.5 0 0 0 0 0 1516.5 2500
LSW-4 1376.8 0 0 0 0 0 2123.2 3500
LSW-5 1770.3 0 0 0 0 0 2729.7 4500
LSW-6 2557.1 0 0 0 0 0 3942.9 6500
LSW-7 0 180.6 0 0 0 0 319.4 500
LSW-8 0 361.2 0 0 0 0 638.8 1000
LSW-9 0 903 0 0 0 0 1597 2500
LSW-10 0 1264 0 0 0 0 2236 3500
LSW-11 0 1625 0 0 0 0 2875 4500
LSW-12 0 2347 0 0 0 0 4153 6500
LSW-13 0 0 127.6 0 0 0 372.4 500
LSW-14 0 0 255.3 0 0 0 744.7 1000
LSW-15 0 0 638 0 0 0 1862 2500
LSW-16 0 0 893 0 0 0 2607 3500
LSW-17 0 0 1149 0 0 0 3351 4500
LSW-18 0 0 1659 0 0 0 4841 6500
LSW-19 0 0 0 262.2 0 0 237.8 500
LSW-20 0 0 0 524.4 0 0 475.6 1000
LSW-21 0 0 0 1311 0 0 1189 2500
LSW-22 0 0 0 1835.4 0 0 1664.6 3500
LSW-23 0 0 0 2359.8 0 0 2140.2 4500
LSW-24 0 0 0 3408.6 0 0 3091.4 6500
LSW-25 19.7 18.1 12.8 183.5 0 0 265.9 500
LSW-26 39.4 36.2 178.6 52.4 0 0 693.4 1000
LSW-27 98.6 632 63.8 131.1 0 0 1574.5 2500
LSW-28 965.3 126.4 89.3 183.5 0 0 2135.5 3500
LSW-29 88.8 731.3 516.8 118 0 0 3045.1 4500
LSW-30 511.5 821.6 580.6 341 0 0 4245.3 6500
FW 5923.4 18310.1 12941.3 6818.2 472.2 1318.6 84216.2 130000
2.2 Methodology
Figure 2 shows a schematic drawing of the experimental procedure for wettability measurement. In this
investigation, the sessile drop method was used to check the wettability alteration via contact angle
measurement. The rock slabs were cut and polished into 3 to 5 mm thin slices. The surfaces of the slices were
cleaned with toluene, and dried at 105°C for 24 hours. All slabs were Saturated with formation water (FW) by
using the vacuum pump for 2 to 4 hours until no gas bubbles were exiting the core slabs and were put on the
oven at temperature of 80 °C for 72 hours. All slabs were removed from FW and aged with Crude oil at an
elevated temperature of 80 °C on the oven for about 3 days. Photos were taken from the slabs by using IFT 700
equipment (fig.3) in order to check the wettability condition of each slab before using Low Salinity Water. All
slabs were removed from oil and aged with Low Salinity Water (LSW1-30) and Formation Water (FW) at an
elevated temperature 80 °C on the oven. To check the wettability alteration it is important to take a photo in
specified times of 0, 6, 12 and 24 hours.
Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
38
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Figure 2: schematic drawing of the experimental procedure for wettability measurement
Figure 3: IFT 700 equipment
3. Results and Discussion
The results are presented in form of graphs and contact angle portraits. Figure 4 depicts Contact angle changes in
presence of formation water, MgCl2 and KCl. Considerable changes in contact angle are verified for KCl brine
composition as compared to MgCl2 both at 500ppm concentration. There is no significant changes in contact
angle when in presence of formation water.
Formation Water (FW-130000ppm)
LSW-13(MgCl2-500ppm) LSW-19(KCl-500ppm)
Figure 4: contact angle changes in presence of formation water, MgCl2 and KCl. (There are many more
depictions for contact angle changes at other concentrations and compositions, however for the purpose of this
study only the best, least and the constant changes were chosen at 500ppm.)
