Accepted Manuscript

Synthesis, characterization and enhanced oil recovery potential

analysis through simulation of a natural anionic surfactant

Neha Saxena, Amit Saxena, Ajay Mandal

PII: S0167-7322(19)30529-X
DOI: https://doi.org/10.1016/j.molliq.2019.03.056
Reference: MOLLIQ 10597
To appear in: Journal of Molecular Liquids
Received date: 28 January 2019
Revised date: 8 March 2019
Accepted date: 9 March 2019

Please cite this article as: N. Saxena, A. Saxena and A. Mandal, Synthesis, characterization
and enhanced oil recovery potential analysis through simulation of a natural anionic
surfactant, Journal of Molecular Liquids, https://doi.org/10.1016/j.molliq.2019.03.056

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 ACCEPTED MANUSCRIPT

Synthesis, Characterization and enhanced oil recovery potential analysis through

simulation of a natural anionic surfactant
1
Neha Saxena, 2Amit Saxena, 1Ajay Mandal*
1
Department of Petroleum Engineering
Indian Institute of Technology (Indian School of Mines), Dhanbad-826 004, India
2
Rajeev Gandhi Institute of Petroleum Technology, Jais,– 229305, India

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*
Corresponding Author, Email: ajay@iitism.ac.in

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Abstract

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Enhanced oil recovery (EOR) especially surfactant slug injection has received a great attention
as an oil recovery technique. Surfactants are capable in reducing the interfacial tension (IFT) and
altering the wettability of rock from subsurface reservoir. Here, a new anionic surfactant was

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synthesized from Madhuca longifolia (Mahua) oil. The surfactant was characterized using FTIR,
GC-MS, FE-SEM and EDX analysis and tested rigorously using IFT, wettability and flooding
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experiments for its application in EOR. The surfactant showed an ultralow IFT value around
1×10-2 at optimal salinity. Thermodynamic parameters were calculated using surface tension as a
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function of temperature and the studies showed that adsorption of molecules at the interface is
favorable over micellization. The surfactant was found to be thermally stable by TGA analysis
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for its application at high temperature reservoir conditions. It showed the ability to alter the
wettability of oil-wet sandstone rock surface to water-wet. The core-flooding experiments were
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conducted using individual surfactant slug and surfactant-polymer slug injection, which showed
an additional recovery of almost 20% over convention water flooding. The experimental results
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were simulated using computational fluid dynamics (CFD) analysis. The results obtained after
simulation study and core-flooding experiment results are very much comparable. The
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comprehensive evaluation of thermal, interfacial and oil recovery studies provides grounds for
potential application in EOR.

Keywords: Madhuca longifolia, Surfactant, IFT, micellization, CFD, Oil recovery

Introduction

In few decades, when there is a slump in the production rates from the mature reservoirs and low
frequency from the green fields, the importance of enhanced oil recovery (EOR) techniques is
gaining pace in the recovery process. Oil companies have made great efforts worldwide to

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improve oil recovery techniques. In spite of the fact that millions of barrels of oil is extracted per
day, only about 30-40% of the original oil in place (OOIP) is recovered from the conventional
methods like primary and secondary oil recovery methods [1]. This unrecovered oil remains
trapped in the pores of the reservoir rocks through strong capillary forces which requires a low
interfacial tension to flow through the capillaries for subsequent recovery. In addition to the
conventional methods, enhanced oil recovery techniques can be implemented in the oil fields to
increase production rates. In chemical EOR processes, chemicals either surfactants, polymers or

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their combination are injected to interact with the reservoir rock/oil/water system. These

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surfactants reduce the interfacial tension and modify rock wettability whereas, polymer enhances

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the mobility of oil towards the production well [2-4].

Surfactant comprises of two regions as whole moiety. Generally, the head is polar in nature and

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is termed as hydrophilic and the tail is non-polar in nature which is termed as hydrophilic,
together they are termed as amphiphile or surface active agents. The concept for application of
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surfactant in recovery process got it grounds from the fact of the existence of naphthenic acid in
crude oil naturally, which has the possible potential for developing the in-situ surfactant aiding to
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the mobility of the trapped crude oil [5]. In the chemical EOR process the combination of the
surfactant, polymers and alkali are employed to enhance the volume sweep efficiency and
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displacement efficiency [6].The effectiveness of the surfactant is also determined by the residual
oil recovered by micro-emulsification, alteration of wettability and reduction in the interfacial
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tension. The use of surfactants has been widely implemented in many industrial processes and its
potentiality for application in enhanced oil recovery have been reported by different researchers
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[7-9]. Since the crude oil is a complex mixture of various combinations of saturates, aromatics,
resin and asphaltenes their interactions with the brine and surfactant are not always similar as
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studied in laboratory scale. During chemical EOR process surfactant nature, rock morphology,
reservoir temperature, pH, salinity, formation type, adsorption behavior play major role in
governing the cost and efficiency of the EOR process. Thus, making it a challenging task for its
implementation at the industrial scale which is not economically feasible. A good surfactant is
not the one having good surface activity or a good wettability property, but has to be
biodegradable and less toxic in nature. The substituents for the commercially available surfactant
are not ecofriendly, which is a main concern for the environmentalist. The natural surfactants
synthesized from natural resources for various processes show an appropriate option in serving

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as a substituent for the commercial surfactant. In the 21st century environmental pollution is at
its maximum so use of green products, bio-based or renewable resources is the demand of the
hour as they help in reducing the pollution. In recent times, a few studies are found on natural
surfactants [10-13], whereas, a huge number of studies on synthetic surfactants [14-19] are
reported in different fields. Natural surfactant though in high demand but only few studies are
carried on their interfacial and wettability properties for their potential use in EOR [11, 20].

