Article

pubs.acs.org/IECR

Nonionic Surfactant for Enhanced Oil Recovery from Carbonates:

Adsorption Kinetics and Equilibrium
Mohammad Ali Ahmadi,† Sohrab Zendehboudi,*,‡ Ali Shafiei,§ and Lesley James∥
†
Faculty of Petroleum Engineering, Petroleum University of Technology, Ahwaz, Iran
‡
Chemical Engineering Department, University of Waterloo, Waterloo, Ontario, Canada, N2L 3G1
§
Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, Ontario, Canada, N2L 3G1
∥
Faculty of Engineering and Applied Science, Memorial University of Newfoundland, St. John’s, NL, Canada, A1B 3X5

ABSTRACT: Around 40% of the current world conventional oil production comes from carbonate reservoirs, dominantly
mature and declining giant oilfields. Tertiary oil production methods as part of an Enhanced Oil Recovery (EOR) scheme are
inevitable after primary and secondary oil production. The goal of surfactant flooding is to reduce the mobility ratio by lowering
the interfacial tension between oil and water and mobilizing the residual oil. This paper highlights adsorption kinetics and
equilibrium of Glycyrrhiza Glabra, a novel surfactant, in aqueous solutions for EOR and reservoir stimulation purposes. A
conductivity technique was used to assess adsorption of the surfactant in the aqueous phase. Batch experimental runs were also
performed at various temperatures to understand the effect of adsorbate dose on the sorption efficiency. The adsorption kinetics
was experimentally investigated at room temperature (27 °C) by monitoring the uptake of the Glycyrrhiza Glabra as a function of
time. The adsorption data were examined using different adsorption equilibrium and kinetic models. The Langmuir isotherm
suits the equilibrium data very well. A pseudo-second order kinetic model can satisfactorily estimate the kinetics of the surfactant
adsorption on carbonates. Results obtained from this research can help in selecting appropriate surfactants for design of EOR
schemes and reservoir stimulation plans for carbonate reservoirs.

1. INTRODUCTION in the porous medium as well as issues with adsorption

Carbonate rocks cover around 20% of the earth crust and
contain over 40% of the world’s proven conventional oil
reserves and also over 20% of the world’s endowment of
heavy oil, extra heavy oil, and bitumen.1−10 More than 40% of
the current world oil production comes from Naturally
Fractured Carbonate Reservoirs (NFCRs), dominantly mature
and rapidly declining giant oilfields in the Middle East.5−10
Primary and secondary oil production methods result in
recovery factors (RF) of, commonly, not greater than 0.45.1−5
Meaning that over 50% of the oil originally in place (OOIP) is
trapped in the reservoir rock as residual oil due to mobility
issues and capillary pressure barriers.1−25 Hence, implementa-
tion of tertiary oil production techniques as part of an
Enhanced Oil Recovery (EOR) scheme is inevitable to unlock
this immense oil resource. Chemical EOR methods have not
historically been responsible for significant additional recovery,
worldwide. Nevertheless, surfactants are being increasingly used
as a well stimulation or wettability alteration agent in EOR
projects in carbonates. This along with the price of oil is a
strong reason for scientists to continue the advancement of
surfactant research in EOR.1−25
Among chemical EOR techniques, surfactant flooding aims
to lower the mobility ratio by reducing the interfacial tension
between oil and water and mobilizing the residual oil to the
production well. This is feasible via adsorption of the
surfactants on the reservoir rock.7,26−30 Surfactant flooding
has been tried for a number of conventional oil reservoirs
around the world with some success stories (e.g., Yates field in
Texas9,31,32 and Cottonwood Creek in Wyoming),5,9,32−36 but
it has largely proved inefficient due to the cost of surfactant loss
efficiency and negative reactions with the reservoir rock.36−38
Surfactants can be classified into different groups based on
the ionic nature of the headgroup, namely anionic, cationic, non-
ionic, and zwitterionic.39,40 Nonionic surfactants are generally
nonvolatile and benign environmentally and are considered as
suitable alternatives for traditional solvents due to their ability
to separate organic compounds from solid samples. Nonionic
surfactants have effective solubilization toward water-insoluble
or moderately soluble organic compounds.41 This property
makes nonionic surfactants proper candidates for the separation
of polar and nonpolar compounds from different solid materials
such as separation of aromatic hydrocarbon from solid environ-
mental phases.42−48 Other factors affecting the rate of surfactant
adsorption include rock surface charge, fluid interface, and
surfactant structure.49−51
Adsorption of various commercial surfactants is well treated
in the open literature.51−56 Surfactant adsorption in porous sys-
tems typically occurs through a range of complex phenomena
(e.g., mass transfer and reaction). Surfactant adsorption is
defined as a phenomenon where transport of surfactant mole-
cules from the bulk phase onto the interface at solid−liquid
boundary occurs. This process can be explained as the interface
is energetically favored by the surfactant compared to the bulk
phase.54,55 The surfactants may adsorb on soils or sediments
as a single monomeric layer at low concentrations of aqueous
Received: January 30, 2012
Revised: May 26, 2012
Accepted: June 15, 2012
Published: June 15, 2012

