SPE-179797-MS

Laboratory Investigation of Polymeric Surfactants for EOR in High Salinity

and High Temperature Reservoir
Lijuan Guo, Ming Han, Alhasan Fuseni, and Abdulkareem AlSofi, Saudi Aramco

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE EOR Conference at Oil and Gas West Asia held in Muscat, Oman, 2123 March 2016.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Great attention has been paid recently to polymeric surfactants due to their structure. The incorporation
of polymer and surfactant properties in one macromolecule offers significant advantages for chemical
flooding. Aiming at high salinity and high temperature reservoirs, several polymeric surfactants were
investigated for their potential in improving oil recovery. Experimental results demonstrated polymeric
surfactants good compatibility with field brines (both injection and produced brines). The interfacial
tension (IFT) can be reduced by one order of magnitude compared to regular polymer solutions that have
no surface activity. The emulsification can be significantly increased, too. The viscosity of the polymeric
surfactants is much higher than regular surfactant solutions. With these unique properties, polymeric
surfactants are considered a potential alternative to traditional surfactant-polymer formulations for
chemical flooding in high salinity and high temperature reservoirs.

Introduction
In the last decades, various researchers have investigated the application and development of chemical
EOR processes for high temperature and high salinity reservoirs (Al-Hashim et al. 1996; Zubari and
Sivakumar 2003; Manrique et al. 2007; Bortolotti et al. 2009; Chen et al. 2012; Levitt et al. 2012; Azad
et al. 2014). Those processes included polymer flooding, alkaline-surfactant-polymer flooding, and
surfactant-polymer flooding. Surfactant-polymer flooding is of particular interest in high salinity condi-
tions due to formulations compatibility with field brines. Thus, surfactant-polymer flooding allows the
attainment of the synergetic effect of low interfacial tension and mobility control with minimal side effects
(primarily the elimination of possible scaling due to Alkaline addition). The works of Ghosh et al. (2013),
Adeniyi et al. (2015), and Quadri et al. (2015) are among recent efforts to develop appropriate surfactants
and polymers for EOR application in high salinity and high temperature conditions. Recent efforts have
also focused on understanding the associated mechanisms and phenomena in order to enlarge the window
of surfactant-polymer application especially toward high salinity and high temperature carbonates (Han et
al. 2011; AlSofi et al. 2012; Han et al. 2014; Wu et al. 2015). Despite the harsh salinity and temperature
conditions, candidate chemicals have been found which can promote a decrease in mobility ratio and an
increase in the capillary number while maintaining an adequate compatibility with field brines. The ability
2 SPE-179797-MS

of surfactant-polymer formulation to realize significant tertiary oil recovery incremental has been
demonstrated (Han et al. 2013).
Studies of polymeric surfactants started in the 1980s (Akstinat et al. 1980; Chen et al. 1981). In recent
years, efforts to combine polymers and surfactants desirable effects on oil displacement under one
macromolecule have received some attention (Paz Bez et al. 2000; Elraies et al. 2012; Voronov et al.
2014). Polymeric surfactants, a single chemical component that can achieve the combined effects of
interfacial tension (IFT) reduction and mobility control, represents a promising alternative to traditional
surfactant-polymer formulations. Nevertheless, due to their high molecular weight and the associated
macromolecular entanglements, polymeric surfactants are considered weak reducers of interfacial tension
compared to low-molecular-weight surfactants (Tadros, 2009). While surfactant flooding requires a
reduction of oil-water IFT to an ultralow level (103 mN/m), polymeric surfactant solutions were
reported to attain a moderate reduction in IFT to values in the order of ~101 mN/m (Co and Tang, 2015).
Sun et al. (1997) reported that HEC/MMA/NPEO4A active tercopolymers showed low equilibrium IFT
with a light oil. Cao et al. (2002) identified a family of polymeric surfactants for enhanced oil recovery
based on carboxymethylcellulose. Babu et al. (2015) studied interfacial tension reduction and wettability
alteration of PMES (polymeric surfactants that are polymerized from acrylamide and sodium methyl ester
sulfonate). At concentrations of 5000 ppm, PMES were reported to reduce IFTs, with Ahmedabad crude
oil, to 102 mN/m.
Accordingly, polymeric surfactants may offer adequate reductions in IFT along higher viscosities
hence both microscopic and macroscopic sweep improvement. In addition, polymeric surfactants are more
effective in emulsion stabilization due to their adsorption at the oil/water or water/oil interfaces; hence
counteracting flocculation, coalescence and Ostwald ripening (Tadros, 2009). In this work, we investigate
the potential of several polymeric surfactants for EOR application at harsh temperature and salinity
conditions.
Experimental Section
Materials
Five polymeric surfactants were tested. Polymeric surfactants HDPI, HDP-85, HDBH and HDQ were
obtained from different chemical manufacturers, with solid contents of 82.92, 84.6, 86.85, and 85.75%
respectively. Psurf-III (with a solid content of 86.91%) was prepared in-house. Other salts (NaCl,
CaCl2.2H2O MgCl2.6H2O, NaHCO3, Na2SO3) (analytical grade) were obtained from Sigma company.
Simulated field brines were prepared according to compositional analyses listed in Table 1.