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In the present study, the surfactant was synthesized from mahua oil, as it is found in abundance

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in central and eastern areas of India and is available at very low cost, this raw material source
served as an appropriate for synthesis of the surfactant. The anionic surfactant used in the study

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was synthesized by trans-esterification of the triglycerides present in the mahua oil followed by
introduction of polar sulfonate group by sulfonation of the fatty acid methyl ester. As derived

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from the natural source the surfactant was found to be ecofriendly and biodegradable in nature.
The chemical and morphological structure of the surfactant was confirmed by FTIR, GC-MS,
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TGA and FE-SEM and EDX. Interfacial properties at air water interface and oil-aqueous
interface were analyzed to study the potential of the synthesized surfactant in reducing the
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interfacial tension. Wettability study for the surfactant was carried out to test its ability in
altering the wettability from oil-wet to water wet. Core-Flooding experiments were conducted to
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study its efficacy in enhanced oil recovery process. The oil recovery experiments were
performed on the core flooding apparatus using the mahua oil surfactants and the results were
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compared with the predicted recovery obtained by simulation studies using the ANSYS (19.1)
software. The software has been reported to be used in numerous petroleum application of water
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flooding, fluid flow through porous media etc. [21-23]. The software can be used for studying
the primary, secondary and tertiary recovery processes of oil. The present computational fluid
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dynamics (CFD) studies focus on estimating the total oil volume swept out from the core. The
studies were performed in successive order of brine flooding, surfactant flooding and surfactant-
polymer flooding on the designed core samples. The comparative study of the experimental data
and the simulation results was conducted to validate the obtained results for the analysis of the
potential of this cost-effective natural surfactant in the EOR process.

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Materials and Experimental Methods

Materials Required

Mahua oil used in the synthesis of the surfactant was procured from the local market. Its
properties and composition are shown in Table 1. Amberlyst 15 resin was obtained from Sigma

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Aldrich. Chlorosulphonic acid, sodium Carbonate anhydrous, sodium bicarbonate, diethyl ether,

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petroleum ether, ethyl acetate, methanol and pyridine were procured from Merck (India). The
crude oil used in the experiments was procured from Oil India Limited, Assam. The obtained

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crude oil has a total acid number 0.84 mg KOH/g, gravity of 18.9º API, density of 0.9244 g/cc
and viscosity of 4.26 cp at 300 K. The given properties were compared with the prescribed upper

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limits of standards of American standards of Testing of Materials (ASTM) and European
Standards (EN).
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Table 1: Properties and composition of Mahua oil
Mahua oil properties
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Properties @ 300 K Value ASTM & EN standards

(upper limits)
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Acid value (mg KOH/g) 18.8 0.5

Density (g/cc) 0.904 <1
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Kinematic Viscosity (cSt) 25.5 5

Saponification value (mg KOH/g) 189 -
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Iodine value (g/100g) 71.5 100

Free Fatty acid content (%) 0.09 <2
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Synthesis method

Mahua oil and methanol were weighted in stoichiometric amounts in a round bottom flask,
mixed with constant stirring and the reaction mixture was heated at temperature of 333K for
about 30 minutes. Ion exchange resin was employed to carry out the transesterification process.
The reaction mixture was constantly stirred for 3-4hours and, in between, the progress of the

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reaction was monitored by checking the TLC (Thin Layer Chromatography) in a mixture of
petroleum ether-ethyl acetate (70:30) as the mobile phase.

The product obtained after the trans-esterification reaction was used to synthesize the desired
product by sulfonation of mahua oil methyl ester. In this reaction, chlorosulphonic acid was
added to pyridine in a round bottom flask in an ice bath as the reaction was exothermic in nature.
Then, the reaction mixture was heated to 338 K till a clear solution was obtained which was then

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quenched with a saturated solution of sodium carbonate and sodium bicarbonate. Normal butanol

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was used to remove the unreacted components of the reaction mixture. The final white solid
product was obtained by vacuum drying the product at 353 K for 24 hours which was

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characterized with FTIR and GC-MS. The mahua oil used in the synthesis chiefly contains oleic
acid, palmitic acid along with small amount of linoleic acid and stearic acid, hence, the resultant

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surfactant formed in the process is a mixture of the sulphonated ester.

FTIR, GC-MS, TGA, FESEM Analyses

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The FTIR analysis was done by Perkin Elmer-Spectrum 2 spectrometer to identify the functional
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groups present in the newly synthesized sulphonated ester surfactant from mahua oil. A pellet of
synthesized surfactant in combination with KBr was used in FTIR analysis. The surface structure
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was analyzed by FE-SEM analysis using SUPRA -55 ZEISS Germany. The synthesized
surfactant was kept in a desiccator for 24 hours for removal of moisture and was coated with
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gold to obtain better accuracy. Gas Chromatography coupled with mass spectrometry (Jeol GC-
Mate II) was used to determine the constituents of surfactant synthesized from mahua oil. The
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TGA analysis of synthesized surfactant was done to determine its thermal degradability by
thermo gravimeter analyser (Netzsch-STA 449 Jupiter).
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Interfacial tension at air-aqueous and oil-aqueous interface

The surface tension at the air-water interface of synthesized sulfonated surfactant was measured
by using Du Nouy ring method (Easy Dyne, Kruss Germany) as a function of temperature and
concentration. Surface tension was calculated for an aqueous solution of synthesized surfactant
at different surfactant concentrations. Solutions used in the experiment were freshly prepared.
Interfacial tension of the surfactant at oil aqueous interface is an important parameter in
determining the oil recovery efficiency of the synthesized surfactant, in which ultralow IFT

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values (less than 10−2 mN m−1) are often needed. The interfacial tension of the sulphonated
mahua oil surfactant at the oil-water interface was measured by using spinning drop tensiometer
(Data physics, SVT 20) where an axisymmetric spinning drop was analyzed, with the numerical
solution of the Laplace-Young (LY) equation. Interfacial tension was measured for an aqueous
solution of synthesized surfactant at different concentrations.