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surfactant. If the surfactant concentration increases, then the
adsorbed surfactant monomers tend to aggregate and form
micelle-like structures. Depending on the number of layers of
the aggregated surfactant, the micelles are called admicelles for
one layer and hemimicelles for the two other layers.52−55
Gaudin and Fuerstenau (1955) showed that when the micelles
structures make an aggregate on a solid surface, the rate of
adsorption might quickly increase until the solid interface is
covered completely by bilayers of the surfactant. They used the
concept of critical micelle concentration (CMC) to explain this
phenomenon. According to their definition, the surfactant aggre-
gation occurs at concentrations lower than the CMC but greater
than the hemimicellar concentration (HMC).52
Adsorption kinetics and equilibrium of surfactants are
dependent on the nature of or properties of the surfactants
and also the solid−liquid surface.53−56 Wayman (1963) and
Scamehorn (1980) independently studied the adsorption of a
dilute solution of sodium alkyl benzene sulfonate (SDDBS) as a
surfactant on various clay minerals (e.g., Kaolinite).57,58 They
concluded that the adsorption isotherms match the Langmuir
equation, and they can be explained by using the Truber
diagram. Moreover, a number of researchers (e.g., Meader
(1952)51 and Trogus (1979)59) investigated the adsorption of
sodium alkyl benzene sulfonate on bioglass, kaolin, and Berea
sand core. They indicated that the Langmuir isotherm is not
appropriate to describe the equilibrium adsorption of these
particular materials.51,59 Based on their experimental results,
a maximum adsorption magnitude was observed, occasionally
followed by a minimum extent. Gogoi (2009) reported the
adsorption equilibrium of Na-lignosulfonate onto reservoir
rocks from Oil India Limited.60 He demonstrated that
adsorption increases with increasing NaCl concentration but
decreases with increasing pH.60
The adsorption mechanism of Glycyrrhiza Glabra on the
surface of carbonate rock is not yet reported in the literature.
This paper highlights the adsorption behavior of Glycyrrhiza
Glabra in aqueous solutions as a new nonionic surfactant to be
implemented for EOR schemes in carbonates. Adsorption of
the studied surfactant was evaluated using a conductivity
technique for aqueous phase. Batch experiments were also
conducted to investigate the influence of adsorbate dose on
sorption efficiency at different temperatures. In addition, the
adsorption kinetics was experimentally investigated at 27 °C
with recording the uptake value of the Glycyrrhiza Glabra versus
time. The adsorption equilibrium data were also examined with
four different adsorption kinetic models (Langmuir, Freundlich,
Temkin, and linear expressions), and the adsorption parameters
were determined for all isotherm models, over the entire range
of the process conditions. The results are useful to screen
surfactants for use in EOR and reservoir stimulation plans for
carbonate petroleum reservoirs.
2. MATERIALS AND METHODS
2.1. Surfactant. Glycyrrhiza Glabra is a tree with small
spiny branches, commonly found in Jordan, Iran, Iraq, and
Egypt. The concentration of the Saponins in Glycyrrhiza Glabra
is fairly high (e.g., 25 wt %).61 Saponins are natural surfactants
existing in more than 500 plant types.62,63 Their molecules
include hydrophobic and hydrophilic parts. The hydrophobic
group is made of a triterpenoid or steroid backbone, and the
hydrophilic part contains numerous saccharide deposits,
joined to the hydrophobic scaffold through glycoside bonds.64
The combination of the nonpolar sapogenin and water-soluble
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side chain enables saponin to change to a foam. A large number
of synthetic surfactants such as lipopeptide biosurfactants,
alkyl poly glycosides, and alkyl sulfates surfactants, with
lipophilic and hydrophilic molecular groups have the same
structure.61
Three cyclopeptide alkaloids, as well as, four saponin
glycosides, and several flavonoids can be extracted from the
leaves of Glycyrrhiza Glabra. Saponin, a biosurfactant, is
produced from Glycyrrhiza Glabra leaves. The leaves were
collected from southern Iran, and the surfactant was extracted
from the leaves using the spray dryer technique. The total
extracted powder contains saponin and flavonoids. The powder
is light brown in color and soluble in water and alcohol.61−64
The powder density is 0.45 g/cm3, and a 1 wt % aqueous solu-
tion has a pH of 5.8−6.0. Saponin is a natural and biodegradable
nonionic surfactant. Properties of this novel surfactant are
summarized in Table 1.
Table 1. Properties of Glycyrrhiza Glabra, a Novel Surfactant
parameter remarks
product total extract powder of Glycyrrhiza
Glabra
used part roots
preparation spray drier
description fine powder
color brown
solubility in cold water soluble
solubility in alcohol soluble
pH value (10 wt % solution) 5.9−6.0
density 0.41 g/cm3
loss on drying (LOD) at 110 °C after 3.48%−4.0%
6h
total ash at 550°C after 4 h 9.7%−10.0%
applications medicine, surfactant
2.2. Adsorbent. Carbonate rock cores were taken from the
upper Sarvak Cenomanian formation of the Azadegan oilfield
located in the Persian Gulf. The Cenomanian Sarvak formation
is mainly composed of highly fractured marly nerritic and
pelagic limestone with interbedded shale layers. This formation
is divided into three main sections. The upper Sarvak mostly
consists of clean limestone with slight argillaceous limestone.
The middle Sarvak is mostly shale and marls are dominant. The
lithology of the lower Sarvak is mostly marly limestone with
some shale bed intercalations. The porosity of the examined
limestone samples were measured to be approximately ∼12%,
and the permeability was on the range of 1−10 mD (very low
permeablility matrix). The average water saturation within the
reservoir is reported on the range of ∼10%.
The carbonate samples were cracked into small parts by jaw
crusher and then grounded into fine particles using a laboratory
mill. After exposing the samples to free-air for one day, a
laboratory oven operating at 105 °C was employed to dry the
carbonate powder. Dried carbonate samples were sieved by
sieves No. 50 and No. 70 to obtain particles with diameter
lower than 297 μm and bigger than 210 μm. The semi-
quantitative mineral composition of the crushed carbonate rock
determined by X-ray diffraction (XRD) is presented in Figure 1.
Based on the XRD, the crushed carbonate samples used in this
research work contain calcite (65.38 wt %), dolomite (3.13 wt %),
orthoclase (28.89 wt %), clay (1.83 wt %), and other minerals
(0.77 wt %).
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Figure 1. XRD of the crushed carbonate rocks tested.

2.3. Preparation of Surfactant Solution. Specific stock

solutions of Glycyrrhiza Glabra with concentrations ranging
from 1000 mg/L to 80000 mg/L were prepared by dissolving
0.10−8.00 g of Glycyrrhiza Glabra in 1000 mL of deionized
water in a volumetric flask. These solutions were then diluted
to obtain standard solutions containing 1000, 5000, 10000,
15000, 20000, 40000, 50000, 60000, 70000, and 80000 mg/L
of Glycyrrhiza Glabra.
2.3.1. CMC Measurements. There are several methods such
as UV−vis spectra, fluorescence emission spectra, and electrical
conductivity to measure the CMC. In this study, the
conductivity method was selected to carry out the CMC
measurements. Concentration of the Glycyrrhiza Glabra
samples used was on the range of 1000−80000 ppm. The
conductivity of the different solutions was determined from
high to low concentrations. The conductivity meter (Crison
Instruments) was calibrated by using a standard solution. The Figure 2. Conductivity versus surfactant concentration for the
Glycyrrhiza Glabra adsorption.
conductivity of the solution was measured by immersing the
probe in the solution as shown in Figure 2. The electrode was
washed with distilled water before and after every trial to ensure Changes in surfactant concentration during the adsorption
accuracy of the conductivity measurements. test runs were determined using the conductometry method.
In this study, the value of CMC is determined as the cross The concentration of surfactant adsorbed on the solid surface
point of the two straight lines drawn in Figure 2 for high and (carbonate rock) was determined from the difference between
low concentrations of the surfactant. Based on this method, the the aqueous phase surfactant concentration before and after
CMC for Glycyrrhiza Glabra is about 3.5 wt %. adsorption. The adsorption rate versus equilibrium surfactant
2.4. Adsorption Experiments. Batch experimental runs concentration is presented in Figure 3, where the adsorption
were performed by equilibrating 8 g of a crushed carbonate rate (q) measured with this technique is calculated as
sample in a 40 mL of Glycyrrhiza Glabra solution ranging from msolution × (C o − C)
1000 to 80,000 ppm. The bottles were then shaken at a q= × 10−3
controlled room temperature. mcarbonate (1)

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Figure 4. Adsorption analysis of experimental data based on the

Langmuir adsorption model.
Figure 3. Adsorption density versus surfactant equilibrium concen-
tration.
an infinite surface coverage inferring multilayer sorption on the
surface.66,67 The Freundlich isotherm model is given as66,67
where qe = K f Ce1/ n (3)
q = surfactant adsorption rate on the rock surface,
mg/g-rock; where n and Kf are the Freundlich constants. Figure 5 presents
msolution = total mass of solution in the original bulk the adsorption behavior of the surfactant on the carbonate
solution, g; samples, based on the Freundlich isotherm.
Co = surfactant concentration in initial solution before
equilibrated with the carbonate rock, ppm;
C = surfactant concentration in aqueous solution after
equilibrated with the carbonate rock, ppm;
mcarbonate = total mass of the crushed carbonates, g.

