Accepted Manuscript

Effects of water soluble ions on wettability alteration and contact

angel in smart and carbonated smart water injection process in oil
reservoirs

Abbas Khaksar Manshad, Iman Nowrouzi, Amir H. Mohammadi

PII: S0167-7322(16)33214-7
DOI: doi: 10.1016/j.molliq.2017.09.011
Reference: MOLLIQ 7847
To appear in: Journal of Molecular Liquids
Received date: 18 October 2016
Revised date: 7 August 2017
Accepted date: 2 September 2017

Please cite this article as: Abbas Khaksar Manshad, Iman Nowrouzi, Amir H. Mohammadi
, Effects of water soluble ions on wettability alteration and contact angel in smart and
carbonated smart water injection process in oil reservoirs, Journal of Molecular Liquids
(2017), doi: 10.1016/j.molliq.2017.09.011

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 ACCEPTED MANUSCRIPT

Effects of Water Soluble Ions on Wettability Alteration and Contact

Angel in Smart and Carbonated Smart Water Injection Process in Oil
Reservoirs

Abbas Khaksar Manshad, a* Iman Nowrouzi,b Amir H Mohammadi c,d, *

a
Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University

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of Technology (PUT), Abadan, Iran
b
Department of Petroleum Engineering, Islamic Azad University, Omidiyeh Branch, Omidiyeh, Iran
c
Discipline of Chemical Engineering, School of Engineering, University of KwaZulu-Natal, Howard
College Campus, King George V Avenue, Durban 4041, South Africa

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d
Institut de Recherche en Genie Chimique et Petrolier (IRGCP), Paris, France

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Abstract - As the demand for crude oil increases, the oil-producing countries try to
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increase production. Enhanced Oil Recovery (EOR) techniques play a significant role in
improving oil production. Improved or smart water injection, among the methods, has
higher performance due to its low cost. Carbonated smart water is injected to improve
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smart water capabilities. Dissolution of carbon dioxide in water will change chemical
properties of the injected water to facilitate wettability alteration from hydrophobic to
hydrophilic more effectively. Besides, it causes swelling and changes of oil density and
viscosity by transferring from the aqueous phase to the oil phase. Adding CO2 to the
smart solution can have other effects, expressed as dissolution and carbonate rock weight
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alteration, in addition to the wettability alteration on carbonate rock. In this

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communication, NaCl, KCl, Kl, MgCl2, CaCl2, Na2SO4, MgSO4, and K2SO4 were used to
produce smart water, and CO2 gas was utilized to carbonate the water.
Observational/visual and contact angle tests were then carried out to express wettability
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alteration of carbonate rock with smart water and carbonated smart water. These
observational tests clearly indicate the wettability alteration property of injected
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materials. Carbonated smart water exposed to rock analysis shows that Mg2+ ion was
higher in comparison with Ca2+ rate in tested carbonate rock. Therefore, we can say that
the rock is a Dolomite one. Finally, by conducting tests on oil production imbibitions, we
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show that the smart water while utilizing the provided mechanism is capable of
improving the oil production in contrast to imbibitions with normal water, such that the
imbibitions with smart water increases the production 33% more in contrast to production
with initial formation water.

Keywords - Wettability; Contact Angel; Smart water; Carbonated smart water; EOR;
Water flooding.

*: Corresponding author: khaksar@put.ac.ir ; amir_h_mohammadi@yahoo.com AND

a.h.m@irgcp.fr

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1. Introduction

Water injection into reservoirs has a long history in the oil industry. The first water

injection operation was taken place in 1907 in the Bradford field. As the usage of this

method expanded in the reservoir secondary production, the water injection process took

more than 11 percent of 6.6 million produced oil barrels of the U.S in 1955 [1]. Brazil

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produces 74 percent of the oil produced in the sea using this method [2]. The technique of

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using improved water and water injection were similarly developed. The smart water

technique attracted attention after being chemically understood, which was once

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recognized as low-salinity water. The research on this technique flourished in the past
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two decades due to its low-cost and the feasibility to use sea water as smart water. As it

will be discussed later, the smart water solution is nothing more than adding small
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amount of salt to the water. There are many salts in the nature, all of which are formed by

acid-base reactions. The salt produced from an acid-base reaction is a neutral

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composition and releases its ions in the water when dissolves. Active ions will have a
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dramatic effect on reducing surface tension between water and oil as well as reservoir

rock wettability. This principle is the fundamental reason for using smart water as an
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effective substance to enhance oil recovery (EOR).

CO2 is another substance that can be added to the injected water. Its properties will be
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further discussed. However, the important case is that water injection is primarily to a

large extent influenced by mobility ration between the injected water and oil. The

viscosity ratio [3] of injected water and oil is very significant in determining the mobility

ratio due to the proximity of relative permeability of water and oil in reservoir. The

research shows that the best recovery coefficient occurs when the mobility ratio is near

unity [4]. Carbonated water injection having its attributes, as will be further dealt with,

can improve oil recovery and be a CO2 source in oil reservoirs. This study attempts to

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cover the combination of carbonated and smart water in addition to defining the

mechanism of those techniques. To perform this, we added 11 kinds of salt at different

concentrations to formation water and distilled water and investigated its mechanism in

effective elements in recovery enhancement. Then, this smart water was carbonated in the

presence of CO2 and investigated.

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1.1. Interfacial tension (IFT)

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The surface tension as an influential element in enhanced oil recovery process has

received much research. Temperature and pressure changes, regardless of water

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additives, can influence this property. The interfacial tension (IFT) behaviour between oil
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and water is not properly understood partly due to the temperature and pressure changes.