Wettability alteration study

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Wettability alteration studies of oil wet rock using Drop shape Analyzer (KRUSS DSA 25,

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Germany) are important to study the effect of surfactant in altering the wettability of oil wet rock

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to water wet as it facilitates the trapped oil from the pores to flow throw channels in actual
reservoir condition. The contact angle measurement was done with sessile the drop method in

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DSA software which analyzes the dynamic contact angle with Young-Laplace fitting of the drop
made from surfactant solution at the interface of oil wet rock surface.
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Core flooding experiments

The efficiency of the mahua oil surfactant to recover the untrapped oil from the reservoir was
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studied using core flooding experiments and the core serve as a prototype of the reservoir. In the
present study sandstone core was used of length 8.49 cm and diameter 3.65 cm which was
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initially saturated with brine solution and the dry and wet weight of the core was measured
before and after brine saturation. In the next step, the flooding was done to calculate the absolute
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permeability, followed by oil saturation to make the core oil saturated. This was done till
approximately 95-97 % connate water saturation achieved. After connate water saturation, brine
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flooding was done till no oil was produced. The third step is the chemical slug injection which
comprises of 0.5 PV of surfactant slug (1.5 times CMC of surfactant and 200 ppm of PHPA
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polymer) injection. The injection of surfactant slugs was followed by chase water flooding.
Injection of all fluids as respective steps was maintained at 0.2 mL/min. The oil recovery profiles
of the surfactant slugs were plotted to evaluate the EOR potential of mahua oil surfactant.

Simulation Procedure: The present simulation study is designed according to the steps shown
in the Fig. 1. The simulations were performed for estimating the total volume of swept oil. The
simulation was executed using the input data obtained from the core flooding experiment

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performed in the laboratory. The simulation study was conducted using the software user guide
(ANSYS, 2013).

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Start ANSYS 19.1 workbench with fluent

Defining the 2D Geometry of the setup, L core = 8.49 cm, Diameter of Core = 3.65 cm,
Additionally 2 cm long section on inlet and outlet of same diameter as core were added

Meshing operation was performed for the above system with an element size of 3.e-004.
A refinement operation was performed on the mesh while keeping the mesh structure to

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be fine for better results. Nodes = 51656 & Elements = 50872 were generated.

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The Multiphase system using the volume of fluid model coupled with the viscous shear
stress transport model was defined for the simulation. The displacing fluid was (water,
water + surfactant, water + surfactant + polymer).
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The Phase interaction were defined for the interfacial tension. IFT for oil and SP9000=0.01
mN/m And IFT for Oil and SP9000+Polymer system = 0.075mN/m
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Boundary condition were specified as per the experimental inputs, Flow rate = 0.0002 m/s,
µoil = 0.004219 Pa.s, µ SP9000 = 0.00372 Pa.S, µ SP9000+polymer = 0.0039 Pa.S,
Inlet pressure for water = 120 psi, Inlet pressure for water + surfactant = 150 psi, water +
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surfactant + polymer = 190 psi

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Solving Routine: Scheme SIMPLE (pressure based algorithm) was coupled with least
square cell based gradient and Body force weighted scheme was used for solving the
pressure system. Further the Momentum and Energy parameters were solved using QUICK
scheme which is 3rd order correct.

Finally the Momentum under relaxation factor for the calculation was reduced to 0.5
(default = 0.7) for better convergence of the results)

Execute

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Fig. 1: Flowchart depicting the designing of simulation study

Numerical Methodology: The present system is similar to the multiphase flow occurring in the
reservoir. The different phases having different properties move with different velocities. They
are dependent upon the porosity and permeability of the core. The interaction based on viscosity
and interfacial tension between the different phases also plays a major role in determining the
actual flow regimes of the system. The ANSYS software is well equipped with numerous

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algorithms which helps in simplifying mass, momentum and energy equation for a multiphase

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system consisting of ‘n’ phases [21, 24]. For the present system the flooding fluid is the primary
phase and the crude oil to be swept out of the core is secondary phase. The core was already

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saturated with crude oil prior to the water flooding operation.

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The continuity equation for 2D asymmetric geometries can be given by the Eq (1):

𝜕𝜌 𝜕 𝜕 𝜌𝑣𝑟
+ (𝜌𝑣𝑥 ) + (𝜌𝑣𝑟 ) + = 𝑆𝑚 (1)
𝜕𝑡 𝜕𝑥 𝜕𝑟 𝑟
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where x is the axial coordinate, r is the radial coordinate, vx is the axial velocity, and vr is the
radial velocity . The source Sm is the mass added to the continuous phase from the dispersed
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second phase.
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For 2D axisymmetric geometries, the axial and radial momentum conservation equations are
given by Eq (2) and Eq (3):
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𝜕 1 𝜕 1𝜕 𝜕𝑝 1 𝜕 𝜕𝑣𝑥 2
(𝜌𝑣𝑥 ) + (𝑟𝜌𝑣𝑥 𝑣𝑥 ) + (𝜌𝑣𝑟 𝑣𝑥 ) = − + [𝑟𝜇 (2 − (∇. 𝑣)]
𝜕𝑡 𝑟 𝜕𝑥 𝑟 𝜕𝑟 𝜕𝑥 𝑟 𝜕𝑥 𝜕𝑥 3
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1 𝜕 𝜕𝑣 𝜕𝑣𝑟
+𝑟 𝜕𝑟 [𝑟𝜇 ( 𝜕𝑟𝑥 + )] + 𝐹𝑥 (2)
𝜕𝑥
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𝜕 1 𝜕 1𝜕 𝜕𝑝 1 𝜕 𝜕𝑣𝑟 2
(𝜌𝑣𝑟 ) + (𝑟𝜌𝑣𝑥 𝑣𝑟 ) + (𝜌𝑣𝑟 𝑣𝑟 ) = − + [𝑟𝜇 (2 − (∇. 𝑣)]
𝜕𝑡 𝑟 𝜕𝑥 𝑟 𝜕𝑟 𝜕𝑥 𝑟 𝜕𝑥 𝜕𝑟 3
1 𝜕 𝜕𝑣 𝜕𝑣𝑥
+ 𝑟 𝜕𝑟 [𝑟𝜇 ( 𝜕𝑥𝑟 + )]
𝜕𝑟