3. EQUILIBRIUM ADSORPTION MODELS

For any adsorption system, an adsorption isotherm model is
necessary in order to forecast the extent of loading on the
adsorption matrix at a particular concentration of the adsorbate.
The four well-known general adsorption isotherms employed
here to describe the equilibrium adsorption behavior are
explained here, briefly.
3.1. Langmuir Isotherm. Assuming an entirely homoge-
neous surface for adsorption, the Langmuir isotherm model
used to predict equilibrium adsorption rate (qe) is obtained as
follows65,66
q KadCe Figure 5. Freundlich isotherm model for the equilibrium data of
qe = o Glycyrrhiza Glabra adsorption.
1 + KadCe (2)
where qo (mg/g) and Kad (L/mg) represent the adsorption
capacity in the Langmuir model and adsorption equilibrium 3.3. Temkin Isotherm. The Temkin isotherm is generally
constant, respectively. expressed in the following linear form66,68,69
If the adsorption equilibrium data follow the Langmuir qe = Bln K t + Bln Ce (4)
isotherm model, a plot of 1/qe against 1/Ce should be linear
(Figure 4). The slope is 1/(qo Kad) and the y-intercept is 1/qo. where B and Kt are the Temkin constant and equilibrium
3.2. Freundlich Isotherm. An empirical equation was binding constant, respectively.
established by Freundlich (1906) to describe the adsorption The experimental adsorption data analyzed according to
equilibrium process, assuming the adsorbent has a heteroge- Temkin is shown in Figure 6.
neous surface with different categories of adsorption sites.67 3.4. Linear Isotherm. The simplest type of adsorption
The results from the study showed that the ratio of equilibrium isotherm model is developed on the basis of the Henry
adsorption, qe, for a particular adsorbent to the concentration of equation as follows66,70
adsorbate in a solution, Ce, is not a constant value over a range qe = KHCe (5)
of solution concentrations.67 This isotherm model is unable to
estimate the amount of adsorbate required to saturate the where qe is the amount of solute adsorbed per unit mass of
adsorbent. Hence, the adsorption model theoretically predicts adsorbent under equilibrium condition, Ce is the equilibrium
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Figure 6. Adsorption equilibrium data based on the Temkin isotherm Figure 8. Adsorption of surfactant versus time for different surfactant
model. concentrations.