Wang and Gupta [5] reported IFT data of crude oil and two distinct brine systems in the

pressure range of 14.7 to 10000 psia and temperature range of 70 to 200 ºF. They
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reported IFT data for oil and distilled water systems at the same temperature and pressure

range in addition to the aforementioned data. When the IFT data against temperature (at
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constant pressures) is drawn for crude oil - brine systems, it is seen that as the
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temperature decreases the IFT also decreases, whereas in another system the decreased
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temperature results in the increased IFT. However, this trend corresponds with the

straight line of IFT temperature data only when the specific data of each point is

considered. Many cases of data dispersion appear that clearly indicates the absence of a

special trend of the effect of temperature on oil-water IFT. Data trend line indicates

increased IFT with an increase in pressure, nevertheless small dispersion in diagrams

indicates the absence of a clear trend. Jennings and Newman [6] expressed IFT data of

water and crude oil in the pressure range of 14.7-12000 psia and temperature range of 74-

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350 ºF. Their IFT data did not have any specific trend when they were drawn as a

function of pressure at different temperatures. IFT data reported by Hjelmeland and

Larando [7] for flash vaporization of crude oil and formation brine shows contradictory

trends of IFT values against the temperature. When the IFT measurements from two

different experimental laboratories are compared, one shows increased IFT as the

temperature increases, whereas the other shows a decreased IFT as the temperature

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increases. A similar contradiction is also evident for the presented oil data in the

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reference [8] in which data of some of the oils, brine as well as fresh water is provided.

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Previous studies on the effects of pressure and temperature on interfacial tension reveal

that the generated trends are dependent upon studied systems. This phenomenon is not
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yet properly defined, and the absence of an appropriate theoretical definition is palpable.

Nevertheless, by using IFT data, oil-brine system is investigated. We can see significant
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results in the references [5, 9-11], that is, in a vast range of temperature and pressure,

most of the IFT data has the mean value of 25 mN/m. Therefore, given the water-oil IFT
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data according to the temperature, pressure as well as important observations derived

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from the literature when there is no experimental value of related temperature and
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pressure, this is not reasonable to consider the mean value of 25 mN/m for water-oil IFT.
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1.2. Wettability

The study of wettability effect on oil extraction/production or saturating the remained oil

is generally limited to water flooding, for which the relationship between the initial

extraction (by reducing the pressure) and wettability is developed. Therefore, we address

the investigation of the relationship between wettability and flooding of the remaining oil

Sor. Amott [12] explained some of the conducted experiments on the relationships

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between rock wettability and oil extraction by water flooding. He conducted several

water flooding tests on the Ohio sandstone cores aiming at comparing oil extraction with

wettability. In the throughput in which 2.4 pore volume was taken into account, the

wettability diagram (X axis at δw, δ o) as a function of oil extraction, for δw the gradual

increased oil extractions from 0.6-1 and a flat surface of high extraction from 0.05-0.6 as

well as an increased δ o value, show a decrease in oil extraction. Amott’s findings of Ohio

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sandstone basically indicate that in each of the high wettabilities, a low extraction or high

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Sor is obtained, whereas with poor or neutral wettablity, high extractions or low S or is

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obtained. Moreover, Jadhunandan and Morrow [13] drew results similar to that of Amott

for wettability index as a function of oil extraction for two different injected pore
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volumes. Their results are based on water flooding in Berea saturated sandstone samples

with two different types of crude oil that were obtained from West Texas and North Sea.
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The trend observed in Alpha wettability index diagrams against the extracted oil is

completely similar to Amott’s observations. A maximum extraction in the near neutral

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wettability (wettability index equals to 0.2) and at the side of water-wet occurred,
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therefore at each high wettabilities (infinite), low oil extraction is observed. Accordingly,
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Amott [12], Jadhunandan and Morrow’s [13] results with respect to the effect of
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wettability on oil extraction include the nearest qualitative similarity. Considering the

observed behaviour, Jadhunandan and Morrow [13] explained that the maximum oil
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extraction occurs near the neutral wettability, for the capillary forces have the minimum

value. In 1995, Kennedy et al., [14] presented ultimate oil extraction data for a silica

synthesis core system, West Texas crude oil and brine (under the surfactant effect) in

order to show the impact of wettability on oil extraction. They used surfactant to change

the wettability. However, they employed the sessile drop technique along with a

consistent silica surface to determine the system wettability. The data provided by

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Kennedy et al, [14] indicates that the maximum extraction (and the actual minimum oil

saturation) occurs in a clear trend similar to the observations of Amott [12], Jadhunandan

and Morrow [13]. Despite similar methods, Amott, Jadhunanda and Morrow’s test shows

a 20 percent margin between low extraction (in case of high wettability) and the

maximum oil extraction, whereas the margin is about 5 percent in the tests of Kennedy et

al,. The change in remaining oil saturation or oil extraction is low, whereas the

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wettability changes from an infinite value to another one. In 1974, Lorenz et al. [15]

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explained the average remaining oil saturation data against USBM wettability index for

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Squirrel oil and Torpedo sandstone core, which were exposed to the organo-chlorosilica.

The remaining oil saturations were obtained by means of centrifugation. Organo

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chlrosilica was used in order to change the sample wettability from a high water wetting

mode to a high oil wetting mode. Moreover, Lorenz et al.’s data indicates a method
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similar to previously discussed tests in which high remaining oil saturation (or low

extraction) occurs at high wettability, whereas the minimum remaining oil saturation (or
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high extraction) occurs around the neutral wettability zone. Their data shows a Sor near 30
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percent when the sample is severely water or oil wetting. However, when the system is
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located in a neutral wettability zone, the Sor value downgrades to near 20 percent.
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Overall, as explained in Figures (2-3), the results obtained from the literature regarding

the relationship between wettability and remaining oil saturation or oil extraction
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basically indicates a bell curve where the oil extraction is drawn against the wettability.

