Accepted Manuscript

Combination of a new natural surfactant and smart water injection for enhanced oil
recovery in carbonate rock: Synergic impacts of active ions and natural surfactant
concentration

Siyamak Moradi, Ali Akbar Isari, Zahra Bachari, Hossien Mahmoodi

PII: S0920-4105(19)30050-6
DOI: https://doi.org/10.1016/j.petrol.2019.01.043
Reference: PETROL 5687

To appear in: Journal of Petroleum Science and Engineering

Received Date: 11 October 2018

Revised Date: 31 December 2018
Accepted Date: 9 January 2019

Please cite this article as: Moradi, S., Isari, A.A., Bachari, Z., Mahmoodi, H., Combination of a new
natural surfactant and smart water injection for enhanced oil recovery in carbonate rock: Synergic
impacts of active ions and natural surfactant concentration, Journal of Petroleum Science and
Engineering (2019), doi: https://doi.org/10.1016/j.petrol.2019.01.043.

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 ACCEPTED MANUSCRIPT
Siyamak Moradi 1, Ali Akbar Isari 2, Zahra Bachari 2, Hossien Mahmoodi 2

1. Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering,

Petroleum University of Technology, Abadan, Iran

2. Department of Chemical Engineering, Abadan Faculty of Petroleum Engineering,

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Petroleum University of Technology, Abadan, Iran

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Combination of a New Natural Surfactant and Smart Water Injection for
Enhanced Oil Recovery in Carbonate Rock: Synergic Impacts of Active
Ions and Natural Surfactant Concentration

Abstract

By increasing oil demand in carbonate reservoirs, enhanced oil recovery techniques play key

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role in improving oil production. Surfactant flooding and smart water injection are already
well known as effective enhanced oil recovery techniques that increase oil recovery by

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reduction of oil-water interfacial tension and the alteration of rock wettability. In this work, a
new plant-base natural surfactant, named Tribulus Terrestris is introduced and combined with
smart water samples (i.e. synthetic seawater with different concentrations of active Ca2+,

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Mg2+ and SO42- ions) to determine their individual and integrated effects on reduction in
interfacial tension, wettability alteration and oil recovery in carbonate rock samples.

It was observed that increasing concentrations of SO42- up to 2.5 times resulted in maximum

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wettability restoration among active ions (by changing contact angle from 145.9° to 54.4°).
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Experimental results also showed that the effect of the concentration of active ions on
wettability alteration was more significant compared to their effect on decreasing oil-water
interfacial tension. In addition, the Tribulus Terrestris surfactant reduced oil-water interfacial
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tension considerably (from 45.3 mN/m to 13.5 mN/m at Critical Micelle Concentration of 0.3
wt. %); hence, it was used as smart water modifier to integrate effects of wettability alteration
(by smart water) and reduction in interfacial tension (by new natural surfactant). Core
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flooding experiments demonstrated increased oil recovery from 45.2% for distilled water
injection up to 64% and 72% for smart water and combined smart water-surfactant
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respectively.

Keywords: enhanced oil recovery, Tribulus Terrestris surfactant, smart water, interfacial
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tension, wettability alteration, carbonate rock

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Graphical abstract

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1. Introduction

More than 60% of the world’s present proven petroleum reserves are held in carbonates[1,2].
In carbonate reserves, oil located in low-permeable host blocks is enclosed by conductive
fracture matrixes. Therefore, the oil recoveries in carbonate reserves rarely exceed 30% [3]
and approximately 70-95% of original-oil-in-place will remain in an oil reservoir as residual
oil after primary production. Water or immiscible gas injection as secondary production, will
usually increase oil production to a total recovery of 40-60% which cannot satisfy the huge

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worldwide energy demand, that could rise by 53% till 2030 [2]. As a result, interests in
Enhanced Oil Recovery (EOR) techniques have increased especially for carbonate reservoirs.
The effect of capillary forces (which are mainly responsible for high residual oil saturation) is

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considered by using a dimensionless capillary number which is defined as[4–7]:

= = (1)

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where µ, , σ, and θ denote for the dynamic viscosity of displacing liquid, characteristic

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velocity, interfacial tension and inter-phase contact angle, respectively. As this number is
increased by decreasing the interfacial tension (σ) or increasing the contact angle (θ) up to
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90°, the capillary barrier is eliminated and residual oil saturation decreases considerably
[8,9].
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Among chemical EOR techniques, surfactant flooding has been favored for more than 45
years since it improves the water injection yield by simultaneously decreasing the Interfacial
Tension (IFT) and modifying the wettability of the surface towards water-wet [10–13]. The
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effect of wettability alteration is more crucial in carbonate oil-wet reservoirs [14–19]. The
mechanism of wettability alteration from oil-wet toward water-wet by using surfactant can be
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described in three steps:

1- Formation of ion-pair due to electrostatic attraction between the organic chemical

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groups adsorbed on the rock surface and the surfactant with opposite charge.
2- Desorption and migration of chemical groups from the rock surface to the oil phase due
to non-solubility of the formed ion-pair in water.
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3- Imbibition of brine into the rock due to capillary forces and repulsion of oil by the
displacing brine owing to hydrophobic interaction.
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As chemical surfactants can cause serious environmental problems, the application of

biodegradable, non-toxic, natural based surfactants in oil recovery have been investigated by
many researchers in the recent years [8,20–23]. The application of this kind of surfactant was
introduced by Chhetri et al. that investigated the saponin extract from soapnut as a natural
surfactant [24]. Deymeh et al. studied the impact of Seidlitzia Rosmarinus natural surfactant
on oil-water IFT for EOR applications [23]. Zizyphus Spina-Christi natural Surfactant for
EOR applications in carbonate reservoirs was introduced and investigated by Pordel Shahri et
al. [21]. Ahmadi et al. explored the influence of surfactants extracted from the leaves of
Glycyrrhiza Glabra and mulberry on oil-water IFT [8,25]. Shadizadeh and Kharrat also
introduced a new natural surface-active agent called Matricaria chamomilla which was
investigated for chemical EOR [20].
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The initial wetting state of the reservoir can be altered by the salinity of the injected brine
since the equilibrium between the crude oil, brine, and rock is strongly influenced by the
composition of the injected fluid. Effect of brine composition on the oil recovery has received
considerable attention so far [25–31]. Laboratory studies show that seawater (SW) has
potential to act as a wettability modifier and give a moderate growth in crude oil recovery
[15,32,33]. Yousef et al. [34–36] investigated the effect of sea water dilution in carbonate
rocks and observed up to 18% incremental oil recovery in the laboratory and 7% decrease in

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residual oil saturation in the field test. Fathi et al. [37], Al-Harrasi et al. [38] and Al-Attar et
al. [39] also showed that lowering the ionic strength of injection water increases recovery in
carbonate cores.

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Effect of increased/decreased concentration of specific ions on performance of low salinity
water injection has been extensively studied as smart water injection in the recent years
[33,40–46]. The mechanism of wettability alteration by smart water flooding is described as a

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symbiotic interaction between the adsorbed carboxylic group on the carbonate rock surface
and the potential determining ions Ca2+, Mg2+, and SO42- [28,33,37,47]. Khaledialidusti and
Kleppe showed that fast kinetic rate of rock dissolution affects the behavior of reactive-

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transport problems in carbonates significantly [48]. Although the rock dissolution could
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happen only a few meters away from the injection well due to saturation of formation water,
it takes place in the whole sample during core flooding experiments and is considered as a
major mechanism of wettability alteration. Some reports also suggest that double layer
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expansion and surface complexation are responsible for wettability change [49–54]. Other
factors like pH of injected fluid and pH variation due to rock dissolution that affect the
geochemistry of the reservoir and alter the surface charge during smart water injection must
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also be considered [52,55–57].