The preceding results are further discussed from the graphs of figure 5 through 9. For the NaCl Composition,
figure 5 illustrates that there are changes in contact angle with time for each NaCl brine concentration. From the
figure, it is patent that the contact angle is decreasing with time. Significant changes are experienced at brine
concentration ranging from LSW-1 to LSW-6 with that of formation water remaining constant. Large changes in
contact angle are at NaCl concentrations of 500ppm and 1000ppm whereby remarkable decrease of contact angle
from 1120
to 730
is verified. For KCl brine composition figure 6, there is sufficiently great changes in contact
angle with time, from 1120
to 62.230
.Relevant changes are noticed for LSW-19 through LSW-24 whereas that of
formation water remains constant.
Initial Saturation
With FW
Cutting the Cores
into 31 slabs
Saturation
With Crude Oil
Saturation with
LSW1 to LSW30
Saturation
With FW
Take
Photos
Take
Photos Resul
t
Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
39
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Figure 5 NaCl Brine composition
Figure 6 KCl brine composition
Figure 7 is representative of contact angle changes for MgCl2 composition. Here, almost same trends as of
foregoing paragraphs are noticed, that is, contact angle decreases with time and distinguishable changes are
detected for LSW-13 through LSW-18 and that of formation water undergoing negligible changes. The contact
angle changed from around 1120
to 850
, which is at lower range than both NaCl and KCl brine compositions.
Figure 8 is illustrative of trends for contact angle change when in presence of CaCl2 brine composition. Here, the
contact angle decreases with time for each concentration. Notable changes are for LSW-7 through LSW-12 brine
concentrations and that of formation brine experiencing no changes. Ideal change in contact angle is experienced
at brine concentration of 500ppm and 1000ppm (from 1120
to 780
). Finally, when all the brine compositions are
mixed, still noticeable changes are present, nevertheless in small range (from 1120
to 750
) figure 9. Moreover,
greatest changes in wettability are seen at concentrations of the monovalent ions.
Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
40
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Figure 7 MgCl2 brine composition
Figure 8 CaCl2 brine composition
Figure 9 Mixed brine composition
Journal of Natural Sciences Research www.iiste.org
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.4, No.13, 2014 – Special Issue
41
Selection and peer review by the scientific conference committee under responsibility of the Australian Society
for Commerce, Industry and Engineering
Overall, outstanding results are noticed for KCl brine composition whereby the contact angle has changed from
1120
to 62.230
at concentrations of 500ppm and 1000ppm followed by NaCl brine composition from 1120
to 730
and finally by the Mixture of all brine compositions which caused changes from 1120
to 750
.
4. Conclusion
This study investigated the wettability alteration of Berea sandstone rock with brine of different ion composition
and salinity. The experimental results revealed that much change of wettability was experienced by the low
salinity water composition of monovalent ion K+
(from 1120
to 62.230
) as compared to other ion compositions
such as the monovalent ion of sodium( Na+
), divalent ions (Ca+2
and Mg+2
) at concentration of 500ppm and
formation water at 130000ppm.
Acknowledgements
I would like to acknowledge the supports that I received form Universiti Teknologi PETRONAS. In addition, I
would like to thank Associate Professor Dr. Ismail Bin Mohd Saaid Head of Petroleum Engineering Department
at Universiti Teknologi PETRONAS for valuable discussions.
References
Fanchi, J.R., 2010. Integrated reservoir asset management: principles and best practices. Elsevier Gulf
Professional Publishing, Amsterdam, Burlington, Mass.
Green D.W. and Willhite G.P.:, "Enhanced Oil Recovery", SPE Text Book Series vol. 6, 1998.
Lager, A.; Webb, K. J.; Black, C.J.J. Impact of brine chemistry on oil recovery. Paper A24 presented at the 14th
European Symposium on Improved Oil Recovery, Cairo, Egypt, 2007.
Ligthelm, D.J., Gronsveld, J., Hofman, J.P., Brussee, N.J., Marcelis, F. and van der Linde,
H.A., 2009. Novel waterflooding strategy by manipulation of injection brine composition. Paper SPE 119835
presented at the 2009 SPE EUROPEC/EAGE Annual conference and exhibition, 8-11 June.
