SPE 113259

Retention of CO
2
-foaming Agents onto Chalk: Effects of Surfactant
Structure, Temperature and Residual Oil Saturation
Ingebret Fjelde, SPE, and John Zuta, SPE, International Research Institute of Stavanger, Ingrid Hauge

,
University of Stavanger
Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 1923April2008.

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
Injection of CO
2
is a well known enhanced oil recovery (EOR) technique. Formation of stable foam inside the reservoir can
improve macroscopic sweep efficiency. On the other hand, retention of surfactants decreases the cost-efficiency of the EOR
process. This paper presents flow through retention experiments with CO
2
-foaming agents onto outcrop Liege chalk plugs.
Two branched ethoxylated (EO) sulphonates with different ethoxylation degree, S1 (EO=7) and S2 (EO=12) were used. The
aim was to investigate the effect of ethoxylation degree on surfactant retention. Furthermore, the effects of temperature and
residual oil on surfactant retention were studied. The effect of waterflooding followed by CO
2
flooding on surfactant
retention at reservoir conditions was also evaluated. Partitioning of the foaming agents between water and oil phases was
studied.
Results show that increasing the ethoxylation degree of the surfactant decreases the retention onto chalk cores saturated with
formation water at 55
o
C. S2 (EO=12), which was found to give the lowest retention at 55
o
C, was found to have a higher
retention at 70
o
C. The presence of residual oil saturation after waterflooding (S
orw
) decreased the retention of S1 (EO=7) and
increased the retention of S2 (EO=12) when compared to the absence of residual oil. The retention of S2 (EO=12) after
waterflooding followed by CO
2
flooding at 340 bar and 55
o
C was in the same range as retention on 100% water saturated
core, but significantly lower than retention in residual oil saturated cores. The experiments have shown that not only
surfactant structure and temperature are important for the retention of surfactants, but also the presence of oil.

Introduction
CO
2
-flooding is a well known Enhanced Oil Recovery (EOR) technology to improve microscopic sweep efficiency.
However, there are major limitations with this method due to the large difference in mobility between displacing and
displaced fluids. High mobility of CO
2
leads to gas fingering with subsequent poor macroscopic sweep efficiency, which is
again augmented by reservoir heterogeneities and gravity segregation (Grigg et al. 2004; Bai et al. 2005). A solution for this
problem can be to use mobility controlling foams. Studies have demonstrated that surfactant stabilized foam could drastically
reduce the gas mobility in the porous media, consequently improving volumetric sweep efficiency and oil recovery
(Schramm and Wassmuth 1994; Green and Willhite 1998; Grigg and Mikhalin 2007). Though this EOR method is promising,
there is a setback. Surfactant molecules tend to retain to the solid media reducing their effectiveness (Grigg and Milkhan
2007) decreasing the cost efficiency for CO
2
-foam processes. The economics of CO
2
foam flooding depend significantly on
the quantity of surfactant required to generate and propagate the foam. It is therefore important to study retention of
surfactants onto reservoir rock.
Surfactants may retain in reservoir rock by several mechanisms. In oil-free reservoir medium retention mechanisms like
precipitation, chemical degradation and adsorption onto the solids have been identified (Meyers and Slater 1980; Zhang and
Somasundaran 2006). If oil is present in the porous medium, additional mechanisms like partitioning of surfactant into the
oil, deactivation of surfactants by binding to crude oil asphaltenes and co-adsorption of surfactant and oil can contribute to
surfactant retention (Green and Willhite 1998; Mannhardt and Novosad 1994). Surfactant loss through partitioning into the
crude oil can be responsible for surfactant losses by as much as 30% (Grigg and Mikhalin 2007). It is often difficult to
distinguish between the different retention mechanisms or isolate the specific cause for retention.

