Journal of Petroleum Science and Engineering 112 (2013) 239–247

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Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol

Induced effect of adding nano silica on adsorption of a natural

surfactant onto sandstone rock: Experimental and theoretical study
Mohammad Ali Ahmadi a,b,n, Seyed Reza Shadizadeh c
a
Department of Petroleum Engineering, Ahwaz Faculty of Petroleum Engineering, Petroleum University of Technology, Ahwaz, Iran
b
Research Institute of Petroleum Industry (RIPI), Tehran, Iran
c
Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran

art ic l e i nf o a b s t r a c t

Article history: Throughout this research work, massive efforts have been made to observe the adsorption behavior of
Received 14 February 2012 surfactant in presence of nano-particles. The depletion solution experiment, as a robust approach, was
Accepted 1 November 2013 conducted to indicate the adsorption density of the referred surfactant. To measure the adsorption
Available online 11 November 2013
density, the electrical conductivity approach was implemented to conduct the adsorption behavior of the
Keywords: addressed surfactant and the nanosilica in aqueous phase. To evaluate the adsorption behavior of the
Adsorption surfactant onto rock surface, various adsorption isotherms such as Langmuir and Freundlich were
Sandstone implemented to facilitate further studies on the adsorption trend of the discussed surfactant. According
Porous media to the calculated statistical indices, it can be inferred that Freundlich isotherm is capable of making
Isotherm
conclusions about the adsorption behavior of systems containing mixtures of nano particles and
Natural surfactant
extracted natural surfactant from leaves of Zyziphus spina-christi onto shale sandstone rock surface.
Nano-silica
Outcomes of this research is a first break prospective in application of nanotechnology to improve
the performance of chemical stimulations in conventional oil reservoirs and also provides better views
of adsorption processes in surfactant and/or nano-surfactant systems within sandstone petroleum
reservoirs.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction size and concentration could affect on the mechanism of the

Implication of surface active agents in petroleum upstream has
high attention in recent decades specifically in chemical stimula-
tion of petroleum reservoirs and enhanced oil recovery (EOR) ends
like as surfactant flooding. But, one of the biggest challenges of
implementation of surfactant for EOR purpose is adsorption fate or
loss to the rock surface while surfactant injected through the
porous media (Lv et al., 2011; Zhang and Somasundaran, 2006). To
figure out this addressed hurdle of surfactant usage, various
researches have been studied in previous studies. Despite this fact
that the authors of this paper in Ahmadi and Shadizadeh (2012)
studied the effect of nano particles on the adsorption of surfactant
onto carbonate rockes but no research has been investigated about
inhibition of surfactant loss through flow in porous media. Nano
particles have wide range of applications which demonstrated
briefly in next. Hamedi Shokrlu and Babadagli, investigated the
effects on nano metals on viscosity reduction of heavy oil and
bitumen for thermal oil recovery applications. Based on their
obtained results, various parameters such as nano particle types,
n
Correspondence to: Research Institute of Petroleum Industry (RIPI), Tehran,
Iran. Tel.: þ 98 912 6364936.
E-mail address: ahmadi6776@yahoo.com (M.A. Ahmadi).
viscosity reduction of heavy oil/bitumen. Moreover, they figured
out the optimum values of the addressed parameters in their
studies (Hamedi Shokrlu and Babadagli, 2010). In 2011, Zhang
et al., studied the effect of nano-particles on the stabilization of
CO2 foam and oil-water emulsions. They carried out sand pack and
low permeable rock samples to figure out the effect of perme-
ability and heterogeneity on the obtained results and performance
of the implemented nano-particles. Based on obtained results,
Surface coated nanosilica improved emulsion stabilization time for
several month at high temperature. In addition, stable foams of
supercritical CO2 in water have been created by co-injecting
nanosilica aqueous dispersion and CO2 through glass-bead pack
while the foam stability domain and the apparent viscosity of
foam figures out threshold values of nano-particle concentration,
phase ratio and critical shear rate (Zhang et al., 2011). Riley et al.,
in 2012, investigated the application of nanosilica particles in
permeability reduction of the shale which is major hurdle in
confidently performing water-based drilling fluids in shale forma-
tions. They utilized the physical concept which is plugging nano-
scale pores by implementing nanosilica particles. They concluded
that, improved water-based drilling fluid (WBM) by using nano-
silica particles illustrates excellent rheological properties and
maintain wellbore stability (Riley et al., 2012). De la Roji et al.,

