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Adsorption of nonionic surfactants in sandstones

Article  in  Colloids and Surfaces A Physicochemical and Engineering Aspects · February 2007

DOI: 10.1016/j.colsurfa.2006.06.038

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 Colloids and Surfaces A: Physicochem. Eng. Aspects 293 (2007) 1–4

Adsorption of nonionic surfactants in sandstones

Fabı́ola D.S. Curbelo a,∗ , Vanessa C. Santanna a , Eduardo L. Barros Neto a ,
Tarcı́lio Viana Dutra Jr. a , Tereza N. Castro Dantas b ,
Afonso A. Dantas Neto a , Alfredo I.C. Garnica c
a
Departamento de Engenharia Quı́mica, Universidade Federal do Rio Grande do Norte, Campus Universitário, 59072-970 Natal (RN), Brazil
b Faculdade Natalense para o Desenvolvimento do Rio Grande do Norte, Tirol, 59014-540 Natal (RN), Brazil
c Departamento de Tecnologia Quı́mica e de Alimentos, Universidade Federal da Paraı́ba, Cidade Universitária, Campus I, João Pessoa (PB), Brazil

Received 28 April 2005; received in revised form 16 February 2006; accepted 28 June 2006
Available online 3 July 2006

Abstract
Adsorption of surfactants from aqueous solutions in porous media is very important in enhanced oil recovery (EOR) of oil reservoirs because
surfactant loss due to adsorption on the reservoir rocks impairs the effectiveness of the chemical slurry injected to reduce the oil–water interfacial
tension (IFT) and renders the process economically unfeasible. In this paper, two nonionic surfactants with different ethoxylation degrees were
studied, ENP95 with ethoxylation degree 9.5 and ENP150 with ethoxylation degree 15. The experiments were carried out in a surfactant flooding
apparatus, with a pressure gradient of 30 psi. The concentration of the injected solutions were 30% above the critical micelle concentration, to
assure micelle formation. The results from the flow experiments of surfactant solutions in porous media showed that the adsorption extent was
higher for ENP95 than for ENP150 because the previous surfactant has a smaller ethoxylation degree, that is, a smaller polar part.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Nonionic surfactant; Adsorption; EOR; Reservoir rock; Surface tension

1. Introduction retain a large amount of hydrocarbons after their natural energy

Oil is the most used nonrenewable source of energy in the
world and this has induced the study of new processes for
exploration and production of oil reservoirs. Oil and service
companies have been investing heavily in increasing the recov-
ery and productivity of old reservoirs, mainly in processes of
enhanced oil recovery (EOR).
Considering only conventional processes, it is believed that
just about 30% of the original oil in place is recoverable. The
use of more advanced methods come to attend the demand for
energy when the reserves based on conventional methods start
to decline. Therefore, the target for EOR processes corresponds
to 70% of the original oil in place, which will remain in the
reservoirs after conventional production.
The enhanced recovery methods are processes that seek
an additional recovery of the reservoirs, which have not been
exploited in a fully efficient manner. As a consequence, they
∗ Corresponding author. Tel.: +55 84 3215 3827; fax: +55 84 3215 3827.
E-mail address: fabiola@eq.ufrn.br (F.D.S. Curbelo).
is depleted.
These methods have been developed with the objective of
allowing for a larger production than that provided just by the
natural energy of the reservoir and consist basically on the flood-
ing of fluids aiming to move the oil out of the pores of the rock.
Thus, the injected or displacing fluid should push the oil, known
as displaced fluid, out of the rock and, at the same time, should
occupy the space left.
Among the methods used in the advanced recovery of
petroleum are the chemical methods, which comprise surfactant
flooding. The surfactant flooding may be used with the pur-
pose of reducing the interfacial tensions between oil and water,
increasing the displacement efficiency [1,2].
According to Agharazi-Dormani et al. [3], the surfactant
flooding is considered to be a method of additional recovery
of oil from partially depleted reservoirs. The mechanism of
action of the surfactant in a porous medium, partially filled with
oil and brine, is still not very well understood. In wet water
systems, for example, the oil in place, after water flooding, con-
sists mainly of isolated oil drops within the pores. In order to
mobilize the residual oil trapped by capillary forces in oil reser-

0927-7757/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.06.038
2 F.D.S. Curbelo et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 293 (2007) 1–4

voirs, many enhanced oil recovery methods rely on reducing

the oil–water interfacial tension (IFT) to extremely low values,
often to 10−2 dyn/cm or less [4]. Therefore, it is important to
keep low interfacial tensions for large periods of time.
The complexity of the system increases with the effects of
other parameters, such as: heterogeneity of the rock, interaction
of the surfactants with reservoir fluids, coalescence of the oil
drops and surfactant adsorption. The surfactant flooding process,
however, encounters problems due to loss of high cost surfactant
in the form of adsorption and retention in the porous media.
The loss of surfactant from the main chemical slurry during
Fig. 1. Schematic of the core flood system for adsorption and oil recovery tests.
surfactant flooding is a major determinant in process perfor-
mance and economy. It has been shown that the nature of the
adsorption isotherm depends to a large extent on the type of
surfactant used, the morphological and mineralogical charac-
teristics of the rock, the type of electrolytes present in solution
and, also, of cosurfactants and alcohols. The adsorption of sur-
factants can be affected by the charge on the rock surface and
fluid interfaces [5,6].
In this work, the understanding of the mechanism whereby
nonionic surfactants adsorb onto rocks has been investigated,
with particular attention to the effect of the surfactants’ ethoxy-
lation degree.