It is remarkable to note that smart water is more effective in contact angle alteration
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compared to IFT reduction. As a result, combination of smart water and surfactant injection
processes has been proposed to improve the oil recovery [14,58–60]. The hybrid method of
surfactant/smart water flooding takes the advantage of surfactants in reducing IFT to mobilize
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and prevent the re-trapping of the residual oil that has been mobilized by smart water
injection [59–61]. In large scale application of surfactant flooding, three flow regimes can be
considered: surfactant solution, microemulsion and oil bank as shown in Fig. 1. Low price
and availability of natural surfactants makes the continuous injection of surfactant solution
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(or injection of a high-volume bank of surfactant solution) economically feasible. Low

adsorption of non-ionic natural surfactants on rock surface also improves the stability of the
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created microemulsion bank, which can grow in size even far away from injection wells and
carry the mobilized oil towards production wells.
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Figure 1. Schematic of idealized flow regimes during surfactant flooding [61].

In this work, a new plant-based natural surfactant is introduced and evaluated for IFT
reduction and wettability alteration of carbonate rock surface. Afterwards, the effect of
increase/decrease in concentration of active ions of smart water (SO42-, Ca2+, Mg2+) on IFT
reduction and wettability restoration is investigated. Finally, a combined solution of
optimized smart water and natural surfactant is selected to study the integrated effect of IFT
reduction (by surfactant) and wettability alteration (by smart water) on oil recovery through

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core-flooding experiments.

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2. Materials and methods
2.1 Materials
2.1.1 Aqueous solution

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Artificial Formation Water (FW) was used for determination of the initial water saturation of
the core samples. The composition of FW is presented in Table 1.

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Table 1: Concentration of FW ions
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Component Concentration (mg/L)
HCO3- 1035.66
Cl- 127652
SO42-
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360.3
Ca2+ 8203.36
Mg2+ 1203
Na+ + K+ 76025.52
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Synthetic Sea Water (SW) and modified SW were also provided for IFT, contact angle and
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flooding experiments. Different smart water solutions with increase/decrease in concentration

of active ions were prepared as given in Table 2. The ionic strength was kept constant by
adjusting NaCl concentration in all solutions.
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The pH of the base solution was measured to be 6.93 which shows neutral state. The way the
addition of different salts affect the pH of the brine solution depends on the strength of acid
and base that have formed the salt; i.e. if a strong acid has been neutralized with a weak base,
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the resulting salt would decrease the solution pH and vice versa. Na2SO4 and KCl are neutral
salts, MgCl2 and CaCl2 are slightly acidic and NaHCO3 is basic. However, since the changes
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in concentration of salts are small in different solutions and the differences are also
neutralized due to opposite interaction of constituents, the pH can be considered neutral for
different smart water solutions.

Table 2: Ionic composition of smart water solutions

Sample Ion Concentration (mg/L)
Na+ HCO3- Ca2+ Mg2+ Cl- SO42- K+
SW 13969 103.7 136.3 1710 25703 2402 277.6
SW-0S 10035 103.7 136.3 1710 24035 0 277.6
SW-xS

SW-0.5S 11045 103.7 136.3 1710 24862 1201 277.6

SW-1S 13969 103.7 136.3 1710 25703 2402 277.6
SW-1.5S 12736 103.7 136.3 1710 24963 3603 277.6
SW-2S 11585 103.7 136.3 1710 23923 4804 277.6
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SW-2.5S 10203 103.7 136.3 1710 22753 6005 277.6
SW-3S 9036 103.7 136.3 1710 22063 7206 277.6
SW-3.5S 8320 103.7 136.3 1710 21362 8407 277.6
SW-4S 7520 103.7 136.3 1710 20203 9608 277.6
SW-0Mg 10753 103.7 136.3 0 24832 2402 277.6
SW-0.5 Mg 11903 103.7 136.3 855 25203 2402 277.6
SW-1Mg 13969 103.7 136.3 1710 25703 2402 277.6
SW-xMg
SW-1.5 Mg 12856 103.7 136.3 2565 25136 2402 277.6
SW-2 Mg 11452 103.7 136.3 3420 24631 2402 277.6
SW-2.5 Mg 10732 103.7 136.3 4275 23532 2402 277.6

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SW-3 Mg 10033 103.7 136.3 5130 22143 2402 277.6
SW-3.5Mg 9425 103.7 136.3 5985 21362 2402 277.6
SW-4 Mg 8623 103.7 136.3 6840 20366 2402 277.6
SW-0Ca 13025 103.7 0 1710 25003 2402 277.6

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SW-0.5Ca 13526 103.7 68.15 1710 25363 2402 277.6
SW-1Ca 13969 103.7 136.3 1710 25703 2402 277.6
SW-xCa

SW-1.5Ca 13426 103.7 204.45 1710 25236 2402 277.6

SW-2Ca 19856 103.7 272.6 1710 25056 2402 277.6

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SW-2.5Ca 19536 103.7 340.75 1710 24752 2402 277.6
SW-3Ca 19125 103.7 408.9 1710 24263 2402 277.6
SW-3.5Ca 18965 103.7 477.05 1710 24012 2402 277.6
SW-4Ca 18369 103.7 545.2 1710 23756 2402 277.6

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2.1.2. Crude Oil
The crude oil utilized in the current study was taken from one of the Iranian carbonate oil
reservoirs. The SARA analysis and composition of crude oil are presented in Tables 3 and 4.
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Table 3: Crude oil composition

Component Mole Percent Component Mole Percent

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H2S 0.73 C6 4.02

N2 1.04 C7 3.20
CO2 2.13 C8 1.05
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C1 35.65 C9 1.79
C2 7.95 C10 1.60
C3 4.51 C11 1.67
C12+
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iC4 1.12 27.76

nC4 2.79 Total 100.00
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iC5 1.26

Table 4: SARA analysis of crude oil

Fraction Quantity
Saturated 40.85%
Aromatic 47.79%
Resin 2.65%
Asphaltene 8.71%

2.1.3. Pours media

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Carbonate outcrops were used to prepare core plugs and pellets in this study. The mineralogy,
porosity and permeability of plugs were determined by X-ray diffraction (XRD), helium
porosimetry and brine injection, respectively. In order to determine initial water saturation,
the dried core samples were saturated with 5 Pore Volume (PV) by FW. Then, the saturated
cores were placed in silica gel desiccator until they reached equilibrium and finally the initial
water saturation percent was obtained. Table 5 presents properties and dimensions of core
samples.

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Table 5. Properties and dimensions of core plugs
Length Diameter Porosity Permeability Swir
Core Aqueous solution
(cm) (mm) (%) (mD)

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C-1 8.69 37 17.1 26.3 9.5 Distilled water
C-2 8.65 38 16.9 25.1 9.9 SW
C-3 8.73 37 17.9 26.5 10.1 SW-2.5S

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C-4 8.60 38 17.2 27.3 9.6 SW-2.5S+0.3 wt.% surfactant

Flat pellets were used for contact angle measurement tests; the prepared pellets were washed

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with toluene and ethanol, and dried in oven to a constant weight. In order to minimize the
hysteresis effect caused by surface roughness, the pellets were polished using sand paper.
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2.1.4. Surfactant

Tribulus Terrestris is a plant from Zygophyllaceae family growing in dry climates. The plant
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contains a steroidal saponin compound called Protodioscin (IUPAC: 26-O-β-D-

Glycopyranosyl-22-hydroxyfurost-5-ene-3β, 26-diol-3-O-β-diglucorhamnoside) [62,63], two
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alkaloids and a phytosterol called hecogenin [64,65]. Saponins are natural biodegradable
nonionic surfactants from which their molecular structure is composed of hydrophilic (i.e.
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one or more sugar chains) and hydrophobic (i.e. triterpene or steroid aglycone backbone also
called a Sapogenin) parts which are attached by glycoside bonds [66–68]. Tribulus Terrestris
plant and chemical structure of saponins are shown in Fig. 2. Saponins are divided into three
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groups (steroidal alkaloid glycosides, steroidal glycosides, or triterpene glycosides) based on

the type of aglycone they have [69]. In aqueous solution, saponin molecules align themselves
vertically on the surface with their hydrophobic ends oriented away from the water. This has
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the effect of reducing the surface tension of the water, causing it to foam [70]. For this
reason, saponins are classified as surface-active agents with detergent, wetting, emulsifying
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and foaming properties. Saponins also show lower adsorption affinities on rock surface
compared to known surfactants and are expected to reduce residual oil saturation and
improve oil recovery [71–75].
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Figure 2: a) The Tribulus Terrestris plant b) Chemical structure of saponins; the

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notations R1-R4 represent either H or
various sugar groups [22,68].