4.1. Pseudo-first Order Kinetic Model. The pseudo-first

order expression of Lagergren is presented as follows69−72
dqt
= K1(qe − qt )
dt (6)
qt and qe correspond to the extent of adsorbate adsorbed onto
unit mass of adsorbent at time (t) and equilibrium condition,
respectively. K1 is the rate constant of pseudo-first order
adsorption reaction.
After integrating over the boundary conditions (qt = 0
@t = 0 and qt = qt @ t = t), the above differential equation
(eq 6) changes to a first-order linear relationship as given
below69−72
Figure 7. Linear isotherm model for the surfactant/carbonate
adsorption system. ln(qe − qt ) = ln(K1qe) − K1t (7)
−1
In eqs 6 and 7, unit of K1 is min . Also, both qe and qt have
the unit of mg/g.
concentration, and KH represents a constant for the linear 4.2. Pseudo-second Order Kinetic Model. The pseudo-
isotherm model in units of L/m2. second order kinetic model is expressed in a differential form as
The linear isotherm model for the experimental data of this the following69−72
study is shown in Figure 7.
dqt
4. ADSORPTION KINETICS = K 2(qe − qt )2
dt (8)
Rate of adsorption reaction is the second important component
for assessment of an adsorption process. The adsorption This adsorption kinetic model is usually valid for solid−liquid
kinetics is strongly dependent on process condition and inter- systems.69−72
actions between adsorbent and adsorbate substances. The By integrating and rearranging eq 8, a linear form for the
retention time needed for completion of the adsorption pseudo-second order reaction rate is obtained as eq 9
reaction is obtained from the rate of adsorbate uptake which t 1 t
= +
can be determined by employing various kinetic equations qt K 2qe2 qe (9)
through a comprehensive study. Several attempts have been
made to elucidate the adsorption kinetics in the form of a where K2 (g/mg·min) is the rate constant of pseudo-second
general correlation for adsorption processes involving liquid/ order adsorption. Other variables contributing in the pseudo-
solid phases. In this paper, four common kinetic models, second order model have the same definitions and units as
namely, pseudo-first order,69−72 pseudo-second order,69−72 those in eqs 6 and 7. The slope and intercept for the linear plot
intradiffusion,69−72 and Elovich kinetic rates,69−72 were of eq 9 enable us to calculate the magnitudes of equilibrium
examined to find out the adsorption rate of Glycyrrhiza Glabra adsorption (qe) and the rate constant (K2). It has been reported
onto the carbonate surface. The adsorption kinetic experiments that the pseudo-second order rate is a suitable kinetic model to
were performed at room temperature (27 °C) by recording predict the adsorption behavior of the most experimental
the uptake of Glycyrrhiza Glabra versus time as presented in liquid−solid cases within the whole range of process
Figure 8. condition.69−72
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To approximate the initial adsorption rate and half-
adsorption time, eqs 10 and 11 are given as69−72
h = K 2qe2 (10)
t1/2 = 1/K 2qe (11)
The variables h and t1/2 are the initial adsorption rate and half-
adsorption time, respectively.
4.3. Intraparticle Diffusion Model. First-order or second-
order kinetic models are basically utilized for determination of
the reaction type and the amount of adsorption rate. In order to
comprehend the diffusion mechanism in an adsorption process,
it is crucial to employ various diffusion models.66,69−72 One of
the proposed models is the intraparticle diffusion that looks
useful as well as simple to determine important aspects of
diffusion mechanism. The intraparticle diffusion model is
expressed as follows66,69−72
qt = K i × t 1/2 (12)
1/2
According to eq 12, the slope of linear plot (qt versus t ) is
the rate constant of the intraparticle diffusion (Ki).
If the regression line relating t1/2 to the adsorption rate (qt)
has an intercept of zero, the dominant mechanism in adsorp-
tion is the intraparticle diffusion. If not, other mechanisms are
also engaged in the adsorption reaction. Figure 11 shows
adsorption rate (qt) versus time squared (t1/2), based on the
intraparticle diffusion model. Relationship between the experi-
mental data and the data predicted by the kinetic model reveals
the multilinearity nature of adsorption kinetics for the
Glycyrrhiza Glabra/carbonate case in this study.
4.4. Elovich Model. The differential form of Elovich
equation is typically expressed as66,70−72
dqt
= αe−βqt
dt (13)
where qt is the adsorption capacity at time t in units of mg/g.
α (mg/g·min) and β (mg/g·min) are the initial adsorption rate
and adsorption constant for a certain experiment, respectively.
Assuming α β t ≫ 1, and then integrating over the boundary
conditions (qt = 0 @ t = 0; qt = qt @ t = t), eq 13 is simplified as
follows66,70−72
1 ln(αβ) ln(t )
= + q
qt β β t (14)
Therefore, if a plot of qt versus ln (t) yields a straight line, the
constants of the Elovich kinetic model (α and β) are calculated
from the slope and intercept of the linear graph (Figure 12).
5. RESULTS AND DISCUSSION
Adsorption equilibrium and kinetics of the aqueous solutions of
Glycyrrhiza Glabra, as a nonionic surfactant, is addressed here
in this section.
5.1. Important Parameters. Major factors affecting
Glycyrrhiza Glabra adsorption on the carbonate samples are
considered to investigate the interaction mechanism of a liquid
phase and a solid phase in a particular case elaborated here.
Quantifying the critical micelle concentration (CMC) is
important to understand the active surface chemistry of
Glycyrrhiza Glabra in the solute and in turn the adsorption
mechanism of the surfactant on the surface of the adsorbent.
Conductivity values versus surfactant concentrations were
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plotted in order to obtain the CMC magnitude from the
inflection point of the data shown in Figure 2. When
concentration of the surfactant solution increases to a definite
value, its ions or molecules will approach the association
reaction and aggregate to form micelles as a change in
conductivity is observed. Precise experimental measurements
using well purified apparatus showed that fairly slow and conti-
nuous variations in physicochemical characterizations of the
solutions take place close to the CMC. In this case, the micelles
alter to be polydisperse, and substantial changes in the monomer
activities occur at the concentrations greater than the CMC.
The influence of initial concentration of the Glycyrrhiza
Glabra on the amount of adsorption is presented in Figure 3.
The equilibrium adsorption, as shown in Figures 3 and 8, was
reached within 10 days for most initial concentrations. An
increase in the concentration of surfactant leads to an increase
in adsorption capacity of the surfactant onto the carbonate
samples. This is due to the increase in the concentration gradient
between the bulk and the surface of the carbonate rock.
The impact of contact time on efficiency of the surfactant
adsorption onto the carbonate rock was studied in order to
determine the rate of surfactant adsorption. The adsorption rate
of the surfactant as a function of contact time was measured for
various initial concentrations of Glycyrrhiza Glabra within the
range of 0.1−8.0 wt % (Figure 8). Clearly, as seen from Figure 3,
the maximum adsorption rates were attained nearly in the first
10 days for all studied initial concentrations of the surfactant. In
the beginning of the process, the adsorption rate is greater, since
more carbonate surface area is available for the surfactant adsorp-
tion. As the adsorbed substance proceeds formation of a mono-
layer, the capacity of the carbonate sample declines, and the
controlling rate for the uptake is the rate at which the solute solution
is moved from the external to the internal sites of the carbonate
particles. It was found that the rate of adsorption decreases in the
next steps. This is possibly due to the slow phenomenon of pore
diffusion which mainly contributes in the transportation of the
surfactant ions into the bulk of carbonate rocks.
5.2. Adsorption Isotherms. Adsorption isotherm models
can help illustrate adsorption mechanism of the surfactant on
the surface of carbonate rocks. Adsorption isotherms are described
by particular constant parameters which determine the surface
characterizations and affinity for the degree of adsorbent substance
toward the adsorbed surfactant. To perform an optimized design
for a sorption process, it is essential to consider the most proper
correlations for equilibrium curves. Langmuir, Freundlich, Temkin,
and linear isotherm models were employed to characterize the
equilibrium adsorption. Experimental sorption tests were carried
out at the equilibrium time for different doses of Glycyrrhiza
Glabra as a new surfactant introduced in this paper.
In the Langmuir isotherm, the constants qo and Kad are
associated to the adsorption capacity and energy of adsorption,
respectively. When 1/qe versus 1/Ce was plotted using the
experimental data, a straight line was obtained with slope of
1/qo Kad and R2 = 0.9964 (Figure 4), indicating that the surfactant
adsorption onto the carbonate rock follows the Langmuir
isotherm model very well. The Langmuir constants Kad and qo
were computed from the slope and intercept of the linear plot
for this isotherm, and their magnitudes are tabulated in Table 2.
The fit of data to the Freundlich isotherm model generally
points out the heterogeneity of the adsorbent surface. The
value of exponent (1/n) is a criterion to determine capability
and capacity of the adsorbent surface/adsorbate solute
system:66,67,69 The values of the Freundlich isotherm
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Table 2. Parameters Calculated for the Different Adsorption
Models Employed
isotherm correlation parameters
Langmuir 1/qe = 0.0722/Ce + 0.0196 R2 qo
0.9964 51.02
Freundlich qe = 9.7946(Ce)0.8412 R2 n Kf
0.9891 0.8412
Temkin qe = 10.599 ln(Ce) + 17.7110 R2 Kt
0.8733 5.31
linear qe = 6.0665 Ce + 4.8148 R2 KH
0.9307 6.0665
parameters are listed in Table 2 for the adsorption system
described in this study.
For the Temkin isotherm model, a plot of qe against ln (Ce)
(Figure 6) gives the magnitudes of the constant parameters
including Kt and B. Kt (L/mg) represents the equilibrium
binding constant which is related to the maximum binding
energy. Parameter B is also corresponding to the adsorption
heat. The values of the constants are listed in Table 2 obtained
based on the adsorption equilibrium data analyzed with the
isotherm model.
A graph of the amount adsorbed per unit mass of the
adsorbent, qe, versus equilibrium concentration, Ce, has a slope
of KH for the linear isotherm as shown in Figure 7. Table 2
includes values of the parameters (e.g., KH and R2) for this
isotherm, as well. The coefficient of determination (R2)
obtained for the Temkin isotherm model is 0.873, much less
than the R2 values for the linear plots obtained from the
Langmuir, Freundlich, and linear isotherm equations. The
values of R2 indicate that the experimental adsorption data are
better fitted with the Freundlich and Langmuir isotherm
models compared to the rest of the isotherms used in this study
(Table 2).
5.3. Adsorption Kinetics. In this section, the experimental
adsorption data were examined with four common kinetic
models in order to comprehend the adsorption kinetics of the
surfactant onto the crushed carbonates.
Surfactant adsorption kinetics onto carbonate rocks was
modeled by the pseudo-first order kinetic rate (Figure 9). The
slope and intercept of the graph of ln(qe − qt) versus t for the
Glycyrrhiza Glabra/carbonate system enabled to determine
the rate constant of this kinetic model (K1) and equilibrium
adsorption rate (qe), respectively. The Lagergren plots for
the sorption process at different initial concentrations of
the surfactant are presented in Figure 9. It is evident that the
adsorption system obeys the Lagergren model just in the
beginning of the process for a short time period. It can be
concluded that only the early stage of the adsorption process
correlates with the Lagergren model. Hence, an appropriate
kinetic reaction model is required to elucidate the kinetics
of the Glycyrrhiza Glabra onto carbonate samples. Table 3
presents the parameters of pseudo-first order kinetic model
for different surfactant concentrations employed in this experi-
mental work.
Adsorption kinetic plot for Glycyrrhiza Glabra on the basis of
the pseudo-second order rate is shown in Figure 10. The
adsorption kinetic data of Glycyrrhiza Glabra, a new nonionic
surfactant, fits very well into the pseudo-second order rate
contrasting the pseudo-first order kinetic model. The
parameters of the pseudo-second order rate at various initial
surfactant dosages are listed in Table 3. As seen in the table, the
Article
Kad
0.27
9.7946
B
10.599
c
4.8148
Figure 9. Pseudo-first order plot for surfactant adsorption onto
carbonate rock: a) surfactant concentration, wt% [0.5, 1.0, 1.5, 2.0]
and b) surfactant concentration, wt% [4.0, 5.0, 6.0, 7.0, 8.0].
correlation coefficients obtained for the pseudo-second order
kinetic model have higher values (R2 > 0.99) compared to the
R2 magnitudes for the pseudo-first order kinetic model. In
addition, the equilibrium adsorption rates (qe) estimated by the
second-order rate model are in an acceptable agreement with
the experimental values of the equilibrium capacity. These
findings propose that the adsorption kinetics of Glycyrrhiza Glabra
on the carbonate adsorbent can be predicted, more suitably, by the
pseudo-second order model, over the whole ranges of surfactant
concentrations and process time periods. According to Figure 10
and Table 3, it can be concluded that Glycyrrhiza Glabra
experiences a high initial adsorption kinetic rate, h, with short half-
adsorption time, t1/2, for the carbonate rocks.
The likelihood of the intraparticle diffusion in the present
experimental work was investigated by using eq 12. If the
intraparticle diffusion is the prevailing transportation mecha-
nism, then the adsorption kinetic rate (qt) should linearly
proportional with t1/2, and the linear plot will have an intercept
of zero. Otherwise, some other controlling mechanisms are
involved in the adsorption process.66,67,69 The intraparticle
diffusion plot of the kinetic data for Glycyrrhiza Glabra is
depicted in Figure 11. More information about the adsorption
reaction rate of this new surfactant onto carbonate samples is
summarized in Table 3, based on this kinetic model. The values
of R2 reveal that the intraparticle diffusion theory is not an
inappropriate kinetic model for the surfactant investigated as
the correlation coefficients (R2) for all examined surfactant
concentrations were found very small (R2 ≪ 1). Furthermore,
Figure 11 and Table 3 demonstrate that other adsorption
mechanisms along with diffusion contribute in the interactions
between the surfactant and adsorbent.
9900 dx.doi.org/10.1021/ie300269c | Ind. Eng. Chem. Res. 2012, 51, 9894−9905
Industrial & Engineering Chemistry Research Article

