Journal Pre-proof

Foaming properties, wettability alteration and interfacial tension reduction by saponin

extracted from soapnut (Sapindus Mukorossi) at room and reservoir conditions

Nurudeen Yekeen, Azlinda Abdul Malik, Ahmad Kamal Idris, Nadia Izwani Reepei,
Kenny Ganie

PII: S0920-4105(20)30659-8
DOI: https://doi.org/10.1016/j.petrol.2020.107591
Reference: PETROL 107591

To appear in: Journal of Petroleum Science and Engineering

Received Date: 30 March 2020

Revised Date: 16 June 2020
Accepted Date: 25 June 2020

Please cite this article as: Yekeen, N., Malik, A.A., Idris, A.K., Reepei, N.I., Ganie, K., Foaming
properties, wettability alteration and interfacial tension reduction by saponin extracted from soapnut
(Sapindus Mukorossi) at room and reservoir conditions, Journal of Petroleum Science and Engineering
(2020), doi: https://doi.org/10.1016/j.petrol.2020.107591.

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 (a) (b) (c) (d) (e) (f)

The pendant drop profiles of crude oil in the saponin solutions environment at constant temperature
(80oC), for 0.5 wt% saponin concentration at (a) 8 MPa (b) 10 MPa (c)16 MPa (d) 20 MPa (e) 22
MPa and (f) crude oil-water
1 Foaming properties, wettability alteration and interfacial tension reduction by saponin
2 extracted from soapnut (Sapindus Mukorossi) at room and reservoir conditions
3
4 Nurudeen Yekeen a,* (peteryekeen@yahoo.com, +60183270381), Azlinda Abdul Malik a,b
c
5 (azlinda.amalik@utp.edu.my, +60102269479), Ahmad Kamal Idris (pe-kamal@utm.my,
6 +60197288000), Nadia Izwani Reepei a (nadia.reepei@utp.edu.my, +60196345317), Kenny
7 Ganie b (kenny.ganie@gmail.com)
a
8 Institute of Hydrocarbon Recovery, Universiti Teknologi PETRONAS, 32610, Bandar Seri
9 Iskandar, Perak, Malaysia
b
10 Department of Petroleum Engineering, Faculty of Geoscience and Petroleum Engineering,
11 Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar, Perak Darul Ridzuan, Malaysia.
c
12 Department of Petroleum Engineering, Faculty of Chemical and Energy Engineering, Univesiti
13 Teknologi Malaysia, 81310 Skudai, Johor Bahru, Malaysia

14 Abstract
15 In this study, a natural surfactant, saponin was isolated from soapnut (Sapindus Mukorossi). The
16 extracted surfactant was characterized by Fourier-transform infrared spectroscopy (FTIR)
17 analysis. The effectiveness of the isolated surfactant as EOR agent was evaluated from foam
18 generation/stabilization properties, wettability alteration of the rock surfaces, as well as oil-water
19 interfacial tension (IFT) reduction characteristics. The performance of the extracted saponin was
20 compared with that of a commercial saponin and sodium dodecyl sulfate (SDS). The foaming
21 properties of the saponin with carbondioxide (CO2) was characterized using Teclis Foamscan
22 instrument at room condition and 60oC. The IFT and contact angles at room conditions and
23 reservoir conditions were measured using KRŰSS Drop Shape Analyzer (DSA 25 and DSA 100)
24 via pendant drop and sessile drop techniques respectively. The foamability of the saponin-
25 stabilized foam was good at ambient condition and 60oC. Moreover, the time taken for almost
26 100% liquid drainage was higher in saponin-stabilized foam than the SDS-stabilized foam. The
27 optimum concentration for attaining maximum foam stability decreased from 0.4 wt% at room
28 temperature to 0.1 wt% at 60oC. Signifying that the quantity of the surfactant to be used in foam
29 generation could reduce at high temperature. The isolated saponin exhibited relatively good
30 interfacial activities individually and in synergistic interaction with silicon dioxide (SiO2)
31 nanoparticles at reservoir conditions. Precisely, at 8 MPa and 80oC, the crude-oil water IFT was

1
1 reduced from 23.24 mN/m to 1.59 mN/m (about 93.2 %) by 0.2 wt% saponin concentration. The
2 IFT was further reduced to 0.87 mN/m (about 96.3%) by a mixed system of 0.5 wt% saponin and
3 0.05 wt% SiO2 nanoparticles concentration. Increasing IFT with increasing temperature were
4 observed at very high temperature due to phase separation resulting from clouding phenomenon.
5 However, the clouding temperature increased with 0.1 wt% saponin concentration, and in
6 presence of SiO2 nanoparticles (0.05 wt% and 0.1 wt%). The study suggests that the extracted
7 saponin could be considered as supplementary alternative to conventional EOR surfactants.

8 Keywords: Saponin; foaming properties; wettability alteration; interfacial tension (IFT);; high
9 temperature; high pressure.

10 1 Introduction

11 The crude oil price is plummeting in such an alarming rate that the world has never
12 experience for several decades due to the impact of corona virus (COVID-19) epidemic on
13 global economy. One of the strategies being adopted for survival by the oil and gas industries is
14 to extract surfactants from natural sources that will be environmentally friendly, stable at
15 downhole conditions and are cost efficient at the present economic conditions. These surfactants
16 could serve as alternatives to expensive conventional chemical surfactants that are presently
17 being used for enhanced hydrocarbon recovery (EOR). Among the chemical EOR techniques,
18 surfactants flooding is very popular due to their versatile applications in different kinds of
19 reservoirs and conditions (Samanta et al., 2013). Surfactants can be applied in conventional and
20 unconventional reservoirs, such as carbonate, sandstone and unconventional shale reservoirs, as
21 well as heavy oil and light oil reservoirs.
22 Surfactants can be classified as nonionic, anionic, amphoteric, and cationic surfactants
23 depending on their hydrophilic group and chemical structure (Mosayebi et al., 2016). A good
24 number of synthetic nonionic, anionic and cationic surfactants have being experimentally
25 investigated for oil-water interfacial tension reduction properties, as reservoir rock wettability
26 modification agents, and as foam generation and stabilization agents (Hussien et al., 2019;
27 Kuang et al., 2018; Lokanathan et al., 2020; Ma et al., 2020; Mirchi et al., 2015; Sagir et al.;
28 Yekeen et al., 2019a; Zhang et al., 2020; Zhang et al., 2019). Results showed that surfactants are
29 ideal hydrocarbon recovery agents from the conventional and unconventional reservoirs, due to

2
1 their excellent surface-acting and foaming properties (Kumar and Mandal, 2019; Mosayebi et al.,
2 2016).
3 Mechanistically, in presence of the surface-active agents, the trapped hydrocarbon in the
4 pore spaces of the reservoir rock due to capillary forces, can be release via decreasing interfacial
5 tension (IFT), and alteration of the wettability of the rock from oil-wet or weakly-water wet state
6 into strongly water-wet conditions (Samanta et al., 2013; Zhang et al., 2006). Besides surfactant
7 flooding, surfactants have been applied as the conventional foam generation and stabilization
8 agents for several decades (Syed et al.; Yekeen et al., 2017a; Yekeen et al., 2018). Significant
9 reduction in oil-water interfacial tension and the enhancement in surfactant-foam stability and
10 propagation in porous formation have been attributed to the concentration of the surfactant
11 molecules at the liquid-liquid and gas-liquid interface (Roy et al., 1997; Yekeen et al., 2017b).
12 The mobility of the injected gas can be enhance through surfactant-stabilized foamed injection.
13 Surfactant-stabilized foams have also been applied as fluid diversion agents in heterogeneous
14 porous formation, to redirect the injected fluid flow from the already swept high permeability
15 layers to the low permeability layer containing the trapped hydrocarbon (Singh and Mohanty,
16 2017).
17 The performance of engineered surfactants as feasible EOR agents have been widely
18 investigated and proven in most of the previous studies. However, the synthetic surfactants are
19 chemically-based, and could be environmentally unfriendly and quite expensive because of the
20 high cost of the raw materials (Nowrouzi et al., 2020; Samanta et al., 2013). The phase
21 separation due to clouding phenomenon at high temperature, as well as loss of surfactants
22 molecules due to adsorption on porous matrix also increases the cost of surfactant applications in
23 EOR. Consequently, recent research efforts are being focused on the designed and synthesized of
24 eco-friendly, sustainable and affordable bio-surfactants that could achieve considerable reduction
25 in oil-water IFT, alteration of wettability of porous system from oil-wet to water-wet systems,
26 and with high stability at reservoir conditions. The advantages of the bio-surfactants over the
27 chemical surfactants have been identified as cost minimization and sustainability, since the
28 former can be synthesized from renewable raw materials. They are also less toxic, easily
29 degradable and resistance to hard water compared to the synthetic surfactants (Samanta et al.,
30 2013).
31 Some attempts have been made in previous studies to characterize natural surfactants for