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For the aim of this study, a clear light brown colored liquid was extracted by soxhlet
extraction of T. Terrestris leaves with methanol for 48 hours. The solution was then passed
through filter paper and placed in the oven for methanol evaporation; the residue was a

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yellow powder which was soluble in water and alcohol. Properties of extracted powder are
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summarized in Table 6.

Table 6: Properties of T. Terrestris powder

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Product Extracted powder of Tribulus terrestris

Used part Leaves
Description Fine powder
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Color Yellow
Odor specific odor
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PH value (0.3 wt.% solution) 6.3

Density (kg/L) (3 wt.% solution) 1.075
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2.1.5 Determination of surfactant Critical Micelle Concentration

There are several techniques to measure the value of Critical Micelle Concentration (CMC)
such as pH, UV-VIS spectroscopy, calorimetric and conductivity methods [76]. CMC of T.
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Terrestris surfactant solution was determined by conductivity-meter apparatus (S230 Seven

Compact, Mettler-Toledo). Fig. 3 displays the effect of surfactant concentration on the
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conductivity of solution. The slope change in conductivity vs. concentration plot at 0.3 wt. %
represents that the conductivity characteristics of the solution change above this point due to
formation of surfactant micelles. Increasing surfactant concentration above CMC would not
be beneficial and in some cases can also be destructive regarding flocculation and deposition
of surfactant micelles. As a result, the optimum concentration of the surfactant was
determined to be 0.3 wt. %.
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7000

6000

Conductivity (µS/cm)
5000

4000

3000

2000
CMC = 0.3 Wt%
1000

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0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Surfactant Concentration (wt%)

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Figure 3: Conductivity of different surfactant concentrations

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2.2 Methods
2.2.1 Interfacial tension and contact angle measurement

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The oil-water IFT for different samples of surfactant and smart water solutions was measured
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by pendant drop apparatus (Vinci IFT-700) which is shown in Fig. 4.
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Figure 4: Schematic of IFT and contact angle measurement setup

The aqueous solution was injected into a quartz cell; the crude oil droplet was then dispensed
from the tip of the needle. Therefore, after the equilibrium condition, the characteristic shape
of the oil drop was analyzed to determine IFT. Three experiments were carried for each
sample and the mean IFT value was reported. Contact angel tests were also carried out by the
same apparatus; the rock pellets were aged with crude oil for 3 weeks at 60oC to restore
wettability and were placed on top of the quartz cell. The aqueous solution was injected into
the cell and left for 24 hours to reach equilibrium, afterwards the oil drop was released by the
needle and contact angle was measured after equilibrium condition (about 24 h) on the rock
surface. Contact angle tests were repeated at three different locations of each sample to
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eliminate possible surface heterogeneity effects. All of the experiments were carried out at
near reservoir conditions (i.e. 70°C and 2000 psi).
2.2.2 Core flooding tests
Core flooding experiments were conducted by Vinci CFS apparatus to determine the recovery
factor of different flooding scenarios. The setup includes fluid accumulators, a high pressure-
pump, a core holder, a backpressure regulator and liquid collectors at the core outlet. The
experimental procedure can be summarized as follows:

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- Core plugs were washed with ethanol and acetone to remove the contaminants and dried in
oven for 5 hours at 70°C.

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- The plugs were placed in core-holder, saturated with FW and flooded by 3PVs of crude oil
in each direction.
- The oil-saturated samples were aged at 70°C for 25 days to restore the reservoir

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wettability conditions.
- The aged samples were flooded with distilled water, SW and different blends of smart
water and natural surfactant samples to determine and compare the oil recovery factors.

3. Results and discussions

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3.1. Rock mineralogy
X-ray diffraction (XRD) is a common technique to study of crystal structures and atomic
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spacing based on constructive interference of monochromatic X-rays and a crystalline

sample. The X-rays are directed toward the sample and the diffracted X-rays are detected,
processed and counted. Conversion of the diffraction peaks to d-spacings allows
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identification of the mineral because each mineral has a set of unique d-spacings. Typically,
this is achieved by comparison of d-spacings with standard reference patterns [77–79].
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The crystallographic phase and structure of the rock were analyzed using XRD. The X-ray
diffractometer used a monochromatic radiation Cu-Kα (λ = 1.5406 Å) as the source of X-rays
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and operated at 40 kV, 30 mA in the angular range of 2θ = 5°–80° with step width of 0.05°
min-1. Fig. 5 depicts the XRD pattern of the rock sample; it is obvious that the rock consists
of dolomite mineral (i.e. 2θ = 31.5°) and a trace content of limestone phase according to the
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Joint Committee on Powder Diffraction Standards (JCPDS) data file number: 96-900-493
[80].
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Figure 5: XRD pattern of carbonate rock sample

3.2. IFT measurements

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3.2.1. Effect of concentration of active ions
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A series of experiments were conducted to investigate the effect of Ca2+, Mg2+ and SO2-4
concentration on oil-water IFT. It is evident in Fig. 6 that increasing concentration of active
ions has decreased the IFT values moderately. It is normally expected that the IFT of
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hydrocarbon/water systems (without natural surfactant such as asphaltene and resin, which
naturally exist in crude oil) increases as the salt concentration increases [81–83]. However,
the opposite trend has been also reported by several researchers [82–85].
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Reduction of IFT due to addition of salts can be explained by the fact that Ca2+ and Mg2+
cations cover the interaction of acid-base between oil and aqueous mediums which results in
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more solubility of oil in brine. Moreover, asphaltene and resin molecules turn into complex
ions with improved solubility in aqueous phase when adjoining Ca2+ and Mg2+ cations,
resulting in further IFT reduction. SO4-2 introduces an adsorption capability of asphaltene and
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resin from crude oil to the water-oil interface which may be responsible for the reported
attitude of IFT [86]. Lashkarbolooki et al. showed that addition of MgSO4 and Na2SO4 to
asphaltenic crude oil decreased oil/water IFT due to the presence of the sulfate ion in Na2SO4
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and MgSO4 aqueous solutions [87].

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On the basis of the results obtained by Alotaibi et al., a critical salt concentration can be
specified at which the IFT reaches to its minimum value in agreement with our results [84].
Extreme increase in the concentration of active ions leads to the overlapping of hydrophobic
chains of different molecules and induces a slight increase in IFT values due to the
deterioration of adsorption equilibrium between oil and water as shown in Fig. 6.
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SW - xMg SW - xCa SW - xS
50

45
IFT (mN/m)

40

35

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0 1 2 3 4 5
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Figure 6: IFT variation versus concentration of active ions

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3.2.2. Effect of natural surfactant concentration

A substantial reduction in IFT (from 45.3 mN/m to 13.5 mN/m) was observed at quite low

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concentrations of Tribulus Terrestris surfactant (0.3 wt. %) as shown in Fig. 7. The Tribulus
Terrestris surfactant contains saponin molecules and is categorized as a non-ionic surfactant.
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The mechanism by which the Tribulus Terrestris surfactant reduces the IFT is related to the
fact that surfactant species attach to oil-water interface at concentrations lower than CMC
value, resulting in IFT reduction [88]. This significant reduction in IFT introduces the new
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natural surfactant as a good candidate to be used, together with smart water, so that the
benefits of IFT reduction and wettability alteration can be integrated into the EOR process.
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50
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40
IFT (mN/m)

30
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20
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10
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0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Surfactant Concentration (wt%)

Figure 7: Variation of IFT versus Tribulus terrestris surfactant concentration

Fig. 8 represents the IFT reduction to minimum values of 7.2, 9.1 and 12.5 mN/m by addition
of optimum concentration of the surfactant to SW-xS, SW-xMg and SW-xCa smart water
samples, respectively. It is obvious that addition of surfactant to brine samples with different
ionic compositions led to additional decrease in IFT for all solutions. The trend of further
decrease in IFT in the presence of salt at fixed surfactant concentration is in agreement with
published literature [89–93].