However, when the impact of wettability on the oil extraction or remaining oil saturation

is investigated, it is determined that the obtained remaining saturation for a wettability

attribute is dependent upon the initial oil saturation. Data of several cores obtained from

different carbonate fields in the Middle East as explained by Masalmeh [16], in fact,

enables us to compare the remaining oil saturation for two different types of wettability

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and initial oil saturation, which changes from 5 to 90 percent. The remaining oil

saturation data for water-wetted cores indicate that as the initial oil saturation increases,

the remaining oil saturation increases. Nevertheless, for cores with mixed wettability, as

the initial oil saturation increases from 10 to 90 percent, the remaining oil saturation stays

at the range 1-10 percent. For example, the comparison of the remaining oil saturation at

the initial oil saturation of 60 percent, the value of Sor for water wetted cores and mixed

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wetted cores is about 25 and 7.5 percent, respectively. Mixed-wetting conditions consist

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of small empty space while the linking point of grains is preferably water-wet and larger

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space surface are oil-wet. Nevertheless, in case of having mixed-wetting systems, if the

oil-wetting path extends through the rock (according to the mixed wettability definition),
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the water is able to move oil from large spaces and keep it by capillary forces in small

empty spaces or at the grain linking points as Salathel [17] explained. Generally
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speaking, the reservoir rock wettability is one of the significant attributes of the reservoir,

for it affects several parameters, including oil, brine and gas placement in the reservoir,
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being saturated by these fluids as well as their explanation and movement through the
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reservoir. When the reservoir rock is water-wet, the water in the presence of brine and oil
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in the reservoir occupies smaller holes and wets larger ones. Water flooding in order to
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extract oil from small holes is simpler, but where the reservoir rock is oil-wet, the oil

resists against the displacement caused by water during water flooding. Hence, extracting
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oil from these reservoir types is much harder [18].

1.3. Smart water application

This technique is also named low salinity water injection (LSWI), smart water injection

as well as advanced ion management [19]. This method has been proposed recently for

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enhanced oil recovery process in carbonate reservoirs due to the change in rock

wettability by the smart water. The advantages of this method include high efficiency in

oil displacement, simplicity of injection, availability and low cost of the method

comparing with other enhanced oil recovery methods [19]. The first low salinity injection

program in carbonate reservoir was reported by Yousef et al, [20]. Two single-well

chemical tracer tests (SWCTT) in the upper Jurassic carbonate reservoir were conducted

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by means of diluted sea water. The test caused a reduction in the remaining oil of about 7

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units of saturation comparing with using normal water. Hognesen et al, [21] concluded

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that the spontaneous imbibitions of water containing sulphate ion into the carbonate rock

at high temperature increases the oil recovery. Given the role of sulfate ion as a factor in
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changing the carbonate rock wettability to water-wet, this is an obvious case. Web et al.

[22] investigated the impact of sulfate on the North Sea oil recovery with carbonate core
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sample through spontaneous imbibitions, and concluded that is capable of changing the

carbonate system wettability into the water-wet mode. Zhang et al. [23] studied the
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change in the North Sea gypsum reservoirs in Ekofisk field by adding Calcium and
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Magnesium ions at high temperatures. They asserted that the wettability change is due to
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the absorption of Ca2+ and Mg2+ ions. Strand et al. [24] observed a 15 percent increase in
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recovery of carbonate rock core comparing with water and sea water. Bagci et al. [25]

reported the 35.5 percent oil extraction from the oil in place by means of 2% w/v solution
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flooding in carbonate core, and they declared the wettability alteration as the cause.

Yousef et al. [26] investigated the low salinity water injection into carbonate rock

application along with the gradual increase in sea water concentration and reported an 18

percent of increase in oil recovery. Al-Harrasi et al. [27] provided direct evidence of low

salinity water injection effect on Omani carbonate rocks through spontaneous and

flooding tests and reported enhanced oil recovery. The extensive research carried out by

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Austad et al. [28,29,23 and 24] who indicated the possibility of wettability alteration and

EOR from carbonate rocks by changes in ionic compositions in injected water.

Wettability alteration in carbonate rocks is the principal and most acceptable mechanism

for oil recovery from this rock type in LSWI method.

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1.4. Carbonated water application

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Low efficiency of CO2 diffusion is one of the prevalent problems in CO2 injection, which

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is an appropriate EOR method. Therefore, the carbonated water injection in oil fields was

introduced in order to obviate this problem. Carbonated water is water saturated by CO2
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that is injected to the reservoir as a displacing fluid. Carbon dioxide is initially in aqueous
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phase and gradually transfers into oil phase, meanwhile it remains as the CO2 solution.

The oil viscosity reduces as CO2 dissolves in oil, moreover the oil volume increases
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which increases the relative permeability of oil and thus increases the ultimate recovery
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coefficient comparing with the conventional flooding. In the flooding carbonate,

miscibility is not the target, hence fewer restrictions on selecting reservoir condition and
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oil type. In addition, the ease of separation of CO2 mixture and water in production well,
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easy transport of injected fluid, the possibility of implementing other tertiary EOR
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methods are among the operational advantages of this method. In the past decades, fewer

studies were conducted on carbonated water injection and there is an absence of

sufficient related data. Carbonated water flooding was employed for the first time in 1940

[30]. Monteclaire’s research group conducting tests on sand pack model indicated that

carbonated water flooding as the tertiary method can reduce the remaining oil up to 15

percent of PV. During 1948-1952, a group of Earlougher engineers conducted a series of

laboratory flooding tests on the core using carbonated water, and the results showed that

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carbonated water flooding has 2-26 % PV of production comparing with water flooding

[31]. In 1951, Martin reported that the recovery factor is increased about 12 percent by

the carbonated water. His studies revealed that the increased oil production is directly

dependent on carbonation level, and if this rate (especially in heavy oils) decreases, the

efficiency of flooding also decreases [32]. In 1963, Holm conducted a series of studies

on core flooding using carbonated water and CO2. He used 1 foot long and 3.5 inch wide

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cores made of sandstone as well as 5.1 cp oil at 70 oF and 2.2 cp oil at 125 oF. He

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observed that the recovery factor is increased 21 and 19 percent than water flooding,