0920-4105/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.petrol.2013.11.010
240 M.A. Ahmadi, S.R. Shadizadeh / Journal of Petroleum Science and Engineering 112 (2013) 239–247

Nomenclature q adsorption density, (mg/g-rock)

qe equilibrium adsorption density, (mg/g-rock)
Acronyms
T Temperature, (C)

CMC critical micelle concentration

Greek letters
EOR enhanced oil recovery
PPM part per million
Γ amount of adsorbed surfactant onto shale sand stone
XRD X-ray diffraction
rock samples, (mg/g-rock)

Variables
Subscript
o
C surfactant concentration in initial solution before
ad adsorption
equilibrium, (ppm)
e equilibrium
msandstone total mass of crushed sandstone, (g)
mtot.solution total mass of solution in original bulk solution, (g)

2012 studied the implication of nano technology in oil well (ZSC) by spray dryer approach. Characterization of the natural
cement. They implemented the cement API class G and applied derived surfactant are illustrated in Table 1. In addition the
the nano technology in the addressed cement. They concluded General Chemical Structure of saponins depicted in Fig. 1 (Pordel
that, the nano enhanced oil well cement significantly stronger Shahri et al., 2012; Ahmadi and shadizadeh, 2012, 2013a; 2013b).
values for compressive strength (De la Roji et al., 2012). In addition
to previous applications of nanotechnology in petroleum up- 2.2. Nano particles
streams, enormous researches have been made on the title of
implementing of nano-particles on the enhanced oil recovery Implemented nano particles throughout this communication
(EOR) from petroleum reservoirs (Mc. Elfresh et al., 2012; Ju which is made from SiO2 and an additive (Al2O3, Fe2O3, TiO2) as
et al., 2006; Miranda et al., 2012; Hendraningrat et al., 2012).
Nevertheless Ahmadi and Shadizadeh (2012, 2013a) investi- Table 1
gated adsorption behavior of extracted natural surfactant from Properties of extracted powder from Zyziphus spina-christi leaves (ahmadi and
leaves of Zyziphus spina-christi onto carbonate minerals with/ Shadizadeh, 2012, 2013a; 2013b).
without nano particles, no records reported around the effect of
Product Total extract powder of Zyziphus spina-christi
nano particles on adsorption trend onto shale sandstone. To
overcome successfully the addressed hurdle of this contribution, Used part Leaves
effect of different nano silica concentrations at different wettabil- Preparation Spray drier
ity state on adsorption behavior in static conditions were system- Description Fine powder
Color Brown
atically executed. It is worth bearing in mind that based on
Solubility in cold water Soluble
intrinsic characteristics of derived natural surfactant conductivity Solubility in alcohol Soluble
method was selected to monitor adsorption density of addressed pH value (10% solution) 5.9–6.0
surface active agent. Furthermore, routinely adsorption isotherms Density 0.09 g/cm3
Residue at 1101c after 6 h 3.48–4%
were carried out to figure adsorption behavior of studied surfac-
Applications Medicine EOR agent
tant in presence of nano particles out. As known for every expert
in chemical stimulation of petroleum reservoirs, adsorption beha-
viors of implemented chemicals have a vital role in robustness and
effectiveness of chemical flooding. Due to this fact results from
current research can be implemented for precise, robust with low
uncertainty selection of chemicals in design of enhanced oil
recovery plans for shale sandstone reservoirs.

2. Materials and methods

2.1. Surfactant

Zizyphus spina-christi is a popular plant in the south of Iran due

to various benefits such as fruit, and surface active agent property
of it leaves. Based on the intrinsic characteristics of the leaves of
Zizyphus spina-christi which are widely known in Iran as “Sedr”
and “konar” have been utilized for washing the hair and body
(Pordel Shahri et al., 2012).
First attention about application of saponin in petroleum
engineering and specifically in oil recovery was studied by Fig. 1. General chemical structure of saponins. Notation R1_R4 represents either
Pordel Shahri et al. (2012). Saponin which is a biodegradable shgar H or different sugar groups (Stanimirova et al., 2011; Ahmadi and Shadizadeh,
based surfactant is derived from the leaves of Zizyphus spina-christi 2013a, 2013b).
 M.A. Ahmadi, S.R. Shadizadeh / Journal of Petroleum Science and Engineering 112 (2013) 239–247 241

100 nm 100nm

Fig. 2. The image of silica nano particles observed under TEM, (a) Hydrophilic Nano Silica, (b) Hydrophobic Nano Silica (Ahmadi and Shadizadeh, 2012).