Cai et al. indicated that salt type does not have any noticeable effect on IFT while Karnada et
al. showed that salt composition has some effect especially at low surfactant concentration,
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and argued that addition of CaCl2 to the NaCl solution had the lowest crude oil–brine solution
IFT [82,89]. The minimum IFT values after blending brine samples with 0.3 wt% surfactant
occurred at 2.5x concentration of active ions; the extra reduction in IFT for hybrid surfactant-
smart water solutions seemed not to be dependent on the salt type since the decreasing trends
were similar to the results presented in Fig. 6 for smart water solutions without surfactant.
Moreover, the considerable reduction of oil-water IFT in the hybrid solution without
interference between the components shows that Tribulus terrestris surfactant is compatible
with smart water solutions and the salts do interrupt the surfactant structure and stability.

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SW - xMg+0.3 wt% Surfactant SW - xCa+0.3 wt% Surfactant
SW - xS+0.3 wt% Surfactant

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17

15

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13
IFT (mN/m)

11

7
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5
0 1 2 3 4 5
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Figure 8: Effect of surfactant on IFT reduction in different smart water solutions

3.3 Contact angle measurements
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3.3.1. Effect of active ions on wettability alteration

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Contact angle measurements were conducted for different Mg2+, Ca2+ and SO42-
concentrations in order to investigate the effect of ionic content of smart water samples on
wettability restoration of rock. The concentration of each ion was changed from 0 to 4 times
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in the base sea water solution of, while the other ions were kept unchanged (ionic strength of
all solutions was held constant by adjusting Na and Cl concentrations). The experimental
results are presented in Fig. 9. It is observed that an increasing concentration of active ions up
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to 2.5 times, decreases the contact angle from 145.9° to 54.4° for sulfate ions, from 150.9° to
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74.02° for calcium ions and from 148.5° to 69.86° for magnesium ions. This defines the
optimum ionic concentration to move the rock wettability towards water-wet end.
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160.00

140.00

120.00
Contact Angle

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60.00

40.00

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SW-0Ca
SW-0.5Ca
SW-1Ca
SW-1.5Ca
SW-2Ca
SW-2.5Ca
SW-3Ca
SW-3.5Ca
SW-4Ca
SW-0Mg
SW-0.5Mg
SW-1Mg
SW-1.5Mg
SW-2Mg
SW-2.5Mg
SW-3Mg
SW-3.5Mg
SW-4Mg

SW-0S
SW-0.5S
SW-1S
SW-1.5S
SW-2S
SW-2.5S
SW-3S
SW-3.5S
SW-4S
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Figure 9: Impact of SO42- , Ca2+ and Mg2+ concentration on contact angle
In spite of much research in to the effect of smart water on wettability of carbonate

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reservoirs, the mechanism of wettability alteration is still under discussion. Neither Na+ nor
Cl- is considered as a potential determining ion toward carbonate surface, which means that
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they are not able to alter surface wettability [26,94]. Austad et al. proposed the
multicomponent ion exchange theory to describe the wettability alteration due to the increase
in concentration of Ca2+, Mg2+ and SO42- ions. Based on this mechanism, the calcium and
M

magnesium ions can react with carboxylic groups and desorb them from the rock surface. The
adsorption of sulfate on the positively charged calcite surface decays the electrostatic
repulsive force against Ca2+ and Mg2+which which leads to an increase in the concentration
D

of these ions close to the surface. Moreover, The adsorption of SO42- also changes the rock
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surface to less positive and more negative, which consequently desorbs the loosely adsorbed
organic compounds from the calcite [57,95,96]. In other words, although the presence of
sulfate ion is not necessary for wettability alteration by Mg2+ and Ca2+, it plays as a catalyst
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for wettability alteration by these ions at temperatures below 90°C [97].

Another mechanism of carbonate wettability alteration includes the dissolution of calcite

according to the following equilibrium equation [48,94,97]:
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"
↔ ! (2)
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The pre-adsorbed organic compounds reduce the repulsive force on Mg2+, and enable it to
come closer to the surface, react with CO32- ions and precipitate MgCO3. Therefore, the
concentration of CO32- on the right side of equation decreases and the equilibrium shifts
toward formation of more CO32-. According to this equilibrium shift, carbonate dissolution is
more encouraged [98]. On the other hand, carbonate dissolution creates extra Ca2+ close to
the surface which react with pre-adsorbed organic groups bonded to the surface and release
some of them based on the mechanism suggested by strand et al. [28,32].
On the other hand, increasing concentration of sulfate ion increases the risk of precipitation
and deposition of calcium sulfate in porous media. Changes in pH, temperature, pressure and
presence of other ions may also contribute to scale formation [99,100]. The slight increase in
contact angle at high SO42- concentrations can be associated to this phenomenon. However,
 ACCEPTED MANUSCRIPT
since no permeability reduction was observed during core flooding with the optimum
SW2.5S solution, as presented in the following sections, the calcium sulfate was shown to be
in soluble state; therefore the hybrid EOR process can be applied without risk of formation
damage. It must be noted that since the solubility of CaSO4 decreases considerably with
increasing temperature, the application of this process in high temperature reservoirs must be
considered with care [101,102].

3.3.2 Effect of surfactant on wettability alteration

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Fig. 10 shows the effect of surfactant concentration on contact angle. It is obvious that
increasing surfactant concentration from 0 to 0.9 wt. % decreases the contact angle from
160.3° to 80.6°. Wettability alteration generally depends on different parameters such as rock

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morphology, electrostatic and hydrophobic forces and the attraction between surfactant
molecules and the polar components of crude oil. The proposed mechanism for wettability

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alteration by non-ionic surfactants could be explained in two ways which could occur
simultaneously: (1) the weak attraction between positive-charged head of surfactant with
negative adsorbed chemicals (e.g. asphaltenes) which leads to desorption of these groups, and

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(2) The hydrophilic part of the surfactant attracts the surfactant molecules towards the brine
at the rock surface, to replace with adsorbed organic molecules, and make the surface more
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water-wet.

180
M
Contact Angle (degree)

160

140
D

120

100
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80

60
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
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Surafctant Concentration (wt.%)

Figure 10: Effect of surfactant concentration on contact angle
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3.3.3 Effect of smart water on wettability alteration in presence of natural surfactant

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In order to investigate the impact of Tribulus Terrestris surfactant on wettability alteration in

the presence of smart water, the optimum concentration of surfactant (0.3 wt. %) was added
to optimum ion concentrations of SW-xS, SW-xMg and SW-xCa solutions. Results in Table
7 reveal that the contact angles do not change significantly when surfactant solution is added
to the smart water samples. Therefore, it is concluded that addition of natural surfactant to
SW, preserve the wettability state of rock surface and faintly alternate it to water-wet.

Table 7: Effect of surfactant on contact angle of optimum smart water solutions

Contact angle Contact angle
Sample Sample
(degree) (degree)
SW-2.5S 54.4±2.7 SW-2.5S+ 0.3% surfactant 53.7±3.2
SW-2.5Ca 74.02±3 SW-2.5Ca+ 0.3% surfactant 72.36±2.1
SW-2Mg 64.9±3.2 SW-2Mg+ 0.3% surfactant 62.1±3.2
 ACCEPTED MANUSCRIPT
3.4 Core-flooding experiments

Oil recovery tests were performed at temperatures and pressures of 70°C and 2000 psia
according to the mentioned procedure. Fig. 11 shows that the ultimate oil recovery for
injection of "distilled water", "SW", "SW-2.5S" and "SW-2.5S+0.3 wt. % surfactant" reaches
45.2%, 52.16%, 64% and 71.8%, respectively. As it was expected from IFT and contact angle
experimental results, increasing concentration of sulfate ion in sea water (up to 2.5 times,
SW-2.5S) improves the oil recovery. Moreover, the combination of optimum smart water and

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surfactant solutions (i.e. SW-2.5S+0.3 wt. %) increases the oil recovery significantly due to
synergy of IFT reduction (by new natural surfactant) and wettability alteration (by optimum
smart water solution).

