SPE 113432

Development of High-Performance Surfactants for Difficult Oils

Ping Zhao, SPE, Adam C. Jackson, SPE, Chris Britton, Do Hoon Kim, Larry N. Britton, David B. Levitt , SPE,
Gary A. Pope, SPE, The University of Texas at Austin

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
We present results for high molecular weight internal olefin sulfonate (IOS) surfactants that show excellent performance
when tested using several crude oils with characteristics such as high wax content and viscosity that have made it very
difficult to achieve high oil recovery with most surfactants used in the past. High carbon number internal olefin sulfonates
when used with appropriate co-surfactants, co-solvents and alkali show the type of phase behavior and ultra-low interfacial
tension needed for almost 100% oil recovery in cores. This work shows how the performance of both surfactant-polymer and
alkaline-surfactant-polymer flooding can be dramatically improved at the same or lower cost than with conventional
surfactants and applied over a wider range of reservoir conditions. High carbon number internal olefin sulfonate surfactants
gave good performance at low concentrations and were found to be compatible with both polymers and alkali such as sodium
carbonate when used with appropriate co-solvents. The extremely efficient and effective approach for finding high
performance surfactants that we previously presented for light crude oils has now been successfully extended to heavier
crude oils. The identification of high-performance surfactants suitable for high-temperature and/or paraffinic oil applications
opens up the potential to recover a vast amount of additional oil outside the range of conditions considered practical in the
past.

Introduction
The selection of surfactants for enhanced oil recovery applications requires laboratory testing with crude oil from the target
reservoir and may involve considerable effort to find a suitable surfactant and other chemical components of the chemical
formulation such as polymer, electrolytes, co-surfactant and co-solvent. Performing systematic screening experiments with
available surfactants can be time and labor intensive as each crude oil is unique and requires careful evaluation for use in
chemical flooding. However, knowledge of structure/performance characteristics of surfactants can greatly reduce the time
and effort needed to develop a formulation with the desired performance characteristics. When surfactants are chosen for
laboratory testing, their selection should reflect a preliminary evaluation process that is based on structural characteristics that
are summarized in Table 1. Using these preliminary design criteria along with reservoir-specific data, a small number of
promising candidates can be selected for laboratory evaluation.
We use a laboratory testing approach described by Levitt et al. (2006), which starts with the screening and optimization
of surfactant formulations by phase behavior experiments incorporating co-surfactants, co-solvents, alkali and electrolytes
and then advances to core flood testing with the most promising formulations. This paper focuses on crude oils that are
characterized as difficult due to their high carbon number, high asphaltene, paraffin and/or wax content and in some cases
high viscosity. Two of the crude oils used are solids at room temperature and one of them precipitates large amounts of
asphaltenes below reservoir temperature. We find that high molecular weight internal olefin sulfonate (IOS) surfactants
perform exceptionally well with these difficult oils compared to many other types of surfactants that we have tested.
Both alpha olefin sulfonate (AOS) and IOS surfactants have been used as EOR surfactants for many years. For example, a
high carbon number IOS surfactant was used as one of the components of the formulation used in the White Castle ASP pilot
reported by Falls et al. (1992). Sanz and Pope (1995) reported formulations with an IOS surfactant gave the best performance
of the surfactants they tested in core floods. Maini et al. (1985) reported AOS surfactants are stable up to 200C; IOS
surfactants are chemically similar and therefore also expected to be stable at high temperature. For these and other reasons,
we included both AOS and IOS surfactants in the screening studies done to develop formulations for several difficult crude
oils.