now with StatoilHydro
2 SPE 113259
Surfactant retention depends on surfactant concentration and structure, temperature, brine salinity and hardness, rock
type, wettability, and the presence of the residual oil phase (Mannhardt et al. 1993; Zhang and Somasundaran 2006; Grigg
and Mikhalin 2007). Borchardt et al. (1985) summarized the evaluation of over 40 surfactants for use in CO
2
foam flooding.
In particular, when using CO
2
gas under miscible conditions, the creation of an effective foam is very difficult because
either the salt concentration of the water in the formation (connate or injected brine), the residual oil in the reservoir, or the
chemical instability of surfactants tends to break the foam or even prevent the foam from forming (Marquis and Kuehne
1994). Kuehne et al. (1992) conducted laboratory studies to find the best surfactant for generating CO
2
foam in the presence
of residual oil for two dolomite reservoirs. Conventional surfactants did not foam well in the dolomite cores containing
residual oil after CO
2
flooding. Grigg and Bai (2005) determined the decreasing order of a CO
2
-foaming agent, anionic
surfactant CD1045, adsorption densities onto five minerals as follows: montmorillonite, dolomite, kaolinite, silica and
calcite. Grigg and Mikhalin (2007) using the same surfactant evaluated that the effect on surfactant adsorption for different
solid to liquid ratios using different rock types in different states and flow conditions. Liu et al. (2005) determined the
influence of salinity, pH and surfactant concentration on CO
2
foam stability and surfactant adsorption on kaolinite powder at
reservoir conditions. In an experimental study, Austad et al. (1987) observed a direct dependence of the adsorption of
surfactants on reservoir minerals with the ethoxylation degree. Adsorption was observed to decrease with increase in
exthoxylation degree. Fabiola et al. (2006) using two commercial nonionic surfactants, nonyl phenol oxyethylenes with
ethoxylation degree 9.5 and 15, studied the effect of ethoxylation degree on adsorption on sandstone cores. Novosad et al.
(1986) reported the results of adsorption measurements at elevated temperatures for two commercially available surfactants,
an alpha olefin sulphonate and a synthetic alkyl toluene sulphonate. The results showed that adsorption of both surfactants on
clean sand were relatively low and decreased with increasing temperature.
However, the need still exits for a surfactant which provides stable foam and can be economically employed in carbonate
reservoirs. The determination of the adsorption of CO
2
-foaming surfactants in carbonate reservoirs is therefore important
during the recovery of residual oil.
The objectives of this work were to perform flow through retention experiments for CO
2
-foaming agents onto Liege
outcrop chalk at 55C, and to investigate whether the selected surfactants exhibited low adsorption levels. The focus of this
work has been retention of surfactants by adsorption, though other retention mechanisms may have occurred.
Two branched ethoxylated (EO) sulphonates with different ethoxylation degree were used in the retention experiments. The
aim was accordingly to inspect whether increased ethoxylation degree of the surfactant could decrease retention onto chalk
surfaces. The retention was evaluated at two different temperatures. The effects of residual oil after water flooding followed
by CO
2
flooding on surfactant retention were also studied.

Experimental

Porous Media.
Cores from an outcrop of Lige chalk were used for all of the experiments as analogues to North Sea chalk reservoirs.
Lige chalk is from the Upper Cambrian age. Lige outcrop chalk is pure and contains only minor amounts of clay and less
than 2 % silica (Strand et al. 2007). The core plugs used were sampled from the same block. All the cores used had a constant
diameter of 3.8 cm and length of approximately 7 cm. A new core plug was used for each retention experiment to avoid
uncertainties associated with cleaning of cores after surfactant flooding.









Tables 1 Compositions of FW, SW, and SW with tracers. Table 2 Composition of SWN

Chemicals and Fluids.
Surfactant solutions were prepared with synthetic seawater (SW) and including tracers (non-adsorbing chemical
substances) SWT and SWL with compositions as listed in Table 1. Thiocyanate was used as a tracer in the first set of
experiments and later changed to lithium in subsequent experiments. Aqueous surfactant solutions were injected at 1.0 wt%
active concentrations. Surfactants used in the experiments are classified as branched ethoxylated sulphonates with varying
ethoxylation degree. They belong to a chemical family of alcohol alkoxyglyceryl sulphonate, sodium salts. Two surfactants
Artificial
formation
water
(FW)
Seawater
(SW)
Seawater
with
thiocyanate
(SWT)
Seawater
with
lithium
(SWL)
Salt
g/l g/l g/l g/l
NaCl 36.81 23.38 23.38 23.38
Na
2
SO
4
------------ 3.41 3.41 3.41
NaHCO3 ------------ 0.17 0.17 0.17
KCI 0.31 0.75 0.75 0.75
MgCl
2
6H
2
0 4.48 9.15 9.15 9.15
CaCl22H20 33.25 1.91 1.91 1.91
KSCN ------------ ----------- 2.33 -----------
LiCl ------------ ----------- ------------ 0.10
Nitrate sea
water
(SWN)
Salt
g/l
NaNO
3
34.00
Na
2
SO
4
3.41
NaHCO3 0.17
KNO3 1.01
Mg(NO3)26H20 11.54
Ca(NO3)24H20 3.07
SPE 113259 3
with different ethoxylation degree, S1 (EO=7) and S2 (EO=12) were used. Also the length of the hydrocarbon chain is
slightly different. S1 (EO=7) has 12 to 15 carbon atoms in its carbon chain while S2 (EO=12) has 12 to 13 carbon atoms.
Stock tank oil from a North Sea reservoir was used for core preparation. All the fluids samples were filtered before use.
Carbon dioxide gas used was of 99.9 % purity.