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respectively [33]. Holm also reported the result obtained from the test of CO2 injection as

the chasing fluid after carbonate water injection. According to this report, the oil
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production increased 3-35 percent compared with water flooding [34]. In 1970’s,

the French Institute of Petroleum (IFP) conducted an extensive research on core flooding
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at 149 oF and 406 psig. Two types of oil having high viscosity (290 cp) and low viscosity

(42 cp) were used. They conducted the tests sequentially with water, CO2 and carbonated
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water within 24 hours for each injection. Finally, 14-15 percent of improvement was
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reported in oil production [35]. Mayers et al. conducted two sets of core flooding tests in
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1981 and 1985. The oil viscosity was 457 and 406 cp at the test temperature, respectively.
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An initial injection velocity was considered and it changed into 1 ft/day after water

production. Improving oil production was reported between 13-24 percent PV with mean
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17 percent PV in the first group and 19.4 percent PV in the second group [36]. Peres et al.

conducted a research on carbonated water imbibitions in fractured reservoirs.

Carbonation pressures were considered variable from 50 to 500 psig. Spontaneous

imbibitions of water and carbonated water in several core samples showed a 10-16

percent increase compared with the past measures. Sohrabi et al. employed a micromodel

in carbonated water flooding tests. The conditions for the test included 200 psia and 100

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°F and 16.5 cp oil and 0.8 cp Dekane normal were employed. For both oil models,

recovery factor increased from 8.8 % PV to 23.8% PV, respectively [38]. During 1960-

1980, Shell also performed some tests on carbonated water. For this purpose, they

employed sand pack and etched-glass model flooding tests. In carbonated water flooding

test, the recovery factor was 12-23% PV higher and this also increased due to the oil

viscosity [39, 40]. K&S project is the first economic project of carbonated water

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injection. In 1958, the simultaneous water and CO2 injection started, and carbonated

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water injection could produce approximately 37% more oil than the conventional

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flooding. Of course, using carbonated water solved the emulsion formation and corrosion

problem in this field [37, 41, 42, 43]. The other field project was in Domes Unit in 1965,
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in which carbonated water injection with high and low CO2 percentage, and also CO2

injection alone were conducted. In this field, the carbonated water injection, compared to
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the water injection, increased the oil production 9 % [44].

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1.5. Carbonate rock dissolution

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During the process of oil production by water, some interactions occur between the
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injected water and the reservoir rock. These interactions are important when carbon

dioxide is used as the injecting fluid in EOR processes or for storage in the formation
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aquifer, particularly in carbonate reservoirs. By dissolving carbon dioxide in water,

carbonic acid is formed. The acid formed reacts with the carbonate salts present in the

rock (calcium carbonate and magnesium carbonate) and causes it to dissolve. Dissolution

changes the rock properties such as porosity and permeability [45, 46]. On the other

hand, the dissolved salt may deposit as very fine grains and cause formation damage in

low permeable carbonate formations. In such circumstances, sediments are the main

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reason for reducing the permeability. [47] Intermittent injection of carbon dioxide and

brine increases the porosity and permeability due to dissolution and decreases the

porosity and permeability due to sediments. [46] Sayegh et al., 1990, showed that

carbonate minerals such as carbonate calcium and carbonate magnesium react rapidly

with carbonated water [48]. The most important reactions of carbon dioxide dissolution

in water include:

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H 2 O  CO2  H 2 CO3 (1)

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H 2 CO3  H   HCO3 NU (2)

In the presence of carbonate calcium and carbonate magnesium, the following reactions
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lead to the formation of water soluble bicarbonates:

H 2 O  CO2  CaCO3  Ca(HCO3 ) 2 (3)

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H 2 O  CO2  MgCO3  Mg (HCO3 ) 2 (4)

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The reaction leads to the dissolution and release of particles in the flow path, which

results in the detached particles accumulation into the bottlenecks and reduces
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permeability. Conversely, if the detached particles are smaller than the size of

bottlenecks, it can lead to an increased permeability. Rose et al. in 1989 and Bathurst in

1975 stated that an increase in the temperature of the constant partial pressure of carbon

dioxide and the pressure at carbon dioxide concentration and constant temperature and

the amount of carbon dioxide dissolved in water lead to an increase in calcite dissolution

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[49, 50]. Therefore, pressure reduction causes calcium sediments in form of calcium

carbonate according to the following reactions:

Ca 2  CO32  CaCO3
Ca 2  2HCO3  CaCO3  H 2 O  CO2 (6)

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These reactions lead to the sediments of calcium carbonate that will reduce the matrix

permeability. This phenomenon can be observed around the mouth of the well due to the

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excessive pressure drop.

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2. Materials
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Brine:

The brine used was an actual formation water sample taken from Asmari oil reservoir in
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Gachsaran, Southern Iran. Analysis of the brine used is given in Table 1:

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Table 1
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Oil:
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In this study, a dead oil sample was used which was originally taken from Asmari

oil reservoir in Gachsaran, Southern Iran (Table 2).

Table 2

Salt:

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Salts used to produce smart solutions, namely NaCl, KCl, Kl, MgCl2, CaCl2, Na2SO4,

MgSO4 and K2SO4 were all provided by MP biomedical company in the Netherlands and

have high purity. Table 3 reports the properties of the salts used.

Table 3

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Rock:

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The outcrop of carbonate rock was used for the wettability alteration tests. Rock samples

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were cut perfectly thin into disc-shaped pieces, having a diameter of 1 inch, in order to

carry out the contact angle tests.

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Gas:
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Carbon dioxide and nitrogen with 99.99 % purities were purchased from Shiraz Industrial

Gases Company, Iran.

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3. Apparatus
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3.1. Accumulator
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An accumulator consisting of a cylinder and piston embedded in a chamber similar to an

oven to apply temperature was used. A high-pressure outlet line is connected to the

accumulator's lower head which is connected to a hydraulic hand pump implementing the

pressure. The other high-pressure line connects the accumulator's upper part to the carbon

dioxide cylinder, which are separated by a valve.