180
Table 2
Physical properties of nano particles (Ahmadi and Shadizadeh, 2012).
160

Properties AEROSIL 200 AEROSIL R 816

140

Behavior with respect to water Hydrophilic Partially

120
Hydrophobic
Intensity/ cps

Appearance Fluffy white Fluffy white powder 100

powder
2
BET-surface area (m /g) 2007 25 1907 20 80
Average primary particle size 12 12
(nm) 60
Tapped density (g/l) 50 40
SiO2 (Wt%) Z 99.8 Z 99.8 40
Al2O3 (Wt%) r 0.05 r 0.05
Fe2O3 (Wt%) r 0.01 r 0.01 20
TiO2(Wt%) r 0.03 r 0.03
HCl (Wt%) r 0.025 r 0.025 0
0 10 20 30 40 50 60 70 80 90 100
2 Theta

illustrated in Fig. 2 is a kind of modified ultra-fine powder.
According to image was obtained under TEM (see Fig. 2) the shape
of a nano particle is like to an approximate sphere. As other
substances, wettability of nanosilica split into three different
groups named as: hydrophilic silica nano particle (NSHI), hydro-
phobic silica nano particle (NSHO) and neutral silica nano particles
(NSNO). To assess goal of this research two different types of
nanosilica were purchased from Degussa. AEROSIL R 816 and
AEROSIL 200 implemented as hydrophobic and hydrophilic nano
particles. Table 2 illustrates characterization of AEROSIL R816 and
AEROSIL 200 in detail.
Fig. 3. XRD of the crushed sandstone rock tested in this study.
297 μm and larger than 210 μm (Ahmadi and Shadizadeh, 2012,
2013a). The main advantage of the sieve is summarized to
repeatability of the adsorption experiment. To determine the
composition of the implemented shale sand stone rock samples,
X-ray diffraction (XRD) was utilized and the gained outcomes
depicted in Figure 3. Based on outcome patterns of the X-ray
diffraction (XRD), the utilized crushed samples contain 54.67%
Quartz, 32.54% Montmonorilite, 8.14% Feldspar, 3.52% Sidrite and
1.13% Mica.