2 SPE 113432
Background
The term microemulsion has been used to describe a micellar phase containing surfactant, brine, and oil in thermodynamic
equilibrium (Bourrel and Schechter, 1988). Winsor (1954) first described microemulsion phase behavior as type I (oil in
water), type II (water in oil), and type III (a bicontinuous oil/water phase also known as a middle phase microemulsion). For
anionic surfactants, increasing the salinity causes a characteristic transition from type I to type III to type II. Healy et al.
(1976) first developed a correlation between oil and water solubilization ratios and the interfacial tension between the
microemulsion and each excess phase. The concept of optimum salinity was introduced as corresponding to the salinity
where an equal amount of oil and water are solubilized in the middle phase (type III) microemulsion. They defined the water
and oil solubilization ratios as the ratio of either the volume of water (V
w
) or oil (V
o
) over the neat (100% active) volume of
surfactant (V
s
). The intersection of the plots of V
o
/V
s
and V
w
/V
s
as a function of salinity occurs at the optimal salinity, and is
defined as the optimum solubilization ratio (). Huh (1979) then derived a theoretical relationship between the solubilization
ratio and interfacial tension (IFT). The IFT () is inversely proportional to the square of the solubilization ratio ():

2
C
=

where C is approximately 0.3 dynes/cm for typical crude oils and surfactants. When the optimum solubilization ratio () is 10
or higher, the IFT at optimum salinity is on the order of 10
-3
dynes/cm or less, which is sufficiently low to mobilize the
majority of residual oil under most conditions. Therefore, we use a target optimum solubilization ratio of 10 or higher for
microemulsion phase behavior screening.
The advantage of using phase behavior experiments for screening surfactants instead of measuring IFT or proceeding
directly to corefloods is that numerous surfactants and chemical formulations can be tested rapidly and with comparatively
little effort. Moreover, these experiments permit qualitative observations such as the presence of undesirable macroemulsions
and/or gels, the rigidity of the interfaces, the viscosity of the phases, and most importantly dynamic observations such as
short equilibration time, which has correlated well with good flood performance. A qualitative indication of IFT is also
possible by observing the size and behavior of the droplets when the pipette is gently inverted. The viscosity is especially
important considering that highly viscous phases will not transport at the very low pressure gradients in oil reservoirs, which
are often on the order of 1 psi/ft or less.
An analysis of surfactant structure can aid in predicting its performance as an EOR surfactant. One of the most important
characteristics of a good EOR surfactant is the degree of branching of the hydrophobe. Branching tends to minimize
undesirable behavior. For example, Aoudia et al. (1995) reported the excellent performance of alcohol propoxy sulfates
(APS) with carbon lengths corresponding to light crude oils. Their performance was attributed partly to the branching of the
Guerbet alcohols used to make these surfactants. The benefits of branching were also demonstrated for several surfactants
and light crude oils by Levitt et al. (2006), Jackson (2006) and Flaaten et al. (2008). These formulations included a medium
molecular weight IOS as co-surfactant to improve both the aqueous and microemulsion phase behavior. Despite the lack of
branching on IOS surfactants, these surfactants do not exhibit the tendency toward formation of ordered arrays and gels
typical of surfactants with linear hydrophobes. An understanding of the molecular conformation of IOS reveals why their
behavior appears more similar to branched-hydrophobe surfactants than linear ones.
Surfactants are self-aggregating molecules, and their molecular shape(s) can determine the functional properties. Figure 1
presents the space-filling molecular structure of the two chemical forms of IOS that are present, the alkene sulfonate and the
hydroxyalkane sulfonate. The positions of the two tails are approximate and are based on energy minimization software.
Although the hydrophobic groups are not branched, the position of the hydrophilic sulfonate group in the middle gives the
molecule the approximate structure of a branched molecule. Two chemical species are formed when internal olefins are
sulfonated: alkene sulfonate and hydroxyalkane sulfonate. Further, two positional isomers of the second species,
hydroxyalkane sulfonate, occur due to formation and subsequent hydrolysis of - and -sultones (ringed sulfur-containing
structures). Figure 1 shows a C
16
-IOS, but commercial products typically have a range of carbon numbers. Therefore, the
number of possible chemical species depends on: (1) the number of homologues (e.g., C
15
, C
16
, C
17
, C
18
in a commercial C
15-
18
IOS); (2) the positioning of the double bond within the starting olefin molecule (i.e., narrow or wide distribution) within
each homologue; (3) the proportion of alkene sulfonate vs. hydroxyalkane sulfonate for each homologue (usually ~60:40);
and (4) the position of the hydroxyl group in the hydroxyalkane sulfonates (i.e., whether from hydrolysis of - or - sultones).
The salient point of this complex chemistry is that a batch of IOS can have a distribution of chemical species, and this
diversity prevents aggregation into viscous phases and other undesirable behavior.
A confounding factor is that the chemical species and their distribution within each production batch can be different and
manufacturer specific. However, these variables can be controlled by good quality control during manufacture. Figure 2
shows HPLC chromatograms of two batches of C
20-24
IOS, both starting from the same internal olefin but with different
procedures for sulfonation. One of these IOS performed better in phase behavior experiments. The differences in elution
profiles signify differing chemical species and concentrations that can affect performance. In spite of the variability in
performance, it is possible to insure the consistency and excellent performance of IOS surfactants for EOR. Results are
presented below that illustrate the excellent performance of these surfactants with crude oils that can be labeled as difficult.