2. Experimental/materials

The chemicals used to prepare the surfactant solutions were

two commercial nonionic surfactants, namely nonyl phenol
Fig. 2. Apparatus for the surfactant flooding experiments.
oxyethylenes, both supplied by Oxiteno (Brazil). The surfac-
tants, ENP95 and ENP150, have ethoxylation degrees of 9.5
and 15.0, respectively. The HLB of ENP95 is 13.0 and that of at different concentrations, with a Surface Tensiometer, Sensa-
ENP150 is 15.0. KCl used in the brine (purchased from Isofar- Dyne Instrument Div. The surfactant was diluted in KCl brine
Brazil) has 99.99% purity. The solid adsorbent (core) was a (2 wt.%).
sample of Açu sandstone, Brazil. All chemicals were used as
received. 5. Procedures/adsorption tests

3. Preparation of cores The adsorption experiments were conducted at room temper-

The cores used were coated with resin and had the follow-
ing dimensions: 3.8 cm diameter, 8.7 cm length and an average
porosity of 24%. Before coating with resin, all cores were roasted
at 700 ◦ C during 18 h, to remove humidity and increase per-
meability. Two distributors were attached to the edges of the
core plug, featuring two ends connected to the injection and
production lines. The assembly formed by the core plug, two
distributors and two ends was fixed together with a coating of
resin as show in Fig. 1.
4. Properties of surfactant solutions
A specific property of surfactant solutions is the concentra-
tion (CMC) above which the first aggregates of monomers or
micelles are formed [7]. Above this concentration, the surfac-
tant solutions display particular solubilizing properties used in
many applications [8,9].
The CMC of the solutions were determined at 26 ◦ C by a
conventional method, from surface tension measurements taken
ature with a known concentration of surfactant in the core plug,
using the surfactant flooding apparatus showed in Fig. 2. For
each surfactant, the flooding was carried out with a concentration
30% above the CMC, assuring the formation of micelle solu-
tions. The flooding experiments were performed in two steps:
First step: surfactant flooding in the core at a constant pressure
of 30 psi.
Second step: collection of samples in different periods of time,
with the purpose of determining the surfactant loss in the rock.
The surfactant solution was continuously injected into the core
until the surfactant concentration in the effluent approached
that of the surfactant solution injected. The surfactant concen-
trations in the effluent were determined by absorbance, using
a UV–visible Spectrophotometer.
6. Results and discussion
The variation of surface tension with surfactant concentra-
tion, for ENP95 and ENP150, is shown in Figs. 3 and 4, respec-
 F.D.S. Curbelo et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 293 (2007) 1–4
Fig. 3. Determination of the CMC for surfactant ENP95.
tively. The break in the curves corresponds to the CMC. It can
be seen that ENP150 has a higher CMC than ENP95, because
it has a larger polar chain, i.e., higher ethoxylation degree and,
consequently, higher solubility in the aqueous phase. Therefore,
a higher concentration of ENP150 than ENP95 is required in
order to form micelles [10].
For nonionic surfactants, polyoxyethylene (POE) polar
chains have a typical size well above the alkyl chain dimen-
sion and fill an extended polar corona. An average volume of
interaction per polar chain must replace the average surface per
ionic head. During the transfer of a POE chain inside this polar
corona, two important contributions should be considered: steric
repulsion and stretching deformation [11].
From the curves used to obtain the CMC, the area of the
surfactant polar chain can be calculated from the Gibbs isotherm,
according to the equations bellow:
1
S = 1.66 × 10−4 ×
Γ hydroxyl groups on the surface [17]. This corresponds to region
 
