Journal of Petroleum Science and Engineering 173 (2019) 1264–1283

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Journal of Petroleum Science and Engineering

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Adsorption analysis of natural anionic surfactant for enhanced oil recovery: T

The role of mineralogy, salinity, alkalinity and nanoparticles
Neha Saxena, Amit Kumar, Ajay Mandal∗
Department of Petroleum Engineering, Indian Institute of Technology (Indian School of Mines), Dhanbad, 826 004, India

A R T I C LE I N FO A B S T R A C T

Keywords: Anionic surfactants are widely used as an effective chemical for enhanced oil recovery because of their unique
Anionic surfactant characteristics of reducing interfacial tension (IFT) between the trapped crude oil and water, and alteration of
Reservoir rock wettability of reservoir rock from oil-wet to water-wet. However, the loss of surfactant by adsorption onto the
Adsorption solid rock surface is a major concern that reduces the efficiency of the surfactant flooding process and must be
Isotherm models
considered while designing the process. Present study highlights the equilibrium adsorption and kinetics of an
Nanoparticles
anionic surfactant synthesized from soap-nut fruit on sandstone, carbonate and bentonite clay as representative
of reservoir rocks. The mineralogy and morphology of the rocks were investigated by FE-SEM, XRD and BET
surface area analysis. UV–Visible spectroscopy was used to measure the amount of surfactant adsorbed on solid
rock/clay surface in batch experiments. The experimental equilibrium adsorption data were analyzed by using
Langmuir, Freundlich, Temkin and Redlich-Peterson isotherm models and adsorption parameters were calcu-
lated. Adsorption kinetics of the surfactant system were studied and pseudo second order kinetic model was best
fitted for the surfactant/rock/clay systems. Presence of salt was found to increase surfactant adsorption on rock/
clay marginally. However, presence of alkali and nanoparticles was found to reduce the loss of surfactant by
adsorption and shows synergistic effects on IFT reduction, which is beneficial for application of the surfactant in
oil recovery. The findings of the study are quite helpful in proper designing of the surfactant flooding for en-
hanced oil recovery.

1. Introduction
Surfactants are amphiphilic compounds that have a hydrophilic
head with a hydrophobic tail. The amphiphilic structure of the surfac-
tants has led to their unique properties which have led to its use in
various industrial application like detergents, foaming agents, wetting
agents, emulsifiers, and oil industry. The application of surfactants in
oil industry is mostly driven by its property to reduce IFT of oil-water
interface and with the adsorption of surfactant molecules on oil wet
surface, it leads to alteration of wettability of rock. These phenomena
collectively lead to the recovery of trapped oil from the reservoir.
The wetting nature of a reservoir is usually intermediate to oil wet
and it is dependent on the rock mineralogy, composition of crude oil
and brine, and temperature and pressure conditions of reservoir (Sohal
et al., 2016). The mechanism of wettability alteration of originally
water wet reservoir to oil wetting have been related to adhesion of
polar components of crude oil, which had migrated into the reservoir
(Rahbar et al., 2012). After the migration of crude oil into reservoir
pores, there exists a layer of brine between crude oil and rock surface,
which prevents the contact of crude oil and rock surface (Hiorth et al.,
2010). The rupture of the brine layer occurs due to the presence of
attractive forces such as charge transfer, van der Waals forces and hy-
drogen bonding between crude oil and rock surface (Hirasaki, 1991).
Thus, these forces lead to adsorption of crude oil components on the
rock surface and oil-wetting state of the reservoir rock. The state of
reservoir rock surface before surfactant flooding can be seen in the
schematic diagram depicted in Fig. 1. When surfactant is injected in the
reservoir, the surfactant molecules interact with the adsorbed compo-
nents of the crude oil like naphthenic acid, asphaltenes and resins.
These adsorbed components of crude oil, which were responsible for oil
wetting state of surface, can have either hydrophilic interaction or
hydrophobic interaction with the injected surfactant molecules. Hy-
drophilic interaction leads to formation of ion pair between the hy-
drophilic head of the surfactant and adsorbed crude oil (Hou et al.,
2015). The bonding of the carbon chain of surfactant molecules with
the adsorbed crude oil components leads to hydrophobic interaction
between crude oil and surfactant molecules (Standnes and Austad,
2000). With the movement of the flood front, the crude oil components

∗
Corresponding author.
E-mail address: ajay@iitism.ac.in (A. Mandal).

https://doi.org/10.1016/j.petrol.2018.11.002
Received 5 September 2018; Received in revised form 1 November 2018; Accepted 1 November 2018
Available online 02 November 2018
0920-4105/ © 2018 Elsevier B.V. All rights reserved.
N. Saxena et al.
Fig. 1. (a) Schematic of preferential adsorption of surfactant on oil aged sandstone rock with wettability alteration; (b) Change of Zeta potential on adsorption of
surfactant on oil aged sandstone rock.
bonded with the surfactant molecules are desorbed into the bulk of the
aqueous phase and the available site gets occupied by surfactant mo-
lecule (Fig. 1a). This can also be seen in the schematic diagram where at
low surfactant concentration, there is partial replacement of adsorbed
crude oil components with surfactant molecules. With increase in sur-
factant concentration, most of the adsorbed crude oil are desorbed and
trapped in the surfactant micelles. The adsorption of surfactant mole-
cules leads to increase in zeta potential of surface as shown in Fig. 1b
(Saxena et al., 2018a). This increase in the surface charge is due to the
dominance of negative charge by sulfonate ions and hydroxyl groups.
Thus, surfactant molecules adsorbed on the rock surface prevent further
interaction of crude oil and rock surface and changes the wettability of
rock to water wet.
However, excess adsorption of surfactant leads to reduction in their
concentration and limits their efficiency during the surfactant based
EOR process. Thus, a comprehensive knowledge of loss of surfactant by
adsorption on the reservoir rock is of utmost importance prior to the
injection of surfactant slugs for chemical EOR. Extensive studies in past
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decades have been carried out to analyze the adsorption behavior of
various ionic and non-ionic surfactant onto the rock surface. The phy-
siochemical properties that affect the adsorption of surfactant are pH,
temperature, ionic strength and electrolyte concentration in the re-
servoir. Any variation in the mentioned physiochemical properties can
result in change in adsorption pattern of the system. It is widely known
that the adsorption of ionic surfactants onto the rock surface is gov-
erned by electrostatic attraction. The similarity of charges of anionic
surfactant and sandstone reservoir surface leads to preference of an-
ionic surfactants over nonionic and cationic surfactants for applicability
in sandstone reservoirs. Scientists throughout the world have worked in
last few years to reduce the surfactant adsorption on to the rock surface
(Bournival et al., 2104; Yekeen et al., 2016; Saha et al., 2017; Bera
et al., 2013; Bai and Grigg, 2005; Somasundaran and Hanna, 1979).
Traditionally sodium carbonate and sodium hydroxide as alkaline re-
agents are used to maintain the negative charge of the rock surface
causing electrostatic repulsion between rock surface and the surfactant
molecules leading to significant decrease in surfactant adsorption in
N. Saxena et al. Journal of Petroleum Science and Engineering 173 (2019) 1264–1283

Fig. 2. Reaction scheme for the synthesis of Soap-nut surfactant.