SPE 113432 3

Experimental
Surfactants. C
15-18
, C
20-24
, C
14-26,
and C
24-28
internal olefins were produced by Shell Chemical Co. and sulfonated by Stepan
Chemical Co. Co-surfactants were provided by either Shell, Stepan or Sasol. The choice of IOS surfactants will depend on
the oil and desired optimal salinity in the surfactant/polymer slug. Table 2 lists the surfactants we initially screened for at
least one of the crude oils under investigation.

Co-solvents. The co-solvents used in this study were methyl-1-propanol (isobutanol), 2-butanol (sec-butanol), 1-pentanol, 2-
methyl-2-butanol (t-pentanol), ethylene glycol monobutyl ether (EGBE), diethylene glycol monobutyl ether (DGBE), and
triethylene glycol monobutyl ether (TGBE).

Alkali and Salt. Alkalis such as sodium carbonate, sodium hydroxide and sodium metaborate (Flaaten et al., 2008) increase
the pH and decrease the adsorption of anionic surfactants on sandstones and carbonates (Zhang et al., 2006). These salts also
provide a lever by which to adjust the electrolyte concentration needed to achieve optimal salinity.

Crude Oils. Table 3 lists the five crude oils used in this study and the reasons why they are considered challenging targets
form the point of view of surfactant formulation.

