Saxena 2017

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ARTICLE IN PRESS [m5G;October 14, 2017;19:19]
Journal of the Taiwan Institute of Chemical Engineers 0 0 0 (2017) 1–13
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Journal of the Taiwan Institute of Chemical Engineers

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Characterizations of surfactant synthesized from palm oil and its

application in enhanced oil recovery
Neha Saxena a, Nilanjan Pal a, Swapan Dey b, Ajay Mandal a,∗
a
Enhanced Oil Recovery Laboratory, Department of Petroleum Engineering, Indian Institute of Technology (ISM), Dhanbad 826 004, India
b
Department of Applied Chemistry, Indian Institute of Technology (ISM), Dhanbad 826 004, India
a r t i c l e i n f o a b s t r a c t
Article history: The present work deals with synthesis of an anionic biodegradable surfactant for application in chemical
Received 19 January 2017 enhanced oil recovery (EOR) process. Alpha sulfonated ethyl ester (α -SEE) was synthesized from palm
Revised 12 September 2017
oil via trans-esterification process. The surfactant was characterized by FTIR, GC, TGA, FE-SEM and EDX
Accepted 12 September 2017
analyses. Critical micelle concentration (CMC) was determined by surface tension measurement at air–
Available online xxx
aqueous interface. The efficiency of α -SEE was studied by calculating the interfacial tension (IFT) between
Keywords: crude oil and surfactant solution, and by investigating the ability of the surfactant to alter the wettabil-
Palm oil ity nature of carbonate and quartz surfaces. Salt effect was studied at CMC of surfactant to obtain an
Surfactant synthesis ultra-low IFT value of the order of 10−3 mN/m at optimal salinity. Addition of organic alkali also showed
Surface tension synergistic effect on IFT between crude oil and surfactant solution. The surfactant favorably altered the
Interfacial tension wettability of oil-wet carbonate and quartz surfaces to water-wet, which is desirable for oil recovery. The
Contact angle
surfactant showed potential application in EOR owing to its enhanced interfacial properties and rock-
Enhanced oil recovery
wetting characteristics. Flooding experiments were conducted with surfactant slugs at different α -SEE
concentrations to achieve about 25%–27% additional oil recoveries after conventional flooding.
© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction chemicals that are known for their use in detergents, cosmetics
and textile sectors [5,6]. Surfactants reduce the interfacial tension
The global energy demand is highly dependent on oil and gas between the injected water and the crude oil trapped in the reser-
extraction in the face of current energy needs. Since 2013, it be- voir to an ultra-low value. Recently, much attention is given on use
came impertinent for petroleum industry to demand and develop of biodegradable and environmental-friendly surfactants in oil re-
better techniques for improving oil production. In the present sce- covery application [7,8].
nario of low crude oil price, there are a few limitations of en- Several efforts are being made to develop low cost chemicals
hanced oil recovery techniques as a consequence of high project from natural resources for successful application in chemical en-
cost and longer lead time periods. Enhanced oil recovery is a hanced oil recovery [9]. Bio-enzyme catalyzed esterification is em-
strained and costly affair in less accessible areas, thereby paving ployed to synthesize fatty acid esters from vegetable oils like cas-
the necessity to extract oil by employing more economical and ef- tor oil, Jatropha oil [10,11]. The efficacy of the chemicals in oil re-
fective methods. Traditionally oil recovery techniques follow pri- covery processes is dependent on capillary pressure, permeability
mary, secondary and tertiary (EOR) processes [1,2]. Among these and wettability of rocks and interfacial tension. Though substantial
recovery processes, chemical flooding with polymers and surfac- amounts of oil are extracted by the injection of surfactant solu-
tants is gaining importance because of its high potential to extract tions in chemical enhanced oil recovery, some oil still remain in
oil that is otherwise not recoverable by primary and secondary re- the rock pores [12]. This is because of high interfacial tension be-
covery [3]. However, as the most of the oil in existing reservoirs tween the oil water interface which traps the oil droplets by capil-
are now matured with lower production rates, it is the right time lary forces. Surfactants help in lowering the interfacial tension be-
to develop cost effective EOR techniques which can be applied ef- tween the oil and water phases, and alter the wettability of the oil-
ficiently in the oil field with existing facilities [4]. Surfactants are wet reservoir rock to water-wet [13,14]. Surfactant selection plays
a pivotal role in achieving cost-effectiveness and favorable interfa-
cial properties in EOR processes. Polyethylene glycol based esters
∗
Corresponding author. are generally produced by chemically catalyzed esterification pro-
E-mail address: ajay@iitism.ac.in (A. Mandal). cesses. However the yield of product is not satisfactory in such
https://doi.org/10.1016/j.jtice.2017.09.014
1876-1070/© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Please cite this article as: N. Saxena et al., Characterizations of surfactant synthesized from palm oil and its application in enhanced oil
recovery, Journal of the Taiwan Institute of Chemical Engineers (2017), https://doi.org/10.1016/j.jtice.2017.09.014
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2 N. Saxena et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–13
Table 1 Lipase was added subsequently to the reaction mixture 10.0%