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3.2. Apparatus for IFT, contact angel and wettability measurements

Briefly, this equipment is composed of the following important parts: Two syringe

plungers that operate manually, a hollow cell equipped with a thermal jacket, a needle

connected to the syringe plunger by steel line, a light source, a camera lens to take photos

of a droplet as well as a personal computer and a software to process the images [11].

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4. Method NU
4.1. Section preparation to start the experiment
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In these tests, 1-inch sections with a thickness of 3 mm were prepared. The pressurized

nitrogen was used to remove dust and loose particles left after cutting. Then, the samples
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were rinsed in distillated water and dried at 50° C for 24 hours in the oven. The samples
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were dipped into a toluene solution for 1 day to remove fatty acids absorbed from

touching. Then, the samples were rinsed in distillated water and dried. Afterwards, the
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sections were soaked with the crude oil at 70° C for 12 days. After ensuring the samples

were oil-wet, they were removed, rinsed in distilled water and dried at 50° C for 24
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hours.

4.2. Test procedure

4.2.1. Formation water compatibility tests

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These are an important series of EOR tests with chemical injection technique.

Incompatibility of injected materials with formation water can lead to sediments and

formation damage. Generally, materials which are incompatible with the formation water

and form sediments are totally rejected. The sediments are composed of the injected

materials, the materials dissolved in the formation water or the inorganic minerals in the

reservoir rock. In this study, for formation water compatibility tests, the optimized

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solutions with respect to the lowest interfacial tension with the sample oil were prepared

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with the formation water of the same optimum concentration and were kept in the oven

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for two weeks at the reservoir temperature of 75° C, then, the results were observed. The

following provides an investigation of the results.

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4.2.2. Surface wettability alteration tests
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As mentioned earlier, the interfacial tension is an affective factor in the surface

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wettability. At this stage of testing, a salt solution at a certain concentration was taken as
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an optimal salt solution based on the minimum interfacial tension and formation water
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compatibility test results and then was carbonized. The impact of this carbonate smart
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solution on the carbonate rock wettability was studied as follows:

A section, already oil-wet, of 3 mm with a diameter of 1 inch taken from carbonate

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reservoir rocks was placed in an accumulator. The accumulator was placed inside the

pressure and temperature device. The optimal solution was added to the cylinder and

piston chamber, and carbon dioxide gas was injected into it. The pressure was set to 1000

psi and the temperature was set to the reservoir temperature, maintaining under these

conditions for 72 hours. Then the conditions imposed on the system were removed and

the section was prepared for the contact angle test. The same tests were done at 1500 and

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2000 psi pressures. The results are reported in the following. Regarding other salts, (of

course salts compatible with formation water) wettability tests can only be performed on

the basis of smart water, without the presence of carbon dioxide. Therefore, each section,

already oil-wet, was placed in every solution and the closed system was kept in an oven

for a week at the reservoir temperature. Then, contact angle test was conducted.

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4.2.3. IFT and contact angel measurements

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For doing interfacial tension tests of aqueous solutions and crude oil, the needle is placed

at the bottom of the cell and instills a drop of oil in the aquatic environment. The camera
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takes photos of the drop continuously and the software analyzes them and displays the

value of interfacial tension as its output using some information such as density of the
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drop and the solution and the gravitational acceleration using Equation 1 [11]. The

pressure of the device can be arbitrarily adjusted using the syringe plunger. The
D

temperature of the device is also adjusted by a thermostat and a thermal jacket embedded
TE

around the cell. To provide high-quality photos, the camera and the light source are also
P

adjustable [11].
CE

gd e
2

 
AC

H
(7)

where g and Δρ are, respectively, gravitational acceleration and the difference between

the density of the crude oil droplet and the aquatic solution. The parameter depending to

the shape of (H) depends on the amount of factor of (S=d/D) [11].

Interfacial tension measurements on smart water and carbonated smart water were carried

out at different concentrations, pressures and temperatures [11].

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To do the experiment of contact angle between the oil drop and the cross section of the

rock, a holder of the cross section is embedded in the cell to keep the cross section above

the cell in the aquatic environment from a short distance of tip of the needle. The

software is able to draw tangent lines on both sides of the drop by putting a baseline that

determines the boundary between the droplet and the surface of the rock and also it

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calculates the size of the contact angles and the mean as its output.

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5. Results and Discussion
SC
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5.1. Formation water compatibility tests
MA

Formation water compatibility test was conducted according to the method explained

previously. The sediments were observed in solutions of three salts, namely NaHCO3,
D
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Na2CO3 and FeSO4 (purchased from MP Biomedicals, Inc with purities higher than

99%). Figures 1 and 2 display the solutions sediments.

P
CE

Figure 1
AC

Figure 2

With this interpretation, NaHCO3, Na2CO3 and FeSO4 salts were not suitable for the

continuation of the tests and EOR processes.

5.2. A pilot study of oil emulsion

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Another important parameter that causes the efficacy of additives to the injected water is

the capability of these substances for oil-in-water emulsion. This allows the water

injection to break the oil trapped in the pores and bottlenecks into smaller droplets so that

the trapped oil is mobilized in the porous media more easily. In this study, the solution of

2000 ppm K2SO4 was tested; the results of which can be seen in Figure 3. To do the test,

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a quantity of the solution and the crude oil was poured in a test tube, and the

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emulsification effect could be observed before and after shaking. It should be noted that

SC
this test will not show interesting results for smart water and it mainly deals with used

surface-active agents.
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Figure 3
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D

5.3. Smart water contact angle tests

P TE

The target solutions of 500, 1000, 2000 and 10000 concentrations in ppm scale were
CE

prepared using NaCl, KCl, Kl, MgCl2, CaCl2, Na2SO4, MgSO4 and K2SO4 salts. Then we

placed an oil-wet section in every solution and concentration. The system including a
AC

smart solution at a specified concentration was placed in an oven at 75 ° C for 3 days.