Results
Initial results with these crude oils indicated that, as previously found with lighter crude oils, far more favorable results were
obtained with IOS surfactants than with conventional surfactants such as alkyl benzyl sulfonates, as illustrated in Fig. 3. In
addition, better results with these crude oils were obtained with IOS surfactants than with AOS surfactants, so a more
systematic study was made using IOS surfactants. Early results indicated a higher carbon number was needed for the heavier
oils than we had previously used, so we then focused on the high carbon number IOS surfactants. However, as would be
expected for most high carbon number surfactants, these presented problems with low aqueous solubility that had to be
overcome.
The choice of IOS surfactants will depend on the oil and desired optimal salinity in the surfactant/polymer slug. With
high equivalent alkane carbon number (EACN) crude oils like the ones under investigation, optimal results will likely be
obtained with a surfactant with a long hydrophobe. In some cases, such as if high salinity injection brine is preferred, a
shorter hydrophobe can be used, although performance may be sacrificed somewhat as illustrated in Fig. 4. If a high salinity
slug is desired C
14-26
IOS which has a lower HLB, may be used rather that the better performing C
24-28
.
Co-solvents are added to reduce formation of gels, liquid crystals and macroemulsions and to promote rapid equilibration
and low-viscosity microemulsions. As the carbon number of the crude oil increases, co-solvents with a higher carbon number
are required to give the desired behavior such as roughly equal partitioning between the oil and brine, so this is the reason for
including co-solvents such as t-pentanol.
The addition of co-solvent lowers the solubilization ratio at optimum salinity, as illustrated in Fig. 5. This has been
observed for all surfactants, co-solvents and crude oils tested. At the same time, co-solvents can speed equilibration and
improve aqueous solubility. The ASP solution must be clear and stable to transport in the reservoir over long distances with
low retention at low pressure gradient, as has been observed through coreflood experiments. For the high carbon number
surfactants needed to solubilize high carbon number crude oils, the aqueous solubility problem becomes more severe. It is
very common to observe phase separation with these surfactants, especially when polymer is present. This is true in particular
for the high carbon number IOS. Addition of a co-surfactant or co-solvent or both is then essential for good reservoir
performance. Since the co-solvent both increases the cost and the IFT, it is desirable to use the minimum amount necessary to
achieve clear aqueous solutions of surfactant and polymer at optimal salinity. Some example aqueous solubility data obtained
for C
20-24
IOS during the initial screening process is presented in Table 4.
Selected phase behavior results obtained with the crude oils discussed above are given in Table 5. For each of the five
difficult oils examined a formulation was identified that resulted in solubilization ratios of at least 10. The results with Crude
# 4 are particularly encouraging since the lowest IFT was created with only 0.3 wt% surfactant and 0.6 wt% co-solvent. For
data presented for Crude #1 through Crude # 4, a water oil ratio (WOR) of 1 was used. For Crude # 5, the WOR is 2.33 (70%
aqueous surfactant solution, 30% crude oil). The WOR is important when dealing with acidic crude oils, which contain
napthenic acids or similar organic structures that become soaps when reacted with alkalis such as sodium carbonate. When
these oils react with alkali, the optimum salinity is lowered by the lipophilic soaps generated, and the optimal salinity is
therefore a function of the ratio of synthetic surfactant injected to the soaps produced through saponification. An activity map
of this response is shown in Fig. 6 for Crude # 5, and it shows the microemulsion types at each of 15 sodium carbonate
concentrations and 5 values of WOR. The data are plotted as a function of the ratio of the oil concentration to the surfactant
concentration. Assuming the amount of soap generated by the alkali is proportional to the oil concentration, this ratio
corresponds to the ratio of soap to surfactant. As this ratio decreases, the more hydrophilic mixture causes the phase behavior
to change from Type III to Type I. This is precisely the favorable direction for an ASP flood as the oil saturation decreases
going upstream, so this type of activity diagram is robust in a way that is similar to the classical negative salinity gradient for
surfactant-polymer flooding.
4 SPE 113432
Another interesting and important feature of the activity diagram shown in Fig. 6 is the large three phase region despite
the low surfactant concentration of just 0.2 wt%. Because 1 wt% co-solvent was used in this formulation, the mixtures
separate into low viscosity microemulsions with sharp interfaces very similar to the ideal behavior of classical
microemulsions at higher surfactant concentration formed with non-reactive oils. We have not seen a single exception to this
type of behavior under any conditions with any crude oil when sufficient time is allowed for the samples to equilibrate under
carefully controlled isotherm conditions. Thus, we conclude that ASP slugs with even very low surfactant concentrations will
behave in a classical way over long time periods in the reservoir. The same approach to modeling and predicting their
transport in reservoirs is therefore appropriate. A companion paper by Mohammadi et al. (2008) contains the details of the
UTCHEM model for this purpose. There are of course many other important implications with respect to surfactant selection
and optimization, properly interpreting laboratory data, and so forth to numerous to mention in this paper.