3
1 enhanced oil recovery applications (Samanta et al., 2013; Samanta et al., 2011; Saxena et al.,
2 2018). Isolation of bio-surfactants, particularly saponin, from soapnut have been reported in
3 literature. Soapnut is a fruit of the soapnut tree, it belong to the plant family of “sapindaceae”.
4 They are largely located in sub-tropical and tropical climatic zones of the world and are
5 popularly known with different names in such regions, like “ritha” “reetha”, “soapnut”,
6 “washnut”, and “soapberry” (Mondal et al., 2017; Samanta et al., 2013). “Sapindus Trifoliatus”
7 and “Sapindus Mukorossi” are the two major varieties of the soapnut that are generally
8 obtainable in Asia, particularly in India, Pakistan, Nepal, and Indonesia (Samanta et al., 2013).
9 The saponaceous constituents of “Sapindaceae” known as “saponin” has been generally
10 studied for enhanced hydrocarbon recovery purposes (Bajad and Pardeshi, 2016; Roy et al.,
11 1997). Saponins were identified as nonionic surfactants comprising of hydrophobic tail and
12 hydrophilic head (Nowrouzi et al., 2020). The structure of saponin is presented in Fig. 1. Despite
13 the existing studies on the potential application of saponins for EOR processes, the oil-field
14 application of these surfactants for enhanced hydrocarbon recovery (EOR) is yet to be fully
15 realized due to several issues. In most of the previous studies, the potential of saponin extracted
16 from Sapindus Mukorossi for reducing oil-water interfacial tension, as well as its foaming
17 properties have been investigated at ambient conditions. The foaming and interfacial properties
18 of this surfactant at downhole conditions have not been extensively investigated.
19 The molecular structure of the synthesized saponin showed that it is a kind of nonionic
20 surfactant. Nonionic surfactant solutions could become turbid and unstable at certain
21 temperature. This temperature is known as the critical solution temperature or the cloud point.
22 This clouding phenomenon usually results in phase separation and thermal instability during the
23 enhanced oil recovery applications at high temperature (Chatterjee et al., 2002; Ribeiro et al.,
24 2014). Meanwhile, the occurrence of clouding phenomenon in saponin solution is still unclear.
25 Some researchers emphasized that saponins are expected to be hydrolyzed and degraded by high
26 pressure and temperature conditions (Ribeiro et al., 2014). They further stated that a reduction in
27 saponin extraction yield is expected at temperature beyond 70oC because of the degradation
28 phenomenon at high temperature (Güçlü-Üstündağ and Mazza, 2007; Ribeiro et al., 2014).
29 Others categorically stated that saponins do not cloud, and that they can even improve the
30 thermal stability of clouding nonionic surfactants(Chatterjee et al., 2002). Results of Chatterjee

4
1 et al. (2002) studies showed that the low concentrations of saponins inhibited the clouding
2 properties of TX-100 and polymer methylcellulose (MC) solutions.
3 Hence, further studies is necessary to understand the performance and effectiveness of
4 saponin, as well as its influence on liquid-liquid and liquid-solid interfacial properties and
5 foaming properties at high temperature and pressure. Moreover, the synergistic influence of
6 saponin and silicon dioxide (SiO2) nanoparticles on crude-oil water IFT are rarely reported in
7 literature. In previous studies, the interfacial and foaming properties of saponin extracted from
8 soapnut is usually compared with the same plant extracts sold in commercial quantity in the
9 market. The performance of saponin extracted from soapnut is hardly compared with the popular
10 synthetic surfactants, such as sodium dodecyl sulfate, while the oil-water IFT reduction
11 effectiveness at extreme temperature (80oC-1500C) and pressure (8 MPa- 22 MPa) is yet to be
12 extensively studied.
13 Motivated by the limitations of previous studies, a bio-surfactant (saponin) was isolated
14 from soapnut (Sapindus Mukorossi) in this study. The effectiveness of the isolated surfactants as
15 EOR agent was characterized by foam generation/stabilization properties, modification of rock
16 wettability, as well as oil-water interfacial tension reduction. The foam stability was investigated
17 at high temperature while the IFT reduction capacity of the synthesized surfactant at high
18 temperature (80oC-1800C) and elevated pressure (8 MPa- 22 MPa), representative of reservoir
19 conditions was then investigated for potential applications at harsh downhole conditions.
20 Influence of the synergistic interaction between the saponin surfactant and silicon dioxide (SiO2)
21 nanoparticles, on oil-water IFT, at high temperature and pressure was also investigated. The
22 performance of the synthesized saponin was compared with that of commercial saponin and an
23 anionic surfactant, sodium dodecyl sulfate (SDS). The choice of SDS surfactant was based on
24 their popular oilfield applications and the fact that this surfactant has demonstrated considerable
25 ability to reduce IFT, alter rock wettability, as well as improve the foaming capacity and stability
26 in previous studies.

5
1

2 Fig. 1 Molecular structure of saponin, adapted from (Nowrouzi et al., 2020)

3 2. Materials and methods

4 2.1. Materials
5 Soapnut pericarp fruits (Sapindus Mukorossi) were purchased from a local market in
6 Ipoh, Perak, Malaysia. N-Hexane (99 % pure) was purchased from Merck Sdn Bhd Malaysia.
7 Ethanol (95% pure) for extraction was purchased from HmbG Reagent Chemicals (Kuala
8 Lumpur, Malaysia). Commercial saponin was purchased from Sigma Aldrich (Sigma Aldrich
9 (M) Sdn Bhd, Selangor, Malaysia). Sodium dodecyl sulfate (with molecular weight of 288.38
10 g/mol and purity of ≥ 99.0%) was purchased from Sigma-Aldrich. Normal heptane (C7H16) was
11 the mineral oil used in the experiment. The model oil was purchased from a local Malaysian
12 Supplier, Merck Sdn. Bhd. Shah Alam, Selangor, with purity of 99%.
13 A light crude oil from Malaysia was used for the high temperature and high pressure
14 experiments. The viscosity and the density of the oil was measured as 5.84 cp and 0.811 g/cm3
15 respectively while the API gravity was determined as 41.37. The dispersant used for the
16 experiments is deionized water. All chemicals used were of analytical grade and were used as
17 received without further purification. Two types of rock substrates, Berea sandstone and shales
18 were used for investigating the influence of the surfactants on the wetting properties of rocks.
19 The black shales were obtained from the Timah Tasoh Formation, Sanai Hill. At the North East
20 of Hutan Lipur Bukit Ayer in Kampung Guar Jentik, Beseri District, Perlis of Peninsular
21 Malaysia, just south of Timah Tasoh Dam. The area is located at the coordinates of 6°33'18.00"N
22 100°12'24.00"E.

6
1 2.2. Methods

2 2.2.1. Extraction of saponin

3 A minor modifications of previous protocols employed by Sharma et al. (2012) and Roy
4 et al. (1997) were adopted for the saponin isolation. Using an oven (Thermo/OGS-100), the
5 soapnut pericarps were dried at a temperature of 60oC for 24hr to remove the moisture. The
6 pericarps were then grinded into a fine powder using conventional grinder
7 (FRITSCH/Pulverisette 2). To ensure that the dried sample was defatted, 100g of the dried
8 saponin powder was then mixed with n-hexane for about 120mins, using the Soxhlet apparatus.
9 The defatted sample was extracted with ethanol. To do this, 40g of the defatted saponin
10 was mixed with 200ml ethanol for 5min using electromagnetic stirrer. The mixture was then
11 loaded into the ultrasound equipment for hours for the extraction process. After the ultrasound
12 extraction, the mixed ethanol was removed from the extracted saponin filtrate, as the saponin
13 filtrate is then dried at a temperature of 60°C in an oven for 24hrs. Further investigations were
14 conducted using the extract obtained from the solvent after the evaporation. A stock solution was
15 prepared from the dry paste by re-dissolving the paste in water. Different concentration of the
16 surfactant solution used in this study were then prepared. For instance, The extraction of 1 g of
17 the fruit pericarp powder in 100 ml of the distilled water was used to make 1 wt% natural
18 surfactant solution (Roy et al., 1997).

19 2.2.2. Spectral analysis of the extracted saponin

20 A confirmatory test was conducted using Fourier Transform Infra-red Spectrometer

21 (FTIR; Model: Perkin Elmer, Spectrum One) to investigate if the synthesized substance is
22 saponin or not. The functional groups and the absorption/ molecular vibration peaks present in
23 the extracted saponin was identified through the FTIR analysis and compared with that of the
24 commercial Saponin. About 10 mg of the grounded sample was mixed with KBr salt and then
25 compressed into a thin pellet with the aid of KBr press (Samal et al., 2017). The sample was
26 placed with care on already cleaned ATR diamond crystal surface. The analysis was conducted
27 and the infrared spectra were recorded within the wavelength interval (wavenumber) of 4000-
28 500cm-1. Background scan was conducted for each sample and the FTIR spectra was recorded as
29 KBr matrix and processed using spectrum Perkin Elmer software. The results was compared with
30 FTIR transmittance spectra of the commercial saponin.