After the required time, the sections were removed from the oven and rinsed in distilled

water. For one day, they were placed in the oven at 50° C to dry. Contact angle tests were

then conducted. The results are provided in Table 4.

Table 4

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The data provided in Table 4 are indicated by means of diagrams in Figure 4.

Figure 4

5.4. Carbonate rock wettability alteration of smart water and carbonated smart

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water

RI
SC
Al-Shalabi stated that the main mechanism of EOR in carbonate reservoirs by using

smart water is the wettability alteration [19]. Based on the results of research, the general
NU
opinion is that the reservoir rocks wettability alternation occurs due to the complex

interactions in the crude oil-brine-rock system. Such interactions are strongly dependent
MA

on the oil and brine composition, rock mineralogy, temperature, pressure and the contact

time between the phases [19].

D
TE

Wettability alteration by carbonated smart water mainly occurs by fines migration, multi-
P

ion exchange, surface charge alteration and double layer expansion [51]. Wettability
CE

alteration by smart water is influenced by the type of ions involved in this process.

According to Strand et al., Ca2+ and SO42- ions are more effective in wettability
AC

alteration. SO42- ions lower the positive charges on the rock surface and thus help cations

to approach carboxylic acids adsorbed on gypsum. Addition of the bivalent cation, Mg2+,

to smart water increases the ability of cations to remove carboxylic acids from the rock

surface. SO42- ions also reduce the positive charges on the surface of carbonate rock. As a

result, bivalent cations will approach the rock surface and adsorbed acids more easily

[52]. As reported by Lager et al., bivalent cations adsorbed on the rock surface are

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replaced with monovalent cations, then polar oil molecules are adsorbed on bivalent

cations and dispersed. This will alter the wettability from hydrophobic to hydrophilic [53,

54]. With dissolution of carbon dioxide in smart water, solution acidity will play an

important role in dissolution of carbonate minerals and acidification of the rock surface.

This will in turn alter the wettability from hydrophobic to hydrophilic.

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5.5. The contact angle alternation tests of carbonated smart water

RI
SC
This test employed three pressures, 1000, 1500 and 2000 psi, and a reservoir temperature

of 75° C. Sections of carbonate rocks were prepared and turned into oil-wet in a similar
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way, and then were placed in the cylinder and piston system. All three pressures, 1000,

1500 and 2000 psi, of carbon dioxide considered for smart solutions were applied. It
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should be noted that at this stage, all the solutions were prepared at 2000 ppm

concentration so that fresh water gets smart. At this stage, the pressure effect and, in
D

consequence, the carbon dioxide dissolution in smart water was checked rather than the
TE

ion concentration. In other words, if the solubility of carbon dioxide in water is

P

considered as a function of the solids dissolved in water, the temperature, and the
CE

pressure, any change in pressure will cause a change in the dissolved carbon dioxide

concentration since the dissolved salt concentration and the temperature were considered
AC

constant in this study. The time for applying the conditions for each pressure was

considered 3 days. After removing the system from pressure and temperature conditions,

we removed the section, rinsed it in distilled water, and dried it for 24 hours at 50° C.

Then the contact angle test was performed. The results are provided in Table 5. Figure 5

shows the data provided in the table by means of a diagram.

Table 5

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Figure 5

5.4. Observatory test of wettability alteration of smart water

In this test, a cross section of carbonate rock was examined (thickness is unimportant). In

this test, a 5-mm section was prepared. Then one side was saturated with crude oil so that

an oil film was formed on the section. Then the section was placed in the target solution

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and the system was kept at the reservoir temperature. At the beginning of the test, and

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then at regular intervals the cross section was photographed.

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The results of the 2000 ppm solution, K2SO4, and the results of using distilled water are

provided in Figure (6) and Figure (7). Gradually, with the loss of oil film, water covers
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the carbonate cross section and oil comes on the surface of the solution. The remarkable

thing is that the rock cross section in this test should be saturated such that a layer of it is
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oil-wet. Otherwise, the buoyancy force displaces the oil from the cross section and places

it on the surface and the soluble salt will have no impact on the test. In this test, the
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section was photographed every hour. The container selected should be such that the
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smart solution does not evaporate in the oven at the reservoir temperature because
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evaporation increases the concentration of the solution and the test results will be
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erroneous.
AC

Figure 6

Figure 7

5.5. The observatory test results of wettability alteration of carbonated smart water

To observe and better understand the wettability alteration, one of the accumulators was

opened as an example every 24 hours. The section was removed and photographed. In

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this study, for example, the accumulator containing 2000 ppm carbonate smart solution

using NaCl salt at 1500 psi pressure was investigated. Given that the total testing time is

3 days, the section can be removed three times and the result can be observed. The results

are provided in Figure 8. This way of observing wettability alteration just enhances the

understanding of the contact angle tests and the conditions of wettability alteration, and

does not have a numerical value since it can be described merely visually.

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Figure 8

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5.6. The contact angle alteration tests of optimum carbonate smart solutions
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In these tests, eight1-inch sections with 3 mm thickness were prepared. The pressurized
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nitrogen was utilized to remove dust and loose particles left after cutting, as mentioned

earlier. The samples were then rinsed in distilled water and were dried at 50 °C for 24
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hours. The samples were placed in toluene solution for 1 day to remove fatty acids
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absorbed from touching. Then they were rinsed in distilled water and were dried.
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Afterwards, sections were placed in the crude oil at 70 °C for 12 days. After ensuring the
CE

samples were oil-wet, they were removed, rinsed in distilled water and dried at 50° C for

24 hours. Then every section was placed in the closed containers containing the smart
AC

solutions (8 solutions compatible with formation water) at their optimum concentration.

The containers were placed in the oven at 75° C reservoir temperature for 3 days. Then

they were removed from the containers, rinsed in distilled water and dried at 50° C in an

oven for 24 hours. Then the contact angle test was performed (Figure 9). The results are

provided in Table 6.