1 d(lnC)
= −RT ×
Γ dg
where S is the area of the surfactant polar chain, in Å2 ; Γ the
excess surface concentration, in mol/m2 ; γ the surface tension,
in mN/m; RT given in J/mol and d(ln C)/dy is the slope of the
curve before the CMC is reached.
The total area (St ) filled with surfactants in the rock was
determined by Eq. (3), considering monolayer adsorption:
St = n × S
where St is given in Å2 ; n the number of moles of surfactant
injected and S is the area of the surfactant polar chain, in Å2 .
Fig. 4. Determination of the CMC for surfactant ENP150.
3
Fig. 5. Normalized ENP95 concentration as a function of the pore volume of
fluid produced in the equilibrium adsorption test.
The structure of the adsorption layer of nonionic surfactants
on surfaces was examined by using fluorescence decay tech-
niques [12,13], made possible due to the existence of hydropho-
bic domains on the surface. Indeed, adsorption occurs by forma-
tion of surfactant aggregates on the surfaces. The size of these
aggregates was measured and found to depend on the structure
of the surfactant and on the coverage of the surface.
The thermodynamic behavior of the system has been studied
by microcalorimetric techniques [14–16]. All of these works
show that the adsorption mechanism of nonionic surfactant is
reversible and that a plateau in the isotherm is reached just after
the critical micelle concentration, as shown in Figs. 5 and 6.
This corresponds to the stabilization of the chemical potential
of the monomer in equilibrium with the adsorbed phase. Non-
ionic surfactant monomers adsorb as individual ions through
(1) hydrogen bonding between the polyoxyethylene chain and the
I in Figs. 5 and 6, without any interaction among the monomers.
(2) The mechanism that governs the adsorption in region II
(Figs. 5 and 6) is due to the association of adsorbed surfac-
tants inside the pores of the rock at the liquid–solid interface.
This association is attributed to the tail–tail interactions of sur-
factants, which are the same hydrophobic interactions by which
micelles are formed. The break point between regions I and II
may be taken as an estimate of the critical surface micellization
concentration, i.e., the concentration in which the first aggregate
is formed at the surface and a monolayer begins to form.
(3)
Fig. 6. Normalized ENP150 concentration as a function of the pore volume of
fluid produced in the equilibrium adsorption test.
4 F.D.S. Curbelo et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 293 (2007) 1–4

Table 1
Surfactant loss in the rock
Surfactant Concentration Molecular Surfactant loss Area filled
of solution weight (mg surfactant/g with surfactant
injected (g/mol) rock) in rock (m2 )
(mol/l)

ENP95 0.0023 640 13.15 651

ENP150 0.0053 882 8.47 841

7. Conclusion

The results of the injection tests suggested for the influence of

Fig. 7. Multilayer adsorption.
In region III, the decrease in slope is ascribed to inversion of
charge at the surface due to adsorbed surfactants ions, whereby
a bilayer is formed, in the beginning of region II, and prolongs
to region III. However, this occurs at a different rate due to a
smaller surface energy in region III. This region, also regarded
as the adsorption landing, usually begins near the CMC and is
characterized by little or almost no increase in the adsorption
with the increase in surfactant concentration. In this region the
predominance of micelles occurs.
Figs. 5 and 6 show the normalized surfactant concentration
in the effluent samples as a function of the pore volume (PV) of
fluid produced. The normalized surfactant concentration is the
ratio between the surfactant concentration in the effluent samples
and the original concentration. In Figs. 5 and 6, the normalized
concentration reached 0.96 at about 74 pore volume produced,
for ENP95, and 0.88 at 16 PV produced, for ENP150, remaining
constant for another 6 and 9 PV, respectively. It was believed that
the equilibrium monolayer adsorption had been reached and that
the continued loss of surfactant after 75 PV for ENP95 and 16
PV for ENP150 was the result of multilayer adsorption (Fig. 7).
The test was stopped at 80 PV for ENP95 and 25 PV for ENP150.
The amount of surfactant adsorbed was obtained by subtract-
ing the amount of surfactant remaining in the effluent samples
from that of surfactant injected. The surfactant adsorption in
the core under the test conditions was found to be 13.15 mg
ENP95/g rock and 8.47 mg ENP150/g rock (Table 1). According
to Austad et al. [18], there is a direct dependence of the extent of
surfactant adsorption with the ethoxylation degree. The adsorp-
tion decreases with the increase of the ethoxylation degree. It
has been verified that ENP95 has a higher adsorption loss than
ENP150, due to the surface area of the polar part of ENP95
(27.7 Å2 ) being lower than that of ENP150 (77.5 Å2 ). In other
words, the amount of ENP95 required to cover the internal sur-
face of the rock is larger than that of ENP150.
the ethoxylation degree on the adsorption of ENP95 and ENP150
in the rock. ENP95 presents a higher adsorption extent than
ENP150 due its ethoxylation degree being lower (9.5) than that
of ENP150 (15.0). This is an important factor in enhanced oil
recovery, because a more adsorbed surfactant has stronger inter-
actions with the rock than with the oil, hence allowing for a better
oil recovery factor. However, it is necessary to carry out an eco-
nomic analysis for an improved, final surfactant selection. It is
believed that the surfactant adsorption forms multilayer and the
polar part area is important to determine the amount of surfac-
tant lost in the rock after adsorption. This demonstrates that the
equilibrium between isolated and aggregated surfactants inside
the adsorption layer can be considered.
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