Properties and composition of Palm oil.
(w/w) of the starting material [6]. The reaction mixture was con-
Palm oil properties Fatty acid constituents of palm oil stantly stirred for 48 h and, in between, the progress of the reac-
Properties @ 27 °C Value Fatty acid Constituents (%) tion was monitored by checking the TLC (Thin Layer Chromatogra-
phy) in a mixture of petroleum ether-ethyl acetate (70:30) as mo-
Acid value (mg KOH/g) 11.34 Oleic 37.0
Density (g/cc) 0.912 Linoleic 10.0
bile phase. Excess lipase was filtered off. Fatty acid residue was
Viscosity (cap) 42.08 Palmitic 42.0 removed by washing with a mixture of diethyl ether and a small
Saponification value (mg KOH/g) 202.7 Stearic 6.6 amount of sodium bicarbonate solution. The lipase-catalyzed es-
Myristic 1.7 terification of palm oil in the presence of polyethylene glycol (PEG
Free fatty acid 2.7
600) aids in conversion of free fatty acids present in oil into ester.
The remaining solution was evaporated under vacuum and a light
yellow semi-viscous liquid (compound 1) was obtained.
reactions and also proceeds toward undesirable side products Sulfonation reaction: The product (compound 1) obtained in es-
[15,16]. In recent decades, esterification reactions carried out in the terification reaction was used to synthesize the desired product
presence of biocatalysts viz. enzymes which include lipases, hy- (α -SEE) by sulfonation of palm oil ethyl ester. In this reaction,
drolases, etc. attracted the attention of scientists and researchers chlorosulfonic acid (2.89 g) was added to pyridine (10.0 mL) in a
for synthesizing fatty acid esters of selective fatty acid and polyol round bottom flask. The reaction was carried out in ice bath un-
systems. The catalytic action of lipases to catalyze fatty acids was der constant stirring for 30 min. Then, the reaction mixture was
investigated by Hayes in different studies [17–20]. According to heated to 60 °C till a clear solution was obtained. The solution
Hayes (1992) the hydroxyl group present on the fatty acid chain was then quenched with a saturated solution of sodium carbon-
is subject to the catalytic action of lipases, and the length of acid ate and sodium bicarbonate in a separating funnel. Normal butanol
chain has a minor effect on the reaction mechanism [17]. Ziemann (30 mL) was poured into the separating funnel to dissolve the com-
and Wagner [21] synthesized wax esters of trihydroxy palmitic acid ponents which remained unreacted in the organic layer to obtain
by Rhizomucor miehei and obtained moderate yields. Lang et al. the desired product in aqueous layer and heated to temperature
[22] studied the laboratory synthesis of wax esters of 17-hydroxy of 120 °C to remove water and pyridine from desired sulfonated
and 3-hydroxy stearic acids using lipase as catalyst and found that product. Organic impurities from the final sulfonated product were
the reaction rates were higher using Mucor miehei as the biocat- removed by washing it with petroleum ether twice. The final white
alyst. Steffen and co-workers [23] also applied the same method solid product (compound 2) was obtained by vacuum drying the
to synthesize monoglycerides of 17-hydroxy and 12-hydroxy stearic product at 60 °C for 24 h which was characterized with FTIR and
acids to achieve higher yields with R. miehei. GC. The palm oil used in the synthesis chiefly contains oleic acid,
The objective of this study is to synthesize an anionic surfac- palmitic acid along with small amount of linoleic acid, myristic and
tant from palm oil which can be used in the field of enhanced stearic acid, hence, the resultant surfactant formed in the process
oil recovery. The chemical and morphological structure of α -SEE is a mixture of the sulfonated ester.
was confirmed by FTIR, GC, TGA and FE-SEM and EDX. Surface ten-
sion studies were conducted in order to determine the CMC value 2.3. Reaction scheme of α -SEE
of the synthesized surfactant. The interfacial tension at surfactant
solution–crude oil interface and contact angle variation of surfac- Fig. 1 shows the reaction mechanism for the synthesis of α -SEE.
tant solution on quartz and carbonate rock with time were also The fatty acid was first esterified in presence of lipase by cleavage
measured to study the efficacy of the α -SEE surfactant. The α -SEE of ethyl group from PEG which gets attached to the oxygen atom
surfactant is expected to be green and biodegradable nature. The of fatty acid to form ethyl ester. In sulfonation step, the pyridine
enhanced oil recovery by injection of small pore volume of surfac- was added as it abstracts the α -hydrogen of the ester group, being
tant slug after conventional water flooding were also investigated the most reactive site for the reaction to take place efficiently as
by performing flooding experiments. compared to other available reactive sites like unsaturation present
in fatty acid. The sulfonate group is attached to α -position of ester
2. Materials and experimental methods group.
2.1. Materials required 2.4. Characterization of α -SEE by FTIR, GC, TGA, FESEM analyses
Palm oil used in the synthesis of the sulfonated ester was pro- The FTIR analysis was done by Perkin Elmer-Spectrum 2 spec-