Corefloods. We show two example core floods. In both cases almost 100% oil recovery was obtained along with low
pressure gradients, indicating the feasibility of transporting the chemicals over long distances at the low pressure gradients
expected in oil reservoirs.
The first example core flood was the initial screening test of the performance of the heavier IOS C
20-24
surfactant with
Crude# 3, a high paraffin content crude, and is not an optimized design. The core flood was performed using a Berea
sandstone core approximately 2 inches in diameter and approximately 1 foot in length. The core was initially saturated with
brine that was composed of 3 wt% NaCl. This solution was injected for several pore volumes before running a salinity tracer
test with 6 wt% NaCl to confirm the pore volume. The core was then oil flooded with the crude oil and water flooded with
the initial brine. Residual oil saturation to water (S
orw
) was about 35%. For the chemical flood, the core was injected with a
surfactant-polymer slug and followed with a continuous polymer drive solution. The injected oil, water and chemical floods
were all run vertically in the gravity stable direction. The core flood was run in a convection oven that was set at average
reservoir temperature of 85C.
We use the terminology PV% to describe the product of concentration and slug size, as this has been shown to be a useful
scaling variable for coreflooding. For this experiment, a surfactant slug of 3 wt% surfactant was injected for 0.1 PV
(PV%=30), and sodium carbonate was included in the design to provide the necessary salinity gradient as well as reduce
surfactant adsorption and raise the pH of the injected fluids. The surfactant slug was composed of 3 wt% IOS C
20-24
, 1 wt% n-
pentanol, 1 wt% SBA, 1.9 wt% NaCl and 1 wt% Na
2
CO
3
with 2500 ppm AN-125 polymer (SNF Floerger). After the
surfactant slug was injected for 0.1 PV, a 2500 ppm AN-125 polymer drive, which included 1 wt% NaCl and 1 wt% Na
2
CO
3

was injected for about 1.6 PV at which time the effluent was clear and stopped producing emulsion. The flow rate was
approximately 0.5 ml/min during both the surfactant slug injection and polymer drive.
Effluent fluid fractions were measured right after collection at reservoir temperature to avoid changes in these interface
levels from evaporation inside the oven or contraction of the oil once samples were removed from the oven. The oil recovery
data are shown in Fig. 7. The oil bank broke through at 0.33 PV and the surfactant breakthrough was at 0.87 PV at which
time more than 80% of the water flood residual oil had been produced as free oil. The remaining oil was produced as excess
oil along with emulsion or microemulsion phases. The pressure data were recorded and indicated that there was no plugging
as illustrated in Fig. 8. The total oil recovery was calculated to be 100% of water flood residual oil within experimental error.
The oil bank was produced at sustained oil cut around 60%. This large oil cut is attributed in part to the low mobility ratio
calculated from the pressure drop of the end brine and end polymer drive to be 0.5.
The purpose of the second example core flood was to test the recovery efficiency of the surfactant formulation selected
for Crude # 5 in a Berea sandstone core. This was again the first core flood using this formulation based upon the phase
behavior tests. The residual oil saturation to water (S
orw
) was 43%. An ASP slug containing 0.2 wt% surfactant was injected
for 0.5 PV (PV%= 10) followed by a polymer drive with 2000 ppm Flopaam 3630S. The surfactant slug was composed of 0.1
wt% IOS C
20-24
, 0.1 wt% C
16
branched alkylbenzene sulfonate, 1 wt% DGBE, 27,500 ppm Na
2
CO
3
, and 3000 ppm Flopaam
3630S (SNF Floerger). The ASP flood was at a constant flow rate of 0.11 ml/min (for a frontal advance rate of ~1.3 ft/day).
Despite the low surfactant mass injected, 95% of the water flood residual oil was recovered, as illustrated in Fig. 9,
corresponding to a residual oil saturation to chemical (S
orc
) of 2.3%. Oil breakthrough occurred at about 0.25 PV with an oil
cut of approximately 55%. Pressure gradients remained low throughout the flood. The pH of the effluent samples was
measured and plotted in Fig. 9. These data show that the pH initially starts at pH=8 and peaks around pH=11 after surfactant
breakthrough before slowly decreasing to pH=8.5 in the polymer drive. This core flood was repeated with a 30% PV ASP
slug (PV%=6) with essentially the same oil recovery.