2.3. Adsorbent
Implemented crushed shale sandstone rock for the goal of this
contribution were taken from the zones 2 and 3 of Mansouri oil
field located in the south of khuzestan, Iran. The addressed
rock samples were broke into pieces by jaw crusher and then
grounded (Ahmadi and Shadizadeh, 2012; 2013a). Same as the
proposed procedure of rock preparation for adsorption experi-
ments, the crushed shale sand stone rock samples were dried at
room pressure and temperature=105 1C by air flowing for one day.
In addition, the dried shale sand stone rock samples were sieved
by sieves No.50 and No.70 to gain crushed samples less than
2.4. Preparation of surfactant solution
To assess different experiments on proposed derived surfactant
such as adsorption tests, critical micelle concentration measure-
ments etc. various stock solution of suggested derived surfactant
with concentrations of between 1000 mg/L and 80,000 mg/L were
prepared by dissolving 0.10–8 g of extracted natural surfactant in
100 mL de-ionized water in a volumetric container. These solu-
tions were then diluted to gain required solutions containing 1000
to 80,000 mg/L of the proposed raw surfactant (Ahmadi and
Shadizadeh, 2013a).
242 M.A. Ahmadi, S.R. Shadizadeh / Journal of Petroleum Science and Engineering 112 (2013) 239–247
Calibrate the conductivity
detector by using the
standard solution
Fig. 4. Graphical demonstration of critical micelle concentration (CMC) determination.
10000
9000
y = 896.5x + 1962
8000
7000
Conductivity( S/Cm)
6000
5000
y = 1424.8x + 191.02
4000
3000
2000
1000
0 q¼
0 1 2 3 4 5
Surfactant Concentration Wt%
Fig. 5. Conductivity vs. Surfactant concentration (Ahmadi and Shadizadeh, 2012, 2013a).
2.4.1. CMC measurement
Different approaches were carried out to figure out critical
micelle concentration of surfactant in aqueous phase such as
interfacial tension, electrical conductivity, thermal conductivity,
gravimetry and surface tension. In this research, electrical conduc-
tivity method was carried out to determine the critical micelle
concentration of introduced natural surfactant. To tackle this issue,
different solution of the introduced raw surfactant samples imple-
mented was on the range of 1–80  103 mg/l. Graphical demon-
stration of the CMC measurement is depicted In Fig. 4. Based on the
mentioned procedure in Fig. 4, the obtained results of conductivity
measurement are illustrated in Fig. 5. As demonstrated in Fig. 5,
electrical conductivity of each solution plotted against relevant
surfactant concentration (Ahmadi and Shadizadeh, 2013a).
2.5. Adsorption experiment
Depletion solution experiments were implemented by allowing an
precisely weighted dose of introduced surfactant to approach equili-
brium condition with crushed shale sandstone solutions of wide initial
surfactant concentrations in ranges of 1000 to 80,000 mg/L. Known
measured weights of crushed shale sandstone samples (2 g) were
added to a 30 mL aqueous solution of the combination of nano silica
and mentioned natural surfactant. Keep in mind that, the mentioned
procedure of adsorption experiment was conducted at room tempera-
ture. The adsorption results of the addressed experiment demonstrate
in Fig. 4. Fig. 4 illustrates the Adsorption density of the different
Determination conductivity The conductivity probe
of highest surfactant washed up and calibrated
concentration by using the standard
solution (Same as first step)
Plot the determined Determination conductivity
conductivity of each of next surfactant
solution versus surfactant concentration
concentrations. The turning
point of the plotted curve
represents CMC of the
surfactant
surfactant concentration at various nanosilica concentrations. (Ahmadi
and Shadizadeh, 2012, 2013a)
Electrical conductance of solutions was carried out to calculate
surfactant concentration changing during the adsorption experi-
ments onto shale sandstone rock. To assess this goal, a plot of
electrical conductance versus surfactant concentration was estab-
lished for expressed rang of surfactant concentration. It should be
mentioned here, this plot named calibration curve and implemen-
ted to determine surfactant concentration by knowing electrical
conductivity of solutions. To determine adsorption density of each
surfactant concentration following expression should be implemented
(Ahmadi and Shadizadeh, 2012, 2013a; Zendehboudi et al., 2013):
V tot:solution  ðC1  CÞ
 10  3 ð1Þ
6 7 8 9 M sandstone
where, q represents the amount of surfactant adsorption density onto
shale sand stone rock sample in terms of (mg/g-rock), Vtot.Solution
denotes the total volume of the bulk solution before adsorption
process in terms of (mL), C1 and C represent the surfactant concentra-
tion before and after adsorption process, respectively, Msandstone stands
for the total mass of the crushed shale sand stone rock samples in bulk
solution.
3. Adsorption models
Adsorption isotherm was utilized to monitor adsorption beha-
vior of the addressed surfactant. In addition, adsorption isotherms
were implemented widely in reservoir simulation of chemical
stimulation. Throughout this section the routinely implemented
adsorption isotherms were introduced briefly. To assess this goal, a
summary of the each adsorption isotherms which includes brief
description and mathematical equations are summarized to Table 3.
Throughout this work, four adsorption isotherms which include
Langmuir, Freundlich, Temkin and Linear isotherms were conducted
to evaluate adsorption behavior of the nano-surfactant system.
4. Results and discussion
Based on previous work of the authors which reported in
Ahmadi and shadizadeh (2013a), critical micelle concentration
(CMC) of the addressed surfactant was gained by implementing
electrical conductivity method. Due to this fact, the amount of
CMC of the studied surfactant is about 3.7 Wt% (See Fig. 5).
Dedicated to the general structure of the saponin depicted in
previous, the proposed schematic of adsorption process of the
 M.A. Ahmadi, S.R. Shadizadeh / Journal of Petroleum Science and Engineering 112 (2013) 239–247 243