7
 1
2 2.2.3 Foam generation and stability experiments
3 The rate of bulk foam generation and foam stability by the saponin was studied using the
4 Teclis Foamscan equipment (Teclis Scientific, France). The use of Teclis foamscan for
5 investigating foam generation and stabilization properties have been reported in previous studies
6 (Ahmed et al., 2017; Hanamertani et al., 2018; Jones et al., 2016; Simjoo et al., 2013). The bulk
7 stability experiment was conducted at room temperature and at 60oC. CO2 gas was used for the
8 foam generation. The foam was generated through sparging of the CO2 gas via a porous plate
9 (with pore size of 40 μm –100 μm) affixed at the base of the glass chamber foam column (with
10 inner diameter ±32 mm).The glass tube foam column was filled with 60 ml of the surfactant
11 solutions, and the foam generation was ensured by sparging of the CO2 gas at a fixed flow rate of
12 100 ml/min through the solution. The foam generation commences and stopped automatically
13 when the foam reached a stipulated volume (100 mL). The foam generation and stability process
14 is monitored by a connected software.
15 The rate of the decrease in foam volume with time after reaching the pre-set generation
16 volume was monitored. The volume of the generated foam throughout the CO2 gas sparging
17 process was measured, and the decay profile of the foam with time just after the generation of the
18 foam was recorded by the Charged-Coupled Device (CCD) camera connected to the foam
19 column. The device determined the foam volume through the gray level of the foam in glass
20 tube. The volume of the liquid in the foam with time was measured with the conductivity
21 electrodes fitted into the foamscan. The high temperature experiment was conducted using the
22 thermo-stated glass chamber at 60oC. The foam bulk stability was estimated from the decay
23 profile of the foam with time, as well as the liquid drainage trend obtained from the plot of liquid
24 volume in the foam with time. Example of visual image of the foam decay profile with time
25 observed in this study is presented in Fig. 2.
26
27
28
29
30
31
32

8
1
2
3
4
5
6
7
Decreasing foam height with time in the foam column
8
9 Fig. 2. Visual image of the foam decay profile with time.
10

11 2.2.4 Surface/Interfacial tension and contact angle measurements

12 KRŰSS Drop Shape Analyzer, KRŰSS DSA25 (KRÜSS GmbH, Germany) was used to
13 measure the surface/interfacial tensions as well as the wetting properties of rocks in presence of
14 the different concentration of the saponin at ambient conditions. Similar protocols used in
15 previous studies were adopted (Yekeen et al., 2020). The surface/interfacial tensions were
16 measured through the Pendant drop techniques. For interfacial tension measurement, the pendant
17 drop of the oil was formed and suspended from a metal syringe needle (with a diameter of 1.825
18 mm) in a surfactant solution environment.
19 For surface tension measurement, the pendant drop of the surfactant was created and
20 suspended from the metal syringe needle in the air environment. To determine the critical
21 micelle concentration (CMC) of the saponin surfactant, the surface tension values were measured
22 at different surfactant concentrations. A plot of the surface tension versus the surfactant
23 concentration was made and the surfactant CMC was taken as the surfactant concentration with
24 no significant change in surface tensions henceforth. Generally, sessile/captive drop analysis
25 techniques are normally employed for measuring contact angles using the KRŰSS DSA25.
26 For contact angle measurement, the rock substrate was prepared by trimming the slides
27 into an appropriate size (length = 2 cm X width = 2cm X height =0.3 cm) with the help of
28 Vinci’s radial core slabbing saw. The trimmed substrate was then gently polished with a silicon
29 carbide abrasive paper to minimize the influence of contact angle hysteresis arising from the
30 roughness of the rock piece (Yekeen et al., 2020). The rock piece was then cleaned with acetone
31 and deionized water before being place on the stage for contact angle measurements. The wetting

9
1 properties of rocks (contact angles) as a function of different saponin concentrations was
2 measured through a sessile drop techniques. The sessile drop profiles (5 μL) of the different
3 surfactant solutions was created and then drop on the rock substrate surface through a metal
4 syringe needle (with diameter of 0.515 mm). The contact angle was taken as the angle formed
5 between the droplet and the solid interface and was measured through the denser phase. The IFT
6 and contact angle measurements were automatically determined through the KRŰSS
7 ADVANCE analyzing software. The capture drop-profile was analyzed, using the Young–
8 Laplace equation to determine the IFT (Zhang et al., 2018).

10 2.2.5 Oil-water interfacial tension measurements at high temperature and pressure.

11 A Krüss drop shape analyzer (DSA 100) apparatus (KRÜSS GmbH, Germany), was used
12 to measure the crude-oil water IFT, in absence and presence of SiO2 nanoparticles at downhole
13 conditions. The oil-water interfacial tension was measured at elevated temperature (80oC -180oC)
14 and pressures (8 MPa – 22 MPa). The maximum operating pressure and temperature of the DSA
15 100 used in this research is 68.95 MPa and 200oC respectively. A pendant drop method was
16 employed for measuring the IFT at reservoir conditions. To measure the IFT, the experimental
17 set-ups were checked for leakages by flushing the whole set-up with nitrogen. Then the
18 temperature was pre-set at the desired temperature. Temperature equilibration was ensured by
19 increasing the temperature step-wisely at every 10oC before progressing with further temperature
20 increase.
21 When the temperature reached the desired temperature. The pressure in the view chamber
22 was increased to the desired level by pressurized through the saponin surfactant solutions.
23 Immediately the pressure stabilization was achieved, the pendant drop of the oil droplet was
24 introduced from the bottom of view chamber using a dispensing needle (0.77 mm). The oil
25 droplets (∼6 ± 1 μL) swiftly expanded, and then suspended at the tip of capillary tube
26 surrounded by the surrounding fluid (different concentrations of the saponin) at the desired
27 temperature and pressure. The density and the viscosity of the brine and oil at the varying
28 temperature and pressure was used in the automatic computation of the interfacial tension (IFT)
29 in (mN/m) by the software. At constant pressure (10 MPa), the IFT was measured at different
30 temperature (80oC, 100oC, 120oC, 140oC, 150oC, 160oC or 180oC). Similarly at constant

10
 1 temperature (80oC), the IFT was computed at different pressure (8 MPa, 10 MPa, 12 MPa, 14
2 MPa, 16 MPa, 18 MPa, 20 MPa or 22 MPa). The IFT values were determined from an average of
3 10 data. The detailed diagram of the DSA 100 used in this study is provided in Fig. 3.
4
5
6
7
8
9
10
11
12
13 b c d e f
j
14
15
16
k
17
l
18 g
19
20
21 m
22
23
h
i
24 a
25
26
27 Fig. 3. Experimental set-up of the Krüss drop shape analyzer (DSA) 100 instrument (High pressure
28 view cell) used in this study showing the equipment with the labelled key parts (a) data acquisition
29 system, (b)CO2 regulator (c) methane regulator (d) N2 regulator (e) Temperature indication (f)
30 pressure indication (g) view chamber (h) Pressure cell (i) Pressure generator (j) capillary tube with
31 dispensing needle (for pendant drop) (k) capillary tube with dispensing needle (l) liquid cell (m)
drain cell.
11
1
2
3 3.0 Result and Discussions

4 3.1 FTIR analysis of Saponin

5 To confirm if the extracted substance is actually a saponin or not, the infrared spectra of
−1
6 the extracted saponin were recorded between 4000 − 500 cm and compare with the infrared
7 spectra of the pure commercial saponin and the identified infrared spectra of saponin reported in
8 literature (Bajad and Pardeshi, 2016; Nowrouzi et al., 2020; Samal et al., 2017; Wang et al.,
9 2014). The similarity between the FTIR transmittance spectrum of the extracted saponin and the
10 commercial (pure) saponin is presented in Table 1 and Fig. 4. The results showed that the
11 transmittance spectra of the extracted saponin is similar to the spectra of the commercial saponin
12 and that of the pure saponin reported in previous studies. For instance, the infrared spectra of the
13 extracted saponin shows the hydroxyl group (-OH stretching) peaks at 3390.62 cm-1, while that
14 of the commercial saponin, was obtained at peak of 3400.45 cm-1.
15 This observation is also consistency with literature, Samal et al. (2017) obtained the
16 transmittance spectra of the -OH stretching of extracted saponin from the aqueous reetha solution
17 and that of the pure saponin at 3455 cm-1 while Bajad and Pardeshi (2016) reported that the
18 infrared spectra of the hydroxyl group of saponin extracted from “Sapindus emarginatus”
19 peaked at 3434 cm-1. In this study, the infrared spectra of the extracted and commercial saponin
20 shows the carbon-hydrogen (-CH2 group) stretching peaks at 2939.60 cm-1 and 2931.69 cm-1
21 respectively (Table 1 and Fig. 4). Similarly, Bajad and Pardeshi (2016) obtained the aliphatic –
22 CH2 stretching at 2928 cm-1while the results of Samanta et al. (2013) shows that the infrared
23 spectra of the saponin extracted from the soapnut shows the aliphatic –CH2 stretching peaks at
24 2931.41 cm−1. Generally, the FTIR analysis of the extracted saponin in comparison with the pure
25 commercial saponin and the infra-red spectra of saponins reported in various literature confirmed
26 that the substance isolated from Sapindus Mukorossi is indeed a saponin.
27
28 Table 1: Functional group of the extracted saponin and commercial saponin