Conclusions
A recently developed protocol for surfactant selection for use in surfactant-polymer or alkali-surfactant-polymer flooding has
been vetted for use with difficult oils, such as those with high viscosity or containing high wax content. The procedure
involves initial selection of candidate surfactants using knowledge of structure/performance relationships, phase behavior
experiments, and limited core flooding with promising formulations identified in phase behavior experiments. A class of
surfactants known as internal olefin sulfonates (IOS) has shown great success by themselves or in combination with other
surfactants. The one-step synthesis through sulfonation of olefins keeps the cost of these high performance surfactants in a
competitive range. The random location of the olefin bond ensures that many species are formed with the attachment of the
SPE 113432 5

sulfonate group. This molecular diversity in the surfactant structure helps keep phase interfaces fluid and increases the
solubilization ratio with complex crude compositions, as is evident in phase behavior experiments. The carbon number of
IOS surfactants can be tailored to apply to difficult oils or reservoir conditions, and co-surfactants can be combined to
improve on surfactant slug design parameters (i.e. altering optimal salinity) and performance as well. The high performance
and low consumption of these surfactants when properly formulated make them a more economical alternative to
conventional surfactants.

Acknowledgements
We would like to thank the industrial affiliates of the chemical enhanced oil recovery project at the University of Texas for
financial support of this research. We would also like to thank Stepan, Shell, and Sasol for providing surfactants, and SNF
Floerger for providing the polymers used in this study. We would also like to acknowledge the resources and staff of the
Center for Petroleum and Geosystems Engineering at the University of Texas at Austin.

References
Aoudia, M.: Optimum Microemulsions Formulated with Propoxylated Guerbet Alcohol and Propoxylated Tridecyl Alcohol Sodium
Sulfates, Journal of Dispersion Science and Technology 16(2), 1995.
Bourrel, M. and Schechter, R. S.: Microemulsions and Related Systems, Marcel Dekker, Inc.: New York, NY, 1988.
Falls, A. H., Thigpen, D. R. and Nelson, R. C.: A Field Test of Co-Surfactant Enhanced Alkaline Flooding SPE 24117, April 1992.
Flaaten, A., Zhang, J., Nguyen, Q. and Pope, G. A..: A Systematic Laboratory Approach to Low-Cost, High-Performance Chemical
Flooding, SPE 113469, presented at the 2008 SPE Symposium on Improved Oil Recovery held in Tulsa, Okalahoma, U.S.A., April
2008.
Handy, L.L., Amaefule, J.O., Ziegler, V.M., and Ershaghi, I.: Thermal Stability of Surfactants for Reservoir Application, SPE 7867,
presented at the SPE of AIME International Symposium on Oilfield and Geothermal Chemistry, Houston, Texas, January 1979.
Healy, R. N., Reed, R. L., and Stenmark, D. K.: Multiphase Microemulsion Systems, SPEJ (June 1976), 147.
Huh, C.: Interfacial Tensions and Solubilizing Ability of a Microemulsion Phase that Coexists with Oil and Brine, Journal of Colloid and
Interface Science (September 1979), 408.
Jackson, A.C.: Experimental Study of the Benefits of Sodium Carbonate on Surfactants for Enhanced Oil Recovery, M.S. Thesis,
University of Texas, December 2006.
Levitt, D.B., Jackson, A.C., Heinson, C., Britton, L.N., Malik, T., Dwarakanath, V., Pope, G.A.: Identification and Evaluation of High
Performance EOR Surfactants, SPE 100089, presented at the 2006 SPE/DOE Symposium on Improved Oil Recovery held in Tulsa,
Okalahoma, U.S.A., April 2006.
Maini, B.B. and Ma, V.: Thermal Stability of Surfactants for Steamflood Applications, Petroleum Recovery Inst. SPE. (April 1985).
Mohammadi, H., Delshad, M., and Pope, G.A.:. Mechanistic Modeling of Alkaline/Surfactant/Polymer Floods SPE 110212, present at
the 2008 SPE/DOE Symposium on Improved Oil Recovery held in Tulsa, Okalahoma, U.S.A., April 2008
Sanz, C.A. and Pope, G.A. Alcohol-Free Chemical Flooding: From Surfactant Screening to Coreflood Design SPE 28956, presented at
the SPE/DOE Symposium on Oilfield Chemistry in San Antonio, Texas, February 1995.
Winsor, P.A. : Solvent Properties of Amphiphilic Compounds, Butterworths, London, 1954.
Zhang, L.D. and Hirasaki, G.J.: Favorable Attributes of Alkali-Surfactant- Polymer Flooding, SPE 99744, presented at the Symposium
on Improved Oil Recovery in Tulsa, Oklahoma, April 2006.
6 SPE 113432