Fluid Properties.
Measurements of pH, density, viscosity and interfacial tension (IFT) have been performed. Density was measured by a
PAAR DMA 45 density meter. A tensiometer from KRSS was applied for interfacial tension measurements, and the
viscosity was measured by an Anton Paar Physica MCR 301 instrument.

Preparation of Cores with Formation Water.
Dried cores were evacuated and then saturated with formation water (FW). The core plugs were mounted in core holders
in an oven at 55C using an overburden pressure of 25 bar and a back pressure of 5 bar. The experimental set-up is shown in
Fig. 1. Sulphate was removed in the core plugs by flooding with at least 6 pore volumes (PV) of FW. Effluent samples of
1PV were collected and analysed for sulphate concentration.

















Fig.1Experimental set-up

Preparation of Cores with Stock Tank Oil.
Initial water saturation, S
wi
, was established by draining sulphate free cores with humidified N
2
at room temperature on
unconfined porous disc by gradually increasing drainage pressure. The resulting saturations, S
wi
, were calculated from
weights of cores after N
2
drainage and dry weights of cores. Wettability conditions were then next established. The cores
plugs were placed in core holders with a 1 cm Liege chalk face plug saturated with a combination Isopar H and toluene (4:1)
(mixture 1) placed on both ends to act as filter media. A net confining pressure of 20 bars was established and nitrogen was
replaced by mixture 1 at an injection rate of 0.2 ml/min. Afterwards, the core holders were heated to 90
o
C and 1.5PV of hot
(90C) in-line filtered mixture of Isopar H/toluene and stock tank oil (STO) (50:50) (mixture 2) was injected to displace
mixture 1 in the cores. The cores were then aged by injecting STO at a rate of 0.08 ml/min for 80 hours at 90
o
C; 40 hours in
one direction and 40 hours in the opposite direction. After the wettability conditions have been established, the cores were
carefully dismounted from core-holders and face plugs removed. The cores were then remounted in the core holders.

Procedure for Surfactant Floodings.
A flow through experimental set-up as shown in Fig. 1 was used for the retention study. Surfactant solution was injected
upward at a constant injection rate of 0.2 ml/min at 55C. The surfactant solution was continuously injected into the core until
the effluent and the injected surfactant concentrations were the same. Approximately 4PV of surfactant solution was used in
all the experiments. Effluent samples of 5 ml were collected by the auto sampler and analysed for surfactant concentrations
and tracers.
Retention studies at residual oil saturation were carried out either after water flooding or after water flooding followed by
CO
2
-flooding. Water flooding was carried out by injecting seawater at rates of 0.1-0.5 ml/min. In the retention study after
CO
2
-flooding, the overburden pressure was after water flooding increased step-wise from 20 to 360 bar maintaining a net
confining pressure of 20 bar. CO
2
gas was injected at 0.2 ml/min and 340 bar until no more oil was produced. The core was
afterwards water flooded at 0.1 ml/min to remove CO
2
gas before surfactant injection at 0.2 ml/min.



4 SPE 113259
Analytical Methods.
The flow through retention studies have been conducted by determining the normalized surfactant concentration at
different cumulative pore volumes produced. The normalized surfactant concentration is the ratio (C/C
o
) of the surfactant in
the effluent samples (C) to the original surfactant concentration (C
o
) injected. Adsorption and desorption of surfactants onto
chalk surface has been measured by using the area embedded between the effluent curves for the surfactant and the tracer.
This method takes into consideration the shape of the effluent profiles as well as the distance between the profiles.
Effluents of samples were analyzed by a two phase titration method using Hyamine, a cationic surfactant (Schmitt, 2001).
The analyses performed in these experiments were done by using the cationic dye methylene blue indicator and chloroform
as organic phase. Thiocyanate in effluent samples were analyzed by diluting an exact sample volume with a mixture of 0.2 M
solution of Fe (NO
3
)
3
dissolved in 1.0 M aqueous HNO
3
solution (Lathi et al.1999). The absorbance was measured using a
MERCK KGaA Spectroquant NOVA 400 spectrophotometer at 447 nm. Lithium analyses were determined using the
inductive couple plasma (ICP) method. Sulphate analyses were done using a sulphate cell test kit (ASTM D516-07). Residual
oil saturation after surfactant flooding (S
orc
) was determined by ion exchange. The plugs were waterflooded with chloride
seawater (SW) after surfactant flooding and later replaced by flooding with nitrate seawater (SWN). (See Table 2). The
amounts of chloride ions present in effluent samples were determined by Mohrs titration.