Fig. 3. Absorbance of the surfactant solution at varying surfactant concentration.

sandstone reservoirs (Gregersen et al., 2013). Gogoi (Gogoi, 2009)
studied the effect of salt concentration and pH on adsorption of sur-
factant on the reservoir rock and reported that with the increase in salt
concentration, adsorption of surfactant increases and increase in pH
leads to decrease in the surfactant adsorption. Wang et al. (Wang et al.,
2015) showed that presence of polymers also lowers the adsorption of
surfactant by forming a thick protective layer over the rock surface and
reduces the active sites available for adsorption. However, it has been
found by some researchers that additives like alkali and polymer are
ineffective in reducing the adsorption in high-saline and high tem-
perature reservoirs (Al-hashim et al., 1996; Gupta and Mohanty, 2007;
Wang et al., 2013). Henceforth, the prevention of adsorption of sur-
factant onto the reservoir rock surface is a challenging task and it is
important to make it an economically viable process for its application
in oil recovery from reservoir.
The main objective of the present paper is to study the adsorption

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Fig. 4. Calibration curve of surfactant solution at wavelength 259 nm.

Fig. 5. Calibration curve for the surfactant solution using conductivity for sandstone rock surface.

Table 1
Properties of the adsorbent used in the adsorption study.
Adsorbent BET SurfaceArea (m2/g) t-plot Micro-pore Area (m2/g) t-plot External Surface Area (m2/g) t-plot Micro-pore Volume (cm3/g) Average Pore Diameter Å

−5
Sandstone 0.51 0.144 0.366 7.5 × 10 19.96
Carbonate 2.80 1.35 1.43 6.9 × 10−4 21.61
Bentonite 51.72 10.71 41.03 5.05 × 10−3 20.95

pattern of anionic surfactant on to rock surface. The adsorption study
was conducted using sandstone, carbonate as a prototype of the re-
servoir rock systems. Bentonite was chosen as it is a clay containing
montmorillonite and they are present in large amount in typical shaly
clastic reservoir. The adsorbate samples were characterized by Field
emission scanning electron microscopy (FE-SEM), X-Ray Diffraction
(XRD) and gas adsorption analysis to measure the surface area available
for adsorption. Anionic surfactant synthesized from soap-nut fruit was
selected as adsorbate in the presented study. Effects of salinity, rock
type, alkali and nanoparticles were studied to analyze their effect in
altering the adsorption of surfactant on the rock surface for making it an
economical system for its application in the field of EOR.
2. Materials required
The surfactant used in this study is a natural surfactant, synthesized
from soap-nut oil through trans-esterification followed by sulfonation
process. The synthesis process has been discussed in our earlier paper
(Saxena et al., 2018b). The chemical structure along with the synthesis
scheme is shown in Fig. 2. The chemical structure of the synthesized
surfactant (compound 2) was confirmed by GC-MS and FTIR analysis.
The particular surfactant was chosen for the study as the surfactant had
shown ultralow IFT and it is also cost effective and biodegradable in
nature. The surfactant solution was also found to be thermally stable up
to reservoir temperature.
Sodium chloride and sodium carbonate were obtained from SRL to

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N. Saxena et al.
Fig. 6. X-Ray Diffractogram images of rock (a) Sandstone, (b) Carbonate and (c) Bentonite.
study the effect of salinity and alkalinity on surfactant adsorption. Silica
nanoparticle of size 15–20 nm and alumina nanoparticles of size
20–30 nm procured from SRL were used to study the effect of nano-
particles on adsorption phenomenon. Sandstone and carbonate rock
samples were collected from Cambay Basin, India. Bentonite clay used
in the experiment was obtained from Loba Chemicals Pvt. Ltd. The
crude oil used in the experiments was procured from Oil India Limited,
Assam. The obtained crude oil has a total acid number 0.84 mg KOH/g,
gravity of 18.9° API, density of 0.924 g/cc and viscosity of 4.26 cP at
27 °C. The SARA composition of the crude oil sample indicated 19.6%
of saturates, 77% of aromatics, and 3.1% of resin and asphaltenes.
3. Experimental
3.1. Characterization of adsorbent samples
Rock samples of sandstone and carbonate rock were grinded and
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sieved to 60–80 mesh. The bentonite clay used in the experiments was
purchased from the market and was used in its original form. These
powders were not washed as it may dissolve the existing components of
the rock sample. The powdered samples were used for characterization
and adsorption study. FE-SEM and EDX analysis (using SUPRA -55
ZEISS, Germany) of the rock sample were performed to study the
morphology and the elemental composition of the adsorbent used in the
analysis. Brunauer–Emmett–Teller (BET) analysis (using Micrometrics
ASAP, 2020) was done to calculate the surface area available for ad-
sorption using liquid nitrogen at degassing temperature of 150 °C. X-
Ray diffractogram of crushed rock samples were analyzed by measuring
the Bragg angle 2θ (10°≤ 2θ ≤ 90°) using XRD instrument (Bruker D8
advanced) with Cu as target radiation of wavelength (λ = 0.15405 nm).
The zeta potential of the suspension of the powdered samples was
tested by Horiba Nano Particle Analyser SZ-100. The pH of the sus-
pension was maintained to acidic range using 0.1N HCl and basic pH
using 0.1N KOH.
N. Saxena et al.
Fig. 7. FE-SEM images (a) Sandstone, (b) Carbonate and (c) Bentonite at 10.00 KX magnification.
Fig. 8. Zeta potential of rock surface at varying pH.
3.2. Adsorption studies
The grinded rock and clay samples were added to the surfactant
solutions of concentration ranging 1000–15000 mg/L. The solutions
were subjected to rotation at 50 rpm for 24 h using Rotospin (Tarsons).
After 24 h the samples were segregated using centrifuge at 3000 rpm for
20 min. Liquid obtained at the upper portion was decanted after cen-
trifugation and was analyzed under UV–Visible spectrophotometer
(SHIMADZU UV-1800) to obtain the equilibrium concentration. The UV
spectroscopy technique is correlated with the interaction of light with
matter. When a monochromatic light is absorbed by compound, it leads
to increase of energy content of the atomic or molecular constituents of
the chemical compound. Thus, for every compound, a peak is obtained
at specific wavelength. The unknown concentration of the supernatant
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liquid was estimated by using the calibration curve, using the surfactant
solutions of known concentrations. The initial and final concentration
of the surfactant solutions were used to calculate the adsorbed amount
of adsorbent at equilibrium concentrations as per Eq. (1):
V (Ci − Ce )
q=
m (1)
where, Ci and Ce are the initial and final equilibrium concentration of
the surfactant in the solution (mg/L) respectively. V represents the
volume of the surfactant solution (L) and mass of the adsorbent (g) used
in the experimental analysis is represented by m. Fig. 3 depicts the
maximum absorbance obtained at the wavelength of 259 nm for the
surfactant solutions of varying concentrations. The maximum absor-
bance obtained for the respective surfactant concentration was used to
plot the calibration curve as shown in Fig. 4. The data obtained from
the adsorption study was fitted to various static and kinetic models and
the respective parameters of the models was used to study the ad-
sorption behavior of surfactant.
To ensure that the adsorption study using UV–Visible spectroscopy
shows consistency in results, the adsorption was also confirmed by
conductivity. The conductivity meter (Hanna HI-2003) was used to
measure the conductance of the surfactant solution. These conductance
values were used to plot the calibration curve for the standard surfac-
tant solution at different concentration from 1000 mg/L to 15000 mg/L.
This technique is also used by other research group around the world to
study adsorption behavior of the surfactant onto the rock surface
(Barati-Harooni et al., 2016; Ahmadi and Shadizadeh, 2013; Barati
et al., 2016). Experiments using conductivity method were conducted
and compared with the results obtained from the UV–Visible spectro-
scopy. The calibration curve for the surfactant solution on the sand-
stone surface is shown in Fig. 5. The calibration curve obtained by
conductivity method was then used to study the adsorption on sand-
stone powder and compared with the result obtained by UV spectro-
scopy method. However, the conductivity method cannot be used to
test the adsorption in presence of salt, alkali and nanoparticle as pre-
sence of these additional constituents changes the values of
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Fig. 9. Comparison of adsorption of surfactant on sandstone rock surface using two different techniques.