cured from the local market. Its properties and composition are trometer to identify the functional groups present in the newly
shown in Table 1. The enzyme lipase from R. miehei was obtained synthesized sulfonated ester surfactant from palm oil. A pellet of
from Sigma Aldrich. Poly ethylene glycol 600 was obtained from synthesized surfactant in combination with KBr was used in FTIR
Loba chemicals. Chlorosulfonic acid, sodium carbonate anhydrous, analysis. The surface structure was analyzed by FE-SEM analysis
sodium bicarbonate, diethyl ether, petroleum ether, ethyl acetate using SUPRA-55 ZEISS Germany. The synthesized surfactant was
and pyridine were procured from Merck (India). The crude oil used kept in desiccator for 24 h for removal of moisture and was coated
in the experiments was procured from Oil India Limited, Assam. with gold to obtain better accuracy. Gas Chromatography (Jeol GC-
The obtained crude oil has a total acid number 0.84 mg KOH/g, Mate II) was used to determine the constituents of surfactant syn-
gravity of 18.9° API, density of 0.9244 g/cc and viscosity of 4.26 cp thesized from palm oil. The TGA analysis of α -SEE was done to
at 27 °C. determine its thermal degradability by thermo gravimeter analyzer
(Netzsch-STA 449 Jupiter).
2.2. Synthesis method
2.5. Interfacial and flooding properties of α -SEE surfactant
Esterification reaction: Palm oil and poly ethylene glycol (PEG)
600 were weighted in stoichiometric amounts in a round bot- 2.5.1. Surface tension measurements
tom flask, mixed with constant stirring and the reaction mixture The surface tension and critical micelle concentration (CMC)
was heated at a temperature of around 60 °C for about 30 min. of synthesized surfactant was calculated by using Du Nouy ring
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N. Saxena et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–13 3
Fig. 1. Reaction scheme for the synthesis of α -SEE.
method (KRUSS Easy Dyne, Germany) at 27 °C. Surface tension was stirred at 20 0 0 rpm for 15 min. Similar procedure was repeated for
determined for aqueous solutions with different surfactant concen- successive salt additions in surfactant solution until surfactant pre-
trations. Surface tension values for individual samples were mea- cipitation occurs.
sured three times to ensure the accuracy of results. The measured
value of surface tension of distilled water was 72.3 mN/m at 27 °C. 2.5.3. Interfacial tension measurements
After each test the platinum ring used in the experiment was Oil–aqueous interfacial tension values between the surfactant
cleaned by acetone and was dried with flame for the next set of solutions of different concentrations and crude oil was calculated
experiments. by spinning drop tensiometer (SVT 20, Dataphysics) at 27 °C.
The surfactant solutions at various concentrations ranging from
2.5.2. Salt tolerance studies 20 0 0 ppm to 12,0 0 0 ppm were used. The α -SEE solution was in-
The concentration of salt in surfactant solution at which surfac- jected into a capillary tube through a syringe. Progressively, a drop
tant starts precipitating is known as salt tolerance of the surfac- of crude oil was injected to the tube through rubber septum. The
tant. Salt tolerance of α -SEE surfactant solution at CMC value was IFT between the two liquids of different densities was determined
measured at 27 °C. Aqueous solutions were prepared by adding using SVT 20 software. The experiment was conducted at room
salt in the range of 1% to 12% NaCl to surfactant solution at CMC. temperature at a speed of 30 0 0 rpm for individual sample. The
Initially, 1 wt.% NaCl was added to the solution. The mixture was equilibrium interface tension for surfactant solution is obtained by
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Fig. 2. Schematic representation of chemical flooding experimental setup α -SEE solution in sandpack system.
Eq. (1) at 240 psig to irreducible water saturation. The initial water sat-
uration was determined on the basis of mass balance. The crude
σ = ω R ρ / 4
2 3
(1)
oil used in the flooding experiments was collected from Oil India
where ω represents the angular velocity of the system, R repre- Limited, Assam (India). The oil has a total acid number of 0.840 mg
sents the radius of crude oil droplet, σ is the interfacial tension KOH/g, gravity of 18.90°API and viscosity of 4.6 cP at 27 °C.
between two fluids under consideration and ࢞ρ is the density dif- Darcy’s law was used to calculate the effective permeability to
ference between surfactant solution and crude oil. The interfacial oil (ko ) and effective permeability to water (kw ) at irreducible wa-
tension between crude oil and distilled water interfaces was found ter saturation (Swi ) and residual oil saturation (Sor ), respectively.
to be 18.0 mN/m at 27 °C. For a horizontal linear system, flow rate is related with permeabil-
ity as shown in Eq. (2)
2.5.4. Contact angle determination kA dp
q= (2)
To carry out a study on alteration of wettability of reservoir μ dx
rock from oil-wet rock to water-wet rock surface, the contact an-
gle between the newly synthesized surfactant solution and oil-wet where, q is the volumetric flow rate (cm3 /s), A is the total cross-