Table 1Components of brines used

Component (g/L)

Brine NaCl CaCl2.2H2O MgCl2.6H2O Na2SO4 NaHCO3

Injection water 41.041 2.3843 17.645 6.3432 0.1652

Produced water 56.6464 29.814 8.7974 0.5678 0.2120

Compatibility
Polymeric surfactants solutions were prepared with the different field brines (refer to Table 1) at a
concentration of 3000 mg/L in 30-ml sealed tubes. Their compatibility with the brines was observed at
95C over a period of 10 days. The bottles were visually inspected. The compatibility codes used in
recording observations were: A: Clear solution; B: light hazy solution; C: Hazy solution; D: Precipitation
(Han, et al. 2013).
SPE-179797-MS 3

Surface Tension
Surface tension was measured using the plate method by DCAT 21 (Dataphysics, Germany). Each
surface tension value was evaluated as the average of at least three replicate measurements at 25C. The
critical micelle concentration (CMC) was obtained from the break point of the curve of surface tension
versus concentration.
Interfacial Tension
The spinning drop interfacial tensiometer SVT20N (Dataphysics, Germany) was used. Interfacial
tensions of polymeric surfactant solutions with Arabian crude oil were measured at a speed of 5000 rpm
and a temperature of 90C. In this experiment, the dimension of an oil droplet centrifuged within a
surrounding aqueous polymeric surfactant solution was measured and used to calculate the IFT.
Rheology
The apparent viscosities of polymeric surfactant solutions were measured using a Hybrid rheometer.
Fluid samples were prepared at different concentrations between 500 and 3000 mg/L. A shear rate of 6.81
s1 was chosen as a representative condition of flow within a reservoir.
Results
Compatibility
Compatibility issues between injection chemicals and various field brines are critical due to possible
blockage and low injectivity issues. Prior to the application of new chemical classes in oil production
operations, their compatibility with field brines must be confirmed. Polymer solutions used in EOR
processes are normally prepared in field brines without substantial treatment; many commercial polymers
exhibit poor solubility or even lose their thickening abilities in brines with high salt concentrations.
Accordingly, solutions of the five polymeric surfactants (HDQ, HDBH, HDPI, HDP-85 and Psurf-III)
were prepared in the different field brines, put in the oven at 95C and observed over 24 hours. As shown
in the Table 2, all polymeric surfactants showed good compatibility with injection water. The solutions
stayed clear after 24 hours at 95C. However, only three out of the five polymeric surfactants HDQ,
Psurf-III and HDP-85 exhibited excellent compatibility with the high salinity produced water. HDBH
exhibited a slightly hazy appearance in produced water that is still acceptable from a compatibility
standpoint, while HDPI exhibited a more hazy appearance indicating possible high concentrations of
suspended solids and potential injectivity issues.

Table 2Compatibility of 0.2 wt% polymeric surfactants at 95C

HDQ HDBH HDPI Psurf-III HDP-85

Injection water A A A A A
Produced water A B C A A

Surface Tension
Fig. 1 plots surface tension () versus concentration for aqueous solutions of the polymeric surfactants
(HDQ, HDBH, HDPI, HDP-85, Psurf-III). HDBH didnt show any surface activity. Surface tensions of
HDBH solutions were similar to the value of distilled water (~ 72 mN/m). Psurf-III reduced the surface
tension only slightly from 72 to 66 mN/m. HDP-85 showed moderate surface activity reducing the surface
tension to 50 mN/m. For those three polymeric surfactants, CMCs cannot be determined. The remaining
two polymeric surfactants (HDQ and HDPI) exhibited higher surface activities and a clearly low CMC.
Both HDQ and HDPI reduced surface tension to ~ 33 mN/m and exhibited CMCs of 260 and 300 mg/L,
respectively.
4 SPE-179797-MS

