SPE 145039

Sustainable Surfactants in Enhanced Oil Recovery

Monika Santa, Cognis GmbH
*
, Gabriela Alvarez-Jrgenson, BASF SE, Stefan Busch, Cognis GmbH*,
Paul Birnbrich, Cognis GmbH*, Christian Spindler, BASF SE, Gregor Brodt, BASF SE
Copyright 2011, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Enhanced Oil Recovery Conference held in Kuala Lumpur, Malaysia, 1921 July 2011.

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 of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.


Abstract
Alkyl polyglucosides (APGs) are recognised as sustainable surfactants based on natural raw materials. They exhibit a low
ecotoxicity profile and are therefore already used in different oil field applications. In this paper it is shown that APGs have
superior solubility properties in high salinity environments. The interfacial tension of crude/brine systems can be significantly
lowered even in high salinity brines. The performance of APGs can be improved by optimising the hydrophobic as well as
the hydrophilic part of the surfactant. In contrast to standard surfactants used in EOR applications the performance of APGs
is not reduced under elevated temperature or high salinity conditions. Their performance is not influenced by typical salinity
and temperature gradients as can occur in the reservoir. Moreover, microemulsions can be formed even under high salinity
and elevated temperature if APGs are used together with co-solvents.


Introduction

Enhanced Oil Recovery With Surfactants
Oil recovery is divided in three phases: primary, secondary and tertiary oil recovery. During the primary recovery the crude is
driven from the rock into the production well by natural reservoir pressure. Throughout the secondary oil recovery phase
water is injected into the reservoir. The injected water prevents the reservoir pressure from dropping; the crude is driven by
the water flood to the producer well. At the end of the secondary oil recovery phase capillary and viscous forces keep the
residual crude trapped in the reservoir rock. The ratio between these forces is described by the capillary number N
c
:

w o
w
c
IFT
v
N
/

=



where
w
is the viscosity of the displacing phase (water), is its velocity and IFT
o/w
the interfacial tension between the crude
oil and water.
It was shown by several researchers that an increase of the capillary number improves the mobilisation of additional oil
(Foster 1973; Lefevre du Prey 1973; Ehrlich et al. 1974; Melrose and Brandner 1974; Abrams 1975; MacDonald et al. 1979;
Oh and Slattery 1979). If the capillary number is modified by adding additional substances to the waterflood one refers to
tertiary or enhanced oil recovery (EOR). The capillary number can be enlarged in the most efficient way by reducing the
interfacial tension IFT
o/w
to ultra-low values. This is achieved by adding a tailor made surfactant system adapted to the
injection water, the nature of the crude oil and the reservoir conditions. At ultra-low IFT values microemulsions containing
water and oil are formed in the reservoir. Due to the ultra-low IFT speric oil drops trapped in rock pores are deformed by the
flood pressure. After being elongated they pass through the pore throats into the producer well.
During the last years research activities on surfactant-based EOR methods have increased significantly. Several surfactant
floods have already been applied in combination with alkaline and polymer in mature oil fields (Manrique, 2010).
While the use of surfactants in tertiary oil recovery is getting more and more accepted, environmental compatibility becomes
an important topic. Regulatory authorities increasingly demand that EOR chemicals are environmentally sound. Sustainable

*
Cognis GmbH is now part of BASF Group
2 SPE 145039
surfactants based on renewable raw materials, showing good biodegradability under aerobic conditions have therefore
become interesting candidates for EOR operations. Developing sustainable surfactants without compromising on surfactant
performance has become a key driver for the chemical industry. Indeed, latest developments show that environmental
friendlyness does not mean to compromise on superior product properties. We will demonstrate in this paper that sustainable
EOR surfactant systems based on alkyl polyglucosides can be applied in conditions of high salinity and elevated temperatures
where conventional surfactants often cannot be used anymore.

Alkyl Polyglucosides (APGs)


Fig. 1: Chemical structure of C
8
-APGs

Alkyl polyglucosides (APGs) are nonionic surfactants which are composed of an alcohol and a glucose based moiety (Fig. 1).
They are already widely used in the oil industry. They are applied in environmentally safe drilling fluids (Walker et al. 1995),
in well cleaning agents (Forgiarini et al. 2009), as foamers in heavy oil recovery (Wael et al. 2009) and for reducing
interfacial tension in surfactant-induced tertiary oil recovery processes (Balzer and Lueders 1988; Kahlweit et al. 1995).
APGs have a superior ecotoxicity profile. Evaluations utilising methods like eco-efficiency analysis, life-cycle inventory,
life-cycle assessment and carbon footprint prove the high sustainability potential of their use in EOR and other applications
(Hill et al. 1997). Some exemplary ecotoxicity results for a C
8/10
modified APG are given in table 1 and table 2. All data
show that APGs are easily biodegradable and not harmful to aqueous organisms.