Sample name Hydroxyl Carbon-hydrogen Carbonyl Alkene Carbon oxygen

group C-H2 C=O C=C single bond

12
 OH (cm−1) (cm−1) (cm−1) (cm−1) C-O-C (cm−1)
Commercial 3400.45 2931.69 1727.34 1613.29 1074.98
Saponin
Extracted 3390.62 2939.60 1622.52 1437.62 1068.99
Saponin
1

3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24 Fig. 4. FTIR analysis chart and functional groups of the extracted and commercial saponin
25
26
27 3.2 Critical micelle concentration (CMC) of the extracted saponin

28 The surface tension of different concentrations (0.01-1 wt%) of the extracted and
29 commercial saponin was measured using DSA 25 and plotted against the surfactant
30 concentrations to determine the critical micelle concentration (CMC). The plot of the surface
31 tension versus the saponin concentration is shown in Fig.5. The plotted graphs showed that the
32 surface tension decreases with the increasing surfactant concentration. After a certain
33 concentration, the change in surface tension was almost insignificant with the increasing

13
1 surfactant concentration. This inflection point was found to be 0.1 wt % saponin for the
2 commercial saponin and 0.2 wt % for the extracted saponin. This concentration is called the
3 critical micelle concentration (CMC) of the surfactant.
4 The CMC showed the critical concentration at which micelles are form due to the
5 occurrence of aggregation of the surfactant molecules in the bulk solution. The aggregate of the
6 surfactant molecules in the bulk solution is the micelle (Balakrishnan et al., 2006). At CMC,
7 formation of micelles occurred because the bulk solution is fully saturated (packed) with the
8 surfactant molecules (Hanamertani et al., 2018) . The concentration of surfactant beyond the
9 CMC have been identified as the realistic and economical concentration for field application of
10 surfactant flooding due to the occurrence of the adsorption of surfactant molecules on reservoir
11 rocks at concentration below the CMC (Karnanda et al., 2013; Yekeen et al., 2019a; Yekeen et
12 al., 2019b).
13 The CMC of a surfactant is a very important property of the surfactant because there is a
14 significant variation in the surfactant physicochemical properties at the concentration above and
15 below the CMC (Yekeen et al., 2017b). The knowledge of surfactant CMC is very essential in
16 investigating the interfacial and foaming/stabilizing properties of the surfactants. The adsorption
17 and aggregation of surfactant molecules at the interface is the principal mechanism of oil-water
18 interfacial tension reduction, modification of rock wettability, as well as stabilization of foam
19 lamellae by the surfactant. As observed in (Fig.5), the added surfactant molecules beyond the
20 CMC did not decrease the surface tension further, since they are only involved in micellar
21 formation.
22 Previous studies suggested that surfactant could demonstrate the most favorable
23 interfacial activity, as well the best foam generation and stabilizing capacity at surfactant
24 concentration close to the CMC. This is due to the fact that surfactant molecules are expected to
25 be optimally and systematically arranged at the oil-water interface as well as at the gas-liquid
26 interface of the foam at CMC (Hanamertani et al., 2018; Mannhardt and Svorstøl, 2001).
27 Generally, the functionality of the isolated saponin for wettability alteration of rock surfaces, oil-
28 water IFT reduction, as well as foams stabilization will depends on the quantity of adsorbed
29 surfactant molecules at the saturated interface as well as amount of monomers in the micelle
30 (Mitra and Dungan, 1997). Hence, it is essential to determine the CMC of the extracted saponin
31 in order to determine the impact of extra surfactant molecules on the interfacial energies (Mitra

14
1 and Dungan, 1997). Moreover, the knowledge of the micelle-forming characteristics of the
2 isolated saponin is vital for predicting the optimum surfactant concentration for maximum foam
3 stability as well as minimal reduction in oil-water interfacial tensions.
4

Extracted Saponin Commercial Saponin

70
Surface tension (mN/m)

60

50

40

30

20

10

0
0.01 0.1 1

Surfactant concentration (wt%)

5
6
7 Fig. 5. A plot of surface tension (mN/m) versus surfactant concentration (wt %) for estimating
8 the critical micelle concentration (CMC) of the extracted and commercial saponin.

9
10 3.3 Foaming properties and stability
11 The foam generation/stabilization properties of the extracted saponin was characterized at
12 room temperature and 60oC using the foamscan. The performance of the saponin-stabilized foam
13 was compared with the performance of the sodium dodecyl sulfate, SDS-stabilized foam. This is
14 to ascertain if the synthesized saponin can be proposed as supplementary alternative to
15 conventional foam-stabilization surfactants. The foam generation property was inferred from the
16 variation of foam volume with time. The foam stability was estimated from the decay profile of
17 foam volume versus time, as well as the foam half-life. The foam half-life is the time taken by
18 the foam to decay into half of its original volume after the termination of the gas sparging. Since
19 the foam volume was fixed as 100 ml in this study, the half-life was the time taken for the foam
20 to decay into 50 ml. The variation of foam volume with time, as well as the foam decay profile

15
1 versus time for the saponin-stabilized foam at room condition is presented in Fig. 6 while that of
2 the SDS-stabilized foam is presented in Fig. 7.
3 For all concentrations investigated in this study, Fig. 6 showed that the saponin-stabilized
4 foam volume increases linearly with time, as demonstrated by the straight-line from time zero to
5 the maximum foam volume. This result is an indication that the buildup of the saponin-stabilized
6 foam during gas sparging was very stable. It can be inferred that the saponin-stabilized
7 foamability is likely not to be affected by the three mechanisms of foam destruction, that is
8 liquid drainage, bubble coalescence and coarsening (Simjoo et al., 2013; Yekeen et al., 2018).
9 The foam stability analysis showed that the volume of foam stabilized by higher saponin
10 concentration (0.3 wt%, 0.4 wt%, 0.5 wt% and 1.0 wt%) was quite stable and eventually attains a
11 fixed value at particular time.
12 The 0.3 wt% and 1.0 wt% saponin-stabilized foams attained fixed volume of 20cm3 after
13 2000 seconds while the 0.5 wt% saponin-stabilized foam attained a fixed volume value of 20cm3
14 after 1000 seconds. The most stable foam was obtained in presence of 0.4 wt% saponin solution.
15 The foam volume decay profile was characterized by a slower destruction in foam volume for a
16 longer time, maintaining a kind of plateau at some specific period, before achieving a constant
17 value of 25 cm3 after 4000 seconds. This result showed that there is an optimum concentration
18 for the maximum stability of saponin-stabilized CO2 foam. This concentration was identified as
19 0.4 wt% in this study.
20 The stability of the saponin-stabilized foam was compared with that of the SDS-stabilized
21 foam, using the surfactant concentration that produced the highest stability for the saponin-
22 stabilized foam. The decay profile for the SDS-stabilized foam shown in Fig. 7, suggests that the
23 foaming characteristics of the SDS-stabilized foam also demonstrated stable buildup almost like
24 that of the saponin-stabilized foam. However, the half-life of the 0.1 wt% and 0.3 wt% SDS-
25 stabilized foam was at 500 seconds while that of different concentration of the saponin-stabilized
26 CO2 foam ranges between 500 seconds to 1500 seconds. The total collapse of the 0.1 wt% and
27 0.3 wt% SDS-stabilized foams occurred before 2000 seconds. The optimum surfactant
28 concentration for the maximum stability of SDS-foam was obtained at 0.2 wt. However, unlike
29 the 0.3 wt% and 1.0 wt% saponin-stabilized foam volume that levels off to a plateau at 20cm, the
30 SDS-stabilized foam volume did not levels off to a plateau at 0.2 wt% SDS. The curve pointed
31 downward suggested that the total collapse of this foam could occur faster than the collapse of

16
1 the similar concentration of the saponin-stabilized foam. These results generally suggest that the
2 extracted saponin can generate more stable foam compared to the SDS-stabilized foam. Fig. 7
3 further confirmed that there is an optimum surfactant concentration for maximum foam stability.