𝑣 2𝜇 𝑣𝑧 2
−2𝜇 𝑟 𝑟2 + (∇. 𝑣 ) + 𝜌 + 𝐹𝑟 (3)
3𝑟 𝑟

𝜕𝑣𝑥 𝜕𝑣𝑟 𝑣𝑟
Where, ∇. 𝑣 = 𝜕𝑥
+ 𝜕𝑟
+ 𝑟

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and vz is the swirl velocity. For multiphase flows, ANSYS Fluent solves transport equations for
two types of scalars: per phase and mixture. For an arbitrary K scalar in phase-1, denoted by φlk,
ANSYS Fluent solves the transport equation inside the volume occupied by phase-l. If the
transport variable described by scalar φlk represents the physical field that is shared between
phases, or is considered the same for each phase, then this scalar is considered as being
associated
with a mixture of phases φk. In our case, the transport equation for the scalar is given as Eq (4)

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𝜕𝜌𝑚 𝜑 𝑘
+ ∇. (𝜌𝑚 𝑢𝑚 𝜑 𝑘 ) = 𝑆𝑘𝑚 (4)
𝜕𝑡

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Where k=1,…..,N

where mixture density 𝜌𝑚 and mixture velocity 𝑢𝑚 , for the scalar are calculated according to

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following Eq (4.1),Eq (4.2), Eq (4.3) and Eq (4.4)
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𝜌𝑚 = ∑𝑙 𝛼𝑙 𝜌𝑙 (4.1)

𝜌𝑚 𝑢𝑚 = ∑𝑙 𝛼𝑙 𝜌𝑙 𝑢𝑙 (4.2)
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𝐹𝑚 = ∫𝑠 𝜌𝑚 𝑢𝑚 . 𝑑𝑆̅ (4.3)
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𝑆𝑚 𝑘 = ∑𝑙 𝑆𝑙 𝑘 (4.4)
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Where 𝑆𝑚 𝑘 is the source term (the mass added to the continuous phase from the dispersed
second phase) which is defined as input before the execution of the simulation.
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Results and discussion

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40
Sulfonaated ester of mahua oil
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30

1137 (S=O)
Transmittance(%)
25

20

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15

1767(C=O)

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3408 (OH stretching)
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2984 (CH2-CH3 stretching)
0 865,646 (S-O)

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber(cm-1)

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Fig. 2: IR spectrum showing the functional group present in mahua oil surfactant
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FTIR analysis of mahua oil surfactant
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Fig. 2 shows the IR spectrum of the sulphonated surfactant synthesized from mahua oil. The
corresponding vibration peaks for the specific functional group are represented in Table 2 which
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indicated the proper sulphonation of the mahua oil methyl ester formed as intermediate product
formed during trans-esterification of mahua oil.
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Table 2 . Characteristic functional groups present in mahua oil surfactant

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Wavenumbers (cm-1) Mode of Vibration Functional Group

3408 -OH stretching H-OH of water

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2985 – 2873 C-H symmetrical mode of – -CH3 methyl group

CH3 group
1767 C=O stretching vibrational esters
peak
1410
C-H asymmetrical bending -C-H alkane group

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1137 S=O stretching vibration S=O of sulfonate

865,646 S-O stretching vibration S-O of sulfonate
667 - 619 =C-H bending =C-H of alkene

GC-MS analysis of mahua oil surfactant

Five major fatty acid methyl esters were identified using gas chromatography coupled with mass

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spectrometry (GCMS) in the mahua oil methyl ester formed after trans-esterification of the
mahua oil. The fatty acid methyl esters identified in the compound were mixture of unsaturated

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and saturated forms mainly palmitic (16:0), linoleic (18:2), oleic (18:1), stearic (18:0) as depicted
in Fig. 3. The fatty acid methyl ester individual composition was identified using mass

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spectrometry and compared to the library, which permitted us to determine the molecular
formulae of different derivatives forming the constituents of the fatty acid. Table 3 also provide
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the retention time of elution along with the relative area of each peak identified in the gas
chromatogram. Among the all identified methyl esters it was observed that oleic acid is the major
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component in the mahua oil. The composition of the mahua oil methyl ester was found similar to
the composition reported by other research group [25, 26]. The composition of the various fatty
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acid constituents of the oil is dependent on geographical, soil type, rainfall etc.

Table 3: Results of the GCMS analysis of mahua oil methyl esters

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Acid Molecular ion Retention Time in Concentration (%±SD of total area in

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methyl M+ (m/z) Chromatogram chromatogram)

Ester (min) Present Prajapati A.Singh &
25
I.S. Singh26
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Study et.al
Myristic 242.4 15.83 (0.13±0.09) 0.17 -
Palmitic 270 17.22 (18.83±1.26) 23.93 3.89
Stearic 298 19.45 (13.58±0.9) 21.04 1.17
Oleic 296 19.63 (45.68±1.99) 37.40 54.19
Linoleic 294 20.68 (17.91±1.10) 16.14 8.24

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Fig. 3. Gas chromatogram for different components of mahua oil methyl ester.
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Reaction Scheme

Fig. 4 shows the mechanism of reaction for the synthesis of sulfonated mahua oil surfactant. The
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fatty acid obtained after extraction was first esterified in presence Amberlyst 15 (resin) catalyst
which acts as a bronsted acid catalyst for trans-esterification of vegetable oil. The advantage of
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this solid catalyst is that it can be reused for the next step of reaction without undergoing any
change in its efficiency. Also, its separation during the work-up process is not a tedious task. In
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sulphonation step, pyridine and chlorosulfonic acid is added as a base to abstracts the α-
hydrogen from the ester group, being the most reactive site for the reaction to take place easily as
compared to other available reactive sites like unsaturation present in fatty acid.