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Distilled Water Sea Water (SW)
SW-2.5S SW-2.5S+0.3 wt% Surfactnt

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80
70
60
Recovery (%OOIP)

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50
40
AN
30
20
10
M

0
0 0.5 1 1.5 2 2.5
Pore Volume Injected
D

Figure 11: Oil recovery for distilled water, SW, SW-2.5S and SW-2.5S+0.3 wt. % surfactant
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in terms of PV injection

Conclusions
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Application a new plant surfactant named Tribulus Terrestris together with smart water to
increase oil recovery in carbonate rock samples was investigated in this study. On the basis of
Sconducted experiments, the following are the main conclusions that were drawn:
C

- Considerable reduction in oil-water IFT from 45.3 mN/m to 13.9 mN/m was observed
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at relatively low concentrations of the new non-ionic natural surfactant (namely

Tribulus Terrestris).
- Increasing concentration of sea-water active ions (Ca2+, Mg2+, and SO42-) up to 2.5
times decreased oil-water IFT and restored the rock wettability towards more water-
wet. Sulfate was found to be the most effective ion where decreased the contact angle
from 145.9° to 54.4°.
- Smart water solutions were more effective in wettability alteration compared to IFT
reduction. As a result, a hybrid solution of optimum smart water and surfactant (i.e.
SW-2.5S+0.3 wt. % surfactant) was used in order to benefit from the integrated effects
of IFT reduction (caused by natural surfactant) and wettability alteration (instigated by
smart water) simultaneously.
 ACCEPTED MANUSCRIPT
- Further IFT reduction due to addition of surfactant to brine solutions was shown not to
be dependent on the salt type since the decreasing trends were similar to the results for
smart water solutions without surfactant. Moreover, the considerable reduction of oil-
water IFT in the hybrid solution without interference between the components shows
that Tribulus terrestris surfactant is compatible with smart water solutions and the salts
do interrupt the surfactant structure and stability.
- The slight increase in contact angle at high SO42- concentrations (above SW2.5S)
concerns with potential precipitation and deposition of calcium sulfate. However, since

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no permeability reduction was observed during core flooding with the optimum
SW2.5S solution, the calcium sulfate was shown to be in soluble state.
- Finally, "distilled water", "sea water", "SW-2.5S" and "SW-2.5S+0.3 wt. % surfactant"

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solutions were injected into core plugs and the ultimate oil recoveries were compared.
As anticipated from IFT and contact angle results, the hybrid solution of smart water

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and surfactant increased oil recovery from 45.2 for distilled water up to 71.8%.

References

[1]
U
P.O. Roehl, P.W. Choquette, Carbonate petroleum reservoirs, Springer Science &
AN
Business Media, 2012.
[2] J.J. Sheng, Review of surfactant enhanced oil recovery in carbonate reservoirs,
Advances in Petroleum Exploration and Development. 6 (2013) 1–10.
M

doi:10.3968/j.aped.1925543820130601.1582.

[3] G. V Chilingar, T.F. Yen, Some notes on wettability and relative permeabilities of
D

carbonate reservoir rocks, II, Energy Sources. 7 (1983) 67–75.

doi:https://doi.org/10.1080/00908318308908076
TE

[4] K. Holmberg, D.O. Shah, M.J. Schwuger, Handbook of applied surface and colloid
chemistry, John Wiley & Sons, 2002.
EP

[5] Q. Liu, Interfacial phenomena in enhanced heavy oil recovery by alkaline flood,
ProQuest, 2007.
[6] J.J. Sheng, Status of surfactant EOR technology, Petroleum. 1 (2015) 97–105.
C

doi:10.1016/j.petlm.2015.07.003.
[7] S. Kumar, A. Mandal, Studies on interfacial behavior and wettability change
AC

phenomena by ionic and nonionic surfactants in presence of alkalis and salt for
enhanced oil recovery, Applied Surface Science. 372 (2016) 42–51.
doi:10.1016/j.apsusc.2016.03.024.
[8] M.A. Ahmadi, Y. Arabsahebi, S.R. Shadizadeh, S. Shokrollahzadeh Behbahani,
Preliminary evaluation of mulberry leaf-derived surfactant on interfacial tension in an
oil-aqueous system: EOR application, Fuel. 117 (2014) 749–755.
doi:10.1016/j.fuel.2013.08.081.
[9] B. Honarvar, A. Azdarpour, M. Karimi, A. Rahimi, M. Afkhami Karaei, H. Hamidi, J.
Ing, E. Mohammadian, Experimental investigation of interfacial tension measurement
and oil recovery by carbonated water injection: A case study using core samples from
an Iranian carbonate oil reservoir, Energy and Fuels. 31 (2017) 2740–2748.
doi:10.1021/acs.energyfuels.6b03365.
 ACCEPTED MANUSCRIPT
[10] R.E. Terry, Enhanced Oil Recovery, Encyclopedia of Physical Science and
Technology. 18 (2001) 503–518.
[11] H.E. Garrett, Surface active chemicals, Elsevier, 2013.
[12] C. Huh, E.A. Lange, W.J. Cannella, Polymer retention in porous media, SPE/DOE
Enhanced Oil Recovery Symposium, Society of Petroleum Engineers, 1990.
[13] H. Jia, X. Leng, M. Hu, Y. Song, H. Wu, P. Lian, Y. Liang, Y. Zhu, J. Liu, H. Zhou,
Systematic investigation of the effects of mixed cationic/anionic surfactants on the
interfacial tension of a water/model oil system and their application to enhance crude

PT
oil recovery, Colloids Surfaces A: Physicochemical and Engineering Aspects. 529
(2017) 621–627. doi:10.1016/j.colsurfa.2017.06.055.
[14] M. Karimi, R.S. Al-Maamari, S. Ayatollahi, N. Mehranbod, Wettability alteration and

RI
oil recovery by spontaneous imbibition of low salinity brine into carbonates: Impact of
Mg2+, SO42−and cationic surfactant, Journal of Petroleum Science and Engineering.
147 (2016) 560–569. doi:10.1016/j.petrol.2016.09.015.

SC
[15] D. Leslie Zhang, S. Liu, M. Puerto, C.A. Miller, G.J. Hirasaki, Wettability alteration
and spontaneous imbibition in oil-wet carbonate formations, Journal of Petroleum
Science and Engineering. 52 (2006) 213–226. doi:10.1016/j.petrol.2006.03.009.

U
[16] G. Hirasaki, D.L. Zhang, Surface chemistry of oil recovery from fractured, oil-wet,
AN
carbonate formations, Spe Journal. 9 (2004) 151–162.
doi:https://doi.org/10.2118/88365-PA
[17] D.C. Standnes, T. Austad, Wettability alteration in chalk 2 . Mechanism for wettability
M

alteration from oil-wet to water-wet using surfactants, Journal of Petroleum Science

and Engineering. 28 (2000) 123–143. doi: https://doi.org/10.1016/S0920-
4105(00)00084-X
D

[18] D.C. Standnes, T. Austad, Wettability alteration in carbonates: Interaction between

cationic surfactant and carboxylates as a key factor in wettability alteration from oil-
TE

wet to water-wet conditions, Colloids Surfaces A: Physicochemical and Engineering

Aspects. 216 (2003) 243–259. doi:10.1016/S0927-7757(02)00580-0.
[19] M. Salehi, S.J. Johnson, J. Liang, Mechanistic study of wettability alteration using
EP

surfactants with applications in naturally fractured reservoirs, Langmuir. 24 (2008)

14099–14107. doi: 10.1021/la802464u
[20] S.S. Shadizadeh, R. Kharrat, Experimental investigation of Matricaria chamomilla
C

extract effect on oil-water interfacial tension: Usable for chemical enhanced oil
recovery, Petroleum Science and Technology. 33 (2015) 901–907.
AC

doi:10.1080/10916466.2015.1020063.
[21] M. Pordel Shahri, S.R. Shadizadeh, M. Jamialahmadi, Applicability test of new
surfactant produced from Zizyphus Spina-Christi leaves for enhanced oil recovery in
carbonate reservoirs, Journal of the Japan Petroleum Institute. 55 (2012) 27–32.
doi:10.1627/jpi.55.27.
[22] M.A. Ahmadi, S.R. Shadizadeh, Experimental investigation of adsorption of a new
nonionic surfactant on carbonate minerals, Fuel. 104 (2013) 462–467.
doi:10.1016/j.fuel.2012.07.039.
[23] H. Deymeh, S.R. Shadizadeh, R. Motafakkerfard, Experimental investigation of
Seidlitzia rosmarinus effect on oil-water interfacial tension: Usable for chemical
enhanced oil recovery, Scientia Iranica. 19 (2012) 1661–1664.
doi:10.1016/j.scient.2012.04.020.
 ACCEPTED MANUSCRIPT
[24] a. B. Chhetri, K.C. Watts, M.S. Rahman, M.R. Islam, Soapnut extract as a natural
surfactant for enhanced oil recovery, Energy Sources, Part A Recover. Util. Environ.
Eff. 31 (2009) 1893–1903. doi:10.1080/15567030802462622.
[25] M.A. Ahmadi, S. Zendehboudi, A. Sha, L. James, Nonionic surfactant for enhanced oil
recovery from carbonates : Adsorption kinetics and equilibrium, Industrial &
Engineering Chemistry Research. 51 (2012) 9894–9905. doi: 10.1021/ie300269c
[26] S.J. Fathi, T. Austad, S. Strand, “Smart Water” as a wettability modifier in chalk: The
effect of salinity and ionic composition, Energy and Fuels. 24 (2010) 2514–2519.