Table 1: Biodegradation data for C8/10 APG (Hill et al. 1997), ultimate degradation screening tests.


Table 2: Ecotoxicity of C8/10 APG (Hill et al. 1997).


As already pointed out, superior EOR surfactant systems must be able to lower the IFT between the crude and connate water
to ultra-low values. Kutschmann et al. (1995) measured IFT values between water and three different model oils in the
presence of APG surfactants. Iglauer et al. (2009) and Kahlweit et al. (1995) determined the IFT in combination with linear
alcohols as co-solvents. They identified surfactant formulations allowing to reach ultra-low interfacial tensions in
brine/alkane or brine/xylene systems. Furthermore, Iglauer et al. (2009) showed that in comparison to other nonionic or
anionic surfactants currently used in EOR processes, APGs are tolerant to elevated salinities or high temperatures.
In the present study, we compare the properties of APGs with different alkyl chain lengths and different hydrophilic moieties
(table 3) using IFT measurements and phase studies. By carrying out experiments with crude oil, we evaluate whether the
studied APGs are promising candidates for surfactant flooding processes.



SPE 145039 3
Experimental

Materials
The APGs used in this study consist of a more hydrophilic (I) or a less hydrophilic (II) glucose moiety and alcohols with
chain lengths of C
8/10
, C
10
or C
12/14
respectively. They are categorised based on their HLB value (Griffin, 1949) which
describes the surfactants hydrophilicity/lipophilicity balance. A hydrophilic surfactant is described by a high HLB value.


Table 3: HLB values of substances tested (calculated according to Davies, 1957).

Decane and crude oil (25 API) were used as oil phases. In the phase behaviour studies discussed in this paper 1-octanol was
applied as a co-solvent. All concentrations are given in weight-percentages (%) or parts per million (ppm).

Solubility
Precipitation during flooding has to be avoided in order to guarantee the performance of the process. Therefore good
solubility of the surfactants at reservoir temperatures and salinities is essential. All solubility tests were performed in high
salinity brines and at elevated temperatures to simulate challenging reservoir conditions. The solubility of surfactants in brine
was determined with a total dissolved salinity of 180,000 ppm, composed by dissolution of 133g/l NaCl, 37.3 g/l CaCl
2
, and
8.3 g/l MgCl
2
in water. If no precipitate was formed within three days of storage at room temperature and 80C, the
surfactants were used for further investigation.

Determination of Interfacial Tension (IFT)
IFT measurements were performed using a Dataphysics SVT20 spinning-drop tensiometer (Filderstadt, Germany). In
addition to the 180,000 ppm brine described above, brines with 100,000 ppm and 50,000 ppm were prepared by dilution.
The surfactants were added to the brines in a concentration of 0.2 weight-%. The brines were brought in contact with the oil
phase and equilibrated for 20 minutes.
IFT values were measured during 10 minutes. An average IFT value was taken as result. Equilibration and measurements
were performed at 20C, 50C and 70C.

Phase Behaviour Studies
Microemulsion formation is a good indication whether a surfactant formulation can be used to mobilise additional oil
effectively. Therefore phase behaviour studies were performed to assess the potential of APGs as EOR surfactants at different
salinities and temperatures.
The APGs were dissolved in the 180,000 ppm TDS brine described above forming a 2.5 weight-% solution. 10 ml of oil were
added to 10 ml of the surfactant solution. Afterwards 2.5 weight-% of 1-octanol were put into the 20 ml oil/brine system,
resulting in an overall surfactant/co-solvent concentration of 3.7 weight-%. The samples were mixed. The formation of
microemulsion was studied by visual obwervation of the Windsor type III microemulsion phasesat 20C, 50C and 80C.