rock surface had been studied using Drop shape Analyzer (KRUSS sectional area of the sandpack system (cm2 ), μ is the fluid viscosity
DSA 25, Germany) at 27 °C. Precisely controlled tempering and hu- (cp), ddxp is the pressure gradient (atm/cm) and k is the permeability
midity chambers were used to provide a realistic model of the pro- in Darcy.
cess conditions to avoid vibration, air effect and other mechanical Water-flooding was initially conducted by subjecting the core-
effects. To calculate the contact angle, 5–10 μL of surfactant solu- holder placed horizontally to a constant injection pressure at
tion was taken in the syringe and carefully dropped onto the sur- 35 psig. After water flooding, when water-cut reached above 95%,
face of oil wet rock (carbonate and quartz). The test was repeated around 0.5 pore volume (PV) of surfactant slug was injected. This
three times to maintain the consistency in the results for individ- was followed by chase water flooding (2.0 wt.% brine solution). The
ual samples. Initially, the rock was suitably prepared for wettabil- flooding tests were repeated for all surfactant systems with varying
ity study by washing it with deionized water, and was then put concentrations.
into the crude oil for ageing in oven at 65 °C for 15 days. After
being aged for 15 days the oil-wet rock was then vacuum dried 3. Results and discussion
overnight.
3.1. Characterization of synthesized anionic surfactant
2.5.5. Flooding experiments
Sandpack flood tests were employed for the evaluation of the 3.1.1. FTIR study of palm oil ethyl ester
effectiveness of the synthesized surfactant (α -SEE) to enhance the The FTIR spectrum of synthesized palm oil ethyl ester derived
oil recovery after conventional water flooding. It consists of four from palm oil is shown in Fig. 3. The FTIR spectrum of palm oil
components viz. a core holder, a displacement pump (Teledyne ethyl ester shows an absorption band at 3471 cm−1 , arising due
Isco), chemical solution cylinder for crude oil, brine and surfactant to the stretching vibration of –OH bond. Peak at 3008 cm−1 cor-
solution and a fraction collector. A schematic of the experimental responds to cisolefinic=C–H double bond. The symmetrical and
setup is depicted in the Fig. 2. As per the homogeneous sand pack- asymmetrical stretching vibrations of methylene group (–CH2 ) is
ing model, the geometry was chosen as L = 45 cm and r = 3.5 cm. indicated by peaks at 2854 cm−1 and 2924 cm−1 . A strong peak
The core holder was tightly packed with uniform sands (60 mesh) at 1746 cm−1 is attributed to C=O bond from ester as the main
and saturated with 2.0 wt.% brine. It was flooded with the brine functional group. The presence of a peak at 1464 cm−1 shows the
at 35 psig and the absolute permeability was calculated from the bending vibration of aliphatic groups –CH2 and –CH3 . The asym-
flow rate and pressure drop through sand pack using the Darcy’s metrical axial stretching of the C–O ester group is identified by the
law equation. The sand pack was then flooded with the crude oil absorption peaks at 1237 cm−1 , 1163 cm−1 and 1116 cm−1 . The
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Fig. 3. FTIR spectrum of Palm oil ethyl ester.
Fig. 4. FTIR spectrum of α -SEE.
peak near 722 cm−1 is due to the out-of-plane vibration of cis- 3.1.3. GC analysis of α -SEE
di-substituted olefins. FTIR spectrum of the synthesized surfactant Fig. 5 shows the gas chromatogram of the surfactant synthe-
proved that palm oil is an ethyl ester of saturated and unsaturated sized from palm oil. The purity of the final product is obtained
fatty acids. at ≥76%. The surfactant synthesized from palm oil is a mixture of
various fatty acid ethyl esters, which is confirmed by GC analy-
3.1.2. FTIR study of α -SEE sis. A strong peak at retention time (RT) 17.22 with 43.09% peak
Fig. 4 shows the FTIR spectrum of synthesized surfactant de- area shows that palmitic acid ethyl ester (C16:0 ) is constituted in
rived from the palm oil. The spectra which appear in palm oil ethyl the synthesized product. The presence of oleic acid ethyl ester
ester are also present in synthesized surfactant. The absorbance for (C18:1 ) is attributed to a peak at RT 19.43 and peak area percent-
different functional groups and bonds are shown in Fig. 4. Addi- age of 21.65%. A peak at RT 19.65 with 11.80% area in the GC chro-
tional peaks at 1116 cm−1 and at 850 cm−1 , 617 cm−1 indicate the matogram corresponds to stearic acid ethyl ester (C18:0 ).
stretching vibration of sulfonate groups (S=O) and (S–O) respec-
tively. Thus, the FTIR data confirms that the sulfonation of palm 3.1.4. FESEM analysis of α -SEE
oil ethyl ester produced the corresponding ethyl ester sulfonate. FESEM analysis of α -SEE was performed to study the surface
The various peaks obtained in the FTIR spectra are discussed in morphology. Fig. 6(a) at 10 KX zoom shows that the surfactant
Table 2. molecules appear to be in cluster form and are compact in nature.
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Table 2
Characteristic adsorption bands corresponding to different functional groups in palm-oil based surfactant.
Characteristic adsorption bands (cm−1 ) Description of functional group
310 0–370 0 Stretching vibration of O–H bonds

