Journal of Petroleum Science and Engineering 190 (2020) 107106
Available online 20 February 2020
0920-4105/© 2020 Elsevier B.V. All rights reserved.
Partitioning of non-ionic surfactants between CO
2
and brine
Albert Barrabino
a, *
, Torleif Holt
a
, Erik Lindeberg
b
a
Petroleum Department, SINTEF Industry, NO-7465 Trondheim, Norway
b
CO
2
Technology, NO-7030 Trondheim, Norway
A R T I C L E INFO
Keywords:
Mobility control of CO
2
Foam
Enhanced oil recovery
Aquifer storage
Surfactant partitioning
ABSTRACT
The partitioning of non-ionic surfactants in a CO
2
/synthetic brine system was studied for a selection of surfac-
tants at reservoir conditions for CO
2
enhanced oil recovery and aquifer storage. Alkyl and alkylphenol ethox-
ylates with different degrees of branching in their hydrophobic moiety were chosen. Generally, higher
temperature and pressure promoted increased solubility in CO
2
. Branching of the hydrophobic moiety tends to
favour CO
2
solubility (higher partition coeffcient). Highly branched moieties were found to hinder solubility
probably due to a decrease of their conformational entropy. The addition of an aromatic ring connecting the
ethoxylate moiety and the hydrophobic moiety seemed to have an adverse effect at lower temperatures. For two
surfactants, the effect of concentration on partitioning was also studied. The partition coeffcient decreased for
increasing concentrations until a plateau was reached above the corresponding surfactant critical micelle con-
centration (CMC). This may indicate micelle formation both in the CO
2
and in the aqueous phase.
1. Introduction
CO
2
is becoming a prominent solvent for different applications. Its
foams and emulsions with water are of interest due to its potential for
various applications (Johnston and Rocha, 2009). Two large scale ap-
plications are enhanced oil recovery (EOR) and subsurface sequestra-
tion. However, these methods encounter various technical challenges.
The relatively low density and low viscosity of CO
2
can lead to gravity
segregation and viscous fngering giving early CO
2
breakthrough and
poor volumetric sweep effciency. The result of this may be low oil re-
covery (in EOR) and reduced utilisation of the storage capacity (in CO
2
sequestration) (Solbakken et al., 2013; Tsau; Grigg, 1997).
Early breakthrough can be counteracted by decreasing the mobility
of the CO
2
. This can be achieved by increasing the viscosity using ad-
ditives to the CO
2
or by dispersing the CO
2
into another fuid (brine). It is
not easy to increase CO
2
viscosity. The additives (direct thickeners) must
solubilize in CO
2
and provide self-interactions that can give the desired
viscosity enhancement. During decades efforts have been made trying to
fnd suitable additives (Enick et al., 2012). However, the best CO
2
ad-
ditives found are not practical due to their high costs and detrimental
environmental impact.
The second method for decreasing CO
2
mobility is through creating
dispersed systems. CO
2
-in-brine dispersions (hereafter called foams)
may have high apparent viscosities depending on the surfactant used.
Foams can also be formed and stabilized by nanoparticles. Even though
nanoparticles adsorb more strongly at interfaces, larger energy input is
required to form foam. This criterion is not met at reservoir fow ve-
locities which typically do not exceed few feet/day (except close to in-
jection wells) (Binks, 2002; Espinosa et al., 2010; San et al., 2016; Yu
et al., 2012).
Surfactant-stabilized foam is so far the most promising CO
2
mobility
reduction method. However, this also faces several challenges. One
potential problem is the presence of oil which may destabilize foam
through different mechanisms including spreading and entering phe-
nomena (Manlowe and Radke, 1990; Schramm and Novosad, 1990;
Wasan et al., 1994). However, the sensitivity of foam to oil may have
both advantageous and disadvantageous consequences. During miscible
CO
2
fooding, the foam may be more stable in pores where the oil has
already been displaced helping to divert CO
2
within the reservoir to
places where the oil is not displaced. There, the lamella will collapse and
release CO
2
in the CO
2
/oil front. On the other hand, if the stability of the
foam is sensitive to minute oil residues it can have an adverse impact on
foam propagation (Vassenden et al., 2000).
Another challenge to face during surfactant-stabilized foam fooding
is surfactant depletion due to adsorption on the pore walls of the
reservoir rock. The adsorption will be determined by the pore wall
mineralogy and charge, type of surfactant, pH, temperature, ionic
strength, electrolyte concentration (Bera et al., 2013; Curbelo et al.,
* Corresponding author.
E-mail address: albert.barrabino@sintef.no (A. Barrabino).
Contents lists available at ScienceDirect
Journal of Petroleum Science and Engineering
journal homepage: http://www.elsevier.com/locate/petrol
https://doi.org/10.1016/j.petrol.2020.107106
Received 1 November 2019; Received in revised form 28 January 2020; Accepted 18 February 2020