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Table 6

Figure 9

5.7. The contact angle alteration test of carbonated smart water

As stated earlier, this test employs three reservoir pressures and the reservoir

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temperature. Sections of carbonate rocks were prepared and turned into oil-wet in a

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similar way, and then were placed in the cylinder and piston system. All three pressures,

SC
1000, 1500 and 2000 psi, were applied for the optimum salt at the optimum concentration

(i.e. K2SO4 solution at 2000 ppm concentration). The time for applying conditions for
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each pressure was considered 2 days. After the removal of system from the pressure and

temperature conditions, the section was removed, rinsed in distilled water and dried at
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50° C for 24 hours. Then contact angle test was performed. The results are provided in

Table 7. Figure 10 displays the table's data by means of a diagram.

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TE

Table 7
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Figure 10
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5.8. The carbonate rocks dissolution tests of the optimized carbonate smart solution
AC

In these tests, 2000 ppm solution of K2SO4 was used. The system for the method was the

same as the pressure and temperature test system in wettability tests. The difference is

that the system was opened every 3 days, and weight tests of the rock sample and the

analysis of solution compounds were performed. Here, instead of sections, a carbonate

rock was used in small pieces. The results are provided in Tables 8 to 11:

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Table 8

Table 9

Table 10

Table 11

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Figures 11 to 14 display the data provided in Tables 8 to 11 by means of diagrams:

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SC
Figure 11

Figure 12
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Figure 13

Figure 14
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5.9. The results of oil production test by spontaneous imbibition

D
TE

In this test, two core plugs with the properties presented in Table 12 were provided and
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after preparation in the same way as previously described, were saturated with crude oil
CE

by the same device described earlier. Then each was placed in two Amott cells, one

containing initial formation water and the other containing the optimum smart solution
AC

(2000 ppm solution using K2SO4 salt). Then both cells were placed in the oven at 75° C

reservoir temperature for 32 days. The oil production from plugs were studied and

compared at every 4-day intervals. After a month, the total cumulative production of

plugs can be compared with each other. It should be noted that before putting the plugs in

cells, the plug rim must be blocked using resin or paraffin such that the top and bottom of

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the plug are unsealed. Therefore, a one-dimensional flow is resulted (Figure 15). The

results are as follows:

Figure 15

Table 12

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Table 13

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SC
Figure 16 displays the data provided in Table 13 by means of a diagram. As can be seen,

the production by imbibition of smart water is more than the production by imbibition of
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initial formation water.

Figure 16
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6. Conclusion
P TE

The results of this study show that the advanced ion management in the process of water
CE

injection into reservoirs can be very effective in the enhanced oil recovery. The low-cost
AC

carbonated smart water technique along with the ease of implementation of the process

makes it a practical method. Carbon dioxide addition to smart solution causes the

improvement of carbonate rocks wettability alteration from oil-wet to water-wet. Carbon

dioxide addition to smart solution causes rock dissolution and forms a type of acid which

can raise the permeability and porosity of the reservoir with large cavities and therefore

enhance the production. Given that most of the salts used in this study are compatible

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with formation water, it can be concluded that this method can prevent the sediments and

damage of formation that can be observed in other methods.

According to literature on smart water and carbonated water techniques,

combination of these two methods and the use of carbonated smart water is more

effective in wettability alteration of the carbonate rock from hydrophobic to hydrophilic

as compared to both methods separately. In other words, enhanced capabilities of both

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methods can be used by combining these two methods. The diversity of ions in

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groundwater and surface water and its availability are the main advantages of the smart

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water method. In addition to optimal use of carbon dioxide as a greenhouse gas in

enhanced oil recovery (EOR) process, carbon dioxide can be stored effectively by this
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method. By identification of compatible and useful ions and their optimum

concentrations before the EOR operation, treatment costs and deposition problems can be
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reduced.
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[52] Strand S., Henningsen S.C., Puntervold T., Austad T.’ Favorable Temperature
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Recovery, Cairo, Egypt, 22 April.

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Table 1: Analysis of the used brine.

Property d PH cond T.D.S NaCl Cl- Na T.H Ca2+ Mg2+ HCO3-

(gr/lit) (µs) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Value
1.045 7.5 95000 74000 64350 39050 25300 5200 3500 1700 64

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Table 2: Oil sample information

Components Separator Separator Oil Reservoir Fluid
Gas (Molar percent)
(Molar (Molar
percent) percent)
H2 S 7..0 7.77 7.70
N2 7.70 7.77 7.70

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CO2 7..0 7.77 7.70
C1 00.66 7.77 66.00

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C2 .6..0 7.70 0.60
C3 0.06 7.06 6.60

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iC4 ..06 7.06 ..60
nC4 0.60 6.66 6.00
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iC5 ..00 ...7 ..67
nC5 ..66 ...7 ..60
..06 0.00 0.00
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C6
C7 7.00 0.66 0.00
C8 7.60 0.07 6.67
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C9 7.7. 0..0 6.66

TE

C10 7.77 6.60 6.00

C11 7.77 6.7. 6.66
C12+ 7.77 6..00 60..6
P

.77.77 .77.77 .77.77

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Total
GOR=60.915 SCF / STB
Molecular weight of separator oil 600
AC

Molecular weight of C12+ 607

Molecular weight of reservoir oil .60
Specific gravity of C12+@ 60 °F 7.0600
Saturation pressure of reservoir fluid @ 60.6 2036 psi
°C

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Table 3: Properties of the salts used in this study.

Molecular Water
Density
Salt Weight Solubility
[g/cm3]
[g/gmol] [g/L]
NaCl 58.44 2.16 359

KCl 74.55 1.98 281–567

MgCl2 95.21 2.32 530–730

CaCl2 110.98 2.15 600–1524

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Na2SO4 142.04 2.66 48–427

MgSO4 120.37 2.66 255–710

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KI 166 3.123 1280–2060
K2SO4 174.25 2.66 111–240

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Table 4: The results of various aqueous solutions contact angles at various salt

concentrations.