0.1 wt% Saponin 0.2 wt% Saponin 0.3 wt% Saponin

120 0.4 wt% Saponin 0.05 wt% Saponin 0.5 wt% Saponin
1.0 wt% Saponin
100
Foam volume (ml)

80

60

40

20

0
0 1000 2000 3000 4000 5000

Time (seconds)
4
5 Fig. 6. Foam decay profile for different concentration of extracted saponin-stabilized foam at
6 room condition
7

120 0.1 wt% SDS 0.2 wt% SDS

0.3 wt% SDS 0.5 wt% SDS
100

80
Foam volume
(ml)

60

40

20

0
0 500 1000 1500 2000 2500 3000
8 Time (seconds)
9
10 Fig. 7. Foam decay profile for different concentration of SDS-stabilized foam at room condition

17
1
2
3 The mechanisms of foam decay was elucidated from the plots of the liquid volume in the
4 foam versus time presented in Fig. 8. Using 0.2 wt% concentration for the two surfactants, the
5 decay profile for the saponin-stabilized and SDS-stabilized foams demonstrated uniform increase
6 in foam volume with time during the gas sparging process. However, after the CO2 gas sparging,
7 the SDS-stabilized foam volume profile showed a sharp decrease in volume with time. No
8 steadied value for liquid volume in the foam was observed in profile of SDS-foam throughout
9 the measurement signifying that the rate of liquid drainage from the SDS-foam was very high
10 compared to the saponin-stabilized foam. Almost 100% of the initial liquid was drained from the
11 SDS-foam after 100 seconds while 100% liquid drainage from the saponin-stabilized foam
12 structure took about 350 seconds. Beyond this period, it is likely that the foam decay process was
13 governed by other decaying mechanisms such as bubble coalescence and coarsening (Simjoo et
14 al., 2013; Tcholakova et al., 2011). Film thinning and rupture could arise from the pressure
15 created in the liquid fraction of foam during liquid drainage. Consequently, the liquid in the film
16 migrate to the Plateau border with low pressure (Ahmed et al., 2017).
17
18

0.2 wt% Saponin 0.2 wt% SDS

Liquid volume in the foam

12

10

8
(ml)

0
0 50 100 150 200 250 300 350

Time (seconds)
19
20 Fig. 8. Time taken for liquid drainage from saponin- stabilized and SDS-stabilized foam. The
21 foam was generated using 0.2 wt% surfactant concentration.
22

18
1 Simjoo et al. (2013) emphasized that bubble coarsening plays a prominent role in foam
2 decay process if the distribution of the bubble size in the foam structure is highly disperse. The
3 morphology of the generated foam under the Leica EZH4 microscope presented in Fig.9
4 provided further insight into the mechanisms of foam decaying process. When the bubble size
5 distribution of the generated foam was quite uniform (Fig. 9a), the foam remained stable with
6 thicker lamellae with time (1800 seconds) as shown in Fig. 9b. However, when the generated
7 foam bubble size distribution was highly disperse and non-spherical as shown in Fig. 9c, the rate
8 of bubble coalescence was faster with the time. The foam lamellae become thinner while smaller
9 unstable and inhomogeneous bubbles quickly merged to become larger bubbles (Fig. 9d). Hence
10 bubble coalescence and Ostwald ripening is a principal foam decay process when the bubble size
11 distribution in the foam structure is highly disperse and irregular.
12 The foam generation/stabilization of surfactants depends on the surface activity of the
13 surfactant molecules at the gas-liquid interface of the foam (Hanamertani et al., 2018). The high
14 stability of the saponin foam compared to the SDS-stabilized foam can be attributed to the
15 presence of hydrophilic sugar part and fat soluble (hydrophobic) sapogenin in their structure.
16 Fig.6 further showed that at concentration above CMC, the extracted saponin has lower surface
17 tension than SDS, indicating that lower pressure could exists in the foam generated with saponin
18 compared to SDS-stabilized foam. Hence, slower flow of liquid and slower rate of oswald
19 ripening is anticipated in the saponin-stabilized foam. Moreover, Fig. 8 showed that it could
20 take longer time from the liquid to drain from the structure of the saponin-stabilized film
21 compared to SDS-stabilized lamellae. These results suggest that the surface viscosity and
22 strength of the saponin-stabilized foam film is high due to the adsorption and aggregation of the
23 molecules of the surface-active species at the foam lamellae. A dense monolayer is formed from
24 the accumulated species at the lamellae, which delayed the diffusion of the gas through the foam
25 film(Chen et al., 2020). Moreover, the strength of the foam lamellae was very significant in
26 delaying bubble coalescence and oswald rippening.
27
28
29
30

19
 (a) (b)

(c) (d)

Fig. 9. Foam structure under the microscope showing that when the bubble size distribution are disperse and irregular, bubble coalescence and Oswald
ripening are prominent mechanisms of foam decay (a) foam with uniform size distribution after generation (b) foam with size uniform distribution after
20 (d) foam with irregular size distribution after 1800 seconds.
1800 seconds (c) foam with irregular size distribution after generation and
1 3.4 Foaming properties and stability at high temperature (60oC)
2
3 The stability of the extracted saponin foam was investigated at 60oC to examine the
4 performance of the saponin-stabilized foam at high temperature. The decay profile of the saponin
5 foam versus time at high temperature is shown in Fig. 10. The plotted curves showed that the
6 foaming procedures of the foam was quite consistent with the foam behaviours at room
7 temperature, indicating that the saponin-stabilized foam can be successfully generated at high
8 temperature with almost the same rate as ambient conditions. However, the foam volume decay
9 profile showed that the foam stability was lower at high temperature. Lower foam stability at
10 high temperature is due to lower solution viscosity. Although the foam stability was lower at
11 high temperature, however, the optimum concentration for attaining maximum foam stability
12 decreased from 0.4 wt% at room temperature to 0.1 wt% at 60oC. This will possibly reduce the
13 quantity of the surfactant to be used in foam generation at high temperature. As the temperature
14 was increased, the surfactant molecules moved faster. The increasing molecular activity of the
15 surfactant can aids in quick formation of the micelles, as well as the aggregation of the surface-
16 active species at the gas-liquid interface of the foam. The thermal agitation can decrease the
17 cohesive forces between the surfactant molecules but increases the adhesion action of the
18 surfactant molecules at the interface at lower saponin concentration. However, this process will
19 not be sustained for a long time due to decreasing solution viscosity at high temperature.
20 It can be inferred from the results, that the saponin-stabilized foam could be generated at
21 high temperature, remaining fairly stable before total collapse. Surfactant concentrations around
22 the critical micelle concentration is recommended for the optimum foam generation and stability.
23 The lower stability of generated foam at high temperature observed in this study is consistent
24 with literature (Hanamertani et al., 2018; Kapetas et al., 2016; Yekeen et al., 2017b). This
25 incident can be attributed to the lower viscosity of the foam film at high temperature due to
26 thermal agitation and movement of the adsorbed surfactant molecules at gas-liquid interface of
27 the foam at high temperature. Moreover, there is possibility of lesser hydrogen bond formation at
28 higher temperatures while the flow and diffusion of the gas through the foam film increases with
29 the increasing temperature (Farajzadeh et al., 2009; Mohajeri and Noudeh, 2012). This
30 eventually results in film thinning, film rupture and bubbles coalescence.

31

21
 120
0.1 wt% Saponin 0.3 wt% Saponin
100
Foam volume (ml)

0.4 wt% Saponin 0.5 wt% Saponin

80

60

40

20

0
0 200 400 600 800 1000
Time (seconds)
1
2 Fig. 10. Foam decay profile for various concentration of saponin-stabilized foam at high
3 temperature (60oC)
4
5 3.5 Rock wettability alteration by the extracted saponin
6 The potential appications of the isolated saponin for the wettability alterations of the
7 conventional and the unconventional reservoir rocks, was inferred from the changes in the contact
8 angles of two types of shales (shale 1 and shale 2) and aged Berea sandstone rock surfaces.. Fig.
9 11 shows the curves of the contact angle versus concentration of the drops of the extracted saponin
10 and sodium dodecyl sulfate on the shale 1 surface. The curves of the contact angle versus
11 concentration of the drops of the extracted saponin and commercial saponin on the aged Berea
12 sandstone surface is presented in Fig. 12. The sessile drop profiles of drop of deionized water in
13 comparison with the drops of the different concentration of the extracted saponin on the shale 1
14 and shale 2 surfaces are displayed in Fig. 13 and 14 respectively. Considerable reduction in
15 contact angles of the shale was generally noticed with the drops of varying concentration of the
16 extracted saponin on the substrate surface.
17 For instance, the drop images in Fig. 13 showed that the contact angle of the shale in
18 presence of deionized water (68.5o) reduced to 34.16o in presence of the lowest saponin
19 concentration (0.01 wt%) and 20.62o in presence of the highest concentration (0.5 wt%). This is
20 about 50% and 70% reduction in the original contact angle of the shale. The contact angle of the
21 shale 2 surface reduced from 52.44o to 38.3o (about 27% reduction ) and 8.85o (83% reduction) in
22 presence of 0.01 wt% and 1.0 wt% saponin concentration respectively. These results suggest that