Table 3. Kinetic Rates of the Surfactant with Various Concentrations on the Absorbent, Based on Four Different Adsorption
Kinetic Models
model C (wt %) correlation R2 model C (wt %) correlation R2
pseudo-first order 0.5 ln(qe-qt) = −0.1304t + 1.0011 R2
= 0.9959 intraparticle diffusion 0.1 qt = 0.5
0.1129(t ) + 0.6129 R 2
= 0.3707
1.0 ln(qe-qt) = −0.3467t + 2.1599 R2 = 0.9822 model 0.5 qt = 0.4305(t0.5) + 2.2650 R2 = 0.3743
1.5 ln(qe-qt) = −0.4516t + 2.6227 R2 = 0.9734 1.0 qt = 1.1046(t0.5) + 3.0269 R2 = 0.5176
2.0 ln(qe-qt) = −0.7245t + 2.8557 R2 = 0.9982 1.5 qt = 1.6541(t0.5) + 5.1497 R2 = 0.5061
4.0 ln(qe-qt) = −0.3729t + 3.4975 R2 = 0.9992 2.0 qt = 1.8706(t0.5) + 8.5173 R2 = 0.4547
5.0 ln(qe-qt) = −0.9521t + 3.6102 R2 = 0.9974 4.0 qt = 4.2719(t0.5) + 11.7251 R2 = 0.5698
6.0 ln(qe-qt) = −0.4428t + 3.5998 R2 = 0.9854 5.0 qt = 3.6436(t0.5) + 18.9280 R2 = 0.4167
6.0 qt = 4.4905(t0.5) + 16.0511 R2 = 0.5042
7.0 ln(qe-qt) = −0.5343t + 3.4470 R2 = 0.8813
7.0 qt = 4.2240(t0.5) + 19.3631 R2 = 0.4992
8.0 ln(qe-qt) = −0.5418t + 3.8242 R2 = 0.9753
8.0 qt = 5.4377(t0.5) + 15.7882 R2 = 0.5923
pseudo-second order 0.1 t/qt = 0.8769t + 0.1682 R2 = 0.9996
Elovich model 0.1 qt = 0.1899 ln(t) + 0.6105 R2 = 0.4251
0.5 t/qt = 0.2334t+ 0.0511 R2 = 0.9995
0.5 qt = 0.7283 ln(t) + 2.2487 R2 = 0.4344
1.0 t/qt = 0.115t + 0.1197 R2 = 0.9947
1.0 qt = 1.9415 ln(t) + 2.8656 R2 = 0.6484
1.5 t/qt = 0.0741t + 0.0581 R2 = 0.9968 1.5 qt = 2.8918 ln(t) + 4.9333 R2 = 0.6274
2.0 t/qt = 0.0571t + 0.0172 R2 = 0.9996 2.0 qt = 3.1524 ln(t) + 8.4659 R2 = 0.5238
4.0 t/qt = 0.0297t + 0.0264 R2 = 0.9972 4.0 qt = 7.4032 ln(t) + 11.2741 R2 = 0.6941
5.0 t/qt = 0.0277t + 0.0057 R2 = 0.9998 5.0 qt = 6.0578 ln(t) + 18.9632 R2 = 0.4671
6.0 t/qt = 0.0261t + 0.0142 R2 = 0.9987 6.0 qt = 7.7024 ln(t) + 15.7070 R2 = 0.6016
7.0 t/qt = 0.0249t + 0.0088 R2 = 0.9997 7.0 qt = 6.8563 ln(t) + 19.6781 R2 = 0.5335
8.0 t/qt = 0.0229t + 0.0176 R2 = 0.9983 8.0 qt = 9.3182 ln(t) + 15.3852 R2 = 0.7027

Figure 11. Intraparticle diffusion plot for surfactant adsorption onto

carbonate rock: a) surfactant concentration, wt% [0.5, 2.0, 4.0, 5.0,
8.0] and b) surfactant concentration, wt% [0.1,1.0, 1.5, 6.0, 7.0].

Figure 10. Pseudo-second order plot for surfactant adsorption onto
carbonate rock: a) surfactant concentration, wt% [0.1,0.5, 1.0, 1.5, 2.0]
and b) surfactant concentration, wt% [4.0, 5.0, 6.0, 7.0, 8.0].
Using the adsorption data, a plot of the Elovich kinetic model
for the surfactant is presented in Figure 12. In this case, there is
a linear correlation between Glycyrrhiza Glabra adsorbed, qt,
9901
and ln(t) over the whole adsorption course with low
coefficients of determination (R2 ≪ 1) for all of the lines
(Table 3). The constant parameters obtained from the Elovich
kinetic model are listed in Table 3 for the surfactant/carbonate
system. Clearly, both α and β constants are functions of the
initial surfactant concentration, Co. Figure 12 and Table 3
demonstrate a weak correlation between the experimental
dx.doi.org/10.1021/ie300269c | Ind. Eng. Chem. Res. 2012, 51, 9894−9905
Industrial & Engineering Chemistry Research
Figure 12. Elovich model plot for surfactant adsorption onto
carbonate rock: a) surfactant concentration, wt% [0.1,1.0, 2.0, 5.0,
7.0] and b) surfactant concentration, wt% [0.5,1.5, 4.0, 6.0, 8.0].
adsorption data and the theoretical data calculated by the
Elovich kinetic model as defined by eq 13. Hence, the Elovich
equation should not be used to predict the adsorption kinetics
behavior of Glycyrrhiza Glabra onto the carbonate samples.
5.4. Adsorption Thermodynamic. The Gibbs free energy
change (ΔGo) is an important thermodynamic parameter when
determining the spontaneity of a process. An adsorption reac-
tion takes place spontaneously at a particular temperature if
ΔGo has a negative value.6,36 Knowing the Langmuir isotherm
model suitably describes the adsorption system, the free energy
change of adsorption is given as follows6,36
ΔGo = −RT ln Kad (15)
where T and Kad represent the absolute temperature (K) and
Langmuir constant, respectively. R is the universal gas constant
that equals 8.314 J mol/K in the above equation. ΔGo has the
unit of J/mol, here.
The magnitude of ΔGo for sorption of the surfactant was
found to be −13.96 kJ/mol according to eq 15. The negative
value of the free energy change (ΔGo) validates possibility and
spontaneous nature of the adsorption process.
Temperature plays an important role in the adsorption of
surfactant on carbonate samples. The temperature has two
main impacts on the adsorption process. First, an increase in
temperature will lower the rate of adsorbate diffusion across the
external boundary layer and in the interior pores of the
carbonate particles because the solution viscosity declines as
temperature increases. Second, the temperature affects the
equilibrium capacity of the carbonate samples depending on
whether the adsorption process is exothermic or endothermic.
Figure 13 shows the adsorption of Glycyrrhiza Glabra at four
temperatures (27 °C, 60 °C, 75 °C, and 150 °C). As the
9902
Article
Figure 13. Adsorption behavior of Glycyrrhiza Glabra at different
temperatures based on the Langmuir isotherm model.
temperature increases, the adsorption capacity of this surfactant
decreases. Thus, the adsorption process is exothermic.
When physisorption of gases or liquids over solids occurs,
the amount of adsorption will increase by increase in pressure.
This is because the adsorbate volume reduces during adsorp-
tion process. It should be noted here that the effect of pressure
is much stronger in gas adsorption cases compared with liquid
adsorption systems. The current study was conducted at the
atmospheric pressure. Investigating the effect of pressure on the
parameters and adsorption kinetics is part of our future research
work.
5.5. Glycyrrhiza Glabra versus Common Surfactants.
There are some main differences between the newly introduced
surfactant and common surfactants available in the market as
follows:
• The price of surfactants such as alkyl poly glycosides and
alkyl sulfates that are commonly employed in oil industry
varies between 3.0 and 5.0 US$ per kilogram; while
Glycyrrhiza Glabra, a new nonionic surfactant, can be
obtained around 1.5−2.0 US$/kg in Middle Eastern
countries such as Iran and Egypt. Hence, Glycyrrhiza
Glabra is very inexpensive.
• Glycyrrhiza Glabra is natural, biodegradable and thus
more environmentally friendly compared to common
artificial surfactants in petroleum industry.
• A surfactant loss between 3 and 8 mg/g of rock in the
absence of oil is common as reported in petroleum
literature.5−10 The adsorption value of Glycyrrhiza
Glabra at CMC point was found to be 4 mg/g. This is
on the lower range of other known surfactants.
• In comparison with the common surfactants examined,
Glycyrrhiza Glabra is shown to more favorably reduce
interfacial tension (IFT). Lower IFT may be achieved
using Glycyrrhiza Glabra, leading to greater pore scale
recovery. The change of interfacial tension with
surfactant concentration in the presence of kerosene oil
is depicted in Figure 14. It should be noted here that IFT
is determined by the drop-weight method in this study.
The reduction percentage of IFT is around 69% when
Glycyrrhiza Glabra is employed, compared to 52% and
41% for alkyl poly glycosides and alkyl sulfates
surfactants, respectively.
5.6. Cost and Environmental Aspects. For a surfactant
flood, it is vital to take into account both technical and
dx.doi.org/10.1021/ie300269c | Ind. Eng. Chem. Res. 2012, 51, 9894−9905
Industrial & Engineering Chemistry Research Article