280 0–30 0 0 Stretching vibration of alkyl C–H bonds (asymmetric CH3 and CH2 stretching and symmetric CH2 )
1735–1750 Stretching vibration of ester groups C = O bonds
1620–1680 Stretching vibration of C = C bonds of alkene
1350–1480 Bending vibration of alkyl C–H bonds
1120–1160 Stretching vibration of the O = S = O bonds of sulfonate
850 & 617 Stretching vibration of S-O bonds
10 0 0–130 0 Stretching of C–O of ester group
1350–1480 CH3 asymmetric bending
Fig. 5. Gas chromatogram showing the retention time for different components of the α -SEE.
Fig. 6. FESEM image of α -SEE at different magnification: (a) 10 KX (b) 100 KX.
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Fig. 7. EDX analysis of the α -SEE.
Image shown in Fig. 6(b) at 100 KX zoom illustrates that particles

are rod-like and irregular in shape, and are well dispersed within
the area under analysis.
3.1.4. EDX spectrum of α -SEE

In EDX analysis of synthesized surfactant, five elements are ob-
served viz. carbon (C), oxygen (O), sodium (Na), sulfur (S) and gold
(Au) as shown in Fig. 7. The gold (Au) peak characterized in the
spectra was due to the presence of coating materials used along
with the surfactant during the analysis. All the remaining elements
present correspond to different components of the α -SEE. EDX data
clearly shows the presence of sulfur as chlorosulfonic acid was
used in the sulfonation reaction. The presence of sodium shows
that the anionic surfactant exists in the form of sodium salt. No
extra peak of any other element is depicted in the EDX spectra,
which indicates that the α -SEE surfactant is pure, without any
other elemental impurities.
Fig. 8. Thermal stability curve for α -SEE surfactant.

3.1.5. Thermal gravimetric analysis of α -SEE
The thermal stability of α -SEE was studied by thermo-
gravimetric analysis (TGA). The conventional reservoir temperature
lies in the range between 80 °C 120 °C [24]. Hence, it becomes
important to investigate the thermal degradation characteristics
of the surfactant for effective application in EOR processes. The
weight loss percentage is depicted with increase in temperature
in Fig. 8. TGA plot shows that the initial thermal loss occurs from
96 °C to 150 °C, wherein about 20% of loss in weight is observed.
No further loss in weight was observed above this temperature,
which shows that the α -SEE surfactant is thermally stable under
reservoir conditions which are pre-requisite for its application in
field of enhanced oil recovery. The presence of both saturated and
unsaturated fatty acids in palm oil supports the good thermal sta-
bility of α -SEE as these fatty acids require high temperature for
its degradation. The anti-oxidants present in palm oil aid in good
thermal stability.
Fig. 9. Variation of surface tension with concentration of synthesized surfactant at

3.2. Interfacial properties of α -SEE surfactant 27 °C.
3.2.1. Surface tension of α -SEE solutions

The surface tension versus concentration curve of α -SEE solu- With the increase in concentration of synthesized surfactant so-
tions with concentration ranging from 0 ppm to 16,0 0 0 ppm is de- lution the surface tension values lowers as there is increase in ad-
picted in Fig. 9. The CMC of this surfactant was obtained as the sorption of surfactant molecules at the interface of air and water
interception between the decreasing slope and horizontal constant [25] and this trend was observed until the concentration reached
line of the surface tension curve plotted against concentration. CMC value of 80 0 0 ppm with surface tension of 32.5 mN/m. After
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Fig. 11. Interfacial tension versus concentration of α -SEE at 27 °C.

Fig. 10. Effect of time elapse on interfacial tension of α -SEE at different concentra-
tions at 27 °C.
the CMC, the surface tension curve attains a constant value as the
surface gets saturated with the surfactant molecules.
3.2.2. Salt tolerance analysis of α -SEE solutions