Results and Discussions
Fluid properties were as listed in Table 3. Tables 4 and 5 lists the core properties and presents an overview of the core
flooding experiments. Parallel retention experiments with both surfactants were conducted in cores prepared with oil.

Temperature Density pH Viscosity IFT
Fluid
C g/ml pH units cp mN/m
Synthetic brine 55 1.013 7.0 0.55 -
Synthetic brine 70 1.007 7.1 0.45 -
S1 (EO=7) 55 1.015 8.0 0.59 -
S2 (EO=12) 55 1.016 8.2 0.61 -
S2 (EO=12) 70 1.018 8.1 0.47 -
STO 55 0.823 - 5.2 -
S1 (EO=7)/STO 55 - - - 2.5
S2 (EO=12)/STO 55 - - - 3.0
Synthetic brine/STO 55 - - - 28.0
Table 2 Density, pH, viscosity and IFT measurements






Table 3 Core properties & an overview of experiments conducted with FW saturated plugs

Length Porosity
Dry
Weight
S
wi
S
orw
* S
orc
** Retention
Core #
cm fraction g % %
k
rw
(S
orw
)
%
K
rw
(S
orc
)
Surfactant
type
mg/g rock
4a 6.9 0.40 120.1 12.2 20.3 0.35 11.3 0.40 S1 (EO=7) 2.1
4b 6.9 0.38 125.3 15.2 17.5 0.35 19.6 0.35 S1(EO=7) 2.2
5a 6.9 0.38 126.2 12.4 26.6 0.37 7.6 0.39 S2(EO=12) 2.9
5b 7.0 0.39 126.3 15.2 30.6 0.45 9.8 0.50 S2(EO=12) 3.2
6 7.1 0.40 123.6 14.8 19.4 0.36 4.0 0.35 S2 (EO=12) 1.4
Table 4 Core properties & an overview of experiments conducted with oil at 55
o
C (
*
determined by
*volume produced; **determined by Mohrs titration)

End-point relative permeability and residual oil saturations after water and surfactant floodings were also listed in Table 4.
The slight differences in S
orw
and S
orc
may be that different procedures were used for the determination of residual oil
saturations.

Effect of Surfactant Structure.
Flow through retention experiments have been performed for the two different surfactants with different ethoxylation
degrees; S1 (EO = 7) and S2 (EO = 12) respectively. The retention of surfactants onto chalk were determined to be 2.7 mg S1
(EO = 7)/ g rock and 1.6 mg S2 (EO = 12)/ g rock from Figs. 2 and 3 respectively. The experiments showed that the retention
of surfactants onto FW saturated chalk plugs decreased as the number of ethoxylation degree increased. The concentrations
Length Porosity
Absolute
Permeability
Dry
weight
Temperature Retention
Core #
cm fraction mD g
Surfactant
type
o
C mg/g rock
1 7.2 0.38 2.1 130.1 S1 (EO=7) 55 2.7
2 7.1 0.39 3.6 124.9 S2 (EO=12) 55 1.6
3 7.1 0.38 3.1 122.5 S2 (EO=12) 70 2.0
SPE 113259 5
of the effluent samples were observed to approach that of the injected solution after approximately 2.5PV. Desorption of the
surfactants by flooding with SW were also measured. A desorption of 0.6 mg/g was observed for most of the experiments,
though there were slight deviations. In effect the actual amount of surfactants retained, decreased with the amount of
surfactant desorbed. This means an irreversible retention of 1.0 mg/g for S2 (EO=12) and 1.1 mg/g for S1 (EO=7).
Ethoxylation of surfactants make them more salt tolerant and more hydrophilic (Rosen 2004; Levitt et al. 2006; Skauge
and Palmgren 1989). A discussion of temperature effects appears later in the next section. Several authors have
experimentally investigated ethoxylated surfactants (Fabola et al. 2006; Austad 1993; Kuhlman et al. 2000; Austad. et al.
1991a; Austad et al. 1992a; Austad et al. 1992b; Austad et al. 1987; Paktinat 1991; Celik et al. 1988).