22
1 the isolated saponin can effective reduce the contact angle of rock surface from strongly water-
2 wetting to weakly-water wetting condition, as well as from or oil-wet state to water-wet state. The
3 tendecy to reduce the contact angle increased with the increasing saponin concentration.
4 Generally, the water-wetting capacities of the shale increased with the increasing saponin
5 concentration. A general comparison between the wettability alteration potential of the extracted
6 saponin and sodium dodecyl sulfate showed that the extracted saponin could be considered as
7 supplementary alternative for the wettability alterations of the reservoir rocks. For instance, Fig.
8 13 showed that 0.2 wt% SDS reduced the contact angle of shale substrate to 26.5o while the same
9 concentration of the extracted saponin decreased the contact angle to 28.48o. Similarly, the contact
10 angle of shale was reduced from 52.44o to 19.66o by 0.5 wt% SDS. The same concentration of the
11 isolated saponin reduced the contact angle to 20.62o. These results also demonstrated that the
12 extractd saponin could be an effective wettability alteration agent for unconventional reservoir
13 rocks such as shale.
14 When the rock wettability alteration capacity of the extracted saponin was compared
15 with that of the commercial saponin, results presented in Fig. 12 clearly showed that the wetting
16 tendency of the rock inclined towards more hydrophilic conditions in presence of the extracted
17 saponin compared to the commercial saponin. Specifically, the contact angle of the aged Berea
18 sandstone were obtained as 64.8o and 24.8o in presence of the 0.2 wt% and 0.5 wt% concentration
19 of the extracted saponin. In presence of the same concentration of the purchased commercial
20 saponin, the contact angles were obtained 73.3o and 46.0o respectively. Previous studies generally
21 showed that the contact angles could increase when the charges on the rock surfaces and the
22 charges on the surface-active species (surfactants) are different. This can be attributed to the
23 formation of hydrophobic bilayer arising from surfactant adsorption on the rock surfaces (Yekeen
24 et al., 2020).
25 Increasing water-wetting tendency and hydrophilic bilayer formation have been attributed
26 to the existence of similar charges on the substrate and surfactants surface because of high
27 disjoining pressure (Bhushan, 2012; Menezes et al., 1989; Yekeen et al., 2020; Zhang et al., 2014).
28 Saponin, being a non-ionic surfactant does not demonstrate any strong adsorption onto charged
29 surfaces. Hence, more surfactants molecules are present in the bulk solutions to increase the
30 water-wetting tendency. Moreover, saponin as a non-ionic surfactant is soluble in water via
31 hydrogen bonds formation of the hydrophilic moieties with water. Hence more surface-active

23
1 components could be released into the bulk solution, resulting in formation of water-wet thin film
2 on the aged Berea sandstone and shale surfaces.
3

35 Saponin SDS
33
31
Contact angle (degree)

29
27
25
23
21
19
17
15
0 0.1 0.2 0.3 0.4 0.5
Surfactant concentration (wt%)
4
5
6 Fig. 11. Comparison of the wetting properties (contact angles on shale1) of different
7 concentrations of the synthesized saponin with the sodium dodecyl sulfate
8
Extracted Saponin Commercial Saponin

100
90
Contact angle (degree)

80
70
60
50
40
30
20
10
0
0 0.2 0.4 0.6 0.8 1
Surfactant concentration (wt%)
9
10
11 Fig. 12. Comparison of the wetting properties (contact angles on berea sandstone) of different
12 concentrations of the extracted saponin with the commercial saponin
13
14

24
 (a) 68.5o
1
2
3
4
5
6
7

10

11 (b) 34.16o (c) 30.58o

12

13

14

15

16

17

18 (d) 28.77o
19 (e) 20.62o

20

21

22

23

24 Fig. 13. Trends of the contact angles of the drops of the synthesized saponin solutions on shale 1
25 surfaces (a) deionized water drop on shale 1 surface (b) 0.01 wt% saponin drop on the shale
26 surface (c) 0.05 wt% saponin drop on shale surface (d) 0.1 wt% saponin drop on shale surface (e)
27 0.5 wt% saponin drop on shale surface

28

29

30

25
 (a) 52.44o
1
(b) 38.3o
2

6 (d) 30.9o (c) 23.9o

10

11
(f) 20.4o (e) 11.4o
12

13

14

15
16
17 (g) 8.85o
18
19
20
21
22
23
24 Fig. 14. Trends of the contact angles of the drops of the synthesized saponin solutions on shale 2
25 surfaces (a) Deionized water drop on shale 2 surface (b) 0.01 wt% saponin drop on the shale
26 surface (c) 0.05 wt% saponin drop on shale surface (d) 0.1 wt% saponin drop on shale surface (e)
27 0.2 wt% saponin drop on shale surface (f) 0.5 wt% saponin drop on shale surface and (g) 1.0
28 wt% saponin drop on shale surface

26
1 3.6 Oil-water interfacial tension at room conditions
2
3 Interfacial tension between the oil and water has a unique role in promoting hydrocarbon
4 recovery, because microscopic displacement efficiency increases as the oil-water interfacial
5 tension decreases (Mosayebi et al., 2016). Influence of varying concentration of the isolated
6 saponin on the oil-water interfacial tension was study and compared with the performance of
7 conventional synthetic surfactant, sodium dodecyl sulfate (SDS). Fig. 15. shows the plots of
8 heptane-water interfacial tension versus surfactant concentrations. The experiments were
9 conducted at room conditions. The plotted curves showed that the increasing surfactant
10 concentration generally resulted in drastic reduction in heptane-water IFT until certain
11 concentration close to the critical micelle concentration. Precisely, at the CMC of the extracted
12 saponin and the SDS (0.2 wt%), the heptane-water IFT decreased from 48.5 mN/m to 11.81
13 mN/m (about 76% reduction) in presence of extracted saponin and decreased from 48.5 mN/m to
14 7.31 mN/m (about 85% reduction) in presence of SDS. Beyond the CMC, the change in heptane-
15 water IFT with increasing surfactant concentration was not very significant.
16 At some surfactant concentration below the CMC, lower interfacial tension were even
17 obtained in the presence of the extracted saponin compared to the sodium dodecyl sulfate. For
18 instance, at 0.1 wt%, the extracted saponin solution reduced the heptane-water IFT from 48.5
19 mN/m to 12.69 mN/m while SDS solution decreased the IFT to 16.07 mN/m (about 67%
20 reduction). These results showed that the extracted saponin could be consider as supplementary
21 alternative to convention EOR surfactants, such as sodium dodecyl sulfate, for reducing
22 interfacial tension and enhancing hydrocarbon recovery.
23 Generally, oil and water interface could be the ideal location for the systematic
24 orientation of the saponin molecules due to their dual molecular structure and the presence of the
25 hydrophobic and hydrophilic components (Mosayebi et al., 2016; Nowrouzi et al., 2020). The
26 change in oil-water IFT can be attributed to arrangement of surface-active species at the oil-
27 water interface such that the hydrophilic head is dissolved in aqueous solution while the
28 hydrophobic tail dissolve in oil (Nowrouzi et al., 2020). The IFT of the system decreased with
29 the increasing surfactant concentration due to the adsorption of the surfactant molecules at the
30 oil-water interface (Wu et al., 2018). The IFT decreases as the surfactant concentration increases,
31 signifying that a rising number of surfactant molecules migrate to the oil/water interface (Zhang
32 et al., 2018).