Table 1Structure vs. Performance Properties for EOR Surfactants
Performance characteristic Corresponding Structural Properties
Not sorbed onto reservoir formation Preference for anionic surfactants
Stable at high reservoir temperature Lack of hydrolysable groups (e.g. sulfates) that would preclude their use at higher
reservoir temperatures
Ultra low IFT Hydrophilic and hydrophobic groups that optimally interact at the oil/water interface
Low IFT at high salt (TDS) concentrations Hydrophile/Lipophile Balance (HLB)> ~11
Low IFT at low salt (TDS) concentrations HLB < ~11
Performs well on crudes with relatively high
Equivalent Alkane Carbon Number (EACN)
HLB < ~11; larger lipophilic groups
Lack of ordered multi-molecular arrays, such
as liquid crystals, that create viscosity and
solubilization problems
Branched hydrophobes; surfactant mixtures; surfactants with multiple chemical
structures (isomers, multiple homologues)


Table 2Candidate Surfactants Tested
Descriptive Name
Abbreviated Chemical Formula
(b = branching in the carbon chain)
C
1518
Internal Olefin Sulfonate (IOS) R-CH(OH)-CH
2
-CH(SO
3
-)-R,
R-CH=CH-CH(SO
3
-)-R,
Where R+R=C
12
-C
15

C
1426
Internal Olefin Sulfonate (IOS) R-CH(OH)-CH
2
-CH(SO
3
-)-R,
R-CH=CH-CH(SO
3
-)-R,
Where R+R=C
11
-C
23

C
2024
Internal Olefin Sulfonate (IOS) R-CH(OH)-CH
2
-CH(SO
3
-)-R,
R-CH=CH-CH(SO
3
-)-R,
Where R+R=C
17
-C
21

C
2428
Internal Olefin Sulfonate (IOS) R-CH(OH)-CH
2
-CH(SO
3
-)-R,
R-CH=CH-CH(SO
3
-)-R,
Where R+R=C
21
-C
25

C
15+
Alkyl Benzene Sulfonate (ABS) bC
15+
-(C
6
H
5
)-SO
3
-
C
14+
Alpha Olefin Sulfonate (AOS) bC
11+
-CH(OH)-CH
2
-CH
2
-SO
3
-
bC
11+
-CH=CH-CH
2
-SO
3
-
C
1416
Alpha Olefin Sulfonate (AOS) bC
11-13
-CH(OH)-CH
2
-CH
2
-SO
3
-
bC
11-13
-CH=CH-CH
2
-SO
3
-
C
2024
Alpha Olefin Sulfonate (AOS) bC
17-21
-CH(OH)-CH
2
-CH
2
-SO
3
-
bC
17-21
-CH=CH-CH
2
-SO
3
-
C
1415
Alcohol 1-Ethoxy Glyceryl Sulfonate C
1415
-O-[CH
2
-CH
2
-O]
1
-CH(OH)-CH(OH)-CH
2
-SO
3
-
C
1415
Alcohol 2-Ethoxy Glyceryl Sulfonate C
1415
-O-[CH
2
-CH
2
-O]
2
-CH(OH)-CH(OH)-CH
2
-SO
3
-
C
1415
Alcohol 3-Ethoxy Glyceryl Sulfonate C
1415
-O-[CH
2
-CH
2
-O]
3
-CH(OH)-CH(OH)-CH
2
-SO
3
-
Nonyl Phenyl 3-Ethoxy Sulfonate bC
9
-(C
6
H
5
-O)- (CH
2
-CH
2
-O)
3
-SO
3
-