Results and Discussion

APG Properties Under High Salinity Conditions
Solubility. EOR surfactant formulations have to be soluble through the whole EOR process. Otherwise the operator would
risk loss of injectivity, loss of performance induced by precipitation of the surfactant in the payzone or even plugging of the
formation. More and more high salinity brines have to be used for injection, especially if fresh water is not available.
Unfortunately standard EOR surfactants have often limited solubility in high salinity conditions.
Therefore, solubility tests in brine with 180,000 ppm TDS containing beside Na
+
, 13,600 ppm Ca
2+
and 2,100 ppm Mg
2+
were
performed for several APG compounds at 80C. In contrast to many standard surfactants APGs having alkyl chain lengths of
14 or less carbon atoms formed clear, stable solutions. Their good solubility in brines is caused by the exceptionally strong
hydration of the hydrophilic glucose moieties in the molecule. A cloud point for APGs is therefore not observable at
surfactant concentration applied in EOR. However, for APGs with alkyl chains lengths exceeding 14 carbon atoms the
hydrophobic interactions between the surfactant molecules dominate. These APGs are insoluble as long as co-surfactants or
co-solvents are not added to the surfactant system. Therefore all further experiments were performed with soluble APGs
having C
12/14
or smaller alkylchains (table 3).


4 SPE 145039
Interfacial Tension. Surfactants having passed successfully the solubility tests were evaluated for their IFT reduction
potential. Decane and a light crude oil (API 25) were used as oil phase. A surfactant concentration of 0.2 % was chosen as it
is a common dosage in EOR applications. In Fig. 2, the IFT values are displayed as a function of the HLB value. It is shown
that low IFT values can be obtained by using APGs under high salinity conditions without any further additives.
With decane, the lowest IFT values were found with the more hydrophobic surfactants (lower HLB). At least an HLB of 11 is
needed to obtain optimum performance (0.15 mN/m). Reducing the HLB from 11 to even lower values does not result in a
further decrease of IFT.
As with any EOR surfactants the performance of APGs is dependent on the nature of the oil. For the investigated crude the
lowest interfacial tension of 0.01 mN/m was found at an HLB value of 11.7 (APG B). Surfactants with lower or higher HLB
values did not perform as well. So, in contrast to decane the best performance was not achieved by the most hydrophobic
surfactants. This can be explained by the complex composition of crude that contains other compounds beside parrafins.



Fig. 2: Interfacial tension vs. value of hydrophilic/lipophilic balance.

In order to better understand the good performance of APG B and its deviation from the overall tendency for the crude, IFT
values are plotted against alkyl chain length taking the nature of the different glucose head groups into consideration (Fig. 3).
Usually a minimum IFT value is found, if the interactions between the surfactant alkyl chains and the oil phase are balanced
by the interactions of the head group and the water phase. In these circumstances the surfactants are packed most densely on
the interface. We assume that this is the case for APG B if the investigated crude is used.
Changing the nature of the hydrophobic alkylchain or the hydrophilic head group of the surfactant influences the performance
of the surfactants. For surfactants A and B which contain both the stronger hydrophilic glucose moiety I, the IFT is changing
drastically with the alkyl chain length. A change from C
12/14
to C
8/10
results in an IFT increase by two orders of magnitude.
For APG D and C which include the less hydrophilic headgroup II, the effect of decreasing alkyl chain length on IFT is
significantly smaller: here the IFT is reduced by 40% only.
The general tendency that the use of a smaller hydrophobe results in higher IFT values can be understood if the interactions
between the surfactant, the oil phase and the water phase are taken into account. If the C
12/14
alkyl chain is replaced with the
significantly smaller hydrophobe C
8/10
the hydrophilic interactions between the aqueous phase and the surfactant dominate
and the IFT increases significantly.

SPE 145039 5


Fig. 3: Interfacial tension vs. alkyl chain length.

A similar behaviour is found if the alkyl chain is kept unchanged but the more hydrophilic head group I in APG B is
substituted by the glucose moiety II (APG D). In this case the surfactant becomes overall more hydrophobic. The surfactant
exhibits a lower tendency to migrate to the oil/water interface. The IFT increases.
Both effects make clear that not only changes in the alkyl chain but also variations of the head group structure play an
important role in optimising the performance of APG surfactants.