27
1

Saponin SDS
60
Oil-water IFT (mN/m)

50

40

30

20

10

0
0 0.1 0.2 0.3 0.4 0.5

Surfactant concentration (wt%)

2
3
4 Fig. 15. The plots of interfacial tension versus surfactant concentrations for Heptane-water
5 interfacial tension
6 However, at CMC, the bulk solutions is essentially saturated with the surfactant
7 molecules, as the molecules attain the adsorption saturation due to significant formation of
8 micelles (Chen et al., 2020; Kumar and Mandal, 2016). At this point, the free migration of the
9 surfactant molecules from the bulk solution to the oil-water interface are inihibited by the denser
10 surfactant monomers. Previous studies showed that the function of the surfactant molecules can
11 diminished with micelles formation (Najimi et al., 2019; Nowrouzi et al., 2020). Beyond the
12 CMC, the added surfactant molecules in solutions are only involved in the micelles formation
13 and formation of larger aggregates in bulk solutions. They do not necessarily increase the
14 migration rate and surface-activity of the surfactants at oil-water interface. Hence, no noticeable
15 change was observed in the oil-water IFT with increasing surfactant concentration beyond the
16 CMC in this study. The aggregation of surfactant molecules in bulk solution prevented their
17 adsorption and accumulation at the oil-water interface to decrease the oil-water interfacial
18 tension (Jiravivitpanya et al., 2017)
19
20 3.7 Influence of changing pressure on crude oil-water interfacial tension
21 To investigate the effectiveness of the isolated saponin at reservoir conditions and
22 identify the temperature range for the possible ocurrence of clouding phenomenon, the crude oil-

28
1 water interfacial tension was determined at elevated temperature and pressure. Firstly, the
2 temperature was kept constant at 80oC, and the crude oil-water IFT was determined at different
3 pressure (8-22 MPa). The pressure was then kept constant at 10 MPa and the oil-water IFT at
4 varying temperature (80oC-180oC) was measured. Fig. 16 shows the plots of variation in crude-
5 oil water IFT with pressure for different surfactant concentrations in absence and presence of
6 SiO2 nanoparticles at constant temperature of 80oC. The pendant drop profiles of crude oil in the
7 surfactant environment at constant temperature (80oC) and varying pressure for 0.5 wt%
8 extracted saponin concentration is presented in Fig. 17. Figs. 16 and 17 clearly showed that the
9 crude oil-water interfacial tension increases with the increasing pressure.
10 This observation is very consistent with literature. Since pressure exert minor influence
11 on oil-water interfacial free energy and rheological properties of liquid compare to temperature,
12 the impact of pressure on oil-water interfacial tension is not very significant like that of
13 temperature (Mosayebi et al., 2016). Unlike the temperature that weakened the liquid-liquid
14 intermolecular forces, the intermolecular forces between the oil and water remained almost
15 unchange when the pressure is increased (Mosayebi et al., 2016). However, the packing density
16 of surfactant molecules at the interface is decreased at high pressures because the distance
17 between the molecules are increased by the increasing pressure. Consequently, the oil-water IFT
18 increased with the increasing pressure.
19 Although the crude-oil water IFT increased with increasing pressure, significant
20 reduction in IFT values were observed in presence of saponin and nano-saponin dispersions.
21 Lower IFT were generally obtained in presence of nanoparticles-saponin mixtures compared to
22 the saponin solutions only. In presence of varying concentration of the saponin solutions, the
23 lowest reduction in oil-water IFT was obtained in presence of 0.2 w% saponin, signifying that
24 surfactant molecules are likely to be optimally arranged at the oil-water interface at the critical
25 micelle concentration of the saponin. Specifically, at 0.2 wt% concentration, the extracted
26 saponin was able to considerably reduce the crude oil-water interfacial tension from 23.24 mN/m
27 to 1.589 mN/m (about 93.2 % reduction) and 3.08 mN/m (about 87% reduction) at pressure of 8
28 MPa and 22 MPa respectively.
29 A comparison of oil-water IFT values in presence and absence of SiO2 nanoparticles
30 showed that much lower IFT were generally obtained in presence of nanoparticles compared to
31 the surfactant solutions only. The surface-active complex formed from the synergistic interaction

29
 1 of the surfactant and nanoparticles were found to be generally effective in reducing the crude-oil
2 water IFT compared to the surfactant solution alone.
3
0.5 Saponin + 0.05 SiO2 0.5 Saponin + 0.01 SiO2
4 0.5 Saponin + 0.1 SiO2 0.2 Saponin
1.0 Saponin 0.5 Saponin
Oil-water interfacial tension (mN/m)

3.5

2.5

1.5

0.5
8 10 12 14 16 18 20 22
Pressure (MPa)
4
5 Fig. 16. Trends of crude-oil water IFT with increasing pressure at constant temperature (80oC)
6
7
(a) (b) (c) (d) (e) (f)
8
9
10
11
12
13
14
15
16
17
18 Fig. 17. The pendant drop profiles of crude oil in the saponin solutions environment at constant
19 temperature (80oC) for 0.5 wt% saponin concentration at (a) 8 MPa (b) 10 MPa (c)16 MPa (d) 20
20 MPa (e) 22 MPa and (f) visual image of crude oil-water interfacial tension reading.
21 .

30
1 The lowest IFT values were obtained from a mixed system of 0.5 wt% saponin
2 concentration and 0.05 wt% SiO2 nanoparticles concentration. The mixed system reduced the
3 crude-oil water IFT from 23.24 mN/m to 0.87 mN/m (about 96.3% reduction) and 2.71 mN/m
4 (about 88.3% reduction) at pressure of 8 MPa and 22 MPa respectively. Increasing nanoparticles
5 concentration to 0.1 wt% did not necessarily resulted in much lower interfacial tension values.
6 The IFT values were generally higher in the presence of the synergistic mixture of 0.1 wt% SiO2
7 nanoparticles and 0.5 wt% saponin concentration compared to 05 wt% SiO2 +0.5 wt% saponin
8 concentration. This observation supports the notion that there is an existence of maximum
9 nanoparticles and surfactant concentration for achieving the lowest reduction in oil-water
10 interfacial tension. Beyond this concentration, there is no significant decrease in IFT with
11 increasing concentration. When the concentration of the saponin and nanoparticles in the
12 solution exceeds a certain critical value, they will start aggregating into individual micelles,
13 hence, their contribution to mixed micellization will either reduce or remain constant (Naqvi and
14 Khatoon, 2011).
15
16 3.8 Influence of changing temperature on crude oil-water interfacial tension

17 Temperature has significant effect on oil/surfactant solutions interfaces more than

18 pressure, since they accelerate the molecules mobility, as well as the rate of surfactant
19 adsorption and diffusion velocity of the saponin molecules at the fluid interface. Influence of
20 pressure on crude-oil water interfacial tension was much more complex than the influence of
21 pressure possibly due to the occurrence of clouding phenomenon at high temperature. In the
22 first scenario, temperature were generally observed to decreased with the increasing
23 temperature. However, this case was only observed for the influence of 1 wt% saponin
24 concentration on crude-oil water interfacial tension values. Fig. 18 shows the plots of crude-oil
25 water IFT changes with changing temperature for 1 wt% saponin concentrations at constant
26 pressure (10 MPa).
27 The plotted graphs showed that the interfacial tension generally decreased with the
28 increasing temperature for 1.0 wt% saponin concentration. The decreasing trend of oil-water
29 interfacial tension with increasing temperature observed in this study is expected and can be
30 attributed to the ability of the temperature to weaken the intermolecular forces at the oil/water

31
1 interfaces, as well as the influence of temperature on the solubility of oil/surfactant solution
2 (Karnanda et al., 2013; Miquilena et al., 2010).

3
interfacial tension (mN/m)

2.9
2.8
2.7
2.6
2.5
2.4
2.3
2.2
2.1
2
90 110 130 150 170

3 Temperature (0C)
4 Fig. 18. Trends of crude-oil water IFT change with temperature for 1.0 wt% saponin at constant
5 pressure (10 MPa)
6 The decreasing oil-water interfacial tension with increasing temperature is consistent with
7 literature. Increasing temperature decreases the free energy of the surface by increasing the total
8 system entropy (Moeini et al., 2014). The increasing kinetic energy at high temperature also
9 results in successful break-up of the solvent (oil and water) molecules, hereby decreasing the
10 force of attraction, as well as the surface free energy between the molecules at the interface
11 (Mahdavi et al., 2017; Wu et al., 2018). The increasing system entropy at high temperature,
12 resulted in decreasing Gibbs free energy, as well as decreasing crude oil-water interfacial tension
13 (Hamouda and Bagalkot, 2018).
14 However, when much lower concentration of saponin (0.2 and 0.5 wt%) were used for
15 the experiments. The crude-oil water interfacial tension did not decreased with temperature,
16 instead the oil-water interfacial tension increased with increasing temperature due to phase
17 separation from clouding phenomenon (Fig. 19). The pendant drop profiles of crude oil in the
18 surfactant solution environment at different temperature and constant pressure (10 MPa) for 0.5
19 wt% saponin concentration presented in Fig. 20 further confirmed the increasing crude-oil
20 water interfacial tension with increasing pressure due to phase seperation resulting from the
21 clouding phenomenon

32
 9
8
7 0.5wt%
0.2 wt%Saponin
Saponin
Interfacial tension (mN/m)

6 0.50.2
wt% Saponin
wt% Saponin

5
4
3
2
1
0
80 100 110 120 130 140 150
Temperature (oC)
1 19. Trends of change in crude-oil water IFT with temperature at constant pressure (10 MPa) for 0.2 wt%
Fig.
and
2 0.5 wt% saponin concentration showing increasing surface tension values with increasing temperature
due
3
to occurrence of phase separation from clouding phenomenon.
(a) IFT = 2.55 mN/m (b) IFT = 2.71 mN/m (c) IFT = 3.55 mN/m
4
5
6
7
8
9
10
11
12
13 (d) IFT = 5.12 mN/m (e) IFT = 8.53 mN/m
14
Fig. 20. The pendant drop profiles of crude oil in
15
the surfactant solution eenvironment at constant
16 pressure (10 MPa) for 0.5 wt% saponin
concentration at (a) 80oC (b) 110 oC (c)130 oC (d)
17
140 oC and (e) 150 oC