Fig. 2Normalized effluent adsorption and desorption profiles for S1 (EO=7) in core #1 at Sw = 100%













Fig. 3Normalized effluent adsorption and desorption profiles for S2 (EO=12) in core #2 at S
w
= 100%

The adsorption mechanism for anionic surfactants onto chalk is thought to mainly be governed by the electrostatic forces
operating between the solid surface and the surfactant species (Celik et al. 1988). Surface charge of the chalk used during this
work is expected to be positive for the conditions present during the core flooding experiments due to pH and brine
compositions (Somasundaran and Agar 1967). Surfactants used for the experiments were anionic which are thought to have
rather large adsorption onto positively charged surfaces due to heavy electrostatic interactions, but it has been suggested that
increasing the ethoxylation degree might reduce the surfactant adsorption (Austad et al. 1987; Zhang and Somasundaran
2006; Fabiola et al. 2006).
Increasing the number of ethoxy groups makes the surfactant more hydrophilic promoting a high solubility for the
surfactant in the aqueous or brine phase (Levitt et al. 2006). The polar or ionic part of a surfactant will interact strongly with
the water phase while the nonionic or hydrocarbon portion of a surfactant will interact very weakly with the water phase. This
is due to the amphiphilic property of ionic surfactants. An EO group has the chemical structure - CH
2
CH
2
O - . It is thought
that the oxygen atom of this structure creates hydrogen bonds to water and thereby increases the water solubility. The
surfactant molecules will therefore, experience increased affinity for the water phase and less surfactant molecules will
choose to adsorb to the solid surface.
Celik et al. (1988) evaluated ethoxylated sulphonates, anionic surfactants, adsorption onto Saudi Arabian limestone, and
studied the effect of ethoxylation degree on adsorption. Surfactants with ethoxylation degrees of 8, 10, 15 and 18 were used
for static experiments. They found that the extent of adsorption of ethoxylated sulphonates onto limestone decreased with
increasing ethoxylation number. The higher the ethoxylation degree, the higher was the effect of reduced adsorption. The
relation was linked to surface activity and size of the surfactant aggregates. Indeed, retention of surfactants by adsorption
occurs by formation of surfactant aggregates on the solid surfaces. Fabiola et al. (2006) in their experiments with nonionic
surfactants measured the sizes of these aggregates and found them to depend on the structure of the surfactant and on the
surface activity. The results of injection studies indicated the influence of the ethoxylation degree on the adsorption of nonyl
phenol oxyethylenes, ENP 95 and ENP 150 with ethoxylation degree 9.5 and 15 on sandstone cores. ENP 95 exhibited a
higher adsorption than the ENP 150. This was attributed to the fact that ENP150 has a higher critical micelle concentration
(CMC) and a bigger polar chain, and will therefore exhibit higher solubility in the aqueous phase.
In order words, the saturation adsorption density is lower for surfactants with a high degree of ethoxylation because of the
increase in the packing area of each surfactant aggregate on the solid surface with increasing degree of ethoxylation (Zhang
and Somasundaran 2006). The relation of decreased surfactant adsorption as ethoxylation degree increases has also been
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
PV produced, ml
C
/
C
o
SCN S1 (EO = 7)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0.0 0.5 1.0 1.5 2.0
PV produced, ml
C
/
C
o
S1 (EO = 7) SCN
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 1.0 2.0 3.0 4.0
PV produced, ml
C
/
C
o
S2 (EO = 12) Li
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.5 1.0 1.5 2.0 2.5 3.0
PV produced, ml
C
/
C
o
S2 (EO = 12) Li
6 SPE 113259
reported by several other authors, and observations for present experiments are in line with work done previously on this
subject (Celik et al. 1988; Austad et al. 1992 b; Austad 1993; Austad et al. 1987; Paktinat et al. 1991; Fabola et al. 2006).

Effect of Temperature.
The effect of temperature on surfactant retention has been evaluated and S2 (EO=12), which was found to retain the least
at 55
o
C was tested at an elevated temperature of 70
o
C. Retention of S2 (EO=12) at 70C was estimated as 2.0 mg/g from Fig.
4 rock compared to 1.6 mg/g rock at 55C from Fig. 3. The retention of S2 (EO=12) was accordingly found to increase as
temperature increased. A temperature increase of 15C caused the retention to increase by 25%.