Generally salt tolerance of surfactants vary between
5 × 104 mg/L (5 wt.%) to 8 × 104 mg/L (8 wt.%) [26,27]. The salt
tolerance level of the surfactant solution is found to fall in this
range. Salt tolerance studies revealed that no surfactant precip-
itation occurred in the range between 1% NaCl and 7% NaCl for
α -SEE surfactant solutions at CMC (80 0 0 ppm). As the salt content
was increased to 8% NaCl, surfactant begins to precipitate in
solution. The surfactant is resistant to salt effects up to 7% NaCl
(7 × 104 mg/L) concentration. Therefore, the synthesized surfactant
shows good tolerance to reservoir salinity and can be effectively
Fig. 12. Effect of salinity on IFT at CMC (80 0 0 ppm) of α -SEE at 27 °C.
used in both low salinity and high salinity reservoirs for oil
recovery applications.
of salt concentration on IFT value of surfactant solutions at CMC
3.2.3. Interfacial tension (IFT) of crude oil and α -SEE is depicted in Fig. 12. The IFT shows a bell shaped curve with an
Studies on dynamic interfacial tension (DIFT) between crude oil optimal salinity of 2% NaCl content in surfactant solution at CMC.
and α -SEE surfactant solutions at 27 °C are depicted in Fig. 10. Initially, it decreases to a minimum value of 8.30 × 10−3 mN/m
The interfacial tension initially decreases to a minimum value, due at 2% salt content followed by an increase in the IFT value. Ini-
to the existence of dynamic equilibrium between adsorption and tially for palm oil-based anionic surfactant, the oil–aqueous inter-
desorption of α -SEE molecules at oil–water interface. As aqueous face is negatively charged. On addition of NaCl salt, some Na+ ions
phase interacts with oil phase, surfactant molecules show diffu- are attracted toward the adsorption layer as counterions, whereas
sion phenomenon from the bulk to the interface, and at interface other cations form the electrical double layer [31]. With further in-
of oil and water phase adsorption occurs. At first, the adsorption crease in salt concentration, more counterions are attracted toward
rate of molecules was higher than desorption rate which lead to the interface, reducing the effective charge in the interface layer
reduction in DIFT. Finally, when an equilibrium state was achieved [32,33]. This reduces the electrostatic repulsive forces between an-
and adsorption and desorption forces were balanced, the DIFT ap- ions carried by polar head group of α -SEE molecule, leading to
proached toward a constant value [28]. thinning of the interface layer. As a result, surfactant molecules
Fig. 11 shows the variation of equilibrium IFT with surfactant are more closely packed at the oil–aqueous interface and IFT is
concentration at 27 °C. With increase in α -SEE (alpha-sulfonated drastically reduced [30,34]. After salt concentration in solution ex-
ethyl ester) concentration in aqueous solution, more surfactant ceeds optimal salinity value, the ionic interactions between the hy-
molecules are adsorbed at the interface and IFT is reduced [29]. drophilic group (negatively charged group of surfactant) and the
When surfactant concentration reaches critical micelle concentra- cationic part of salt (Na+ ) are subsequently decreased in surfactant
tion (CMC) value, the oil–aqueous interface is saturated with sur- solution [35].
factant molecules and micelles begin to form in the aqueous bulk
phase. At 80 0 0 ppm (CMC), the value of IFT was found to be 3.2.5. Effect of pH on IFT
1.17 × 10−2 mN/m. As the surfactant concentration is further in- Alkalis play a synergistic effect on the oil–aqueous interfacial
creased, the micelle formation takes place resulting in slight in- tension. Addition of alkali improves pH of the solution and makes
crease in IFT. This is attributed to change in the distribution of sur- the solution more alkaline in nature. On alkali addition, the re-
factant molecules in the oil and water phase, caused as a result of activity with acidic component of crude oil is increased due to
increase in surfactant concentration [30]. the formation of in-situ surfactants by the deprotonation of acids
present in crude oil [36–38]. Fig. 13 shows the influence of pH due
3.2.4. Effect of salt concentration on IFT to addition of mono-ethanolamine (MEA) on IFT between crude
Addition of salt plays a synergistic effect on the interfacial ac- oil and surfactant solution at CMC. IFT was found to decrease
tivity of surfactant molecules at oil–aqueous interface. The effect with increase in pH value. Initially, this decrease was sharp at
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Fig. 13. Effect of pH on IFT at CMC (80 0 0 ppm) of α -SEE at 27 °C.
Fig. 14. FTIR spectrum of dry quartz rock and crude oil aged quartz rock.
low pH values. IFT decrease by alkali addition is likely a con-

sequence of the synergism among surfactant molecules, ionized
acid and unionized acid to form a mixed adsorbed interfacial layer
[28,39]. Consequently, adsorption of surfactant molecules at oil–
aqueous interface is increased, resulting decrease of IFT. However,
IFT trend showed gradual and slower reduction with increase in
organic alkali concentrations (pH value). Minimum IFT value of
6.81 × 10−3 mN/m was achieved at solutions with 12 pH. Reduction
in IFT with pH may be attributed to the increased ionic strength,
which prevents the surfactant from adsorbing onto the surface of
rocks. Furthermore, MEA causes lesser reservoir damage due to its
organic nature and low alkali consumption in the reservoir [40,41].
3.3. Wettability alteration studies
3.3.1. Characterization of quartz and carbonate rock surfaces

A water-wet rock surface possesses greater oil recovery that can
be achieved by water flooding. When the calculated amount of sur-
factant solution is injected to the oil-wet or intermediate wet rock
Fig. 15. FTIR spectrum of dry and aged carbonate rock with crude oil.
the trapped oil is recovered efficiently due to the change in wetta-
bility of rock from oil-wet to water-wet. This change in wettability
is governed by three factors: the electrostatic force between the
1794 cm−1 corresponding to stretching vibration for Ca–CO3 bonds
ions, the forces of attraction between surfactant and polar compo-
for calcite. Carbonate rock aged in the crude oil show absorption
nents of crude oil, and surface characteristics of the rock.
bands at about 3436 cm−1 , depicting bending vibration of O–H
The FTIR analysis of quartz rock, dry and aged with crude oil
bonds. A new peak at 2947 cm−1 corresponds to alkyl C–H bond,
is depicted in Fig. 14. The spectrum of dry quartz show bands
thereby confirming that the rock was aged with crude oil.
at 458 cm−1 and 689 cm−1 corresponding to asymmetric and
symmetric bending vibrations of Si–O bonds whereas peaks at
782 cm−1 and 1081 cm−1 , corresponds to stretching vibration 3.3.2. Effect of surfactant concentration on contact angle
for Si–O bond. The Si–O bond between the quartz rock surfaces The contact angle values of surfactant solution at different con-
clarifies the presence of silica as its main component, whereas centrations with time were measured to study the wettability al-
the aged quartz rock shows bending vibrations of C–H of sub- teration of oil-wet rock surfaces. The sessile drop method was used
stituted benzene at 1076 cm−1 and C=C stretching vibration at to calculate the contact angle of oil wetted rock surfaces at differ-
1630 cm−1 respectively. The absorption band at 2850 cm−1 and ent surfactant concentrations. Initially the test was conducted with
2922 cm−1 depicts C–H symmetric vibration of the saturated hydro- distilled water and the contact angle calculated were found to be
carbons and O–H band due to stretching vibration at 3435 cm−1 . greater than 90° at the start, indicating that the rock surface under
C=O stretching peaks appeared between 1627 cm−1 to 1870 cm−1 study was oil-wet. In the presence of surfactant, the contact angle
which confirms the presence of carbonyl components like acids, gradually decreased with elapse of time and reached a constant
aliphatic esters and aldehydes in the crude oil. Many new peaks value after 10 0 0 s, showing that the rock surface had changed its
are observed which corresponds to the components of crude oil, wettability to water-wet. This decrease in contact angle value is
thereby confirming the ageing of quartz with crude oil. dependent on the type of rock surface, type of surfactant used
Characterization of the functional groups present in, dry and and the acid components of crude oil adsorbed onto the surface
oil-wet carbonate rock were done using the FTIR technique, and of rock used [42]. The plot of contact angle versus time for carbon-
the results are shown in Fig. 15. The FTIR spectrum of dry car- ate and quartz rock surfaces at different concentrations is shown in
bonate rock surface shows absorption peaks at 868 cm−1 and Figs. 16 and 17 respectively.
JID: JTICE
Fig. 16. The contact angle of oil wet carbonate surface through surfactant dosing at
different concentration at 27 °C.
Fig. 18. Effect of salinity on contact angle at CMC (80 0 0 ppm) of α -SEE solution at
27 °C on Quartz surface and Carbonate rock surface.
quently, α -SEE surfactant synthesized from palm oil proves to be