Table 3
Summary of the adsorption isotherms

Isotherm Formulation Parameters Description

Langmuir qo K ad C e
qe ¼ 1þK qe=equilibrium adsorption density (mg/g-rock) The classical Langmuir isotherm approach assumes
ad C e
qo=maximum adsorption density (mg/g-rock) monolayer coverage on an energetically homogeneous
Kad=energy of adsorption (L/g) surface with a finite adsorption capacity. In addition, another
Ce=equilibrium surfactant concentration (mg/L) important assumption of the addressed model is
summarized to eliminate the interactions between adsorbed
molecules (Sainio and Turku, 2010; Do, 1998; Guiochon, 1994;
Langmuir, 1916)
Freundlich qe ¼ K f C 1=n qe=equilibrium adsorption density (mg/g-rock) The Freundlich equation is purely empirical owing to the
e
KF and 1/n are the Freundlich constants related adsorption onto heterogeneous surface (Freundlich, 1906;
to adsorption capacity and adsorption intensity, Rahman and Islam, 2009)
correspondingly.
Ce=equilibrium surfactant concentration (mg/L)
Redlich–Peterson K R Ce
qe ¼ 1þbC β
The parameters KR and b have units of (L/mol) The Redlich–Peterson isotherm can be used to describe
e
and (L/mol)β, correspondingly. adsorption on heterogeneous surfaces (Sainio and Turku , 2010;
The value of the dimensionless parameter β lies Allen et al., 2003). A value of β=1 relevant to an entirely
between 0 and 1 homogeneous surface, and the approach changes to the Langmuir
model. All the same, for bcβ⪢1 the isotherm converts identical
with the Freundlich approach (Sainio and Turku , 2010;
Allen et al., 2003).
Temkin qe ¼ BlnK t þ BlnC e qe=equilibrium adsorption (mg/g-rock) Temkin isotherm assumes the indirect adsorbate–adsorbent
B=Temkin constant interactions on adsorption isotherms which is developed by
Kt=equilibrium binding constant some experimental investigations. Due to this fact, the adsorption
Ce=equilibrium surfactant concentration (mg/L) process is explicated by a uniform distribution of the bonding
energies, until some maximum binding energy (Rosen, 1989;
Temkin and Pyzhev, 1940; Ruthven, 1982; Ahmadi et al., 2012)
Linear qe ¼ K H C e qe=amount adsorbed, This type of adsorption isotherms, assume that adsorption
Ce=surfactant concentration, KH=constant in process follow the linear behavior. Due to this assumption, this
units of L/m2 isotherm predicts the adsorption density until specific values
which is lower than saturation point of adsorption process
(Rosen, 1989; Langergren, 1898).

16

14
Adsorption Density (mg/g)

12

10
Hydroxyl group
8
Attraction Force 6
Repulsion Force

2
Shale Sandstone surface
0
Fig. 6. Graphical demonstration of adsorption behavior of Zyziphus spina-christi 0.1 0.5 1 1.5 2 3 4 5 6 7 8
onto shale sandstone surface. Initial Surfactant Concentration (Wt%)

2000 PPM Hydrophobic Nanosilica 1500 PPM Hydrophobic Nanosilica

derived surfactant onto shale sandstone surface is illustrated in 1000 PPM Hydrophobic Nanosilica 500 PPM Hydrophobic Nanosilica
Fig. 6. As demonstrated in Fig. 6, the addressed surfactant 0 PPM Hydrophobic Nanosilica
adsorbed onto shale sandstone surface by means of electrostatic
force between positive charges of rock surface and surfactant
hydroxyl groups which contain negative charges. As early men- 16
tioned in this text, depletion solution experiments were utilized to
Adsorption Density (mg/g)

14
figure out the amount of the adsorption of new surfactant onto 12
shale sandstone crushed rocks. Based on the previous described 10
adsorption procedure, throughout this research the ratio of liquid 8
and solid was 15:1, correspondingly. Keep in mind that the 6
thermodynamic condition of all experiments are T¼ 28 1C and 4
P ¼ ambient pressure. The implemented surfactant concentrations 2
were in the range of 0.1 to 8 Wt% with the crushed shale sandstone 0
0.1 0.5 1 1.5 2 3 4 5 6 7 8
rocks. The adsorption experiments indicate that an increasing in
Initial Surfactant Concentration Wt%
the surfactant concentration of new proposed surfactant caused
adsorption density of the addressed surfactant increased. As clear 2000 PPM Hydrophilic Nanosilica 1500 PPM Hydrophilic Nanosilica
be seen from Fig. 7, an increase in the surfactant concentration 1000 PPM Hydrophilic Nanosilica 500 PPM Hydrophilic Nanosilica
tend to an increase in adsorption density of the surfactant onto 0 PPM Hydrophilic Nanosilica
shale sandstone surface due to the rising in the concentration Fig. 7. Amount of Adsorption density against initial surfactant concentration,
difference between the surface of the crushed shale sandstone and (a) With various hydrophobic nano silica concentrations, (b) With various hydro-
the bulk solution and. Fig. 7 shows comparison between philic nano silica concentrations.
244 M.A. Ahmadi, S.R. Shadizadeh / Journal of Petroleum Science and Engineering 112 (2013) 239–247