Fig. 10. Equilibrium profiles for adsorption of soap-nut surfactant against the initial concentration.

Fig. 11. Variation in IFT at oil-aqueous interface after adsorption.

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Fig. 12. Langmuir adsorption isotherm fitting curves of (a) Sandstone (b) Carbonate (c) Bentonite.

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Fig. 13. Freundlich adsorption isotherm fitting curves of (a) Sandstone (b) Carbonate (c) Bentonite.

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Fig. 14. Temkin adsorption isotherm fitting curves of (a) Sandstone (b) Carbonate (c) Bentonite.

conductance. Thus, the conductance values of supernatant surfactant
solution will not correspond to the actual surfactant concentration of
the solution.
3.3. IFT study of soap-nut surfactant before and after adsorption
The measurement of IFT before and after adsorption provides an
indication of loss of IFT reduction capability of surfactant which occurs
due to loss of surfactant. The IFT between surfactant solution and crude

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Fig. 15. Redlich- Peterson adsorption isotherm fitting curves of (a) Sandstone (b) Carbonate (c) Bentonite.

oil was measured using spinning drop tensiometer (SVT15 Data phy-
sics). The IFT of oil-water interface was measured before adsorption
and compared with the IFT obtained for the supernatant surfactant
solution collected after the adsorption study. The supernatant surfac-
tant liquid was retreated with fresh adsorbent samples for 12 h and the
surfactant solution was recollected to check its IFT reduction capability.
The process of treating the surfactant solution with rock samples was
repeated at least 4 times or till IFT in ultralow range was obtained.
Greater repetition of process signifies greater tolerance of surfactant to
adsorption loss.

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Table 2
Adsorption parameters of isotherm model of adsorption of soap-nut surfactant at rock interface.
Isotherm Model Parameters Sandstone Carbonate Bentonite

2
Langmuir Model R 0.9954 0.9677 0.9998
KL(L/mg) 6.6 × 10−4 1.59 × 10−3 9.24 × 10−4
qo(mg/g) 45.45 50.12 67.56
Freundlich Model R2 0.9601 0.9689 0.9324
b(mg/g) 0.4932 0.952 0.9514
n 2.04 2.12 2.07
Temkin Model R2 0.9811 0.9453 0.9956
B 10.11 12.40 13.42
Km(L/g) 6.53 × 10−3 1.1 × 10−2 1.1 × 10−2
Redlich-PetersonModel R2 0.9957 0.9825 0.9992
K (L/mg) 3.5 × 10−1 2.08 × 10−1 6.01 × 10−2
α (L/mg)β 3.7 × 10−3 1.1 × 10−1 9.02 × 10−4
β 0.819 0.607 1

7000 mg/L
60
(a) Sandstone Carbonate bentonite
Amount adsorbed mg/g

50

40

30

20

10

0
0% 1% 2% 3%
Salt content (%)

9000 mg/L
70
Sandstone Carbonate bentonite
60 (b)
Amount adsorbed mg/g

50

40

30

20

10

0
0% 1% 2% 3%
Salt content (%)

Fig. 16. Effect of salt content on adsorption of surfactant molecules at concentration of (a) 7000 mg/L (b) 9000 mg/L.

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Fig. 17. Effect of alkali on adsorption of surfactant molecules at concentration (a) 7000 mg/L (b) 9000 mg/L.
4. Result and discussion
4.1. Characterization of rocks/clay
4.1.1. BET analysis
The amount of adsorption of an adsorbate on adsorbent is directly
correlated to the available surface area of the adsorbent. BET analysis
measures the dissolution rate, which is proportional to the specific
surface area. Thus, this surface area helps to predict the availability of
porous media for adsorption. Table 1 depicts the characteristics of the
rock samples used as an adsorbent for the adsorption study. The BET
surface area and average pore volume was calculated by gas adsorption
analyser. It was assumed that for the micro-porous adsorbents, the BET
surface area is the equivalent area rather than actual surface area (Sing
and Everett, 1973). As depicted in Table 1, the BET area was observed
to be maximum for bentonite sample and minimum for sandstone
sample. The average pore diameter for all the three rock samples under
considerations was found to be similar.
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4.1.2. XRD analysis
Adsorbent sample usually possesses a charge on their surface oc-
curring due to the mineralogy and crystalline-amorphous structure of
the adsorbent. The presence of these surface charges affects the cou-
lombic forces between the adsorbate molecules and adsorbent surface.
Thus, XRD analysis was used for the identification of mineralogical
constituents (e.g. minerals, or inorganic compounds) of adsorbent
sample. Fig. 6 (a) shows the X-ray diffraction pattern of the crushed
sandstone sample. Characteristic peak for the quartz are obtained at
21°, 27.74°, 28.57°, 47.23°, 60° with the sharpest peak at 27.47°. All the
major peaks represented in the figure corresponds to quartz, thus in-
dicating high quartz content with fewer impurities like siderite and
kaolinite clay. XRD pattern of carbonate sample presented in Fig. 6 (b)
shows 2θ peaks of 23.04°, 31.4°, 39.2°, 47.4° and 48.7° which corre-
sponds to the presence of calcite and aragonite. Carbonate sample also
contained slight impurities such as quartz for which a lower intensity
peak was obtained at 27.6°. XRD patterns of fresh bentonite is shown in
Fig. 6 (c). It is shown in the diffractogram that the 2θ peaks of mon-
tmorillonite are visible at 6.93°, 21.21°, 29.04°, 36.31°, and 66.28°,
whereas 2θ peaks of quartz are identified at 27.74°, 47.23°, 60°. This
N. Saxena et al. Journal of Petroleum Science and Engineering 173 (2019) 1264–1283

Fig. 18. Effect of alumina nanoparticles on adsorption pattern of surfactant molecules at concentration (a) 7000 mg/L (b) 9000 mg/L.