McGuire, P.L, SPE, J.R. Chatham, F.K. Paskvan, D.M. Sommer, SPE, F.H. Carini, "Low Salinity Oil Recovery:
An Exciting New EOR Opportunity for Alaska's North Slope,*' Paper SPE 93903 presented at SPE Western
Regional Meeting, Mar 30 - Apr 01,2005. Irvine, California.
Nasralla, R. A., Alotaibi, M. B., Nasr-El-Din, II. A., "Efficiency of Oil Recovery by Low Salinity Water Flooding
inSandstone Reservoirs," Paper SPE 144602-MS presented at SPE Western North American Region Meeting, 7-
11 May 2011, Anchorage, Alaska, USA.
Ramez, |A.N., Bataweel, M.A., and Nasr-El-Din, H.A. (2011). Investigation of Wettability Alteration by Low
Salinity. Paper SPE 146322 presented at the Offshore Europe, UK, 6-8 September.
Tang, G. and Morrow, N.R. 1996. Effect of Temperature, Salinity, and Oil Composition on Wetting Behavior and
OilRecovery by Waterflooding. Paper SPE 36680.
Tang, G.-Q. and Morrow, N.R., 1999a. Influence of brine composition and fines migration on crude
oil/brine/rock interactions and oil recovery. Journal of Petroleum Science and Engineering, 24: 99-111.
Tang, G. and Morrow, N.R., 1999b. Oil recovery by waterflooding and imbibition - Invading brine cation
valency and salinity. Paper SCA9911 presented at the International Symposium of the Society of Core Analysts,
Golden, CO, USA, 1-4 Aug 1999.
Wideroee, H.C., Rueslaatten, H., Boassen, T., Crescente, CM., Raphaug, M., Soerland, G.H., UrkedaL, H.,
"Investigation of Low Salinity Water Flooding by NMR and Cryoesem,” paper presented at International
Symposium of the Society of Core Analysts held in Halifax, Nova Scotia, Canada, 4-7 October, 2010.
Zhang, P., Tweheyo, M.T. and Austad, T., 2007. Wettability alteration and improved oil recovery by spontaneous
imbibitionof seawater into chalk: Impact of the potential determining ions: Ca2+
, Mg2+
and SO4
2
-. Colloids and
Surfaces A:Physicochem. Eng. Aspects, 301: 199-208.
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Effect of water

  • 1. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 34 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Effects of Low Salinity Water Ion Composition on Wettability Alteration in Sandstone Reservoir Rock: A Laboratory Investigation Abdolmohsen Shabib-Asl* Mohammed Abdalla Ayoub Mohammed Massoud Kermanioryani Pedro Paulo Jose Valentim Department of Petroleum Engineering, Faculty of Geoscience and Petroleum Engineering, Universiti Teknologi PETRONAS (UTP), Bandar Seri Iskandar, 31750, Tronoh, Perak, MALAYSIA. *Email address of corresponding author: msn.shabib@gmail.com Abstract For various decades, water-flooding mechanisms have been playing important role for improving oil recovery. It was not until recently that researchers discovered that the ionic strength of the brine was substantial. With regard to this, many studies started being published which focused more on the comparison of effects of having high ionic strength and low ionic strength for brine during flooding processes. Low salinity water comprises brine concentration below 5000ppm. At optimum concentration, low salinity water (LSW) when injected into the reservoir enhances the oil recovery considerably. This is attributed to the change of reservoir rock wettability. The process governing these changes are not well understood thus requiring a scrupulous investigation. Moreover there is no a certain fixed salinity range. This study investigates wettability alteration of Berea sandstone rock with brine of different ion composition (NaCl, KCl, MgCl2, CaCl2, and formation water-mostly Mg2+ and Ca2+ ions) and strength (500ppm-6500ppm with exception of formation water which consisted of 13000ppm). For the study, (31) core slabs were extracted from the core plug then saturated with formation water (FW). Next, the slabs underwent aging process in crude oil at ambient pressure and a temperature of 800 c. Later, the slabs were removed and immersed in containers with low salinity water at different ionic composition and strength, which is mentioned. The wettability was measured by applying the sessile drop method in certain range of time. According to the results, there have been significantly great change of wettability at Low salinity water in case of KCl was observed. Keywords: ionic strength, wettability, low salinity water, saturation, brine composition 1. Introduction In the last two