18

33
1 The increasing crude-oil water interfacial tension with increasing pressure can be
2 attributed to phase seperation resulting from the clouding phenomenon. As a result of this phase
3 separation, we were unable to proceed with IFT measurement for lower saponin concentration
4 (0.2 wt% and 0.5 wt %) up to 180oC. The measurement was stopped at 150oC as the IFT value
5 keep rising with increasing temperature. The temperature at the clouding points is the threshold
6 temperature for surfactant solubility. Beyond this temperature, the surfactant undergo phase
7 separation into two phases (Naqvi and Khatoon, 2011). The two distinct phases during phase
8 separation consists of the bulk aqueous solution and the phase comprising of virtually the entire
9 surfactant with little amount of water. The latter phase will go down while the former phase will
10 remain on top due to the density difference. The saponin dispersion becomes ineffective and
11 thermally unstable, hence when the IFT supposed to decrease with the increasing temperature.
12 Contrary results were obtained as the IFT increased with the increasing temperature due to
13 occurrence of phase separation. The result for the 1 wt% saponin concentration was different
14 possibly because of less amount of water in the dispersions. The higher the rate of dilution, the
15 greater the tendency for liquid-liquid phase separation
16 However, in presence of SiO2 nanoparticles there was an improvement in the
17 performance of saponin, lower IFT were reported and thermal stability of the saponin improved
18 even at low saponin concentration (Fig.21). While the presence of 0.05 wt% nanoparticles
19 concentration in 0.5 wt% saponin solution seems to delay the clouding temperature, the crude
20 oil-water IFT in presence of mixed system of 0.5 wt% saponin and 0.1 wt% SiO2 nanoparticles
21 demonstrated decreasing IFT with increasing temperature up to 120oC. This study suggests that
22 the clouding temperature of saponin solutions could be delayed at high saponin concentration or
23 in presence of moderate concentration of SiO2 nanoparticles. Further studies will be necessary to
24 ascertain this result.
25
26

34
 2.5 0.5 Saponin +0.1 SiO2 0.05 Saponin + 0.05 SiO2
Interfacial Tension (mN/m)

1.5

0.5

0
80 100 120
Temperature (oC)
1
2 Fig. 21. Trends of crude-oil water IFT change with temperature at constant pressure (10 MPa)
3 for 0.5 wt% Saponin concentration in presence of 0.05 and 0.1 wt% SiO2 concentration
4
5 The saponin/SiO2 mixtures had significantly influence on clouding temperature and the
6 reduction of the crude oil-water interfacial tension than the saponin solution alone, due to the
7 formation of surface-active complex resulting from the synergistic interaction between the
8 nanoparticles charged surfaces and the surfactants molecules. Since the saponin is a nonionic
9 surfactant, the micelles formed by the saponin will be neutral. However, addition of negatively
10 charged SiO2 nanoparticles into the surfactant solution will give negative charge to the micelles
11 through formation of mixed micelles with the nonionic saponin. The added surface charge will
12 increase the repulsion within the micelles, consequently, increasing the clouding point and
13 preventing phase separation until 120oC (Naqvi and Khatoon, 2011).
14 Spatial attraction could decrease when the saponin molecules approach the negatively
15 charged surfaces of the SiO2 nanoparticles, resulting in slow formation of the micelle in bulk
16 solution and higher packing density of the surface-active species at the oil-water interface. The
17 electrostatic interaction between the nanofluids and surfactants molecules could prevent phase
18 separation, contribute to a high molecules packing density of the surface-active species at the oil-
19 water interface. This incident eventually results in significantly lower interfacial tension data at
20 high temperature in presence of saponin/SiO2 mixtures compared to the saponin solution only.
21 The increasing temperature reduces the IFT by promoting the dissolving and mutual solubility of

35
1 the hydrophilic part of the saponin in water and that of the hydrophobic part in oil (Wu et al.,
2 2018).
3
4 4. Conclusion and recommendations

5 An isolated saponin from a natural source, soapnut (Sapindus Mukorossi), was investigated as an
6 enhanced oil recovery (EOR) agent and as a prospective supplementary alternative to
7 conventional EOR surfactants, such as sodium dodecyl sulfate (SDS), in this study.
8 The following conclusions and recommendations can be establish from the results of this study.

9 The extracted saponin is recommended as a supplementary alternative to conventional

10 EOR chemical surfactants, with versatile oil-field application, such as sodium dodecyl
11 sulfate (SDS), due to their comparable influence on oil-water interfacial tension (IFT),
12 wettability alterations of the conventional and unconventional rock wetting properties, as
13 well as high foam generation/stabilization properties.
14 Based on the foaming properties of the isolated saponin determined at 60oC using Teclis
15 Foamscan equipment and the results of crude-oil water IFT measurement with KRŰSS
16 Drop Shape Analyzer 100 at high temperature and pressure. The isolated surfactant can
17 be considered for application at unfavorable downhole conditions of high temperature
18 and pressure.
19 The buildup of the saponin-stabilized foam was very stable at ambient condition and high
20 temperature (60oC), suggesting that the foamability of the saponin-foam is unaffected by
21 liquid drainage, bubble coalescence and coarsening.
22 Although the foam stability was lower at high temperature, however, the optimum
23 saponin concentration for attaining maximum foam stability decreased from 0.4 wt% at
24 room temperature to 0.1 wt% at 60oC, suggesting that the quantity of the surfactant to be
25 used in foam generation could reduce at high temperature.
26 Although the extracted saponin did not reduce the oil-water interfacial tension to very
27 low and ultra-low values, however, the IFT values achieved at critical micelle
28 concentration (0.2 wt% saponin) in comparison to the original IFT values of Heptane
29 (48.50 mN/m) and crude oil (23.24 mN/m) showed a considerable reduction of almost
30 76% at room temperature and about 93.2% at high temperature. Much lower IFT

36
1 reduction could be achieve in presence of nanoparticles and with the use of much
2 sensitive equipment for interfacial tension measurement.
3 The saponin extracted from soapnut (Sapindus Mukorossi) can be considered as fair EOR
4 agent for wettability alteration of unconventional shale reservoir with upto 50% reduction
5 and 83% reduction in the original contact angle of the shale substrate in presence of 0.01
6 wt% and 1.0 wt% saponin concentration respectively.
7 Since the synergistic interaction of the saponin and SiO2 nanoparticles showed almost
8 97% reduction in crude-oil water interfacial tension, Modification of the mixed micellar
9 aggregates, formed from the synergistic combination of the saponin and nanofluids, is
10 recommended to achieve ultra-low IFT values at reservoir conditions and inhibited the
11 clouding properties of saponin
12 The clouding properties seemed suppressed by nanoparticles addition to the surfactant
13 solution, hence optimization of mixed system of the SiO2 nanoparticles and saponin
14 could be exploited for improving the thermal stability at high temperature and prevents
15 quick attainment of the critical solution temperature by the saponin solution.

16

17 Acknowledgment
18 The authors would like to thank Universiti Teknologi PETRONAS for supporting this research
19 through YUTP grant awarded to Azlinda Abdul Malik.

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3
4

43
Interfacial and foaming properties of saponin extracted from soapnut was studied
Synergistic interaction between the isolated saponin and SiO2 nanoparticles on IFT was
studied
IFT at elevated temperature (80oC -180oC) and pressure (8 MPa – 22 MPa) was measured
The optimum concentration for maximum foam stability decreased from 0.4 wt% to 0.1
wt% at 60oC
Contact angle of the rock surface was reduced from 52.44o to 8.85o by 1.0 wt% saponin
solution
0.5 wt% saponin and 0.05 wt% SiO2 nanoparticles solution reduced the crude-oil water
IFT by 96.3%
Nurudeen Yekeen was involved in writing of the original manuscript as well as review and
editing, He was also involved in conducting and supervising of the experiments reported in this
manuscript

Azlinda Abdul Malik supervised the research that produced this manuscript. The research was
also funded by the YUTP grant awarded to Azlinda Abdul Malik

Ahmad Kamal Idris supervised the research and contributed to the concept development for the
research.

Nadia Izwani Reepei was involved in the saponin extraction process. She also assisted with
the wettability and interfacial tension experiments.

Kenny Ganie assisted in the saponin extraction process.

The authors would like to state that this manuscript titled “Oil-water interfacial tension
reduction, wettability modification and foaming properties of saponin extracted from
soapnut (Sapindus Mukorossi)” has not been published and is not under consideration for
publication elsewhere. Also, there is no conflicts of interest to disclose concerning this
manuscript.