Contact Angle (Degree)

Concentration NaCl KCl KI MgCl2 CaCl2 Na2SO4 MgSO4 K2SO4
(ppm)
677 45.67 37.46 44.13 34.69 34.73 41.28 29.04 24.14
.777 42.39 37.51 37.45 33.78 34.16 37.45 23.71 24.71

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6777 37.42 25.13 37.24 33.15 28.14 24.91 23.44 23.64
.7777 40.37 36.41 37.61 31.47 27.02 36.14 23.37 23.17

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Table 5: Contact Angle (Degree) changed by carbonated smart water at optimum

concentrations (at reservoir temperature 75 °C).

Contact Angle (Degree)

Pressure NaCl KCl KI MgCl2 CaCl2 Na2SO4 MgSO4 K2SO4
(Psia)

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1000 21.19 25.14 20.67 23.15 26.17 27.46 25.12 21.78
1500 20.76 23.61 20.40 21.75 24.31 23.65 22.07 19.32

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6777 20.02 20.50 19.16 21.63 21.86 23.24 19.71 18.93

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Table 6: The results of contact angle tests for smart solutions at the optimum
concentration at 14.7 psi pressure and reservoir temperature.
NaCl KCl MgCl2 CaCl2 Na2SO4 KI MgSO4 K2SO4
Smart water 2000ppm 2000ppm 1000ppm 2000ppm 2000ppm 1000ppm 1000ppm 2000ppm

Contact angle
(Degree) 37.42 25.13 33.78 28.14 24.91 37.45 23.71 23.64

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Table 7: The results of contact angle tests of 2000 ppm solution using K2SO4 carbonate
salt at different pressures and at reservoir temperature.
1000 1500 2000
Pressure
psi psi psi

Contact angle (degree) 21.78 19.32 18.93

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Table 8: The concentration of calcium ions in the dissolution process.

Pressure Concentration (ppm)
(psi)
Step 1 Step 2 Step 3

0111 ..67 .6.7 .007

0611 .007 .007 6.77
0111 6667 6607 60.7

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Table 9: The concentration of magnesium ions in the dissolution process.

Pressure Concentration (ppm)
(psi) Step 1 Step 2 Step 3
0111 66.7 6067 6007
0611 0667 0007 6.77
0111 0.67 0667 0007

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Table 10: The concentration of bicarbonate ions in the dissolution process.

Pressure Concentration (ppm)

(psi) Step 1 Step 2 Step 3
0111 .667 .007 .007
0611 60.7 6767 6667
0111 6.77 6067 6007

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Table 11: Changes in the rock weight in the dissolution process.

Pressure Weight (gr)
)psi( Start Step 1 Step 2 Step 3
0111 35.5414 35.4712 35.2013 35.0314
0611 42.1471 41.9563 41.6324 41.6156
0111 38.1563 37.9251 37.8457 37.5412

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Table 12: The properties of plugs used in imbibition test.

Number Weight Length Diameter Bulk Pore Porosity Permeability

of plug (gr) (cm) (in) volume volume (%) (md)
3 3
(cm ) (cm )
Sample 1 141.312 5.00 1.5 228.018 39.560 17.35 14.50

Sample 2 140.143 5.00 1.5 228.018 40.360 17.70 14.72

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Table 13: Plugs production by imbibition process in 32 days.

)days(Time 4 8 12 16 20 24 28 32
Sample 1: production with
0.10 0.65 1.30 2.08 2.86 3.64 4.16 4.22
smart water (ml)
Sample 1: production with
0.08 0.481 0.900 1.88 2.53 2.80 2.98 3.86
initial formation water (ml)

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Figure 1: Smart solutions in the presence of formation water (Before applying the

reservoir temperature and time).

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Figure 2: Smart solutions in the presence of formation water (after applying the reservoir
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temperature and time)
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Figure 3: The emulsifying ability of 2000 ppm solution using K2SO4 salt with crude oil.

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Left: Before shaking. Right: After shaking at three given time intervals.
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Figure 4: The results of various aqueous solutions contact angle at various salt

concentrations.
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Figure 5: Contact Angle (Degree) changed by carbonated smart water at optimum
concentrations and different reservoir pressure (at reservoir temperature 75 °C).
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Figure 6: The results of wettability observatory test of distilled water in given time

periods.
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Figure 7: The results of wettability observatory test of smart solution (2000 ppm solution

using K2SO4 salt).

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Figure 8: Observing the results of wettability alteration of carbonated smart water over

time, at a pressure of 2000 psi and at a temperature of 75 ° C. Respectively, from left,

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after 1, 2 and 3 day periods.

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Figure 9: The results of contact angle tests for smart solutions at the optimum
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concentration at 14.7 psi pressure and reservoir temperature.

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Figure 10: Contact angle tests diagram for 2000 ppm solution using K2SO4 carbonate
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salt at different pressures and at reservoir temperature.

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Figure 11: Changes in the calcium ions concentration in the dissolution process.
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Figure 12: The concentration of magnesium ions in the dissolution process.
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Figure 13: The concentration of bicarbonate ions in the dissolution process.
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Figure 14: The diagram of changes in the rock weight in the dissolution process.
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Figure 15: Oil saturated plug with a rim blocked by paraffin.
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Figure 16: The diagram for the production by imbibition of smart water and initial

formation water.
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Research Highlights

 The effects of water soluble ions on

wettability alteration and contact angel are
investigated.

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 NaCl, KCl, Kl, MgCl2, CaCl2, Na2SO4, MgSO4, and

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K2SO4 were used to produce smart water.

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 CO2 gas was utilized to carbonate the water.
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 The tests indicate the wettability alteration
property of injected materials.
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 Adding CO2 to the smart solution can also have

dissolution effect and carbonate rock weight
alteration.
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