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Scheme 1:

O O O O
Amberlyst 15,353K,12 h ClSO3H-Py
O O R OMe R
O MeOH Na2CO3 + NaHCO3 OMe
R SO3Na
O R
Triglyceride Fatty acid methyl ester Sulphonated methyl ester

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R= alkyl chain of different saturated and unsaturated fatty acids

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Fig. 4: Scheme for synthesis of mahua oil surfactant

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Thermo gravimetric and differential thermal analysis

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The thermal analysis of mahua oil surfactant was studied by TGA and DTA analysis. The weight
loss percentages as a function of temperature is shown in Fig. 5. TGA plot shows that the initial
thermal loss occurs around 353-393K, wherein about 19% of loss in weight was observed. This
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initial decomposition marks the removal of moisture present in the surfactant. Since no further
loss in weight was observed above this temperature, which indicates the mahua oil surfactant is
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thermally stable over a wide range of high temperature. The presence of both saturated and
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unsaturated fatty acids and the anti-oxidants present in mahua oil promotes its good thermal
stability. The DTA curve shows only one single dip at a temperature around 373K which
supports that no further loss was observed due to the breakage of chemical bond in the
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surfactant. This clearly indicates that mahua oil can be used for this application where high
temperature stability is a pre-requisite condition [27, 28].
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Fig. 5: Thermal stability curve for mahua oil surfactant
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FESEM and EDX analysis of mahua oil surfactant
FESEM analysis of mahua oil surfactant was done to study surface morphology at 100 KX zoom
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as depicted in Fig. 6 (a). The surfactant molecules appear like compact clusters attached to the
vicinal molecules. The image presented in (Fig. 6,b) shows the EDX analysis of the surfactant
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comprising of carbon (C), oxygen (O), sodium (Na), sulphur (S) and gold(Au). Presence of Au is
due to the conductive coating done on the surfactant molecules during the analysis. Sulphur and
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sodium marks the proper sulphonation of the product. There is no extra peak in the spectrum
which indicates that the compound was free from other elemental impurities.
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Fig. 6. FESEM image (a) 100 KX (b) EDX analysis of mahua oil surfactant

Physicochemical properties of Mahua oil surfactant

Surface Tension at air-aqueous interface

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Surfactant when added to water, it has an ability to reduce the surface tension at air-water

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interface as the surfactant molecules are adsorbed on the interface which eventually reduces the
free energy of the aqueous solution. As the concentration of the surfactant increases in the

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solution, surfactant molecules are adsorbed at the interface and results in a reduction of surface
tension. The concentration when the surfactant molecules aggregate to form micelles is called the

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critical micelle concentration (CMC) [29, 30]. At this concentration, the interface is fully
adsorbed with the surfactant molecules and the excess molecules are forced into the bulk phase
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where they aggregate to form micelle structures. Fig. 7 shows the surface tension vs.
concentration plot as a function of temperature, the plots represents the similar trend of
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decreasing surface tension with increasing concentration of surface tension up to it reaches a

minimum value around CMC. After CMC there is no further decrease in surface tension value
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and the plot becomes constant and show a slight increase in the value of surface tension. In the
curve there is two distinguishable region, first, where the concentration of surfactant molecules
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in the solution is low it is observed that there is a large variation in the slope and it is called as a
pre-micellization region. Second is the post micellar region where CMC is achieved and
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concentration of surfactant molecules is high at the interface and in the bulk there we observe a
constant slope as the surfactant monomer and the formed micelle structure are in thermodynamic
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equilibrium state [31]. It was observed in Fig. 2 that the surface tension of the surfactant solution
decrease with the increase in temperature initially after that a slight increment is observed. This
decrease is more pronounced with long chain surfactant system as there is the breaking of
hydrogen bond at high temperature which makes the surfactant molecules more hydrophilic in
nature. When the temperature is further increased beyond the CMC value there is a slight
increase in the surface tension value due to the decrease in hydration of polar group which favors
micellization. The high-temperature results in breaking of water structure surrounding the alkyl
group and reduces micellization and the surface tension values slightly increase after CMC [32].

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65

60
303K
323K
353K
55
Surface Tension(mN/m)

T
50
CMC

IP
45

CR
40

35

US
30
AN
25
0 2000 4000 6000 8000 10000 12000
Concentration (ppm)
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Fig. 7: Surface tension vs. concentration plot as a function of temperature

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Adsorption parameters and behavioral pattern of mahua oil surfactant.

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Effectiveness (Πcmc) and efficiency (pC20) of surfactant molecules

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The difference between the surface tension of the surfactant system at CMC ant the surface
tension of distilled water at a specified temperature is termed as effectiveness and is denoted by
AC

Eq (5)

Πcmc= γo – γcmc (5)

where pC20 is that concentration at which reduce the surface tension of the system with 20mN/m
takin reference of surface tension of distilled water. High pC20 value predicts more surface active
surfactants and vice versa. Table 1 represents the Πcmc and pC20 values as a function of time.

Maximum surface excess (Γmax) and minimum surface area (Amin) at the interface

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Maximum surface area Γmax represents the agglomeration of surfactant molecules at air-aqueous
interface and is calculated by using Eq (6) as explained by Gibbs isotherms [33]. This term is
referred as the surface pressure and is represented by slope of surface tension and –log of
concentration curve. High surface pressure represents the excess accumulation of surfactant
molecules at the interface

Γ max= -1/RT(∂γ/(∂lnc))T (6)

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The surface excess values Γ max were used to calculate the average area occupied by the single

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molecule of surfactant at air-aqueous (𝐴min ) and is denoted by Eq (7)

CR
1020
𝐴min = 𝑁 (7)
𝐴 𝛤𝑚𝑎𝑥

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On analyzing the Table 4 it is observed that on increasing the temperature Γ max values decreases
which conclude that as the temperature is increased there is a decrease in surfactant molecules at
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the interface and average surface area per molecule shows slight increment. This is due to the
repulsion between the molecules from the bulk phase due to breaking of hydrogen bond formed
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in the bulk phase [34].