Figure 1Surface tension plotted as a function of the concentration for polymeric surfactants

Interfacial Tension
Obviously, conventional EOR polymers do not exert much influence on the interfacial tension. Actually,
a slight increase of the interfacial tension is sometimes observed. IFTs between Arabian crude oil and
varying concentrations of the polymeric surfactants are shown in Fig. 2. With two polymeric surfactants
(HDBH and HDP-85), IFTs were reduced only slightly. With concentrations up to 3000 mg/L, IFTs
remained at the same order of magnitude of that observed with field brines. The remaining three polymeric
surfactants (HDQ, HDPI and Psurf-III) showed better interfacial activity with Arabian crude oil. IFTs
were lowered to values between 2 and 7 mN/m (i.e. a one order of magnitude reduction). To the exception
of Psurf-III results, IFT behavior corresponded well with surface tension observations (refer to Fig. 1). In
general, the results while proving polymeric surfactants capability of achieving a bilateral viscosifying and
IFT reduction effects, none of the tested polymeric surfactants achieved ideal IFT reductions (i.e. in the
orders of 101 ~ 102 mN/m). Therefore, and at least for conditions of high temperature and high salinity,
there is a need to developed improved polymeric surfactants.

Figure 2Interfacial tension of polymeric surfactants as a function of concentration at 90C.

SPE-179797-MS 5

Rheology
Viscosity is another technical consideration for evaluating polymeric surfactants performance for EOR
applications. Concentrations required to achieve a target viscosity at reservoir conditions is an important
factor affecting the economics of a chemical flood. The apparent viscosities of the polymeric surfactants
were measured as a function of concentrations at 90 C (Fig. 3). Two of the polymeric surfactants
(Psurf-III and HDQ) exhibited low viscosities. The remaining three polymeric surfactants (HDP-85,
HDBH, and HDPI) exhibited sufficiently high viscosities with viscosities ranging from 7 and 16 mPa.s
at concentrations of 2000 mg/L. HDPI showed the highest viscosity. While its viscosities at low
concentrations (below 2000 mg/L) were comparable to those obtained with HDP-85 and HDPI, at higher
concentrations (above 2000 mg/L) HDPI exhibited significant viscosity.

Figure 3Viscosity of polymeric surfactants at 90C in injection water

Summary
We investigated the potential of several polymeric surfactants for EOR application at high salinity and
high temperature conditions. Five types of polymeric surfactants (HDQ, HDBH, HDPI, HDP-85, Psurf-
III) were evaluated in terms of compatibly with high salinity field brines, surface activity, IFT reduction,
and viscosity.
1. Four of the five polymeric surfactants (HDQ, HDBH, HDP-85, Psurf-III) were found compatible
with injection and produced brines containing TDS ranging from 67 and 96 kppm.
2. Two of the five higher polymeric surfactants (HDQ and HDPI) exhibited high surface activities
and a low CMC. Both HDQ and HDPI reduced surface tension to ~ 33 mN/m and exhibited CMCs
of 260 and 300 mg/L, respectively.
3. Three polymeric surfactants (HDQ, HDPI and Psurf-III) exhibited a one order of magnitude
reduction in interfacial tension with Arabian oil at high temperature and high salinity. IFTs were
reduced from 72 to values between 2 and 7 mN/m.
4. Three of the five polymeric surfactants (HDBH, HDP-85, HDPI) provided sufficient viscosifying
ability at high salinity and high temperature conditions.
While the results prove polymeric surfactants capability of achieving a bilateral viscosifying and IFT
reduction effects, there is a need to developed more surface active polymeric surfactants for conditions of
high temperature and high salinity. A polymeric surfactant that combines the advantages of both polymer
6 SPE-179797-MS

and surfactant properties to achieve improved oil recovery is a potential direction for future applications
of chemical flooding technology in carbonate reservoirs with harsh conditions.

Acknowledgments
The authors would like to thank the management of Saudi Aramco EXPEC Advanced Research Center
for granting permission to present this paper.

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