Influence of Salinity and Temperature Changes
The influence of changes in brine salinity and temperature on the IFT performance of the APG B system is shown in Figs. 4
and 5 respectively. In regard to temperature changes the behaviour of APGs differs significantly from other common
surfactants like e.g. alkylalkoxylates or petroleum sulfonates, currently used in EOR processes.
The solubility of alkylalkoxylates decreases often with increasing temperature. This is due to reduced intermolecular forces
between the surfactant and the surrounding water molecules. As soon as these interactions become too weak, the surfactant
becomes insoluble. With decreasing solubility the interfacial performance of the surfactants is drastically reduced.
Compared to alkylalkoxylates the interaction between water molecules and APGs is significantly stronger due to the
chemical structure of the glucose surfactant headgroup. The hydration of the glucose stays nearly unchanged with increasing
temperature. Therefore the IFT of the water/oil/surfactant system remains low as soon as a certain threshold value is
exceeded. This is exactly the behaviour observed with APG B. While between 20C and 50C the IFT decreases by
approximately 50 %, between 50C and 70C the IFT remains nearly unchanged.


6 SPE 145039


Fig. 4: Interfacial tensions of APG B at 180,000 ppm salinity and 20, 50, 70C.

The IFT was also determined at different salinities (Fig. 5). In the investigated salinity range the IFT remains nearly
unchanged when the brine salinity is increased from 50,000 ppm to 100,000 ppm TDS. This is an ideal behaviour for a
surfactant in EOR applications where salinity gradients are commonly encountered.
If the brine salinity is further increased to 180,000 ppm TDS, the IFT is reduced by a half (Fig. 5). Under these high salinity
conditions common surfactants like e.g. alkylbenzene sulfonates or soaps are not even soluble. These differences can be
explained by changes in surfactant hydration with increasing salinity and by the shielding effects caused by divalent ions
being present in the connate water in the reservoir.
From these measurements we conclude that the performance of APG B will not be strongly influenced by fluctuations over a
broad temperature and salinity range in the reservoir.



Fig. 5: Interfacial tensions of APG B at 50,000 ppm, 100,000 ppm and 180,000 ppm salinity.



SPE 145039 7
Microemulsion Formation With APGs
Best results in regard to additional oil are obtained if ultra-low IFT values can be reached. An indication for reaching ultra-
low IFT is the formation of microemulsions. As APG B has shown the best performance in regard to IFT reduction, the
potential of APG B to form microemulsions was investigated more in detail. Normally microemulsions can be created if
APGs are used together with a co-solvent. For the following investigations 1-octanol was chosen as an additional compound
for creating suitable surfactant systems.
Both, decane and crude could be microemulsified at 50C and 80C with the chosen surfactant/co-solvent ratio. With decane
the microemulsion volume is increasing by 20 % if the temperature is raised from 50C to 80C. For crude this effect is much
more pronounced. The microemulsion volume is increasing by 100 % even under the chosen brine salinity of 180,000 ppm.
Again it is observed that due to the differences in hydrophobicity and chemistry of decane and crude oil, different
microemulsion volumes are determined with APG and 1-octanol (table 4). One microemulsion phase is exemplarily shown
in Fig. 6.

Table 4: Microemulsion formation for APG B with 1-octanol as co-solvent for water/decane and water/crude oil at 20C, 50C, 80C:
volume of microemulsion (ml) formed from a 20 ml sample.



Fig. 6: Observed microemulsion phase formed with APG B/1-octanol and crude oil at 80C.


Conclusion
In the industry APGs are recognised as sustainable surfactants. They exhibit a superior ecotoxicity profile. At relatively low
surfactant concentrations APGs are capable to decrease the IFT of crude oil/water systems significantly even under high
salinity conditions and elevated temperature. Furthermore it was shown that the performance of APGs is not strongly
influenced by salinity or temperature variations as they can occur in typical oil reservoirs. Together with co-solvents APGs
can be used to form stable microemulsions even in extremely high salinity brines (180,000 ppm TDS) and at elevated
temperatures (80C).


Acknowledgement
The authors would like to thank BASF SE for permission to publish this paper.

Abbreviations
APG alkyl polyglucoside
BOD biological oxygen demand
COD Chemical oxygen demand
DOC dissolved organic carbon
EC effective concentration
HLB hydrophilic lipophilic balance
IFT interfacial tension
LC letal concentration
NOEC no observed effect concentration
OECD Organization for Economic Cooperation and Development
TDS total dissolved salt
TOC total organic carbon
8 SPE 145039
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