16 adsorption efficiency of novel surfactant at different concentration

Hydrophilic Nanosilica
14 of hydrophilic and hydrophobic nano-silica particles. Before tack-
Hydrophobic Nanosilica
12
ling by details to the effect of nanosilica concentration on adsorp-
tion behavior of the introduced surfactant, the adsorption
q max(mg/gr)

10
behavior of sole surfactant onto shale sandstone should be
8 investigated. Due to this fact, as illustrated in Fig. 7 the amount
6 of adsorbed surfactant onto shale sand stone rock surface
4 increased linearly from 0.810394 mg/g to 11.57651 mg/g over the
range of initial surfactant concentrations vary from 0.1 to 4 Wt%.
2
However; for the greater surfactant concentration than 4 Wt% the
0
slope of increasing in adsorption density is very low. For the lower
0 500 1000 1500 2000 2500
surfactant concentrations the availability of surfactant was not
Nanosilica Concentration (ppm)
sufficient to meet stable or plateau condition (Salari et al., 2011).
Fig. 8. The effect of nanosilica concentration on maximum adsorption capacity of Adsorption density for crushed shale sandstone rocks in the range
surfactant.
of initial concentrations of 0.1 to 8 Wt% increased with

100 nm

1 um

Fig. 9. The image of Zyziphus spina-christi and silica nano particles observed under TEM, (a) without nano silica, (b)with Hydrophilic Nano Silica, (c) with Hydrophobic
Nano Silica.
 M.A. Ahmadi, S.R. Shadizadeh / Journal of Petroleum Science and Engineering 112 (2013) 239–247
concentration of surfactant with a major difference of adsorption
from 0.810394 mg/g to 13.983 mg/g, correspondingly. Part (a) in
Fig. 7 depicts the effect of hydrophobic nanosilica on the adsorp-
tion trend of the addressed surfactant onto rock surfaces. As
illustrated in addressed Figure, by increasing hydrophobic nano-
silica concentration, the amount of the adsorbed surfactant onto
rock surfaces declined exponentially. For example, for the system
contains 2000 ppm hydrophobic nanosilica and 4 Wt% of surfac-
tant the amount of adsorbed surfactant is about 2.315 mg/g but
the amount of adsorbed surfactant without nanosilica particles is
about 11.57 mg/g. Fig. 7b illustrates the effect of hydrophilic
nanosilica concentration on the adsorption of extracted surfactant
onto crushed shale sandstone at different surfactant concentra-
tions. As depicted in Fig. 7b, by increasing concentration of
hydrophilic nanosilica in aqueous solution, more reduction in
adsorption of ZSC on crushed shale sandstone observed. This is
because increasing of hydroxyl groups of nano particles which
exist in aqueous solution and these hydroxyl groups can create
hydrogen bond with hydroxyl groups of surfactant. Also another
reason for this event is summarized to adsorption losses of some
nanosilica particles on crushed shale sandstone surface from
aqueous solution by means of electrostatic attraction force how-
ever this part is unfavorable for us because some of nanosilica
particles losses from solution and declined their performance. To
clarify the discussed results in another point view, the effect of
nanosilica concentration on the maximum adsorption capacity are
depicted in Fig. 8. As clear be seen from the addressed Figure,
hydrophobic nanosilica is much more effective than hydrophilic
nanosilica in inhibition surfactant loss onto rock surface. For
example, by increasing hydrophobic nanosilica concentration to
2000 PPM the maximum adsorption density of the surfactant
declined to near 2 mg/g for hydrophobic nanosilica and 10 mg/g
for hydrophilic nanosilica. As depicted in Fig. 8, by increasing
concentration of nano silica in aqueous solution, more reduction in
adsorption of derived raw surfactant on crushed shale sandstone
observed while the performance nanosilica particles in inhibition
of surfactant loss onto rock surface is highly depend on the
wettability of implemented nanosilica particles. Due to this fact,