that for an aqueous system without carbonate. This is

Figure 14. Interfacial tension versus surfactant concentration for three
different surfactants.
economic factors. The economic viability is essentially
dependent on parameters such as the cost of surface-active
substance and the oil price. The surfactant is normally the most
costly part in the EOR surfactant flooding scheme.1−4
Surfactant expenses consist of purchasing the surfactant at the
start of the project and also the cost for surfactant replacement
diminished during the adsorption process.1−4
Glycyrrhiza Glabra is a natural surface-active substance found
in oil-producing countries such as Iran. It is inexpensive and
attributed to attraction forces between the negatively
charged Glycyrrhiza Glabra and the positively charged
carbonate.
2 With increase in the surfactant concentration, the
adsorption on the carbonate surface increases until the
saturation point. To predict the saturation condition, a
suitable adsorption model was proposed for this
particular surfactant.
3 The linear and Freundlich and Temkin equilibrium
adsorption models are not suitable for predicting the
surfactant/carbonate adsorption; however, there is a
good agreement between the experimental data and the
model results with R2 = 0.9964 while using the Langmuir
adsorption isotherm.
4 Pseudo-second order kinetic model can satisfactorily
estimate the kinetics of surfactant adsorption on the
carbonate rock. The adsorption mechanism is expected
to be quite complex for the surfactant/carbonate system
and perhaps is a combination of diffusion and external
mass transfer.
5 The adsorption process is exothermic as amount
adsorbed decreases with increasing temperature.
6 Availability and the reasonable cost of the Glycyrrhiza
Glabra make it economically viable for surfactant
flooding. Moreover, the newly introduced surfactant
poses less risk to the environment.

■
easily available; thus the question of cost does not come up for
this new introduced surfactant. In addition, this natural AUTHOR INFORMATION
compound is considered as an environmentally friendly
Corresponding Author
surfactant that causes minimal or no harm to the environment.
*Phone: 519-888-4567 ext. 36157. E-mail: szendehb@
5.7. Potential EOR Application of Glycyrrhiza Glabra.
uwaterloo.ca.
The key purposes of surfactant flooding method in fractured
carbonate reservoirs are wettability alteration and interfacial Notes
The authors declare no competing financial interest.

■
tension (IFT) reduction, leading to enhancing the imbibition
process.1−10 Surfactant injection as a chemical stimulation
process has been examined in carbonate porous media such as ACKNOWLEDGMENTS
Cottonwood Creek and Yates Fields in the USA.5,9,32−36 These The first author would like to acknowledge the Petroleum
oilfields were operated under depletion previously. As the University of Technology (PUT) for providing financial support
pressure declined, free gas produced and quickly escaped via throughout this research.
the fractures to form a gas cap. Some EOR methods such as
surfactant injection and thermal assisted gravity segration in
pilot plant scales are ongoing to increase oil production from
■ NOMENCLATURE
Acronyms
these oil reservoirs.5,9,32−36 In addition, there are underway CMC Critical Micelle Concentration
Alkali-Surfactant-Polymer (ASP) and Surfactant−Polymer (SP) EOR Enhanced Oil Recovery
projects in both carbonate and sandstone formations such as HMC Hemimicellar Concentration
Delaware Childers Field (Oklahoma), Lawrence Field NFCR Naturally Fractured Carbonate Reservoir
(Illinois), Nowata Field (Oklahoma), and Grayburg Carbonate OOIP oil originally in place
Formation (Texas), based on the EOR review by Moritis PPM part per million
(2008).1−10,32−36,73 Therefore, this new surfactant can have SDDBS sodium alkyl benzene sulfonate
EOR applications in chemical flooding for sandstone and XRD X-Ray Diffraction
carbonate oil reservoirs in North America. Variables
B Temkin constant which is related to the heat of
6. CONCLUSIONS
adsorption
The adsorption of Glycyrrhiza Glabra onto crushed carbonates C surfactant concentration in aqueous solution after
was systematically investigated in this paper. Equilibrium and equilibrium, (ppm) and (mg/L)
kinetic behaviors of the surfactant were discussed in detail, and Ce equilibrium concentration, (ppm) and (mg/L)
adsorption parameters for the Langmuir, Freundlich, linear, and Co surfactant concentration in the initial solution before
Temkin isotherms were determined. equilibrium, (ppm) and (mg/L)
The following conclusions can be drawn based on the results h initial kinetics rate, (mg/g)
of this study: K1 pseudo-first order rate constant, (min−1)
1 The adsorption of surfactant onto carbonate causes the K2 pseudo-second order adsorption rate constant, (g/
dose to achieve micellization being much greater than mg·min)
9903 dx.doi.org/10.1021/ie300269c | Ind. Eng. Chem. Res. 2012, 51, 9894−9905
Industrial & Engineering Chemistry Research Article

Kad energy of adsorption, (L/mg) (14) Webb, K. J.; Black, C. J. J.; Tjetland, G. A. Laboratory Study
Kf Freundlich constant Investigating Methods for Improving Oil Recovery in Carbonates.
KH constant in linear model, (L/m2) IPTC-10506, International Petroleum Technology Conference, Doha,
Kt equilibrium binding constant at maximum binding Qatar, 21−23 November 2005.
energy, (L/mg) (15) Haugen, Å.; Fernø, M. A.; Graue, A. Numerical Simulation and
Sensitivity Analysis of In-situ Fluid Flow in MRI Laboratory
mcarbonate total mass of crushed carbonate, (g)
Waterfloods of Fractured Carbonate Rocks at Different Wettabilities.
msolution total mass of solution in original bulk solution, (g) SPE-116145, SPE Annual Technical Conference and Exhibition, Denver,
n Freundlich constant CO, USA, 21−24 September 2008.
q adsorption capacity, (mg/g-rock) (16) Delshad, M.; Najafabadi, N. F.; Sepehrnoori, K. Scale-up
qe equilibrium adsorption, (mg/g-rock) Methodology for Wettability Modification in Fractured Carbonates.
qo adsorption capacity in Langmuir model, (mg/g-rock) SPE-118915, SPE Reservoir Simulation Symposium, Woodlands, TX,
R universal gas constant, (J/mol·K) USA, 2−4 February 2009.
t time, (h) and (day) (17) Mohanty, K. K. Dilute Surfactant Methods for Carbonate
T temperature, (K) Formations: Final Report; Report no. DE-FC26-02NT 15322; U.S.
t1/2 half-adsorption time, (h) Department of Energy: Washington, DC, USA, February 2006.
ΔG° Gibbs free energy change, (kJ/mol) (18) Adibhatia, B.; Mohanty, K. K. Simulation of Surfactant-Aided
Gravity Drainage in Fractured Carbonates. SPE-106601, SPE Reservoir
Greek letters Simulation Symposium, Houston, TX, USA, 26−28 February 2007.
α initial adsorption rate for the Elovich model, (mg/g·min) (19) Al-Dhafeeri, A. M.; Nasr-El-Din, H. A.; Al-Mubarak, H. K.; Al-
β adsorption constant for the Elovich model, (mg/g·min) Ghamdi, J. Gas Shut-off Treatment in Oil Carbonate Reservoirs in
Saudi Arabia. SPE-114323, SPE Annual Technical Conference and
Subscript
Exhibition, Denver, CO, USA, 21−24 September 2008.
ad adsorption (20) Kumar, A.; Al-Ajmi, M. F.; Al-Anzi, E.; Clark, R. A.; Khater, M.;
e equilibrium Lantz, J. Water Shut off Techniques to Combat Premature Water
f Freundlich Breakthrough in Mauddud Carbonate ReservoirAn Efficacy
o maximum capacity of adsorption Analysis. IPTC-11713, International Petroleum Technology Conference,