PT
doi:10.1021/ef901304m.
[27] A. Khaksar Manshad, M. Olad, S.A. Taghipour, I. Nowrouzi, A.H. Mohammadi,
Effects of water soluble ions on interfacial tension (IFT) between oil and brine in smart

RI
and carbonated smart water injection process in oil reservoirs, Journal of Molecular
Liquids. 223 (2016) 987–993. doi:10.1016/j.molliq.2016.08.089.
[28] P. Zhang, M.T. Tweheyo, T. Austad, Wettability alteration and improved oil recovery

SC
by spontaneous imbibition of seawater into chalk: Impact of the potential determining
ions Ca2+, Mg2+, and SO42-, Colloids Surfaces A: Physicochemical and Engineering
Aspects. 301 (2007) 199–208. doi:10.1016/j.colsurfa.2006.12.058.

U
[29] A.K. Manshad, M. Rezaei, S. Moradi, I. Nowrouzi, A.H. Mohammadi, Wettability
alteration and interfacial tension (IFT) reduction in enhanced oil recovery (EOR)
AN
process by ionic liquid flooding, Journal of Molecular Liquids. 248 (2017) 153–162.
doi:10.1016/j.molliq.2017.10.009.
[30] T. Puntervold, S. Strand, R. Ellouz, T. Austad, Modified seawater as a smart EOR
M

fluid in chalk, Journal of Petroleum Science and Engineering. 133 (2015) 440–443.
doi:10.1016/j.petrol.2015.06.034.
D

[31] A.K. Manshad, I. Nowrouzi, A.H. Mohammadi, Effects of water soluble ions on
wettability alteration and contact angle in smart and carbonated smart water injection
TE

process in oil reservoirs, Journal of Molecular Liquids. 244 (2017) 440–452.

doi:10.1016/j.molliq.2017.09.011.
[32] S. Strand, E.J. Høgnesen, T. Austad, Wettability alteration of carbonates - Effects of
potential determining ions (Ca2+ and SO42-) and temperature, Colloids Surfaces A:
EP

Physicochemical and Engineering Aspects. 275 (2006) 1–10.

doi:10.1016/j.colsurfa.2005.10.061.
[33] P. Zhang, M.T. Tweheyo, T. Austad, Wettability alteration and improved oil recovery
C

in chalk: The effect of calcium in the presence of sulfate, Energy and Fuels. 20 (2006)
AC

2056–2062. doi:10.1021/ef0600816.
[34] A.A. Yousef, S.H. Al-Saleh, A. Al-Kaabi, M.S. Al-Jawfi, Laboratory investigation of
the impact of injection-water salinity and ionic content on oil recovery from carbonate
reservoirs, SPE Reservoir Evaluation & Engineering. 14 (2011) 578–593.
doi:https://doi.org/10.2118/137634-PA
[35] A.A. Yousef, J.S. Liu, G.W. Blanchard, S. Al-Saleh, T. Al-Zahrani, R.M. Al-zahrani,
H.I. Tammar, N. Al-Mulhim, Smart waterflooding: industry, SPE Annu. Tech. Conf.
Exhib., Society of Petroleum Engineers, 2012. doi: https://doi.org/10.2118/159526-MS
[36] A.A. Yousef, S. Al-Saleh, M. Al-Jawfi, Improved/Enhanced oil recovery from
carbonate reservoirs by tuning injection water salinity and ionic content, Eighteenth
SPE Improved Oil Recovery Symposium, Society of Petroleum Engineers. (2012) 1–
18. doi:10.2118/154076-MS.
[37] S.J. Fathi, T. Austad, S. Strand, Water-based enhanced oil recovery (EOR) by “smart
 ACCEPTED MANUSCRIPT
water”: Optimal ionic composition for EOR in carbonates, Energy and Fuels. 25
(2011) 5173–5179. doi:10.1021/ef201019k.
[38] A. Al Harrasi, R.S. Al-maamari, S.K. Masalmeh, Laboratory investigation of low
salinity waterflooding for carbonate reservoirs, Abu Dhabi Int. Pet. Conf. Exhib.,
Society of Petroleum Engineers, 2012. doi: https://doi.org/10.2118/161468-MS
[39] H.H. Al-Attar, M.Y. Mahmoud, A.Y. Zekri, R. Almehaideb, M. Ghannam, Low-
salinity flooding in a selected carbonate reservoir: experimental approach, Journal of
Petroleum Exploration and Production Technology. 3 (2013) 139–149.

PT
doi:https://doi.org/10.1007/s13202-013-0052-3
[40] E.J. Hognesen, S. Strand, T. Austad, Waterflooding of preferential oil-wet carbonates:
Oil recovery related to reservoir temperature and brine composition, SPE Eur. Annu.

RI
Conf., Society of Petroleum Engineers, 2005. doi: https://doi.org/10.2118/94166-MS
[41] R. Gupta, G.G. Smith, L. Hu, T. Willingham, M. Lo Cascio, J.J. Shyeh, C.R. Harris,
Enhanced waterflood for carbonate reservoirs-impact of injection water composition,

SC
SPE Middle East Oil Gas Show Conf., Society of Petroleum Engineers, 2011.
doi:https://doi.org/10.2118/142668-MS
[42] J. Romanuka, J. Hofman, D.J. Ligthelm, B. Suijkerbuijk, F. Marcelis, S. Oedai, N.

U
Brussee, H. van der Linde, H. Aksulu, T. Austad, Low salinity EOR in carbonates,
SPE Improv. Oil Recover. Symp., Society of Petroleum Engineers, 2012.
AN
doi:https://doi.org/10.2118/153869-MS
[43] A. Awolayo, H. Sarma, A.M. AlSumaiti, A laboratory study of ionic effect of smart
water for enhancing oil recovery in carbonate reservoirs, SPE EOR Conf. Oil Gas
M

West Asia, Society of Petroleum Engineers, 2014. doi: https://doi.org/10.2118/169662-

MS
D

[44] K.J. Webb, C.J.J. Black, G. Tjetland, A laboratory study investigating methods for
improving oil recovery in carbonates, Int. Pet. Technol. Conf., International Petroleum
TE

Technology Conference, 2005. doi: https://doi.org/10.2523/IPTC-10506-MS

[45] S. Strand, T. Puntervold, T. Austad, Effect of temperature on enhanced oil recovery
from mixed-wet chalk cores by spontaneous imbibition and forced displacement using
seawater, Energy and Fuels. 22 (2008) 3222–3225. doi:10.1021/ef800244v.
EP

[46] S. Strand, T. Austad, T. Puntervold, E.J. Høgnesen, M. Olsen, S.M.F. Barstad, “Smart
Water” for oil recovery from fractured limestone: A preliminary study, Energy and
Fuels. 22 (2008) 3126–3133. doi:10.1021/ef800062n.
C

[47] H.O. Yildiz, N.R. Morrow, Effect of brine composition on recovery of Moutray crude
AC

oil by waterflooding, Journal of Petroleum science and Engineering. 14 (1996) 159–