highly efficient in altering the wettability of rock from oil-wet to
water-wet,which ultimately aids in enhancing the oil recovery.
3.3.3. Effect of salinity on contact angle

Salinity plays a crucial role in wettability alteration behavior of
surfactant solutions. Hence, there is a need to study the effect of
salt on alteration of wettability of oil wet rock surfaces at opti-
mal surfactant concentration of 80 0 0 ppm at 27 °C. Fig. 18 shows
the influence of salinity on contact angle behavior of quartz and
carbonate rocks respectively for 600 s. Addition of salt (NaCl) im-
proves the wettability behavior of oil-wet rock due to increased
Fig. 17. The contact angle of oil wet quartz surface through surfactant dosing at
rate of accumulation of surface active components at oil–aqueous
different concentrations at 27 °C.
interface. The contact angle value decreases with the increase in
salt percentage in surfactant solution at CMC. This may be due
Surfactant concentration plays a pivotal role in controlling the to the salting-out of surfactant molecules in aqueous phase in the
dynamic wetting characteristics of both quartz and carbonate presence of NaCl [50]. As salt concentration in CMC surfactant so-
rocks. The interaction between SO4 2− ions in the palm oil-based lution increases, some water molecules are attracted by salt ions.
surfactant and organic compounds on the rock surface displaces This reduces the availability of water molecules to interact with
the adsorbed fatty acids (in crude oil) adsorbed on rock surface surfactant molecules in bulk solution. As a result, faster diffusion
and, therefore, reduces oil-wetness [43,44]. This improves the oil- rate of surfactant molecules from bulk to interface is achieved and
displacing ability of the surfactant at the interface between oil-wet additional surfactant molecules precipitate to the rock–aqueous in-
rock and aqueous solution of surfactant [45]. The lowest drop in terface to form stronger hydrophobic surfactant-surfactant inter-
contact angle is observed at CMC value (80 0 0 ppm) of the synthe- actions [13,51]. This phenomenon is observed till optimal salin-
sized surfactant. For carbonate rock surface, surfactant solution at ity value is reached. At optimal salinity (2% NaCl), wetting char-
CMC showed contact angle decrease from 82.5° to 20.7° in 10 0 0 s. acteristics are more favorable than other solutions for application
Contact angle is found to decrease from 80.3° to 17.3° in 10 0 0 s in EOR. Contact angle values are found to decrease from oil-wet
for quartz surface at CMC (80 0 0 ppm). This shows that ability to conditions to 7.7° for quartz and 12.9° for carbonate rock surfaces
alter nature of the rock surface from oil-wet to water-wet surface respectively in 600 s. The decrease in value of contact angle at op-
is most favorable at CMC. At surfactant concentrations above CMC, timal salinity is due to the reduced electrostatic repulsion force as
rate of decrease of contact angle with time is reduced, showing more sodium ions are bound to oil wet surface which results in al-
that adhesion tension between rock and surfactant solution does teration of wettability [52]. Beyond optimal salinity, the repulsive
not increase with concentrations beyond CMC [46]. Variation in electrostatic and hydration forces at the rock–solution interface in-
contact angle shows that the alteration of wettability of rock is due crease in order to avoid droplet spreading at the surface [53]. This
to the effect of two mechanisms predicted: first is ion-pair attrac- reduces the adsorption of the surfactant onto the rock surface and
tion between the anionic polar head groups of the surfactant units thus, increases the value of contact angle with increase in salinity
and cationic charged components present in the crude oil adsorbed above the optimal salinity [54]. It is, therefore, concluded that salt–
on the rock surface [47,48]. Another possible reason for this varia- surfactant mixtures show better wettability characteristics as com-
tion can be the adsorption of negatively charged group of anionic pared to surfactant solutions on both quartz and carbonate rock
surfactant onto the positively charged surface of rock [49]. Conse- surfaces [55].
JID: JTICE
Fig. 19. Flooding performance of α -SEE slugs in sandpack system at different surfactant concentrations: (a) 80 0 0 ppm, (b) 10,0 0 0 ppm, (c) 12,0 0 0 ppm, and (d) additional oil
recoveries.
Table 3
Flooding results of the different systems.
Sandpack Porosity Permeability, k (Darcy) Design of chemical Oil Recovery Additional % Saturation