■
REFERENCES
(1) Worldwide EOR Survey, Oil Gas J. 1996, Vol. 94(16), pp 45−61.
(2) Worldwide EOR Survey, Oil Gas J. 2004, Vol. 102(14), pp 53−
65.
(3) Worldwide EOR Survey, Oil Gas J. 2006, Vol. 104(15), pp 45−
57.
(4) Special Report: EOR/Heavy Oil Survey: 2010 worldwide EOR
survey. Oil Gas J., 2010, Vol. 108(14).
(5) Xie, X.; Weiss, W. W.; Tong, Z.; Morrow, N. R. Improved Oil
Recovery from Carbonate Reservoirs by Chemical Stimulation. SPE J.
2005, 10 (3), 276−285.
(6) Seethepalli, A.; Adibhatla, B.; Mohanty, K. K. Physiochemical
Interactions during Surfactant Flooding of Carbonate Reservoirs. SPE
J. 2004, 9 (4), 411−418.
(7) Thomas, M. M.; Clouse, J. A.; Longo, J. M. Adsorption of
Organic Compounds on Carbonate Minerals: 1- Model Compounds
and their Influence on Mineral Wettability. Chem. Geol. 1993a, 109
(1−4), 201−213.
(8) Thomas, M. M.; Clouse, J. A.; Longo, J. M. Adsorption of
Organic Compounds on Carbonate Minerals. 3. Influence on
Dissolution Rates. Chem. Geol. 1993b, 109 (1−4), 227−237.
(9) Yang, H. D.; Wadleigh, E. E. Dilute Surfactant IORDesign
Improvement for Massive, Fractured Carbonate Applications. SPE
59009, SPE International Petroleum Conference and Exhibition,
Villahermosa, Mexico, 1−3 February 2000.
(10) Chen, H. L.; Lucas, L. R.; Nogaret, L. A. D.; Yang, H. D.;
Kenyon, D. E. Laboratory Monitoring of Surfactant Imbibition with
Computerized Tomography. SPE Reservoir Eval. Eng. 2001, 4 (1),
16−25.
(11) Manrique, E. J.; Muci, V. E.; Gurfinkel, M. E. EOR Field
Experiences in Carbonate Reservoirs in the United States. SPE
Reservoir Eval. Eng. 2007, 10, 667−686.
(12) Najafabadi, N. F.; Delshad, M.; Sepehrnoori, K.; Nguyen, Q. P.;
Zhang, J. Chemical Flooding of Fractured Carbonates Using
Wettability Modifiers. SPE-113369, SPE/DOE Symposium on Improved
Oil Recovery, Tulsa, OK, USA, 20−23 April 2008.
(13) Tabary, R.; Fornari, A.; Bazin, B.; Bourbiaux, B.; Dalmazzone, C.
Improved Oil Recovery with Chemicals in Fractured Carbonate
Formations. SPE-121668, SPE International Symposium on Oilf ield
Chemistry, Woodlands, TX, USA, 20−22 April 2009.
Dubai, UAE, 4−6 December 2007.
(21) Al-Taq, A. A.; Nasr-El-Din, H. A.; Beresky, J. K.; Naimi, K. M.;
Sierra, L.; Eoff, L. Simultaneous Acid Diversion and Water Control in
Carbonate Reservoirs: A Case History from Saudi Arabia. SPE-106951,
SPE Reservoir Eval. Eng. 2008, 11, 882−891.
(22) Smith, D. D.; Giraud, M. J.; Kemp, C. C.; McBee, M.; Taitano,
J. A.; Winfield, M. S.; Portwood, J. T.; Everett, D. M. The Successful
Evolution of Anton Irish Conformance Efforts. SPE-103044, SPE
Annual Technical Conference and Exhibition, San Antonio, TX, USA,
24−27 September 2006.
(23) Portwood, J. T. The Kansas Arbuckle Formation: Performance
Evaluation and Lessons Learned from More than 200 Polymer-Gel
Water-Shutoff Treatments. SPE-94096, SPE Production Operations
Symposium, Oklahoma City, OK, USA, 16−19 April 2005.
(24) Sengupta, T. K.; Singh, R.; Avtar, R.; Singh, K. Successful Gas
Shut Off Using Latest Gel Technology in an Indian Offshore
Carbonate FieldA Case Study. SPE-72118, SPE Asia Pacif ic
Improved Oil Recovery Conference, Kuala Lumpur, Malaysia, 6−9
October 2001.
(25) Hirasaki, G. J.; Miller, C. A.; Pope, G. A. Surfactant Based
Enhanced Oil Recovery and Foam Mobility Control3rd Annual & Final
Technical Report; Report No. DE-FC26-03NT15406; Rice University
and U.S. Department of Energy: Houston, TX, USA, July 2006.
(26) Freer, E. M.; Svitova, T.; Radke, C. J. The Role of Interfacial
Rheology in Reservoir Mixed Wettability. J. Pet. Sci. Eng. 2003, 39,
137−158.
(27) Buckley, J. S. Effective Wettability of Minerals Exposed to Crude
Oil. Curr. Opin. Colloid Interface Sci. 2001, 6, 191−196.
(28) Morrow, N. R. Wettability and its Effect on Oil Recovery. J. Pet.
Technol. 1990, 42, 1476−1484.
(29) Buckley, J. S.; Liu, Y. Some Mechanisms of Crude Oil/Brine/
Solid Interactions. J. Pet. Sci. Eng. 1998, 20, 155−160.
(30) Hassenkam, T.; Pedersen, C. S.; Dalby, K.; Austad, T.; Stipp,
S. L. S. Pore Scale Observation of Low Salinity Effects on Outcrop and
Oil Reservoir Sandstone. Colloids Surf., A 2011, 390, 179−188.
(31) Moritis, G. EOR Continues to Unlock Oil Resources-Report on
Enhanced Oil Recovery. Oil Gas J., 12 April 2004a.
(32) Levine, S.; Sigmon, R.; Douglas, S. Yates FieldSuper Giant of
the Permian Basin. Houston Geol. Soc. Bull. 2002, 45 (3), 39−45.
(33) Moritis, G. Report on Enhanced Oil Recovery. Oil Gas J., 15
April 2000.