Table 4. Characteristic parameters derived from surface tension for mahua surfactant at
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different temperatures.
PT

Temp CMC γcmc Γmax Amin pC20 Πcmc

(K) (M) (mN⋅ (µmol/m2)*10-3 (Å2/ (mN⋅m-1)
CE

m1) mole
cule)
AC

303 7500 35.2 4.98 33.29 2.24 35.9

333 8000 32.5 4.94 33.59 2.26 36.1
353 9000 27.2 4.85 34.17 2.27 36.8

Thermodynamics parameters of mahua oil surfactant

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The association and dissociation pattern of micelles and surfactant molecules existing in the
aqueous phase is called as micellization process. The repulsive columbic forces that are between
the polar head group and the attractive forces between hydrophobic alkyl chains tend to
agglomerate the surfactant molecules in the bulk phase. The thermodynamic parameters for
micellization like standard free energy (ΔG), entropy (ΔS) and enthalpy (ΔH) were calculated
using Eq (8),Eq (9) and Eq(10) and the values as a function of temperature are summarized in
Table 5.

T
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ΔG mic= RT lnΧCMC (8)

CR
∂ ln(𝑋𝐶𝑀𝐶 )
𝛥𝐻𝑚𝑖𝑐 = −𝑅𝑇 2 ( ) (9)
∂𝑇

𝑇𝛥𝑆𝑚𝑖𝑐 = 𝛥𝐻𝑚𝑖𝑐 − 𝛥𝐺𝑚𝑖𝑐 (10)

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In the mentioned equations R represents the universal gas constant (8.314 J/K/mol) and T
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denotes the temperature (K). XCMC is the ratio of the molar concentration of the surfactant in the
bulk phase at CMC and the solvent phase.
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Table 5. Micellization parameters for soap-nut surfactant at different temperatures.

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Temperature ΔGmic ΔHmic ΔSmic TΔSmic

(K) (kJ/mol) (kJ/mol) (kJ/mol/K) (kJ/mol)
PT

303 -19.77 -2.72 0.056 17.04

333 -21.55 -3.29 0.054 18.26

CE

353 -22.50 -3.70 0.053 18.80

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The free energy change, ΔG mic for the micellization process of surfactant system at air-aqueous
interface represents the thermodynamic equilibrium among the single molecule of surfactant and
the micelle formed. As the overall process involves micellization and adsorption both to study
the surface tension mechanism of mahua oil surfactant. It was very important to measure the
gibbs free energy of adsorption which calculates the number of surfactant molecules adsorped at
air-aqueous interface per unit area. Gibbs free energy of adsorption ΔGads (kJ/mol) was
calculated from the value of ΔGmic (kJ/mol) as in Eq. (11)

ΔGads = [ΔGmic − 6.023 π𝐶𝑀𝐶 𝐴𝑚𝑖𝑛 ] × 10−3 (11)

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Fig. 8 shows the comparison between the free energy change of micellization and adsorption as a
function of temperature in the plot which clearly indicates that the adsorption of surfactant
molecules at the air-aqueous interface in more favorable than micellization of the surfactant
molecules in the bulk phase. This results in decreasing of surface tension value to the minimum
value during the micellization process. On increasing temperature it was observed that the
magnitude of ΔGads and ΔGmic are raised due to the equilibrium stability achieved between the
micellized and adsorbed molecules of surfactant. This equilibrium stability is also the reason of

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closeness between the two free energies (micellization and adsorption) [34].

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CR
25
Gads (kJ/mol)

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Gmic (kJ/mol)

20
AN
G (kJ/mol)

15
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10
300 310 320 330 340 350 360
PT

Temperature (K)
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Fig. 8: Comparison of ΔGmic and ΔGads values surfactant solutions at different temperatures.

Interfacial Tension at the oil-aqueous interface

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Injection of surfactant slug in the reservoir improves the mobility of residual oil by reducing the
interfacial tension at oil-aqueous interface consequently increases the capillary number for
efficient tertiary oil recovery processes. Fig. 9 shows the IFT versus concentration curve which
shows that initially IFT show a decreasing trend and reaches to a minimum value and after which
it shows almost a constant trend which increases slightly on increasing the concentration beyond
CMC. The initial decreasing trend of the IFT may be due to the fact that at low concentration
surfactant molecules are adsorbed at the oil-aqueous interface. But when this surfactant

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concentration is further increased the interface gets saturated with the surfactant molecules and
the excess molecules move towards the bulk phase forming the micelles which reduces the
effective surfactant concentration in the bulk phase. The solubilization of micelle in bulk
medium and number of adsorbed surfactant molecule at the interface collectively effect the
increase in IFT value [35]. The minimum IFT value at CMC (9000 ppm) was approx. 3×10-2 at
353 K.

T
IP
0.6

CR
IFT

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IFT (mN/m)

0.3 CMC
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0.0
M

0 4000 8000 12000

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Concentration (ppm)
PT

Fig. 9: IFT versus concentration curve of surfactant solution at 353 K.

Effect of salinity on interfacial tension at oil aqueous interface

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The salinity of formation water and injected water play a very important role on interfacial
properties. Thus an elaborate study was conducted on the effect of salinity on surfactant
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properties. The effect of salt content on the IFT reduction property of mahua oil surfactant is
represented in Fig. 10. Generally the IFT for oil/water system is very high around 20 mN/m. Salt
content plays a crucial role in measuring the interfacial tension at the oil-aqueous interface.
Salinity in the crude oil system promotes the formation of in-situ surfactant from crude oil which
gets adsorbed at the interface with the passage of time. But when salinity is increased beyond the
optimum limits the surface active agents have reached to an equilibrium condition where no
adsorption takes place rather desorption of surfactants from crude oil to interface begins. When

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NaCl is used as salt there is a noticeable reduction in IFT due to the electrical repulsion between
the polar head groups which reduces the size of the micelle that results in reduction in the IFT
values [36, 37].The minimum IFT attained in the present system is around 1×10-2 at an optimal
salinity of 2%. This decrease in IFT is due to the in-situ surfactant formation at the oil-aqueous
interface. When the salinity is further increasing above optimum value there is an increase in the
IFT value as the repulsive hydration forces and electrostatic forces comes into play which
reduces the adsorption of the surfactant molecules at the interface of crude oil and the aqueous

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solution. Due to the increase in concentration of salt the electrostatic forces influences the

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synergistic effect of salt and surfactant molecules which decreases the surface energy of the

CR
crude oil [38].