the bonding between hydrophobic groups of hydrophobic nano-
silica and hydrophobic part of the addressed surfactant are very
Hydrophobic Tail of
Surfactant
Hydroxyl Group
of Surfactant
Hydrophilic Group of
Nanosilica
Fig. 10. Schematic of surfactant adsorption process in presence of (a)Hydrophobic Nanosilica (b) Hydrophilic Nanosilica.
245
strong which proved by TEM experiment. However; hydrophilic
nanosilica can create hydrogen bond between hydroxyl groups of
the surfactant and hydroxyl groups of nanosilica which is very
weaker than hydrophobic bond. Owing to this fact, the perfor-
mance of the hydrophobic nanosilica in inhibition of surfactant
losses onto shale sandstone is higher than hydrophilic nanosilica.
To prove previous claims about inhibition of surfactant adsorption
onto rock samples by means of nano particles, the images of
surfactant with/without nanosilica observed under the TEM were
utilized. The addressed TEM images are illustrated in Fig. 9. As can
be seen from Fig. 9, the shape of particles in part b is near to
spherical and it means that bonding between hydroxyl groups of
the surfactant and hydrophilic surfactant is week because no
coagulation observed however; the shape of the particles in part
(c) not followed any regular shape. Reported Figure in part (c) of
Fig. 9 means that very strong bond between hydrophobic part of
surfactant and hydrophobic groups on nanosilica occurred due to
coagulation of the particles observed in the addressed TEM image.
Finally to present the proposed mechanisms in one smart figure,
the schematic of the surfactant adsorption onto shale sandstone
rock samples in presence of hydrophobic and hydrophilic nanosi-
lica is demonstrated in Fig. 10.
4.1. Equilibrium adsorption models
As mentioned previous throughout this text, the experimental
data were evaluated with four conventional adsorption models.
Reported Figures through attached supplementary materials depict
the adsorption isotherms plot for adsorption of nanosilica-surfactant
onto the shale sandstone surface, in terms of the amount of adsorbed
surfactant per gram of shale sandstone versus equilibrium concen-
tration of surfactant at different nanosilica concentration.
Finally the values of the addressed parameters of each adsorption
isotherm are summarized in the Table 4. As noted in Table 3, the
addressed constants qo and Kad in Langmuir isotherm are corre-
sponding to the adsorption capacity and the energy of adsorption,
correspondingly. The Langmuir constants Kad and qo were figured out
from this model and the relevant values are demonstrated in Table 4.
The plot of Langmuir for nano-surfactant system demonstrated in the
supplementary Figures. It worth mentioning that, the magnitude of
Hydrophobic Nanosilica
Hydrophobic Group of
Nanosilica
Hydrophilic Nanosilica
246 M.A. Ahmadi, S.R. Shadizadeh / Journal of Petroleum Science and Engineering 112 (2013) 239–247

Table 4
Parameters of adsorption adsorption models employed in this study.

NSHO (PPM) Langmuir R2 qo Kad Freundlich R2 KF n

0 1/qe ¼ 0.1085/Ce þ0.0878 0.9853 11.389 0.8092 qe ¼4.0772(Ce)0.6729 0.991 4.0772 0.6729
500 1/qe ¼ 0.1597/Ce þ 0.1292 0.9853 7.7399 0.8090 qe ¼2.7706(Ce)0.6729 0.991 2.7706 0.6729
1000 1/qe ¼ 0.1973/Ce þ0.1724 0.9833 5.8004 0.8737 qe ¼2.1538(Ce)0.6602 0.9912 2.1538 0.6602
1500 1/qe ¼ 0.2817/Ce þ 0.2727 0.979 3.6670 0.9680 qe ¼1.4286(Ce)0.6473 0.9908 1.4286 0.6473
2000 1/qe ¼ 0.5233/Ce þ 0.4495 0.9826 2.2246 0.8589 qe ¼0.8194(Ce)0.6649 0.9911 0.8194 0.6649

NSHI (PPM)
500 1/qe ¼ 0.1214/Ce þ0.0976 0.9853 10.245 0.8039 qe ¼3.6523(Ce)0.6729 0.991 3.6523 0.6729
1000 1/qe ¼ 0.1286/Ce þ 0.112 0.9833 8.928 0.8709 qe ¼3.3071(Ce)0.6602 0.9912 3.3071 0.6602
1500 1/qe ¼ 0.1226/Ce þ 0.1304 0.9728 7.6687 1.0636 qe ¼3.1216(Ce)0.6378 0.9902 3.1216 0.6378
2000 1/qe ¼ 0.1348/Ce þ0.1364 0.973 7.3313 1.0118 qe ¼2.9224(Ce)0.6489 0.9907 2.9224 0.6489