Fig. 4Normalized effluent adsorption and desorption profiles for S2 (EO=12) in core #3 at 70
o
C and Sw = 100%

In general it was expected that increasing temperature would increase the solubility of the surfactants (Mannhardt and
Novosad 1994; Celik et al.1988; Rosen 2004). But this seems not to be the case for ethoxylated surfactants (Celik et al.1988;
Rosen 2004). It is found that as the temperature increases the solubility of ethoxylated surfactants in water or brine phase
decreases. The hydrogen bonds created between water molecules and the oxygen atom of the ethoxylation group structure are
thought to be broken as the temperature increases. Breaking of hydrogen bonds would lead to lesser affinity for the surfactant
to the water phase. The surfactant would no longer want to stay in solution with water but rather create hydrophobe
connections with other surfactant molecules which already are adsorbed to the solid surface. The surfactant aggregates on the
solid surface thereby take a more compact structure and the adsorption would further increase as hydrocarbon chains from the
aqueous phase are transferred into the hydrophobic interior of the aggregates. Celik et al. (1988) observed a similar relation
when they investigated the adsorption of anionic surfactants with different ethoxylation degree onto limestone at 25, 50, and
90C. Increased adsorption as the temperature increased was suggested to have been caused by the gradual desolvation of the
EO chain with increasing temperature. This phenomenon increased the hydrophobicity of the surfactant aggregates which
lead to enhanced surface activity of the surfactant leading to high adsorption. It was thought that the forces which hold
ethylene oxide chain together are nullified upon heating and breaks up the surfactant molecule which then assume a water
insoluble form. Celik et al. (1988) also found that the surfactants with the lowest ethoxylation degree are less prone to
temperature increase than the surfactants with higher ethoxylation degree.

Effect of Residual Oil after Waterflooding.
Retention experiments onto cores at residual oil saturation after water flooding were performed with both surfactants. The
second set of parallel retention experiments are thought to be most accurate and will be discussed in this section. From Table
5, a value of 2.1 mg/g rock was determined for S1 (EO=7) in core #4a and 2.2 mg/g rock in core #4b in a parallel experiment
(Figs. 5a & 5b), whiles 2.9 mg/g rock was measured for S2 (EO=12) in core #5a and 3.2 mg/g in core #5b (Figs. 6a & 6b) in
another parallel experiment.












Figs. 5a&5bNormalized effluent adsorption profiles for S1 (EO = 7) in cores #4a & #4b at S
orw


Retention of surfactants in residual oil saturated cores will be compared to 100% FW saturated cores. It is also noticed that
retention do not vary greatly though residual oil saturation after water flooding (S
orw
) and surfactant flooding (S
orc
) varied
between the cores. Oil saturation affects adsorption of surfactants though adsorption is related to the oil wettability of the
rock surface and not to the amount of residual oil in the middle of the pores (Austad et al. 1991b).
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
PV produced, ml
C
/
C
o
S2 (EO = 12) Li
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.5 1.0 1.5 2.0 2.5
PV produced, ml
C
/
C
o
S2 (EO = 12) Li
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
PV produced, ml
C
/
C
o
S1 (EO = 7) Li
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 1.0 2.0 3.0 4.0
PV produced, ml
C
/
C
o
S1(EO=7)^1 Li
SPE 113259 7
Effluent samples were yellowish colored during surfactant flooding after approximately 1PV. This indicates that some
amount of oil was solubilized in the surfactant phase. The surfactant solutions had low viscosities; 0.59 and 0.61 centipose
(cp) for S1 (EO=7) and S2 (EO=12) at 55
o
C. Almost no free oil was produced during the flooding of surfactants. This was
expected because the interfacial tensions were rather high, 1-3 mN/m (Table 3). The retention of S1 (EO=7) in residual oil
saturated core #4a was estimated as 2.1 mg/g rock (see Fig. 5a) compared to 2.7 mg/g rock in the absence of oil as shown on
Fig. 2. In a parallel experiment with core #4b, the retention was determined as 2.2 mg/g rock (Fig. 5b). The retention was
approximately 19% lower in the presence of oil than in the 100% FW saturated core. S
orw
and S
orc
for core #4b were
estimated as 17.5% and 19.6% respectively. It is however, not possible that the residual oil saturation increased during
surfactant flooding so it is assumed that S
orw
and S
orc
are within experimental errors. The slight differences may be attributed
to the different methods used in determining them.
The behavior of decreased S1 (EO=7) retention in presence of oil may be explained by the fact that residual oil could
block some of the relevant adsorption sites for the surfactant (Mannhardt and Novosad 1994). Some of the residual oil may
be situated at the pore walls and making the surface of chalk more oil-wet in some regions. Similar behavior has been found
by Austad et al. (1991a & b 1992b). A product containing a mixture of an ethoxylated sulphonate and the corresponding
nonionic alcohol was studied during a dynamic adsorption experiment at 70C (Austad et al.1991 a & b; Austad et al.1992 b).
The surfactant had an EO degree of 6 which resembles S1 (EO=7), in present work, with 7 ethoxy groups. Decreased
adsorption in presence of oil was explained by blocking of pore throats by the residual oil and by phase trapping of nonionic
components.