confirms that bentonite clay is a composite mixture with montmor- between the rock surfaces and charged molecules in aqueous medium
illonite and quartz as its major constituents. (Alroudhan et al., 2016). Zeta potential for the sandstone, carbonate
and bentonite clay surface as a function of pH is presented in Fig. 8. It
was observed that for pH variation from 2.3 to 11.5, the rock surface
4.1.3. FE-SEM analysis
showed negative zeta potential indicating that the ionic interaction
FE-SEM analysis of adsorbent sample helps in the study of surface
mechanism for all three surfaces will be same (Hirasaki et al., 2008).
characteristics, such as morphology, texture and roughness. These
The negative charge of sandstone surface is due to dispersion of the
characteristics affect the adsorption capacity of the adsorbent surface
water molecules at the surface and formation of SiOH groups
and film thickness of the adsorbate particle. Thus, the surface of sam-
(Michalske and Freiman, 1983). Zeta potential of natural calcite is
ples was characterized using FE-SEM analysis and captured micro-
controversial as some researchers have reported it as negative, whereas
photographs of fresh sandstone, carbonate and bentonite rock surfaces
some have reported it as positive. This may be due to variation in
are depicted in Fig. 7. The images of sandstone and carbonate depicts
dissociation of calcium ions in water and presence of some amount of
that the sample surfaces have less porous structures as compared to the
quartz in the original composition (Douglas and Walker, 1950; Huang
surface of bentonite. The surface morphology of the samples as pre-
et al., 1991; Monfared et al., 2015). Bentonite sample possesses nega-
dicted by FE-SEM analysis was also supported by the BET results which
tive zeta potential due to the presence of surface hydroxyl groups on the
showed that the bentonite sample had the largest surface area in
basal planes of layered bentonite structure (Baik and Lee, 2010).
comparison to sandstone and carbonate samples.

4.1.4. Effect of pH on charge distribution at rock surface 4.2. Adsorption behavior of surfactant on to the rock
The zeta potential of the natural rock surfaces plays an important
role in various subsurface processes, affecting the ionic interaction The adsorption profile as obtained for the sandstone sample by UV

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N. Saxena et al.
Fig. 19. Effect of silica nanoparticles on adsorption pattern of surfactant molecules at concentration (a) 7000 mg/L and (b) 9000 mg/L.
spectroscopy and conductivity technique is shown in Fig. 9. It was
observed that the two techniques showed comparable results. As stated
earlier, that the conductivity technique cannot be used for further
analysis in presence of salt, alkali and nanoparticle, thus the data ob-
tained by UV spectroscopy technique was used to calculate the ad-
sorption density. The adsorption density as calculated by Eq. (1) was
plotted against their initial concentration before adsorption and is
shown in Fig. 10. According to the experimental data, as the surfactant
concentration was increased, more amount of surfactant was adsorbed
on to the sample surface. At low surfactant concentration, the molecules
of surfactant are attracted to the charge dispersed on the rock surface as
electrical double layer (as explained by Helmontz, 1879; and further
modified by Stern in 1924) (Helmholtz, 1853; Stern, 1924). This dis-
persed charge is responsible for attracting the surfactant molecules. At
higher surfactant concentration, the molecules of surfactant start ag-
gregating and forming hemi-micelles. When the CMC of the surfactant
is reached, the surfactant molecules are present in the bulk as micelles.
The adsorption of these surfactant micelles causes a subsequent in-
crease in the adsorption level at CMC. For surfactant concentration
higher than CMC, most active sites are adsorbed with surfactant and
micelles of surfactants are repelled by the adsorbed surfactant mole-
cules. This phenomenon can also be seen from Fig. 10, where the slope
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Journal of Petroleum Science and Engineering 173 (2019) 1264–1283
of plot is steep for surfactant concentration up to its CMC (8000 mg/L),
but for surfactant concentration higher than the CMC, there is a re-
duction in the slope of the curve.
4.3. IFT study of soap-nut surfactant before and after adsorption
The reduction of IFT of oil-water interface is maximum when the
surfactant concentration is greater than its CMC. However, due to loss
of surfactant due to adsorption, its concentration in solution decreases
below its CMC, leading to increase in IFT and ineffective displacement
of trapped crude oil during flooding process. Thus, IFT between sur-
factant solution and crude oil before and after repeated adsorption was
compared to test for the IFT reduction capability of surfactant against
repeated adsorption. The IFT obtained between surfactant solution and
crude oil have been shown in Fig. 11. As shown in the figure, the IFT of
surfactant solution and crude oil is 2.13 × 10−3 mN/m before adsorp-
tion process. The IFT was found to be in ultralow range for 36 h for
sandstone and carbonate samples and for 24 h for bentonite sample.
This signifies that the process of adsorption was repeated 3 times for
sandstone and carbonate samples and 2 times for bentonite sample. The
greater number of times for which an ultralow IFT in range of
10−2 mN/m is achieved, higher is the resistance of surfactant molecules
N. Saxena et al. Journal of Petroleum Science and Engineering 173 (2019) 1264–1283

against adsorption on to the rock (Yan et al., 2017). This indicates that
the surfactant has excellent resistance to adsorption on sandstone and

Weber and Morriss

Wang et al. (2007)
carbonate samples. The IFT reduction property was reduced after ad-
Lagergren (1898) sorption process was repeated third time on bentonite sample due to its
larger surface area leading to greater adsorption as compared to sand-
References

stone and carbonate samples.

(1963)
4.4. Static modelling of adsorption isotherms
Pseudo-first order kinetic equation pioneered by Lagergren in the year 1898 to evaluate the kinetics of liquid and solid phase

The intraparticle mass transfer diffusion model was given in 1963 by Weber and Morris to study the mechanism of diffusion and
In this model, the rate-limiting step is the surface adsorption that involves chemisorption, where the removal from a solution is

The adsorption profile as shown in Fig. 10 was modelled using

Langmuir, Freundlich, Temkin and Redlich-Peterson models and the
parameters of the respective models are analyzed in the following
sections.

4.4.1. Langmuir adsorption isotherm

Langmuir isotherm model was proposed by Irving Langmuir in 1916
which was originally proposed for solid-gas phase bio-sorbents. In its
derivation, Langmuir adsorption isotherm is a homogenous adsorption
where individual molecule has constant enthalpy and activation en-
ergy. This model assumes that the surfactant molecules adsorbs on the
rock surface are limited and there exist no interaction in between the
adsorbed molecules (Langmuir, 1916). The experimental data acquired
from adsorption study of the soap-nut surfactant at varying con-
centration was plotted and was fitted according to the Langmuir
equation represented as Eq. (2). Fig. 12 depicted the Langmuir fitting to
the experimental data at different rock surfaces.
due to physicochemical interactions between the two phases

q o KCe
qe =
KL Ce + 1 (2)
where, qe is amount of adsorbate adsorbed (mg/g); qo is the maximum
amount of adsorbate adsorbed (mg/g); KL is the Langmuir constant (L/
mg); Ce is equilibrium concentration (mg/L). In its linearized form Eq.
(2) can be written as Eq. (3):
1 1 1
= +
qe q0 KL Ce q0 (3)
adsorption process.

4.4.2. Freundlich adsorption isotherm

Fruendlich isotherm was the first sorption model proposed by
adsorption.