decades, the level of investigation into low salinity water flooding has sharply increased. Nasralla et al. 2011, by conducting injection studies with deionized water and seawater, demonstrated that former improved oil recovery significantly rather than later. With the purpose of enhancing oil recovery, low salinity water (LSW) with adequate composition and salinity is injected into the reservoir, which changes the wetting properties of the reservoir rock into that favoring oil recovery (Tang and Morrow (1999) and McGuire et al. (2005)). Lager et al. (2007) in their studies, demonstrated that the effects of low salinity water are linearly proportional to the amount of clay minerals in the rock. There are many theories regarding the mechanisms of wettability alteration in presence of low salinity water. Ligthelm et al. (2009) proposed the double layer effect. They suggested that the application of low salinity water results in an expansion of the ionic electrical double layer between the clay and the oil interfaces. This causes the oil to be desorbed from the rock surface thus increasing the water wetness. Another mechanism is that proposed by Tang and Morrow (1996) which attributes wettability changes by decrease in ion binding as microscopic mechanism. The wettability of the reservoir rock plays an important role in the determination of residual oil saturation and recovery efficiency during the Low salinity water flooding process. Rock wettability can be indicated by using contact angle technique which is measured by several methods such as sessile drop method and Zeta potential. Fanchi et al.,2010 classified the wettability, in terms of contact angle, as per below.
  • 2. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 35 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Table 1. wettability classification according to Fanchi et al.,2010 Wetting conditions for a water-oil system Wetting Condition Contact Angle [degrees] Strongly water-wet 0-30 Moderately water-wet 30-75 Neutrally wet 75-105 Moderately oil-wet 105-150 Strongly oil-wet 150-180 The injection of low salinity water(<1500ppm) has revealed to improve oil recovery up to 16% of Reserves initially in Place (OOIP) (Zhang et al. 2007). Many Researchers have been more focused on comparative studies between the low and high salinity water, It has been verified that most of them were effective at brine concentration below 5000ppm (Tang and Morrow (1999), Mc Guire et al. (2005), Wideroee et al. (2010), Ramez et al, (2011)). Wang and Gupta (1995) when investigating the effect of temperature and pressure on wettability, made important observation in that contact angle was not sensitive to pressure changes whereas remarkable changes in wettability were experienced with temperature for the crude-oil/brine/quartz system. Another study that supports change in wettability due to change in temperature was presented by Ramez et al, (2011) who noticed that low salinity water decreased significantly the contact angle as compared to high salinity water. Furthermore, they also concluded that temperature changes affected greatly on contact angle alteration. In addition, the authors suggested that low salinity water injection is potential for improving oil recovery in various ranges of reservoir temperature. This study investigates the wettability alteration of Berea sandstone rock with brine of different ion composition and salinity in order to understand which ion composition is more effective during LSW flooding. 2. Materials and Methods 2.1 Materials 2.1.1 Cores In this experiment Berea sandstone core was used. The core was received from the KOCUREK Company (USA) with the properties that are shown in the table 2. It is around 50 years ago that the Berea sandstone rock has been employed for experimental work due to its homogeneity and petro-physical properties. The mineralogy of the rock is presented in the table3. Tale 2: Properties of core Product ID A-101 Formation Kipton Permeability 100mD- Brine permeability Porosity 20% UCS 6,500-8,000 psi Dimension 1.5 inch D * 12 inch L