0.04
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IFT
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0.03
M
IFT (mN/m)

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0.02
PT

0.01

1 2 3 4
CE

Salt content (%)

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Fig. 10: Effect of salinity at CMC of surfactant solution 353 K.

Effect of alkali on interfacial tension at oil aqueous interface

Alkali as a component of surfactant flooding in enhanced oil recovery process has more than one
advantages for its application. Alkali helps in reducing IFT at the crude oil interface, effecting in
reducing wettability, promotes emulsification and prevents the adsorption of the surfactant
molecules onto the rock surface [39].Effect of organic alkali (monoethylamine) and inorganic

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alkali (sodium carbonate) is shown in Fig. 11. The interfacial tension depends on the natural
acidic components of crude oil interacts with alkaline solution at the interface which results in
lowering of IFT at the interface. It has been observed that monoethylamine and sodium
carbonate were able to reduce the IFT to an ultra-low value with IFT of 8×10-3 and 9×10-3 mN/m
respectively. For each set of experiments with alkalis, it was found that IFT first decreases to a
minimum value than with increasing concentration of alkali and then the interfacial tension value
increases. For an application point of view sodium carbonate presents itself as a better option for

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its implementation in the EOR process due to its favorable properties and low cost [40].

IP
CR
0.035 Sodium Carbonate
Monoethylamine

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0.030

0.025
AN
IFT (mN/m)

0.020
M

0.015
ED

0.010

0.005
PT

0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

Alkali(%)
CE

Fig. 11: Effect of alkali at CMC of surfactant solution 353 K.

Wettability alteration study of mahua oil surfactant

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Wettability of rock is an important phenomenon during the multiphase flow of crude oil, water
and gas flow through the reservoir. Alteration of wettability of reservoir rock from oil wet to
water wet involves various chemical phenomenon like surface chemistry, electro-chemistry,
solution chemistry, geo-chemistry combined governing this phenomenon. Surfactant adsorption
on the rock surface and ion-pair mechanism are the major forces responsible for this alteration of
wettability from oil wet to water wet [41]. The wettability alteration study of oil-wet sandstone
surface was conducted at different concentrations as a function of time as presented in Fig. 12.

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Sessile drop method was used to analyze the contact angle of oil-wet sandstone rock surfaces as
Fig.12 depicts how the contact angle decreases, when it is oil wet the contact angle between the
two surfaces is greater than 90° as the surface becomes intermediate water wet the contact angle
lowers to less than 90° and it reduces around 15° when the surface is completely water wet [42].

150
140 0 ppm
5000 ppm
130
8000 ppm

T
120 9000 ppm
110

IP
100
90
Contact angle ()

CR
80
70
60
50

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40
30
20
AN
10
0
0 100 200 300 400 500 600 700 800 900
Time Elapse (sec) at 353 K
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Fig. 12: The contact angle of oil-wet sandstone surface through surfactant dosing at different
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concentrations at 353K

Oil aged sandstone rock surface was analyzed as a function of time at 353 K and it was observed
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that at initially stage when the rock surface is completely oil aged, the angle at the rock interface
was around 115°. Gradually with the passage of time as observed in Fig. 12, the angle between
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the two surfaces decreases to 8.5° at CMC of the mahua oil surfactant indicating that the
wettability of the rock surface has been altered to water wet. This decrease in contact angle is
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govern by various factors like surfactant nature, rock mineralogy, crude oil constituents being
adsorbed on the rock surface. The surface molecules being negatively charge attracts the
positively charge components of the crude oil inducing the ion pair formation between the rock
surface and the surfactant that facilitates the altering of wettability to water wet [43].

Effect of salinity on Contact angle

The alteration of wettability of the rock surface is an intricate process that is governed not only
the rock mineralogy but also with the salinity and the chemical composition of the crude oil. The
salinity effect is more pronounced at the rock-liquid interface than at liquid-liquid interface, it it
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was observed that the effect of brine composition dominates the oil composition precisely the
polar organic component [44]. The effect of salinity in altering the wettability for sandstone rock
surface was studied at reservoir condition at 9000 ppm, the CMC of the mahua oil surfactant at
80° C was studied for 500 sec and the contact angle versus salinity plot is depicted in Fig. 13.
With the increase in salt concentration in the solution, it was observed that the contact angle
reduced to a minimal value due to salting-out of surfactant molecules at a particular
concentration of the salt called as the optimal salinity [45]. This minimum value of contact angle

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helps us to predict that the wettability of the rock sample has been altered to the water wet. This

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decrease is due is to the reduction in the electrostatic repulsion forces due to the cationic ions

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which are bound to the oil wetted rock surface [46].

US
24
Sandstone rock surface
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18
Contact angle ( )

Optimal Salinity
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12
PT

6
CE

0 1 2 3 4 5
Salt Content (%)

Fig. 13. Effect of salinity on contact angle at CMC of surfactant at 80℃

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Surfactant-Polymer flooding using core flood experiment

Core flooding experiments were conducted using the surfactant-polymer solution as chemical
slugs to compare and analyse their respective oil recovery potential. The oil recoveries obtained
after core flooding experiments of the respective cores are plotted against the pore volume of
injected fluid and the pressure differential measured during the flooding experiment as shown in
Fig. 14. The oil recovery and pressure differential pattern obtained during the initial brine

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flooding is similar for both cores. It can be seen that with the injection of initial brine, oil
recovery increases and then reaches a plateau after the breakthrough of the injected brine. At this
stage, more than 98% of water is produced and the pressure differential across the cores have
achieved a constant value. It can also be seen that the oil recovery by initial brine flooding is
nearly same for both cores, which was 54.035% for core I and 53.15% for core II. When
surfactant slug was injected in core I, it was observed that the oil recovery increased. This
increase is due to ultra-low IFT and wettability alteration by surfactant slug. The emulsification