Fruendlich in 1906. It was the earliest model proposing a relationship

Comments

between non-ideal and reversible sorption process. The amount ad-

sorbed it the summation of adsorption on all sites each having a specific
bond energy. This model assumes that the adsorbent surface is het-
adsorbed

adsorbed

erogeneous and the adsorption occurs in multiple layers (Freundlich,

k1 (hr−1), rate constant

kid (mg/g/hr), rate

k2 (g/mg/hr), rate

1906). Experimental data obtained by plotting the adsorption curve

Kinetic Parameters

between the amount adsorbed at the rock surface and the equilibrium
concentration of the surfactant solution were fitted using Freundlich
(mg/g),

(mg/g),

model as represented by Eq. (4):

constant

constant
amount

amount

q e = bCe1/n (4)
Various kinetic models to study the rate of adsorption.

qe

qe

where Ce is equilibrium concentration (mg/L), q e is the amount ad-

ln (qe − qt ) = ln(qe ) − k1 t

sorbed onto the rock surface (mg/g). 1/n and b are the Freundlich
adsorption parameters and their values are related with adsorption
capacity and adsorption intensity. Eq. (4) can be written in its simpli-
qe
t

fied linear form as Eq. (5):

+

qt = Kid + C
Equations

k 2 qe2

1
1

log qe = logb + logCe

n (5)
=
qt
t

Lower value of Freundlich constant 0.1 < 1/n < 0.5 predicts that
Intra particle Diffusion

adsorption is favorable and value greater than 0.5 predicts difficulty in

Pseudo Second-Order

adsorption. The fitting of adsorption data to Freundlich model is de-

Pseudo First-Order

picted in Fig. 13.

4.4.3. Temkin adsorption isotherm

Kinetic
Table 3

model

Temkim isotherm model was proposed by Tempkin and Pyzhev in

1940 which explains the effect of interaction between the adsorbate

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N. Saxena et al. Journal of Petroleum Science and Engineering 173 (2019) 1264–1283

Table 4
Kinetics adsorption parameters of surfactant on different rock surface.
Adsorbent Sandstone Carbonate Bentonite

Adsorbate concentration (mg/L) 7000 9000 7000 9000 7000 9000

−1 −2 −2 −2 −2 −2
Model Pseudo First Order k1 (hr ) 6.09 × 10 6.55 × 10 6.24 × 10 7.54 × 10 8.15 × 10 6.57 × 10−2
Qe (mg/g) 60.08 54.40 46.34 71.87 56.33 60.53
R2 0.963 0.987 0.979 0.9164 0.987 0.986
Pseudo Second Order k2 (g/mg/hr) 5.03 × 10−5 5.54 × 10−5 4.93 × 10−5 2.92 × 10−5 4.54 × 10−5 2.14 × 10−5
Qe (mg/g) 92.59 73.52 69.93 90.91 71.42 94.74
R2 0.985 0.9925 0.992 0.9903 0.9902 0.997
Intra-particle diffusion model kid (g/mg/hr) 0.1146 0.1276 0.1272 0.0995 0.1222 0.1132
R2 0.996 0.992 0.948 0.9604 0.9438 0.988

and adsorbing molecules. The Temkin isotherm model states that the
heat of adsorption for the surfactant molecules in the system decreases
linearly as there is an increase in surface coverage area of the adsorbent
and the adsorption process is illustrated with smooth dispersal of
binding energies of molecules, up-to maximum binding energy (Temkin
and Pyzhev, 1940). The adsorption data were modelled by Temkin
isotherm model as represented by Eq. (6):
monolayer. The value of β parameter of Redlich-Peterson model was
found to be 1 and 0.817 for bentonite and sandstone samples respec-
tively. These values of β also suggests that the adsorption is governed
by Langmuir adsorption model. The maximum amount of adsorbate
adsorbed (qo) obtained from Langmuir model was found to be greatest
for bentonite sample as bentonite had maximum surface area as cal-
culated from BET analysis.

qe = B ln Km + B ln Ce
Where, B = RT/b and b represents the Temkin constant associated with
heat of sorption (J/mol), Km is the equilibrium binding constant that
relates to maximum binding energy (L/g), R represents the gas constant
and its value is assumed to be 8.314 J/mol K, and T is the temperature
(K). Fitting of adsorption data to Temkin model is shown in Fig. 14.
(6)
4.5. Gibbs free energy of adsorption
The Langmuir adsorption constant KL can be used to analyze the
spontaneity of the adsorption by calculation of change in gibbs free
energy of adsorption (ΔG). The change in gibbs free energy of adsorp-
tion can be calculated by Eq. (9) (Zhou and Zhou, 2014):

ΔG = -RT ln (55.5KL) (9)

4.4.4. Redlich- Peterson adsorption isotherm
The Redlich-Peterson (R-P) isotherm proposed by Redlich and
Peterson in 1959 is a three-parameter model that comprises of funda-
mentals from both the Langmuir and Freundlich isotherm models (Vidal
et al., 2011; Liu et al., 2010). Redlich–Peterson equation includes 3
adjustable parameters into an empirical isotherm model. The adsorp-
tion mechanism is distinctive and do not follow the assumption of ideal
monolayer adsorption. Experimental data obtained through adsorption
study of the surfactant solutions at varying concentration was fitted
according to Redlich-Peterson model depicted in Fig. 15. Table 2 re-
presents the parameters calculated from the modelling of Eq. (7):
KCe
qe =
1 + αCβe
Where, R is the universal gas constant (8.314 Jmol/K), T is the tem-
perature (K), KL is the Langmuir constant (L/mol). The change in gibbs
free energy was calculated to be −26.382 kJ/mol, −28.597 kJ/mol
and −27.230 kJ/mol for sandstone, carbonate and bentonite respec-
tively. Similar results for ΔG adsorption at air-aqueous interface are
reported by other researchers (Zdziennicka and Jańczuk, 2017). The
negative value of ΔG indicates that the adsorption process is sponta-
neous in nature for all the samples. The values of ΔG for respective
samples for found to be similar indicating that each sample had similar
affinity for surfactant adsorption.
(7) 4.6. Effect of salt content on adsorption of surfactant on adsorbent