168. doi: https://doi.org/10.1016/0920-4105(95)00041-0
[48] R. Khaledialidusti, J. Kleppe, Significance of the kinetics of minerals in reactive-
transport problems geochemical interactions, SPE Eur. Featur. 79th EAGE Conf.
Exhib. Paris, Fr. 12–15 June. SPE-185844-MS. (2017) 12–15.
doi:https://doi.org/10.2118/185844-MS
[49] H. Mahani, A.L. Keya, S. Berg, W.-B. Bartels, R. Nasralla, W.R. Rossen, Insights into
the mechanism of wettability alteration by low-salinity flooding (LSF) in carbonates,
Energy & Fuels. 29 (2015) 1352–1367. doi: 10.1021/ef5023847
[50] H. Ding, S. Rahman, Experimental and theoretical study of wettability alteration
during low salinity water flooding-an state of the art review, Colloids Surfaces A:
Physicochemical and Engineering Aspects. 520 (2017) 622–639.
doi:10.1016/j.colsurfa.2017.02.006.
 ACCEPTED MANUSCRIPT
[51] M.M. Koleini, M.F. Mehraban, S. Ayatollahi, Effects of low salinity water on
calcite/brine interface: A molecular dynamics simulation study, Colloids Surfaces A:
Physicochemical and Engineering Aspects. 537 (2018) 61–68.
doi:10.1016/j.colsurfa.2017.10.024.
[52] H. Mahani, A.L. Keya, S. Berg, R. Nasralla, Electrokinetics of carbonate/brine
interface in low-salinity waterflooding: Effect of brine salinity, composition, rock type,
and pH on ζ-potential and a surface-complexation model, SPE Journal. 22 (2017) 53–
68. doi: https://doi.org/10.2118/181745-PA

PT
[53] P. V Brady, G. Thyne, Functional wettability in carbonate reservoirs, Energy & Fuels.
30 (2016) 9217–9225. doi: 10.1021/acs.energyfuels.6b01895
[54] A.O. Alghamdi, M.B. Alotaibi, A.A. Yousef, Atomistic simulation of calcite

RI
interaction with ionic species and oil components in water-flooding, Colloids Surfaces
A: Physicochemical and Engineering Aspects. 529 (2017) 760–764.
doi:10.1016/j.colsurfa.2017.06.069.

SC
[55] Y. Chen, Q. Xie, A. Sari, P. V. Brady, A. Saeedi, Oil/water/rock wettability:
Influencing factors and implications for low salinity water flooding in carbonate
reservoirs, Fuel. 215 (2018) 171–177. doi:10.1016/j.fuel.2017.10.031.

U
[56] R. Khaledialidusti, J. Kleppe, Significance of geochemistry in single-well chemical-
tracer tests by coupling a multiphase-flow simulator to the geochemical package, SPE
AN
Journal. 23 (2018) 1126–1144. doi:10.2118/189971-PA.
[57] R. Khaledialidusti, J. Kleppe, Surface-charge alteration at the carbonate/brine interface
during single-well chemical-tracer tests: Surface-complexation model, SPE Journal. 23
M

(2018) 14. doi:10.2118/191356-PA.

[58] E. Alagic, A. Skauge, Combined low salinity brine injection and surfactant flooding in
D

mixed− wet sandstone cores, Energy & Fuels. 24 (2010) 3551–3559.

doi:10.1021/ef1000908
TE

[59] E. Alagic, K. Spildo, A. Skauge, J. Solbakken, Effect of crude oil ageing on low
salinity and low salinity surfactant flooding, Journal of Petroleum science and
Engineering. 78 (2011) 220–227. doi:10.1016/j.petrol.2011.06.021.
EP

[60] A.M. Johannessen, K. Spildo, Enhanced oil recovery (EOR) by combining surfactant
with low salinity injection, Energy & Fuels. 27 (2013) 5738–5749.
doi:10.1021/ef400596b
C

[61] S. Tavassoli, A. Kazemi Nia Korrani, G.A. Pope, K. Sepehrnoori, Low-salinity

surfactant flooding-A multimechanistic enhanced-oil-recovery method, SPE Journal.
AC

21 (2016) 0744–0760. doi:10.2118/173801-PA.

[62] M. Ganzera, E. Bedir, I.A. Khan, Determination of steroidal saponins in Tribulus
terrestris by reversed-phase high-performance liquid chromatography and evaporative
light scattering detection, Journal of Pharmaceutical Sciences. 90 (2001) 1752–1758.
doi:10.1002/jps.1124.
[63] Z. Arsova-Sarafinovska, M. Shishovska, S. Memeti, A simple method for
determination of protodioscin in Tribulus Terrestris L. and Pharmaceuticals by high-
performance liquid chromatography using diode-array detection, Journal of Chemical
Engineering Research Updates. 2 (2015) 12–21. doi:10.15377/2409-
983X.2015.02.01.2.
[64] C.A. Bourke, G.R. Stevens, M. CARRIGAN, Locomotor effects in sheep of alkaloids
identified in Australian Tribulus terrestris, Australian veterinary journal. 69 (1992)
163–165. doi: https://doi.org/10.1111/j.1751-0813.1992.tb07502.x
 ACCEPTED MANUSCRIPT
[65] K. Gauthaman, A.P. Ganesan, R.N. V Prasad, Sexual effects of puncturevine (Tribulus
terrestris) extract (protodioscin): an evaluation using a rat model, The Journal of
Alternative & Complementary Medicine. 9 (2003) 257–265.
doi:https://doi.org/10.1089/10755530360623374
[66] K. Hostettmann, A. Marston, Saponins, Cambridge University Press, 2005.
[67] Ö. Guclu-Ustundag, G. Mazza, Saponins: Properties, applications and processing,
Critical reviews in food science and nutrition. 47 (2007) 231–258.
doi:10.1080/10408390600698197.

PT
[68] P. E, Surface rheology of saponin adsorption layers, Langmuir. 27 (2011) 12486.
doi:10.1021/la202860u.
[69] A. Barati, A. Najafi, A. Daryasafar, P. Nadali, H. Moslehi, Adsorption of a new

RI
nonionic surfactant on carbonate minerals in enhanced oil recovery: Experimental and
modeling study, Chemical Engineering Research and Design. 105 (2016) 55–63.
doi:10.1016/j.cherd.2015.10.047.

SC
[70] J. Bruneton, Principles and practice of phytotherapy, Princ. Pract. Phyther. (2013)
183–350. doi:10.1016/B978-0-443-06992-5.00010-4.

U
[71] Z.W. Wang, M.Y. Gu, G.Z. Li, Surface properties of Gleditsia saponin and synergisms
of its binary system, Journal of dispersion science and technology. 26 (2005) 341–347.
AN
doi:10.1081/DIS-200049604.
[72] C. Sarnthein-Graf, C. La Mesa, Association of saponins in water and water-gelatine
mixtures, Thermochim. Acta. 418 (2004) 79–84. doi:10.1016/j.tca.2003.11.044.
M

[73] E. İbanoğlu, Ş. İbanoğlu, Foaming behavior of liquorice (Glycyrrhiza glabra) extract.,

Food Chemistry. 70 (2000) 333–336. doi: https://doi.org/10.1016/S0308-
8146(00)00098-4
D

[74] S. Mitra, S.R. Dungan, Micellar properties of quillaja saponin. 1. Effects of

temperature, salt, and pH on solution properties, Journal of Agricultural and Food
TE

Chemistry. 45 (1997) 1587–1595. doi:10.1021/jf960349z.