Figs.6a & 6bNormalized effluent adsorption profiles for S2 (EO=12) in cores #5a & #5b at S
orw

In the first set of experiments with S2 (EO=12), the retention was determined as 2.9 mg/g rock in core #5a (Fig. 6a). A
parallel experiment with core #5b also confirmed this behavior (Fig. 6b). The retention of S2 (EO=12) in the presence of
residual oil was estimated as 3.2 mg/g rock. A value of 1.6 mg/g rock was estimated for core #2 (Fig. 3) when no oil was
present. (i.e. the amount of retained surfactant doubled). The retention for S2 (EO=12) was almost 45% higher than for S1
(EO=7) in the presence of residual oil.
Since S2 (EO=12) is more hydrophilic than S1 (EO=7) due to higher ethoxylation degree, it was expected that it would have
even lesser affinity for the oil phase than S1 (EO=7). Also S2 (EO=12) has slightly shorter hydrocarbon tail than S1 (EO=7).
By increasing the hydrocarbon chain length the surfactant becomes more hydrophobic and will thereby exhibit larger affinity
for the oil phase (Paktinat 1991). Li and Gallus (2007) also observed that the hydrophobic part of a surfactant has minimal
influence on surfactant adsorption via cation exchange, but a longer chain length promotes stronger hydrophobic interaction
resulting in a higher surfactant adsorption. In addition S
orw
for core #5b injected with S2 (EO=12) estimated as 30.6% was
rather high compared to 17.5% for core #4b injected with S1 (EO=7). It was then expected that even more adsorption sites
could have been blocked by the oil for S2 (EO=12). This seemed not to be the case. A possible explanation for the behavior
of increased loss of S2 (EO=12) in presence of oil might be that the surfactant is more lipophilic than first expected and
chooses to partition into the oil phase.

Dry
weight
PV S
wi
S
orw

V oil
produced
V oil
left
Retention by
phase partition
Measured
Retention
Corrected
retention Core #
Surfactant
type
g ml % % ml ml mg/g rock mg/g rock mg/g rock
4a S1 (EO=7) 120.1 31.0 12.2 20.3 20.9 10.1 0.04 2.1 2.06
4b S1 (EO =7) 125.3 30.0 15.2 17.5 20.2 9.8 0.04 2.2 2.16
5a S2 (EO =12) 126.3 29.6 12.4 26.6 18.1 11.6 0.05 2.9 2.85
5b S2 (EO =12) 126.3 30.5 15.2 30.6 16.5 13.9 0.06 3.2 3.14
6 S2 (EO =12) 125.4 31.9 14.8 4.3 25.8 6.1 0.02 1.4 1.38
Table 5 Corrected retentions after partitioning of surfactants into oil phase at 55
o
C

Phase partitioning of the surfactants between water and oil phases were also studied. Equal volumes of 1.0 wt% surfactant
solutions and stock tank oil were placed in beakers and stored in a heating cabinet at 55
o
C. The surfactant concentrations
partitioned into the oil phases were determined after 30 days. Retention by phase partitioning was observed to be rather low
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 1.0 2.0 3.0 4.0
PV produced, ml
C
/
C
o
S2 (EO=12) Li
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
PV produced, ml
C
/
C
o
S2 (EO=12)^1 Li
8 SPE 113259
depending on the amount of oil remaining after waterflooding. (See Table 6). If the surfactant is lost also due to phase
partitioning, it would be more precise to describe the loss mechanism as retention and not adsorption. Surfactant molecules
however, tend to reside in several aggreggates: as surfactant monomers or micelles in the adsorbed surfactant phase or in the
oil phase. The increased loss of S2 (EO=12) may be attributed to both the surfactant and oil molecules having a high affinity
for the solid-liquid interface, and are both co-adsorbed.
Nevertheless, the behavior of increased adsorption in the presence of oil for ethoxylated surfactants has been observed by
Celik et al. (1988). Static retention experiments onto limestone at 90C were performed in the presence of oil and retention
was found to increase significantly. This was explained to have been caused by co-adsorption of surfactant and oil molecules,
creating multilayers at the solid-liquid interface. As oil gets co-adsorbed with the surfactant, the repulsion between already
adsorbed surfactant monomers is reduced creating additional and multi-layered adsorption. A surfactant with EO degree of 15
was applied for this experiment which resembles S2 (EO=12) used in present work.
Notwithstanding, it seems as if there is a limit between seven and twelve ethoxy groups which changes the adsorption or
retention behavior from decreasing to increasing in the presence of oil and the relation has been confirmed by literature. To
summarize: Celik et al. (1988) studied a surfactant with 15 ethoxy groups and found that adsorption increased in the presence
of oil while Austad et al (1991b) found that adsorption decreased for a surfactant with 6 ethoxy groups.