sample No. (%) slug for flooding (%OOIP) at 95% recovery (%
kw (Sw = 1) ko (Swi ) water cut OOIP) Swi Soi Sor
I 31.24 4.47 0.58 0.5 PV 80 0 0 ppm 51.10 25.80 21.14 78.86 19.20
SMES + Chase water
II 31.64 4.75 0.65 0.5 PV 10,0 0 0 ppm 51.70 26.10 20.35 79.65 18.10
SMES + Chase water
III 31.97 5.10 0.70 0.5 PV 12,0 0 0 ppm 51.50 26.30 20.10 79.90 17.00
SMES + Chase water
3.4. Oil recovery by flooding of synthesized surfactant solutions breakthrough was found to occur after injection of small pore vol-
ume of displacing fluid during flooding test due to lower viscosity
While planning for surfactant flooding in chemical enhanced of water as compared to that of crude oil. Almost 52% of original
oil recovery, it is important to design the surfactant slug with oil in place (OOIP) is recovered after conventional water flooding
optimum concentration of surfactant. Optimum surfactant concen- due to high porosity of the sandpack system. When water-cut
tration basically depends on the CMC of surfactant, adsorption of reached up to ∼95%, injection of surfactant slug improved the
surfactant onto the reservoir rock, salt tolerance and interfacial oil recovery rate with drastic reduction in water-cut percentages.
behavior at oil–aqueous interface. In this study, flooding tests were However, with further increase in pore volume of slug injected,
conducted with the injection of α -SEE surfactant slugs at three the oil recovery increased with simultaneous increase in water-cut.
different concentrations. During surfactant flooding, a significant The flooding performance of different surfactant slugs (80 0 0 ppm,
amount of surfactant is adsorbed on the rock surface. Hence, 10,0 0 0 ppm, 12,0 0 0 ppm) injected into the sandpack systems are
flooding studies are carried out with surfactant slugs at concen- depicted in Fig. 19(a), (b) and (c) respectively. After injection of
trations higher than CMC value (80 0 0 ppm) to account for these surfactant slug, the oil droplets trapped in pores are mobilized
adsorption losses. This ensures that under reservoir conditions, at due to reduction of interfacial tension between oil and displac-
least CMC of surfactant is maintained for efficient recovery of oil. ing fluid [56,57]. With increase in surfactant concentration, oil
Sandpack saturated with crude oil (obtained from Oil India, saturation increases due to increase in the coalescence of mobi-
Assam) was initially flooded with brine solution (2% NaCl). Water lized oil droplets to form oil bank [58–60]. This allows better oil
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The authors gratefully acknowledge the financial assistance pro-
tension, emulsification, and surfactant concentration on oil recovery in surfac-
vided by Oil India Limited [Contract No. 62O6917], Duliajan, Assam, tant flooding process for high temperature and high salinity reservoirs. Energy
India to the Department of Petroleum Engineering, Indian Institute Fuels 2015;29:6165–76.
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thank Central Research Facility, IIT (ISM), Dhanbad, India for tech- 2011;383(1–3):114–19.
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ARTICLE IN PRESS [m5G;October 14, 2017;19:19]

Journal of the Taiwan Institute of Chemical Engineers 0 0 0 (2017) 1–13

Contents lists available at ScienceDirect

Journal of the Taiwan Institute of Chemical Engineers

Characterizations of surfactant synthesized from palm oil and its

Table 1 Lipase was added subsequently to the reaction mixture 10.0%

Fig. 1. Reaction scheme for the synthesis of α -SEE.

Fig. 3. FTIR spectrum of Palm oil ethyl ester.

Fig. 4. FTIR spectrum of α -SEE.

Characteristic adsorption bands (cm−1 ) Description of functional group

310 0–370 0 Stretching vibration of O–H bonds

Fig. 7. EDX analysis of the α -SEE.

Image shown in Fig. 6(b) at 100 KX zoom illustrates that particles

3.1.4. EDX spectrum of α -SEE

Fig. 8. Thermal stability curve for α -SEE surfactant.

Fig. 9. Variation of surface tension with concentration of synthesized surfactant at

3.2.1. Surface tension of α -SEE solutions

Fig. 11. Interfacial tension versus concentration of α -SEE at 27 °C.

3.2.2. Salt tolerance analysis of α -SEE solutions

Fig. 13. Effect of pH on IFT at CMC (80 0 0 ppm) of α -SEE at 27 °C.

low pH values. IFT decrease by alkali addition is likely a con-

3.3. Wettability alteration studies

3.3.1. Characterization of quartz and carbonate rock surfaces

quently, α -SEE surfactant synthesized from palm oil proves to be

3.3.3. Effect of salinity on contact angle

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