  • 3. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 36 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Table 3: Mineralogy of Sandstone Rock Properties SiO2 (Silica) Al2O3 (Alumina) FeO/Fe2O3 (Iron Oxide) TiO2 (Titanium Oxide) CaO (Calcium Oxide) MgO (Magnesium Oxide) Alkalies H2O (water) Undetermined Total % 86.47 7.31 1.14 0.70 1.21 0.11 1.65 1.20 0.21 100 Figure 1: Sandstone Rock before and after cutting 2.1.3 Crude Oil The oil must contain polar components, which are naturally occurring surface-active agents, like acids, and bases, which can change the wettability. No effect has been observed by the use of oil free from polar components. The acid number (AN) is another important component. It is defined as the amount of potassium hydroxide (KOH) in milligrams, required for neutralizing 1 g of the petroleum acid in the crude oil, and reversely, the base number (BN) is defined as the amount of KOH in milligrams, required neutralizing 1 g of the petroleum base (Green & Willhite, 1998). When water is present, the oil and rock surfaces become charged. Their polar components behave as acids and bases by giving up a proton and becoming negatively charged, and gaining a proton and becoming positively charged, respectively (Buckley and Liu, 1998). These surface charges influence the adsorption behavior and thus wettability during injection of smart water. In this, research the crude oil with the following properties used Table 4: properties of the crude oil TAN (mgKOH/g) TBN (mgKOH/g) Density (g/cm3 ) 0.667 0.146 0.821 2.1.2 Brine In this research, two types of brine were employed o Formation Water termed “FW” was used for establishing initial and connate water saturations. It was composed of the following ions (Ca2+ , Na+ , Mg2+ , Cl- , K+ , HCO3 - ,SO4 2- ). o Low Salinity Water abbreviated “LSW” was prepared with distilled water that contained the (Ca2+ , Na+ , Mg2+ , Cl- ) with different TDS and concentration. All Salts were received from the AVANTIS Company (Ipoh, Malaysia). Properties and concentration of all brines shown in table 5.
  • 4. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 37 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Table 5: brine composition and concentration Composition Na+ Ca2+ Mg2+ K+ HCO3 - SO4 2- Cl- TDS Name (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) LSW-1 196.7 0 0 0 0 0 303.3 500 LSW-2 393.4 0 0 0 0 0 606.6 1000 LSW-3 983.5 0 0 0 0 0 1516.5 2500 LSW-4 1376.8 0 0 0 0 0 2123.2 3500 LSW-5 1770.3 0 0 0 0 0 2729.7 4500 LSW-6 2557.1 0 0 0 0 0 3942.9 6500 LSW-7 0 180.6 0 0 0 0 319.4 500 LSW-8 0 361.2 0 0 0 0 638.8 1000 LSW-9 0 903 0 0 0 0 1597 2500 LSW-10 0 1264 0 0 0 0 2236 3500 LSW-11 0 1625 0 0 0 0 2875 4500 LSW-12 0 2347 0 0 0 0 4153 6500 LSW-13 0 0 127.6 0 0 0 372.4 500 LSW-14 0 0 255.3 0 0 0 744.7 1000 LSW-15 0 0 638 0 0 0 1862 2500 LSW-16 0 0 893 0 0 0 2607 3500 LSW-17 0 0 1149 0 0 0 3351 4500 LSW-18 0 0 1659 0 0 0 4841 6500 LSW-19 0 0 0 262.2 0 0 237.8 500 LSW-20 0 0 0 524.4 0 0 475.6 1000 LSW-21 0 0 0 1311 0 0 1189 2500 LSW-22 0 0 0 1835.4 0 0 1664.6 3500 LSW-23 0 0 0 2359.8 0 0 2140.2 4500 LSW-24 0 0 0 3408.6 0 0 3091.4 6500 LSW-25 19.7 18.1 12.8 183.5 0 0 265.9 500 LSW-26 39.4 36.2 178.6 52.4 0 0 693.4 1000 LSW-27 98.6 632 63.8 131.1 0 0 1574.5 2500 LSW-28 965.3 126.4 89.3 183.5 0 0 2135.5 3500 LSW-29 88.8 731.3 516.8 118 0 0 3045.1 4500 LSW-30 511.5 821.6 580.6 341 0 0 4245.3 6500 FW 5923.4 18310.1 12941.3 6818.2 472.2 1318.6 84216.2 130000 2.2 Methodology Figure 2 shows a schematic drawing of the experimental procedure for wettability measurement. In this investigation, the sessile drop method was used to check the wettability alteration via contact angle measurement. The rock slabs were cut and polished into 3 to 5 mm thin slices. The surfaces of the slices were cleaned with toluene, and dried at 105°C for 24 hours. All slabs were Saturated with formation water (FW) by using the vacuum pump for 2 to 4 hours until no gas bubbles were exiting the core slabs and were put on the oven at temperature of 80 °C for 72 hours. All slabs were removed from FW and aged with Crude oil at an elevated temperature of 80 °C on the oven for about 3 days. Photos were taken from the slabs by using IFT 700 equipment (fig.3) in order to check the wettability condition of each slab before using Low Salinity Water. All slabs were removed from oil and aged with Low Salinity Water (LSW1-30) and Formation Water (FW) at an elevated temperature 80 °C on the oven. To check the wettability alteration it is important to take a photo in specified times of 0, 6, 12 and 24 hours.