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of crude oil causes an increase in the pressure differential across the core [47]. These properties

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of surfactant led to an additional oil recovery of 17.74% after chase water injection. However,

CR
when the polymer was injected along with the surfactant slug, it was observed that the additional
oil recovery was 20.31%. This greater additional oil recovery in case of surfactant-polymer slug

US
injection is due to improved mobility control and macroscopic efficiency due to presence of
polymer in the injected chemical slug [48]. The greater viscosity of polymer also led to the
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greater pressure differential across the core as shown in the Fig.14. This also led to greater
pressure differential at the stage of chase water flooding in case of SP flooding.
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100 200
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Oil recovery (surfactant flooding)

90 Oil recovery (surfactant-polymer flooding) 175
Pressure drop (surfactant flooding)
80 Pressure drop (surfactant-polymer flooding) 150
Pressure Drop (psi)
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Oil Recovery(%)

70
125

60
100
CE

50
75

40
50
AC

30
25
20
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Pore Volume

Fig. 14: Cumulative oil recoveries and pressure drop as a function of injected pore volume in
core flooding system.

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Table 6. Core flooding results of surfactant and surfactant-polymer slug

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Core Porosity Absolute Design of Oil Additio Oil Saturation

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sample (%) Permeability chemical Recovery nal
No. (millidarcy) slug (%OOIP) recover Initial After After

CR
flooding with 95% y (% primary chase
water cut OOIP) brine water
flooding flooding

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S1 31.96 350 0.5 PV 54.03 17.74 77.92 35.81 21.99
9000 ppm
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Surfactant
S2 32.24 368 0.5 PV 53.12 20.31 79.94 35.41 21.23
9000 ppm
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Surfactant+
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0.02%
PHPA
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Verification and Validation of Result

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The present method for the validation of the core flooding results had been used for numerous
cases reported in the literature (21, 49). The VOF (volume of fluid method, used in
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computational fluid dynamics) is coupled with implicit volume fraction parameter was used for
the validation. VOF assumes that each control volume contains just one phase (or the interface
between phases) and solves one set of momentum equations for all the fluids. The present
simulation study illustrates the results of oil mobility through porous media when subjected to
different flooding fluids. All the input parameters used at different stages of the workflow to
simulate the results are enlisted in Fig. 1. The major dominant forces for the current system
(viscous + IFT + gravitational force) are considered during the execution of the simulation.
Initially, when the core was completely saturated with oil, experimentally it was observed that

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the oil recovery after the brine flooding was 54 %. The results observed from the simulation
were found to be in confluence with the experimental data. The following volume fraction of the
swept oil was observed from the volume rendering routine performed after different flooding
operations. The Fig. 15(a) shows the volume of oil remaining in the core which was saturated
with oil after brine flooding. It can be observed from Fig. that nearly half of the oil has been
swept out of the core. The red color of the contour shows the maxima of the volume fraction of
oil whereas the blue color shows the minima. The results show that a major portion of the oil has

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been accumulated in the upper section of the core. This can be attributed due to the effect of

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gravitational force which has been observed in the simulation results. The gravitational force

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initiates the downward flow of injected fluid as soon as it is introduced into the core. The Fig.15
(b) is the simulation result obtained after surfactant flooding at 9000 ppm of surfactant

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concentration. It can be observed from the volume rendering operation that for surfactant
flooding operation an additional recovery of around 18% oil in place was obtained. Whereas the
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similar experiment was performed on the core which was water flooded by the surfactant and
polymer (9000 ppm surfactant and 200 ppm of PHPA polymer). Additional recovery of around
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25 % was observed which was evident from the Fig.15 (c). This resulted in a cumulative
recovery of around 80 %. The portions from where more oil has been swept in comparison to the
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surfactant flooding operation have been highlighted in Fig. 15 (c). The relative error in the
experimental and simulation result was observed to be less than 10%.
PT
CE
AC

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IP
CR
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AN
M
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Fig. 15: Volume rendering of crude oil when subjected to different fluid injections.

Conclusions
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In this present study, a novel anionic surfactant derived from mahua oil has been used and
evaluated for its efficiency in enhanced oil recovery. The surfactant was found to be quite
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efficient with an ultra-low IFT at the oil-aqueous interface, which was further reduced at
optimum salinity to 0.01 mN/m. Addition of alkali in surfactant solution shows a synergistic
AC

effect with a significant decrease in IFT due to the formation of in-situ surfactant. The surfactant
shows good wetting properties leading to change of oil-wet rock to water-wet and improves the
oil recovery. The contact angle studies indicate a substantial decrease in the dynamic contact
angle which shows good wetting properties of the surfactant as it was potential enough to alter
the wettability of rock to water wet. Core Flooding experiments show an additional recovery of
around 20% of OOIP by the injection of different surfactant-polymer slugs after conventional
water flooding. Comparison of the experimental data of the surfactant-polymer flooding process

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with the simulation analysis using CFD illustrated a better oil recovery profile. The enhanced
recovery is attributed to the lower diffusion rates of surfactant-polymer into the oil phase thereby
displacing more oil as compared to the surfactant slug.

Acknowledgment

The authors appreciatively thank the Oil India Limited [Contract No. 6206917], Duliajan,
Assam, India for providing financial assistance to Department of Petroleum Engineering, Indian

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Institute of Technology (ISM), Dhanbad, India. Authors would like to acknowledge Central

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Research Facilities at IIT (ISM), Dhanbad, IIPE (Vishakhapatnam) and INSA, India for

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technical, software and manpower support.

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Graphical Abstract

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Highlights

1 Synthesis of natural surfactant from Madhuca longifolia.

2 Ultralow IFT achieved by surfactant in presence of salt and alkali.
3 Rock wettability is altered using surfactant from oil-wet to water-wet.
4 Core flooding experiments recovered up to 20% additional recoveries.
5 Simulation studies of experimental data using computational fluid dynamics.

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