[75] A. Barati-Harooni, A. Najafi-Marghmaleki, S.M. Hosseini, S. Moradi, Experimental
investigation of dynamic adsorption-desorption of new nonionic surfactant on
EP

carbonate rock: Application to enhanced oil recovery, Journal of Energy Resources

Technology. Trans. ASME. 139 (2017). doi:10.1115/1.4036046.
[76] M.A. Ahmadi, S.R. Shadizadeh, Adsorption of novel nonionic surfactant and particles
C

mixture in carbonates: Enhanced oil recovery implication, Energy and Fuels. 26 (2012)
4655–4663. doi:10.1021/ef300154h.
AC

[77] Payan, A., Isari, A.A. and Gholizade, N.Catalytic decomposition of sulfamethazine
antibiotic and pharmaceutical wastewater using Cu-TiO2@ functionalized SWCNT
ternary porous nanocomposite: influential factors, mechanism, and pathway studies,
Chemical Engineering Journal, (2018) doi: 10.1016/j.cej.2018.12.118
[78] Hayati, F., Isari, A. A., Fattahi, M., Anvaripour, B. and Jorfi, S, Photocatalytic
decontamination of phenol and petrochemical wastewater through ZnO/TiO2 decorated
on reduced graphene oxide nanocomposite: influential operating factors, mechanism,
and electrical energy consumption. RSC Advances, 70 (2018), 40035-40053 doi:
10.1039/C8RA07936F
[79] H.P. Klug, L.E. Alexander, X-ray diffraction procedures for polycrystalline and
amorphous materials, Wiley Online Library, 1974.
[80] Joint committee on powder diffraction standards, Anal. Chem. 42 (1970) 81A–81A.
 ACCEPTED MANUSCRIPT
doi:10.1016/j.biolcel.2003.12.008.
[81] N. Ikeda, M. Aratono, K. Motomura, Thermodynamic study on the adsorption of
sodium chloride at the water/hexane interface, Journal of colloid and interface science.
149 (1992) 208–215. doi: https://doi.org/10.1016/0021-9797(92)90405-B
[82] B.Y. Cai, J.T. Yang, T.M. Guo, Interfacial tension of hydrocarbon + water/brine
systems under high pressure, Journal of chemical & engineering data. 41 (1996) 493–
496. doi:10.1021/je950259a.
[83] A. Badakshan, P. Bakes, The influence of temperature and surfactant concentration on

PT
interfacial tension of saline water and hydrocarbon system in relation to enhanced oil
recovery by chemical flooding, SPE-20295, 1990.
[84] M.B. Alotaibi, H.A. Nasr-El-Din, Effect of brine salinity on reservoir fluids interfacial

RI
tension, SPE-121569, 2009.
[85] E. Serrano-Saldaña, A. Domıń guez-Orti, H. Pérez-Aguilar, I. Kornhauser-Strauss, F.

SC
Rojas-González, Wettability of solid/brine/ n-dodecane systems: Experimental study
of the effects of ionic strength and surfactant concentration, Colloids Surfaces A:
Physicochemical and Engineering Aspects. 241 (2004) 343–349.
doi:https://doi.org/10.1016/j.colsurfa.2004.04.025

U
[86] W. Qiao, J. Li, Y. Zhu, H. Cai, Interfacial tension behavior of double long-chain 1, 3,
AN
5-triazine surfactants for enhanced oil recovery, Fuel. 96 (2012) 220–225. doi:
https://doi.org/10.1016/j.fuel.2012.01.014
[87] M. Lashkarbolooki, S. Ayatollahi, M. Riazi, The impacts of aqueous ions on interfacial
M

tension and wettability of an asphaltenic − Acidic crude oil reservoir during smart
water injection, Journal of Chemical & Engineering Data. 11 (2014): 3624-3634.
doi:10.1021/je500730e
D

[88] S.J.D. Sofla, M. Sharifi, A.H. Sarapardeh, Toward mechanistic understanding of

natural surfactant flooding in enhanced oil recovery processes: the role of salinity,
TE

surfactant concentration and rock type, Journal of Molecular Liquids. 222 (2016) 632–
639. doi: https://doi.org/10.1016/j.molliq.2016.07.086.
[89] W. Karnanda, M.S. Benzagouta, A. AlQuraishi, M.M. Amro, Effect of temperature,
EP

pressure, salinity, and surfactant concentration on IFT for surfactant flooding

optimization, Arabian Journal of Geosciences. 6 (2013) 3535–3544.
doi:10.1007/s12517-012-0605-7.
C

[90] G.Q. Tang, N.R. Morrow, Influence of brine composition and fines migration on crude
oil/brine/rock interactions and oil recovery, Journal of Petroleum Science and
AC

Engineering. 24 (1999) 99–111. doi:10.1016/S0920-4105(99)00034-0.

[91] T. Al-Sahhaf, A. Elkamel, A.S. Ahmed, A.R. Khan, The influence of temperature,
pressure, salinity, and surfactant concentration on the interfacial tension of the n-
octane-water system, Chemical Engineering Communications. 192 (2005) 667–684.
doi:10.1080/009864490510644.
[92] T.M. Okasha, A. Alshiwaish, Effect of brine salinity on interfacial tension in Arab-D
carbonate reservoir, Saudi Arabia, SPE Middle East Oil Gas Show Conf. (2009).
doi:10.2118/119600-MS.
[93] A. Tunnish, E. Shirif, A. Henni, The influence of ionic liquid type, concentration, and
slug size on heavy oil recovery performance, Brazilian Journal of Petroleum and Gas.
11 (2017) 15–29. doi:10.5419/bjpg2017-0002.
[94] A. Hiorth, L.M. Cathles, M. V Madland, The impact of pore water chemistry on
 ACCEPTED MANUSCRIPT
carbonate surface charge and oil wettability, Transport in Porous Media. 85 (2010) 1–
21. doi: https://doi.org/10.1007/s11242-010-9543-6
[95] T. Austad, S. Strand, E.J. Høgnesen, P. Zhang, Seawater as IOR fluid in fractured
chalk, SPE Int. Symp. Oilf. Chem., Society of Petroleum Engineers, 2005.
doi:https://doi.org/10.2118/93000-MS
[96] T. Austad, S. Strand, M.V. Madland, T. Puntervold, R.I. Korsnes, Seawater in chalk:
an EOR and compaction fluid, Int. Pet. Technol. Conf., International Petroleum
Technology Conference, 2007. doi: https://doi.org/10.2523/IPTC-11370-MS

PT
[97] S. Rashid, M.S. Mousapour, S. Ayatollahi, M. Vossoughi, A.H. Beigy, Wettability
alteration in carbonates during “Smart Waterflood”: Underling mechanisms and the
effect of individual ions, Colloids Surfaces A: Physicochemical and Engineering

RI
Aspects. 487 (2015) 142–153. doi:10.1016/j.colsurfa.2015.09.067.
[98] Surface Chemistry Study of Low Salinity Waterflood, Jeelaja Kaliyugarasan, Master
thesis, Petroleum Technology – Reservoir Chemistry Centre for Integrated Petroleum

SC
Research ( Uni CIPR ) Department of Chemistry University of Bergen , June 2013,
(2013).
[99] J. Moghadasi, M. Jamialahmadi, H. Müller-Steinhagen, A. Sharif, A. Ghalambor, M.R.

U
Izadpanah, E. Motaie, Scale formation in Iranian oil reservoir and production
equipment during water injection, Int. Symp. Oilf. Scale, Society of Petroleum
AN
Engineers. (2003). doi:10.2118/80406-MS.
[100] G. Atkinson, K. Raju, R.D. Howell, The thermodynamics of scale prediction, SPE Int.
Symp. Oilf. Chem, Society of Petroleum Engineers. (1991). doi:10.2118/21021-MS.
M

[101] M.A. Mahmoud, K. Fahd, Evaluating the damage caused by calcium sulfate scale
precipitation during low- and high-salinity-water injection, Journal of Canadian
D

Petroleum Technology. 53 (2014) 141-150. doi: https://doi.org/10.2118/164634-PA

[102] M. Mahmoud, S. Elkatatny, K.Z. Abdelgawad, Using high- and low-salinity seawater
TE

injection to maintain the oil reservoir pressure without damage, Journal of Petroleum
Exploration and Production Technology. 7 (2017) 589–596. doi:10.1007/s13202-016-
0279-x.
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Highlights

• A new plant-based natural surfactant is introduced for EOR applications.

• Sea water modified with different concentrations of active ions was used as smart-
water.
• Application of smart water in presence and absence of natural surfactant was studied
by IFT, contact angle and core flood experiments.
• A novel EOR approach is proposed by integration of IFT reduction (introduced by a
new natural surfactant) and wettability alteration (via smart water) mechanisms.

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