  • 5. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 38 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Figure 2: schematic drawing of the experimental procedure for wettability measurement Figure 3: IFT 700 equipment 3. Results and Discussion The results are presented in form of graphs and contact angle portraits. Figure 4 depicts Contact angle changes in presence of formation water, MgCl2 and KCl. Considerable changes in contact angle are verified for KCl brine composition as compared to MgCl2 both at 500ppm concentration. There is no significant changes in contact angle when in presence of formation water. Formation Water (FW-130000ppm) LSW-13(MgCl2-500ppm) LSW-19(KCl-500ppm) Figure 4: contact angle changes in presence of formation water, MgCl2 and KCl. (There are many more depictions for contact angle changes at other concentrations and compositions, however for the purpose of this study only the best, least and the constant changes were chosen at 500ppm.) The preceding results are further discussed from the graphs of figure 5 through 9. For the NaCl Composition, figure 5 illustrates that there are changes in contact angle with time for each NaCl brine concentration. From the figure, it is patent that the contact angle is decreasing with time. Significant changes are experienced at brine concentration ranging from LSW-1 to LSW-6 with that of formation water remaining constant. Large changes in contact angle are at NaCl concentrations of 500ppm and 1000ppm whereby remarkable decrease of contact angle from 1120 to 730 is verified. For KCl brine composition figure 6, there is sufficiently great changes in contact angle with time, from 1120 to 62.230 .Relevant changes are noticed for LSW-19 through LSW-24 whereas that of formation water remains constant. Initial Saturation With FW Cutting the Cores into 31 slabs Saturation With Crude Oil Saturation with LSW1 to LSW30 Saturation With FW Take Photos Take Photos Resul t
  • 6. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 39 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Figure 5 NaCl Brine composition Figure 6 KCl brine composition Figure 7 is representative of contact angle changes for MgCl2 composition. Here, almost same trends as of foregoing paragraphs are noticed, that is, contact angle decreases with time and distinguishable changes are detected for LSW-13 through LSW-18 and that of formation water undergoing negligible changes. The contact angle changed from around 1120 to 850 , which is at lower range than both NaCl and KCl brine compositions. Figure 8 is illustrative of trends for contact angle change when in presence of CaCl2 brine composition. Here, the contact angle decreases with time for each concentration. Notable changes are for LSW-7 through LSW-12 brine concentrations and that of formation brine experiencing no changes. Ideal change in contact angle is experienced at brine concentration of 500ppm and 1000ppm (from 1120 to 780 ). Finally, when all the brine compositions are mixed, still noticeable changes are present, nevertheless in small range (from 1120 to 750 ) figure 9. Moreover, greatest changes in wettability are seen at concentrations of the monovalent ions.