Taking natural log on both sides, the linearized form of Eq. (7) is
presented as Eq. (8):
C
ln ⎛⎜K e − 1⎞⎟ = βlnCe + lnα
⎝ qe ⎠ (8)
β
Where, K (L/mg) and α [(L/mg) ] are Redlich-Peterson isotherm
constants. β represents the exponential constant, with its value lying
between 0 and 1 and helps to illustrate the adsorption isotherm model.
If β = 1, Eq. (7) condenses to the Langmuir model, and if β = 0, Eq. (7)
reduces to the linear isotherm model (Belhachem and Addoun, 2011).
The adsorption pattern of soap-nut surfactant is dependent on the
interaction of surfactant molecules and the adsorbent surface. These
interactions are in the form of various intermolecular forces existing as
electrostatic attraction, hydrogen bonding, covalent bonding and hy-
drophobic bonding (Curbelo et al., 2007). For ionic surfactants, elec-
trostatic interaction between the surface and surfactant molecules is the
major driving forces facilitating adsorption phenomenon. The charged
micelles of surfactant are attracted to the charged surface of the rock
leading to adsorption of the surfactant molecules at the surface
(Wisniewska et al., 2015). From the data presented in Table 2, it can be
seen that the R2 values of Langmuir model is closest to 1, concluding
that the adsorption of the anionic surfactant on the samples is
The presence of salt affects the physical and chemical adsorption of
anionic soap-nut surfactant by interfering with the electrostatic inter-
actions during the adsorption process. The effect of salt was studied at
the surfactant concentration below and above CMC at 7000 mg/L and
9000 mg/L respectively and is shown in Fig. 16. It can be seen in the
figure that the adsorption of surfactant increases with the increase in
the salt concentration. Ions produced by dissolution of salt in aqueous
phase are able to influence the chemisorption of ionic surfactants on
solid (Chang et al., 2018). The increase in salt concentration can lead to
lead to adsorption of counterions on the surfactant micelles causing the
reduction electrostatic charge on micelle surface (Kolev et al., 2002).
However, this phenomenon is dominated by the suppression of elec-
trical double layer of adsorbent surface. This compression of electrical
double layer of adsorbent surface leads to increase in adsorption of
surfactant with increase in salt concentration in the system (Pethkar
and Paknikar, 1998).
4.7. Effect of alkali on adsorption of surfactant on adsorbent
Alkali like sodium carbonate have been applied as sacrificial agent
to reduce the adsorption of the surfactant in various reservoir rocks
(ShamsiJazeyi et al., 2014). Fig. 17 shows that with increase in

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Fig. 20. The kinetic study for adsorption of surfactant on (a) sandstone (b) carbonate and (c) bentonite by pseudo-second order kinetics.

concentration of sodium carbonate, the adsorption of surfactant on all causes an increase of pH of the system and increases the negativity of
the samples have decreased. The decrease in adsorption of surfactant is the surface of sample. This leads to electrostatic repulsion between
due to dissociation of sodium carbonate into weak carbonic acid and surfactant molecules and surface of rock, causing a significant reduction
generation of OH− ions upon interaction with water molecules. This of surfactant adsorption. Sodium carbonate molecules also forms in-situ