Effect of Residual Oil after Water Flooding followed CO
2
-flooding.
The effect of CO
2
flooding after water flooding on the retention of S2 (EO=12) in a residual oil saturated plug was also
studied at reservoir conditions. Retention after CO
2
and surfactant flooding was estimated as 1.4 mg/g rock from Fig. 7.
Retention was approximately 11 % less than in the 100% FW saturated core (i.e. in the same range).











Fig.7Normalized effluent adsorption profile for S2 (EO=12) after CO
2
flooding in core #6 at S
or
(CO
2
)

When compared to retention on residual oil saturated plugs after water flooding (Figs. 6a & 6b), the retention after water
flooding followed by CO
2
-flooding was 55% lower. The plug was after CO
2
flooding, waterflooded to remove CO
2
gas
before surfactant flooding. This may have reduced the immobile oil phase, leaving a lesser amount of oil for surfactant-oil
interactions. Residual oil saturations after CO
2
and surfactant floods were estimated as 4.3 % and 4.0 % respectively.

Conclusions
Retentions of branched ethoxylated sulphonates onto Lige outcrop chalk has been studied, mainly at 55C by flow-through
experiments. The experiments have been performed in cores with residual oil and in cores saturated with formation water.
1. Increasing the number of ethoxylation degree decreased the retention on 100% FW saturated cores. Although,
the retentions were higher than acceptable economical limits. Two surfactants with ethoxylation degrees seven
and twelve were used.
2. The retentions were estimated as 2.7 mg/g rock for S1 (EO=7) and 1.6 mg/g rock for S2 (EO=12) respectively.
3. Irreversible retentions of 1.1 mg/g rock for S1 (EO=7) and 1.0 mg/g rock for S2 (EO=12) were measured in
100% FW saturated cores.
4. Increasing the temperature from 55C to 70C increased the retention of S2 (EO=12) from 1.6 to 2.0 mg/g rock.
5. The presence of residual oil both increased and decreased retention. The retention of S1 (EO=7) decreased to
2.2 mg/g rock, whiles that of S2 (EO=12) increased to 3.2 mg/g rock.
6. Phase partitioning of the surfactants between water and oil phases were found to be low and not contribute much
to the retention.
7. Retention after water flooding followed by CO
2
flooding at reservoir conditions was determined as 1.4 mg/g
rock, in the same range as in 100% FW saturated cores, but lower than in residual oil saturated cores after water
flooding.

Acknowledgements
The authors acknowledge the Norwegian Research Council, Dong Energy, Shell, ConocoPhillips and the Ekofisk
Coventurers, including TOTAL, ENI, Hydro, Statoil and Petoro, for financing the work from the research center COREC.

0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 1.0 2.0 3.0 4.0
PV produced, ml
C
/
C
o
S2 (EO=12) Li
SPE 113259 9
Nomenclature
C = effluent surfactant concentration during surfactant flooding, mg/g
C
o
= initial concentration of surfactant, mg /g
EO = exthoxylation degree
FW = formation water
PV = pore volume, ml
S1, S2 = surfactants 1 & 2
S
orw
= residual oil saturation, % PV
S
orc
= residual oil saturation after surfactant flooding, % PV
SW = seawater
SWL = seawater with lithium
SWN = seawater with nitrate
SWT = seawater with thiocynate

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SI Metric Conversion Factors
cp x 1.0* E0-03 = Pa.s
bar x 1.0* E0+05 = Pa
ml x 1.0* E0+00 = ml

o
F (
o
F -32)1.8 =
o
C