  • 7. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 40 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Figure 7 MgCl2 brine composition Figure 8 CaCl2 brine composition Figure 9 Mixed brine composition
  • 8. Journal of Natural Sciences Research www.iiste.org ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online) Vol.4, No.13, 2014 – Special Issue 41 Selection and peer review by the scientific conference committee under responsibility of the Australian Society for Commerce, Industry and Engineering Overall, outstanding results are noticed for KCl brine composition whereby the contact angle has changed from 1120 to 62.230 at concentrations of 500ppm and 1000ppm followed by NaCl brine composition from 1120 to 730 and finally by the Mixture of all brine compositions which caused changes from 1120 to 750 . 4. Conclusion This study investigated the wettability alteration of Berea sandstone rock with brine of different ion composition and salinity. The experimental results revealed that much change of wettability was experienced by the low salinity water composition of monovalent ion K+ (from 1120 to 62.230 ) as compared to other ion compositions such as the monovalent ion of sodium( Na+ ), divalent ions (Ca+2 and Mg+2 ) at concentration of 500ppm and formation water at 130000ppm. Acknowledgements I would like to acknowledge the supports that I received form Universiti Teknologi PETRONAS. In addition, I would like to thank Associate Professor Dr. Ismail Bin Mohd Saaid Head of Petroleum Engineering Department at Universiti Teknologi PETRONAS for valuable discussions. References Fanchi, J.R., 2010. Integrated reservoir asset management: principles and best practices. Elsevier Gulf Professional Publishing, Amsterdam, Burlington, Mass. Green D.W. and Willhite G.P.:, "Enhanced Oil Recovery", SPE Text Book Series vol. 6, 1998. Lager, A.; Webb, K. J.; Black, C.J.J. Impact of brine chemistry on oil recovery. Paper A24 presented at the 14th European Symposium on Improved Oil Recovery, Cairo, Egypt, 2007. Ligthelm, D.J., Gronsveld, J., Hofman, J.P., Brussee, N.J., Marcelis, F. and van der Linde, H.A., 2009. Novel waterflooding strategy by manipulation of injection brine composition. Paper SPE 119835 presented at the 2009 SPE EUROPEC/EAGE Annual conference and exhibition, 8-11 June. McGuire, P.L, SPE, J.R. Chatham, F.K. Paskvan, D.M. Sommer, SPE, F.H. Carini, "Low Salinity Oil Recovery: An Exciting New EOR Opportunity for Alaska's North Slope,*' Paper SPE 93903 presented at SPE Western Regional Meeting, Mar 30 - Apr 01,2005. Irvine, California. Nasralla, R. A., Alotaibi, M. B., Nasr-El-Din, II. A., "Efficiency of Oil Recovery by Low Salinity Water Flooding inSandstone Reservoirs," Paper SPE 144602-MS presented at SPE Western North American Region Meeting, 7- 11 May 2011, Anchorage, Alaska, USA. Ramez, |A.N., Bataweel, M.A., and Nasr-El-Din, H.A. (2011). Investigation of Wettability Alteration by Low Salinity. Paper SPE 146322 presented at the Offshore Europe, UK, 6-8 September. Tang, G. and Morrow, N.R. 1996. Effect of Temperature, Salinity, and Oil Composition on Wetting Behavior and OilRecovery by Waterflooding. Paper SPE 36680. Tang, G.-Q. and Morrow, N.R., 1999a. Influence of brine composition and fines migration on crude oil/brine/rock interactions and oil recovery. Journal of Petroleum Science and Engineering, 24: 99-111. Tang, G. and Morrow, N.R., 1999b. Oil recovery by waterflooding and imbibition - Invading brine cation valency and salinity. Paper SCA9911 presented at the International Symposium of the Society of Core Analysts, Golden, CO, USA, 1-4 Aug 1999. Wideroee, H.C., Rueslaatten, H., Boassen, T., Crescente, CM., Raphaug, M., Soerland, G.H., UrkedaL, H., "Investigation of Low Salinity Water Flooding by NMR and Cryoesem,” paper presented at International Symposium of the Society of Core Analysts held in Halifax, Nova Scotia, Canada, 4-7 October, 2010. Zhang, P., Tweheyo, M.T. and Austad, T., 2007. Wettability alteration and improved oil recovery by spontaneous imbibitionof seawater into chalk: Impact of the potential determining ions: Ca2+ , Mg2+ and SO4 2 -. Colloids and Surfaces A:Physicochem. Eng. Aspects, 301: 199-208.
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