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N. Saxena et al.
surfactants by interacting with the naphthenic acids present in the
crude oil which facilitates in recovery of trapped oil.
4.8. Effect of nanoparticle on adsorption of surfactant on adsorbent
Figs. 18 and 19 depict the influence of alumina and silica nano-
particles respectively on the adsorption behavior of the soap-nut sur-
factant on to the sample surfaces. Alumina nanoparticle was selected
for this adsorption study as it has been reported in the literature that
alumina nanoparticle is effectively able to reduce oil brine IFT and
viscosity of oil. Alumina nanoparticle aid in alteration of wettability of
intermediate oil wet rock to water wet which results good recovery of
oil. Silica nanoparticle was selected as silicon dioxide popularly called
as silica is amongst the abundant material in the earth crust and it is an
essential component of sand stone and it can be easily synthesized to
nanoparticles. Researches have proved that silica nanoparticle barely
show any change in the specific area when heated for temperature up to
650 °C proving high thermal stability (Wang et al., 1999). These
properties have made silica as most cost effective and commonly used
nanoparticle. The researchers around the world have recommended
these nanoparticles as an EOR agent for heavy oil reservoirs. (Negin
et al., 2016; Hendraningrat and Torsæter, 2015).
The plots clearly show that the surfactant adsorption decreases in
presence of nanoparticle. In the current study the effect of nanoparticle
was studied by varying the weight percentage of nanoparticle ranging
from 0.1% to 0.3% for the surfactant concentration of 7000 mg/L and
9000 mg/L. In absence of nanoparticles, the surfactant molecules are
adsorbed on the surface of the samples. However, when nanoparticles
are added to the system, it also acts as an adsorbent leading to com-
petitive adsorption of surfactant molecules onto the surfaces of nano-
particles and samples (Suleimanov et al., 2011). It was observed that
the adsorption of surfactant molecules on the nanoparticles surface was
higher due to stronger hydrogen bonding leading to less amount of
surfactant molecules available to be adsorbed onto the rock interface.
The bonded nanoparticles and surfactant molecules stay in the bulk of
the solution leading to reduction of surfactant adsorption on rock sur-
face (Yekeen et al., 2017). It is also reported that most surfactant mo-
lecules collide with the nanoparticles rather than interacting with rock
surface causing reduction of surfactant adsorption (Yining et al., 2017).
On comparison of data plotted in Figs. 18 and 19, it can be con-
cluded that the adsorption reduction capability of silica nanoparticle is
greater than the reduction capacity of alumina nanoparticle. The
greater adsorption reduction capacity of silica nanoparticle can be ex-
plained by almost rounded structure as compared to alumina nano-
particles which have sharp edges (Yining et al., 2017). Studies by Ah-
madi and Shadizadeh (Ahmadi and. Shadizadeh, 2013) also suggested
creation of a strong hydrophobic bond between hydrophobic groups of
silica nanoparticles and the surfactant hydrophobic tail leading to an
increased adsorption of surfactant molecules onto the silica nano-
particle surface and reduction in adsorption of surfactant molecules on
the adsorbent surface.
4.9. Theory of adsorption kinetics of the soap-nut surfactant
Adsorption of surfactant onto the rock surface is the result of in-
teraction of solid/liquid surface and mass transfer from aqueous phase
to the rock interface. Kinetic study of adsorption helps us to predict the
adsorption rate and provide information about adsorption mechanism.
Adsorption data was analyzed by three most commonly used kinetic
models viz. pseudo-first order, pseudo second-order and intra particle
diffusion model. The equations of the models and their respective
parameters are shown in Table 3.
The above mentioned kinetic models were used to explain the ad-
sorption pattern of surfactant on to the rock surface as a function of
time. Kinetic parameters for different kinetic models which includes
pseudo-first-order model, pseudo second-order model and intra-particle
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Journal of Petroleum Science and Engineering 173 (2019) 1264–1283
mass transfer diffusion model were calculated for surfactant con-
centrations of 7000 mg/L and 9000 mg/L and the data obtained were
analyzed and fitted with the models as depicted in Table 4. It was ob-
served that pseudo second order kinetic model fits well for sandstone,
carbonate and bentonite per the high values of R2 and the fitted pseudo
second order model have been shown for the respective samples in
Fig. 20. The value of R2 for intra-particle diffusion model also had value
closer to 1, however, the model equation did not pass through the
origin point indicating that the adsorption is not governed by intra-
particle diffusion model.
5. Conclusions
Surfactant adsorption pattern was observed through experimental
and modelling studies on different reservoir rock surface viz. sandstone,
carbonate and bentonite clay, considering its application for designing
of surfactant based chemical enhanced oil recovery. Mineralogy and
morphological analysis obtained by FE-SEM, XRD and BET surface area
measurements predicted that bentonite had more surface area available
for adsorption due to more porous rock surface. Zeta potential of
samples suspended in aqueous solution of varying pH showed that the
surfaces were negatively charged. The presence of negatively charged
surface and large surface area have led to the adsorption of surfactant
molecules on the sample surface. When the surfactant concentration
was increased in the system the adsorption onto the rock surface was
also enhanced due to the more molecules available for adsorption. The
experimental data was analyzed by mathematically fitting with ad-
sorption isotherms like Langmuir, Freundlich, Temkin, and Redlich-
Peterson models. Adsorption pattern for the surfactant-rock system was
best clarified by Langmuir adsorption isotherm along with the Redlich-
Peterson model that supports the Langmuir isotherm model for the
monolayer adsorption behavior. Increase in salinity was found to in-
crease the adsorption of surfactant molecules, however, presence of
alkali and nanoparticles were found to be effective in reducing the
adsorption of surfactant molecules onto the rock surface, the best re-
sults were obtained using silica nanoparticles that showed reduction in
adsorption pattern. On comparing the results of adsorption study for the
surfactant on the different rock surfaces, it was observed that rock
mineralogy plays a crucial role in surfactant adsorption. Bentonite
being highly porous in nature adsorbed highest amount of surfactant in
comparison of sandstone and carbonate rock surfaces. The selected
anionic surfactant showed least adsorption on sandstone rock surface
which also supports that the application of anionic surfactant in sand-
stone reservoirs is favorable for enhance oil recovery. Kinetic adsorp-
tion study for the present surfactant system was modelled according to
various kinetic models and pseudo second order kinetic model was
found to be most appropriate in explaining the adsorption kinetic for
sandstone, carbonate and bentonite surfaces.
Acknowledgement
The XRD, FE-SEM and BET surface area analysis were conducted at
Central Research Facility (CRF) at Indian Institute of Technology
(Indian School of Mines), Dhanbad, Dhanbad. The present work was
financed by Oil India Limited with the contract number 6206917.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.petrol.2018.11.002.
References
Ahmadi, M.A., Shadizadeh, S.R., 2013. Induced effect of adding nano silica on adsorption
of a natural surfactant onto sandstone rock: experimental and theoretical study. J.
Petrol. Sci. Eng. 112, 239–247.
N. Saxena et al.
Ahmadi, M.A., Shadizadeh, S.R., 2013. Induced effect of adding nano silica on adsorption
of a natural surfactant onto sandstone rock: experimental and theoretical study. J.
Petrol. Sci. Eng. 112, 239–247.
Al-hashim, H., Obiora, V., Al-yousef, H.Y., Fernandez, F., Nofal, W., 1996. Alkaline sur-
factant polymer formulation for saudi arabian carbonate reservoirs. In: Paper SPE/
DOE 35353 Presented at the SPE/DOE Tenth Symposiumon Improved Oil Recovery,
Tulsa, OK, USA.
Alroudhan, A., Vinogradov, J., Jackson, M.D., 2016. Zeta potential of intact natural
limestone: impact of potential-determining ions Ca, Mg and SO4. Colloids Surf., A
494, 83–90.
Bai, B., Grigg, R.B., 2005. Kinetics and equilibria of calcium lignosulfonate adsorption
and desorption onto limestone. SPE J., SPE-93098-MS. https://doi.org/10.2118/
93098-MS.
Baik, M.H., Lee, S.Y., 2010. Colloidal stability of bentonite clay considering surface
charge properties as a function of pH and ionic strength. J. Ind. Chem. Eng. 16,
837–841.
Barati, A., Najafi, A., Daryasafar, A., Nadali, P., Moslehi, H., 2016. Adsorption of a new