9904 dx.doi.org/10.1021/ie300269c | Ind. Eng. Chem. Res. 2012, 51, 9894−9905

Industrial & Engineering Chemistry Research Article

(34) Moritis, G. Report on Enhanced Oil Recovery. Oil Gas J., 15 Cloth Studied by In-Situ UV Spectroscopy. J. Hazard. Mater. 2007,
April 2002. 148, 75−82.
(35) Allan, J.; Qing Sun, S. Controls on Recovery Factor in Fractured (57) Wayman, C. H. Surfactant Sorption on Heterionic Clay
Reservoirs: Lessons Learned From 100 Fractured Fields. SPE 84590, Minerals. Intern. Clay Conf., Stockholm 1963, 1, 329−350.
SPE Annual Technical Conference and Exhibition, Denver, USA, 5−8 (58) Scamehorn, J. F. Equilibrium Adsorption of Surfactants on
October 2003. Mineral Oxide Surfaces from Aqueous Solutions. Ph.D. Dissertation,
(36) Schramm, L. L. Surfactants: Fundamentals and Applications in the University of Texas at Austin, 1980.
Petroleum Industry; United Kingdom, 2000. (59) Trogus, F. J.; Schechter, R. S.; Wade, W. H. A New
(37) Kwok, W.; Hayes, R. E.; Nasr-El-Din, H. A. Modeling Dynamic Interpretation of Adsorption Maxima and Minima. J. Colloid Interface
Adsorption of an Anionic Surfactant on Berea Sandstone with Radial Sci. 1979, 70 (2), 293−305.
Flow. Chem. Eng. Sci. 1995, 50, 769−783. (60) Gogoi, S. B. Adsorption of Non-Petroleum Base Surfactant on
(38) Curbelo, F. D. S.; Santanna, V. C.; Barros Neto, E. L.; Dutra, Reservoir Rocks. Curr. Sci. 2009, 97, 1059−1063.
T. V., Jr.; Dantas, T. N. C.; Dantas Neto, A. A.; Garnica, A. I. C. (61) Kjellim, M.; Johansson, I. Surfactants from Renewable Resources;
Adsorption of Nonionic Surfactants in Sandstones. Colloids Surf., A John Wiley & Sons, Ltd. Publication: 2010; p 242.
2007, 293, 1−4. (62) Hostettmann, K.; Marston, A. Saponins; Cambridge University
(39) Sheng, J. J. Modern Chemical Enhanced Oil Recovery: Theory Press: New York, 1995.
and Practice. Elsevier Inc.: 2011; ISBN: 978-1-85617-745-0. (63) Guglu-Ustundag, O.; Mazza, G. Saponins: Properties,
(40) Ottewill, R. H.; Tadros, T. F. Introduction to Surfactants; Applications and Processing. Crit. Rev. Food Sci. Nutr. 2007, 47,
Academic Press: London, 1984; pp 1−18. 231−258.
(41) Prevot, A. B.; Gulmini, M.; Zelano, V.; Pramauro, E. Microwave- (64) Stanimirova, R.; K. Marinova, S.; Tcholakova, N. D. Surface
Rheology of Saponin Adsorption Layers. Langmuir 2011, 27 (20),
Assisted Extraction of Polycyclic Aromatic Hydrocarbons from Marine
12486−12498.
Sediments Using Nonionic Surfactant Solutions. Anal. Chem. 2001, 73,
(65) Langmuir, I. The Constitution and Fundamental Properties of
3790−3795.
Solids and Liquids: Part I. solids. J. Am. Chem. Soc. 1916, 38, 2221−
(42) Bezerra, M. A.; Arruda, M. A. Z.; Ferreira, S. L. C. Cloud Point
2295.
Extraction as a Procedure of Separation and Pre-Concentration for (66) Rosen, M. J. Surfactants and Interfacial Phenomena; John Wiley
Metal Determination Using Spectra-Analytical Techniques: A Review. & Sons, Inc.: 1989; pp 3363−3374.
Appl. Spectrosc. Rev. 2005, 40, 269−299. (67) Freundlich, H. M. F. Ü ber die adsorption in lösungen. Z. Phys.
(43) Prevot, A. B.; Gulmini, M.; Zelano, V.; Pramauro, E. Microwave- Chem. 1906, 57 (A), 385−470.
Assisted Extraction of Polycyclic Aromatic Hydrocarbons from Marine (68) Temkin, M.; Pyzhev, V. Recent Modifications to Langmuir
Sediments Using Nonionic Surfactant Solutions. Anal. Chem. 2001, 73, Isotherms. Acta Physiochim. USSR 1940, 12, 217−222.
3790−3795. (69) Ruthven, D. M. Principles of Adsorption and Adsorption Processes;
(44) Pelizzetti, E.; Pramauro, E. Analytical Applications of Organized Wiley Inter-science; New York, 1982.
Molecular Assemblies. Anal. Chim. Acta 1985, 169, 1−29. (70) Lagergren, S. Zur theorie der sogenannten adsorption gelöster
(45) Pino, V.; Ayala, J. H.; Afonso, A. M.; Gonzalez, V. stoffe, Kungliga Svenska Vetenskapsakademiens. Handlingar 1898,
Determination of Polycyclic Aromatic Hydrocarbons in Marine 24 (4), 1−39.
Sediments by High-Performance Liquid Chromatography after (71) Mckay, G.; Ho, Y. S. Pseudo-Second Order Model for Sorption
Microwave-Assisted Extraction with Micellar Media. J. Chromatogr., Processes. Process Biochem. 1999, 34, 451−465.
A 2000, 869, 515−522. (72) Low, M. J. D. Kinetics of Chemisorptions of Gases on Solids.
(46) Pino, V.; Ayala, J. H.; Afonso, A. M.; Gonzalez, V. Cloud-point Chem. Rev. 1960, 60, 267−317.
Pre-concentration and HPLC Determination of Polycyclic Aromatic (73) Moritis, G. Worldwide EOR Survey. Oil Gas J. 2008, 106, 41−
Hydrocarbons in Marine Sediments. Anal. Bioanal. Chem. 2001, 371, 42, 44−59.
526−531.
(47) Hinze, W. L.; Singh, H. N.; Fu, Z.; Williams, R. W.;
Kippenberger, D. J.; Morris, M. D.; Sadek, F. S. Chemical Analysis of
Polycyclic Aromatic Compounds; Wiley: New York, 1989; p 151.
(48) Yeom, I. T.; Ghosh, M. M.; Cox, C. D.; Robinson, K. G.
Micellar Solubilization of Polynuclear Aromatic Hydrocarbons in Coal
Tar-Contaminated Soils. Soils Environ. Sci. Technol. 1995, 29, 3015−
3021.
(49) Leja, J. Surface Chemistry of Froth Flotation; Plenum: New York,
1982; Vol. 1.
(50) Stumm, W. Aquatic Chemistry; Wiley: New York, 1970; Vol. 2,
Chapter 3.
(51) Meader, A. C. Adsorption in the Detergent Process. Ind. Eng.
Chem., July 1952, pp 1636−1648.
(52) Gaudin, A. M.; Fuerstenau, D. W. Quartz Flotation with
Cationic Collectors. Trans. AIME 1955, 202, 958−962.
(53) Somasundaran, P.; Fuerstenau, D. W. Mechanisms of Alkyl
Sulfonate Adsorption at the Alumina-Water Interface. J. Phys. Chem.
1966, 70, 90−96.
(54) Paria, S.; Khilar, K. C. A Review on Experimental Studies of
Surfactant Adsorption at the Hydrophilic Solid-Water Interface. Adv.
Colloid Interface Sci. 2004, 110, 75−95.
(55) Zhang, R.; Somasundaran, P. Advances in Adsorption of
Surfactant and their Mixtures at Solid/Solution Interfaces. Adv. Colloid
Interface Sci. 2006, 123−126, 213−229.
(56) Ayranci, E.; Duman, O. Removal of Anionic Surfactants from
Aqueous Solutions by Adsorption onto High Area Activated Carbon

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