NSHO (PPM) Temkin R2 Kt B Linear R2 KH C

0 qe ¼ 3.4096ln(Ce) þ 6.133 0.8841 6.042 3.4096 qe ¼1.7387Ce þ 2.6119 0.9077 1.7387 2.6119
500 qe ¼ 2.3185ln(Ce) þ4.1681 0.8841 6.036 2.3185 qe ¼1.1811Ce þ1.7761 0.9077 1.1811 1.7761
1000 qe ¼ 1.7643ln(Ce) þ3.1973 0.884 6.124 1.7643 qe ¼0.8966Ce þ1.3806 0.9085 0.8966 1.3806
1500 qe ¼ 1.1491ln(Ce) þ 2.0925 0.8815 6.177 1.1491 qe ¼0.5833Ce þ 0.9092 0.9093 0.5833 0.9092
2000 qe ¼ 0.6803ln(Ce) þ 1.2232 0.8836 6.037 0.6803 qe ¼0.344Ce þ 0.5261 0.9082 0.344 0.5261

NSHI (PPM)
500 qe ¼ 3.0686ln(Ce) þ5.4983 0.8841 6.0002 3.0686 qe ¼1.5539Ce þ2.3507 0.9077 1.5539 2.3507
1000 qe ¼ 2.7144ln(Ce) þ4.9108 0.884 6.1053 2.7144 qe ¼1.3753Ce þ 2.1241 0.9085 1.3753 2.1241
1500 qe ¼ 2.4778ln(Ce) þ 4.5273 0.8793 6.2161 2.4778 qe ¼1.2577Ce þ 1.9738 0.9088 1.2577 1.9738
2000 qe ¼ 2.372ln(Ce) þ 4.2883 0.8796 6.0975 2.372 qe ¼1.2025Ce þ1.8472 0.9088 1.2025 1.8472

the exponent 1/n represents the competence and capacity of the
adsorbent/adsorbate system (Rosen, 1989; Freundlich, 1906; Ruthven,
1982). The relevant parameters of the Freundlich isotherm for each
nano-surfactant system are illustrated in Table 4. In addition, the plot
of the addressed isotherm for each system is depicted in supporting
information. The data fit to Freundlich isotherm represents the
heterogeneity of the sorbent surface. Due to this fact and obtained
results of this research, prove the heterogeneity of the shale
sandstone surface as a sorbent. Also, the addressed parameter of
other adsorption models such temkin and linear isotherms are
reported in Table 4. The plot of the temkin and linear adsorption
isotherms for addressed adsorption system are illustrated in support-
ing Figures. In addition, the corresponding regression correlation
coefficients for each system are given in Table 4. Based on the
obtained regression correlation coefficient (R2) of each addressed
adsorption isotherms, Freundlich model has highest value between
other models. It worth bearing in mind that, regression correlation
coefficient (R2) only used for statistical analysis of each models and
couldn't lead us into any further result about adsorption process of
addressed surfactant onto shale sandstone rock.
5. Conclusions
The following extensive conclusions can be gained owing to the
outcomes from this research:
1. The superior-fit isotherm approach was selected owing to the
correlation of determination values (R2). Due to this fact, all the
experimental adsorption value proved better compliance with
Freundlich adsorption isotherm in terms of higher correlation
coefficient values.
2. Mechanism of adsorption of saponin onto hydrophilic nano silica
is hydrogen bonding between hydroxyl groups of nano silica and
hydroxyl groups of saponin. Hydrogen bonding mechanism in
inhibition of surfactant loss onto sandstone rock is lower and
weaker than hydrophobic bonding between hydrophobic part of
nano silica and hydrophobic tail of surfactant.
3. Hydrophobic nano silica is more effective than hydrophilic
nano silica to inhibit Adsorption losses onto shale sandstone.
Because hydrophobicity in hydrophobic nano silica is much
more than hydrophilic nano silica. Owing to this fact, the
hydrophobic nano silica particles can create more hydrophobic
bonds between hydrophobic tail of surfactant and hydrophobic
part of nano silica particles.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.petrol.2013.11.010.
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