nonionic surfactant on carbonate minerals in enhanced oil recovery: experimental
and modeling study. Chem. Eng. Res. Des. 105, 55–63.
Barati-Harooni, A., Najafi-Marghmaleki, A., Tatar, A., Mohammadi, A.H., 2016.
Experimental and modeling studies on adsorption of a nonionic surfactant on sand-
stone minerals in enhanced oil recovery process with surfactant flooding. J. Mol. Liq.
220, 1022–1032.
Belhachem, M., Addoun, F., 2011. Comparative adsorption isotherms and modeling of
methylene blue onto activated carbons. Appl. Water Sci. 1, 111–117.
Bera, A., Kumar, T., Ojha, K., Mandal, A., 2013. Adsorption of surfactant on sand surface
in enhanced oil recovery:Isotherms,kinetics and thermodynamics studies. Appl. Surf.
Sci. 284, 87–99.
Bournival, G., Du, Z., Ata, S., Jameson, G., 2014. Foaming and gas dispersion properties of
non -ionic surfactants in the presence of an inorganic electrolyte. Chem. Eng. Sci. 116
5 36-546.
Chang, Z., Chen, X., Peng, Y., 2018. The adsorption behavior of surfactants on mineral
surfaces in the presence of electrolytes– A critical review. Miner. Eng. 121, 66–76.
Curbelo, F.D., Santanna, V.C., Neto, E.L.B., Dutra Jr., T.V., Dantas, T.N.C., Neto, A.A.D.,
Garnica, A.I., 2007. Adsorption of nonionic surfactants in sandstones. Colloids Surf.,
A 293, 1–4.
Douglas, H., Walker, R., 1950. The electro-kinetic behaviour of Iceland Spar against
aqueous electrolyte solutions. Trans. Faraday Soc. 46, 559–568.
Freundlich, H.M.F., 1906. Over the adsorption in solution. J. Phys. Chem. 57, 1100–1107.
Gogoi, S.B., 2009. Adsorption of non-petroleum base surfactant on reservoir rock. Curr.
Sci. 97, 1059–1063.
Gregersen, C.S., Mahdi, K., Vladimir, A., 2013. ASP design for the Minnelusa formation
under low-salinity conditions: impacts of anhydrite on ASP performance. Fuel 105,
368–382.
Gupta, R., Mohanty, K., 2007. Temperature effects on surfactant-aided imbibition into
fractured carbonates. SPE J. 15, 588–597.
Helmholtz, H., 1853. Ueber einige Gesetze der Vertheilung elektrischer Ströme in
körperlichen Leitern mit Anwendung auf die thierisch-elektrischen Versuche.
Annalen der Physik und Chemie 165, 211–233 (in German).
Hendraningrat, L., Torsæter, O., 2015. Metal oxide-based nanoparticles: revealing their
potential to enhance oil recovery in different wettability systems. Appl. Nanosci. 5,
181–199.
Hiorth, A., Cathles, L., Madland, M., 2010. The impact of pore water chemistry on car-
bonate surface charge and oil wettability. Transport Porous Media 85, 1–21.
Hirasaki, G., 1991. Fundamentals and surface forces. SPE Form. Eval. 6, 217–226.
Hirasaki, G.J., Miller, C.A., Puerto, M., 2008. Recent advances in surfactant EOR. In: SPE
Annual Technical Conference and Exhibition, Denver, USA, vol. 2008.
Hou, B.F., Wang, Y.F., Huang, Y., 2015. Mechanistic study of wettability alteration of oil-
wet sandstone surface using different surfactants. Appl. Surf. Sci. 330, 56–64.
Huang, Y.C., Fowkes, F.M., Lloyd, T.B., Sanders, N.D., 1991. Adsorption of calcium ions
from calcium chloride solutions onto calcium carbonate particles. Langmuir 7,
1742–1748.
Kolev, V.L., Danov, K.D., Kralchevsky, P.A., Broze, G., Mehreteab, A., 2002. Comparison
of the van der Waals and frumkin adsorption isotherms for sodium dodecyl sulfate at
various salt concentrations. Langmuir 18, 9106–9109.
Lagergren, S., 1898. Zur theorie der sogenannten adsorption gelöster stoffe. K. - Sven.
Vetenskapsakademiens Handl. 24, 1–39.
Langmuir, I., 1916. The constitution and fundamental properties of solids and liquids.
Part I. Solids. J. Am. Chem. Soc 38, 2221–2295.
Liu, Q.S., Zheng, T., Wang, P., Jiang, J.P., Li, N., 2010. Adsorption isotherm, kinetic and
mechanism studies of some substituted phenols on activated carbon fibers. Chem.
Eng. J. 157, 348–356.
Michalske, T.A., Freiman, S.W., 1983. A molecular interpretation of stress corrosion in
vitreous silica. J. Am. Ceram. Soc. 66, 284–288.
1283
Journal of Petroleum Science and Engineering 173 (2019) 1264–1283
Monfared, A.D., Ghazanfari, M.H., Jamialahmadi, M., Helalizadeh, A., 2015.
Adsorptionof silica nanoparticles onto calcite: equilibrium, kinetic, thermodynamic
and DLVO analysis. Chem. Eng. J. 281, 334–344.
Negin, C., Ali, S., Xie, Q., 2016. Application of nanotechnology for enhancing oil
recovery–A review. Petroleum 2, 324–333.
Pethkar, A.V., Paknikar, K.M., 1998. Recovery of gold from solution using
Cladosporioides biomass beads. J. Biotechnol. 63, 211–220.
Rahbar, M., Roosta, A., Ayatollahi, S., Ghatee, M.H., 2012. Prediction of three-dimen-
sional (3-D) adhesion maps, using the stability of the thin wetting film during the
wettability alteration process. Energy Fuels 26, 2182–2190.
Saha, R., Uppaluri, R.V.S., Tiwari, P., 2017. Effect of mineralogy on the adsorption
characteristics of surfactant-Reservoir rock system. Colloid. Surface. Physicochem.
Eng. Aspect. 531, 121–132.
Saxena, N., Kumar, S., Mandal, A., 2018a. Adsorption characteristics and kinetics of
synthesized anionic surfactant and polymeric surfactant on sand surface for appli-
cation in enhanced oil recovery, Asia-Pac. J. Chem. Eng. 13 (4) e2211.
Saxena, N., Pal, N., Ojha, K., Dey, S., Mandal, A., 2018b. Synthesis, characterization,
physical and thermodynamic properties of a novel anionic surfactant derived from
Sapindus laurifolius. RSC Adv. 8, 24485–24499.
ShamsiJazeyi, H., Verduzco, R., Hirasaki, G.J., 2014. Reducing adsorption of anionic
surfactant for enhanced oil recovery: Part II. Applied aspects. Colloids Surf., A 453,
168–175.
Sing, K.S.W., 1973. In: Everett, D.H. (Ed.), Colloid Science. Chemical Society Specialist
Periodical Report, London.
Sohal, M., Thyne, A.G., Søgaard, E.G., 2016. Review of recovery mechanisms of ionically
modified waterflood in carbonate reservoirs. Energy Fuels 30, 1904–1914.
Somasundaran, P., Hanna, H.S., 1979. Adsorption of sulfonates on reservoir rocks. SPE J.
19, 221–232.
Standnes, D.C., Austad, T., 2000. Wettability alteration in chalk 2. Mechanism for wett-
ability alteration from oil-wet to water-wet using surfactants. J. Petrol. Sci. Eng. 28,
123–143.
Stern, Otto, 1924. Zur theorie der elektrolytischen doppelschicht. Zeitschrift für
Elektrochemie und angewandte physikalische Chemie 30 (21‐22), 508–516.
Suleimanov, B., Ismailov, F., Veliyev, E., 2011. Nanofluid for enhanced oil recovery. J.
Petrol. Sci. Eng. 78, 431–437.
Temkin, M.J., Pyzhev, V., 1940. Recent modifications to Langmuir isotherms. Acta
Physiochim URSS 12, 217–225.
Vidal, C.B., Barros, A.L., Moura, C.P., A de Lima, A.C., Dias, F.S., Vasconcellos, L.C.G., A
Fechine, P.B., Nascimento, R.F., 2011. Adsorption of polycyclic aromatic hydro-
carbons from aqueous solutions by Modified Periodic Mesoporous Organosilica. J.
Colloid Interface Sci. 357, 466–473.
Wang, L., Wang, Z., Yang, H., Yang, G., 1999. The study of thermal stability of the SiO2
powders with high specific surface area. Mater. Chem. Phys. 57, 260–263.
Wang, H., Zhou, A., Peng, F., Yu, H., Yang, J., 2007. Mechanism study on adsorption of
acidified multi-walled carbon nanotubes to Pb (II). J. Colloid Interface Sci. 316
277–28.
Wang, J., Han, M., Fuseni, A., Fuseni, A.B., Cao, D., 2013. Surfactant adsorption in sur-
factant-polymer flooding for carbonate reservoirs. In: SPE Middle East Oil and Gas
Show and Conference.
Wang, J., Ming, H., Alhasan, B.F., Dongqing, C., 2015. Surfactant adsorption in surfac-
tant-polymer flooding for carbonate reservoirs. In: SPE Middle East Oil & Gas Show
and Conference. Society of Petroleum Engineers.
Weber, W.J., Morriss, J.C., 1963. Kinetics of adsorption on carbon from solution. J.
Sanitary Eng. Div. Am. Soc. Civ. Eng. 89, 31–60.
Wisniewska, M., Chibowski, S., Urban, T., 2015. Adsorption properties of the nano-
zirconia/anionic polyacrylamide system minuseffects of surfactant presence, solution
pH and polymer carboxyl groups content. Appl. Surf. Sci. 370, 351–356.
Yan, L.M., Li, Y.L., Cui, Z.G., Song, B.L., Pei, X.M., Jiang, J.Z., 2017. Performances of
guerbet alcohol ethoxylates for Surfactant−Polymer flooding free of alkali. Energy
Fuels 31, 9319–9327.
Yekeen, N., Idris, A.K., Manan, M.A., Samin, A.M., Risal, A.R., Kun, T.X., 2016. Bulk and
bubble scale experimental studies of influence of nano-particle on foam stability.
Chin. J. Chem. Eng. 25, 347–357.
Yekeen, N., Manan, M.A., Idris, A.K., Samin, A.M., Risal, A.R., 2017. Experimental in-
vestigation of minimization in surfactant adsorption and improvement in surfactant-
foam stability in presence of silicon dioxide and aluminum oxide nanoparticles. J.
Petrol. Sci. Eng. 159, 115–134.
Yining, W., Chen, W., Dai, C., Huang, Y., Li, H., Zhao, M., He, L., Jiao, B., 2017. Reducing
surfactant adsorption on rock by silica nanoparticles for enhanced oil recovery. J.
Petrol. Sci. Eng. 153, 283–287.
Zdziennicka, A., Jańczuk, B., 2017. Thermodynamic parameters of some biosurfactants
and surfactants adsorption at water-air interface. J. Mol. Liq. 243, 236–244.
Zhou, X., Zhou, X., 2014. The unit problem in the thermodynamic calculation of ad-
sorption using the Langmuir equation. Chem. Eng. Commun. 201, 1459–1467.