Table 3Descriptions of Crude Oils
Crude I.D. Temperature, C Oil Viscosity Comments
# 1 119 1.9 cp >15% waxes (C
15
-C
35
)
# 2

104 15 cp Very high asphaltene content
# 3 85 3 cp Very high paraffin content, solid at room temperature
# 4 46 80 cp High viscosity, high asphaltene content
# 5 62 19 cp Solid at room temperature

SPE 113432 7

Table 4Aqueous Solubility Screening Data
IOS C2024
(wt%)
Co-solvent
(wt%)
NaCl
(ppm)
Alkali Polymer
(ppm)
Maximum Conc. before
surfactant precipitation
0.3 EGBE 0.3 2800* Na
2
CO
3
scan AN125 1% Na
2
CO
3

0.3 EGBE 0.6 2800* Na
2
CO
3
scan AN125 3% Na
2
CO
3

0.3 t-pent. 0.6 2800* Na
2
CO
3
scan AN125 2.5% Na
2
CO
3

1 EGBE 1 2800* Na
2
CO
3
scan AN125 2% Na
2
CO
3

1 t-pent. 2 3100* Na
2
CO
3
scan 3330S 0.5% Na
2
CO
3

2 t-pent. 2 scan 1wt% NaOH AN125 2% NaCl
2 t-pent. 2 scan 1wt% NaOH AN125 2% NaCl


Table 5Summary of Phase Behavior Data at Optimum Conditions
Crude I. D. Surfactant Co-solvent Alkali Salinity
Solubilization
Ratio
Calculated IFT
(dyne/cm)
# 1 2% C
24-28
IOS 2% t- pentanol 1% NaOH

2.1% NaCl 12 2.0 x 10
-3
# 2 2% C
20-24
IOS 2% t-pentanol 1% NaBO
2
3.5% NaCl 10 3 x 10
-3

# 3 3% C
20-24
IOS 1% 1-pentanol, 1% sec-butanol 1% Na
2
CO
3
1.8% NaCl 19 8.3 x 10
-4
# 4 0.3% C
20-24
IOS 0.6% t-pentanol 1.25% Na
2
CO
3
(same as alkali) 71 6 x 10
-5

# 4 0.15% C
20-24
IOS +
0.15% TDA-7PO-SO
4

1.0 % DGBE 2.25% Na
2
CO
3
(same as alkali) 15 1.3 x 10
-3

# 5 0.1% C
20-24
IOS +
0.1% C
16
bABS
1% DGBE 2.75% Na
2
CO
3
(same as alkali) 50 1.2 x 10
-4


Alkene sulfonate Hydroxyalkanesulfonate

Fig. 1Space-filling molecular structure of the alkene sulfonate and the hydroxyalkane sulfonate forms of IOS.
8 SPE 113432

Fig. 2HPLC chromatograms of two C
20-24
IOS. The starting olefin was the same, but the IOS in Batch A gave better performance.
IOS C
20-24
ABS bC
15-18
Crude # 3
Temp. 85 C

Fig. 3Solubilization ratios for C
20-24
IOS compared to ABS for crude oil #3.
SPE 113432 9

Crude # 3
Temp. 85 C
IOS C
20-24
IOS C
14-26
I
n
c
r
e
a
s
i
n
g

I
O
S

s
i
z
e

Fig. 4Effect of hydrophobe length on optimal salinity and solubilization for Crude #1.
0
5
10
15
20
25
30
0 20,000 40,000 60,000 80,000 100,000 120,000
Electrolyte Concentration, ppm NaCl
S
o
l
u
b
i
l
i
z
a
t
i
o
n

R
a
t
i
o
,

c
c
/
c
c
Without
co-solvent
With
co-solvent
0
5
10
15
20
25
30
0
5
10
15
20
25
30
0 20,000 40,000 60,000 80,000 100,000 120,000
Electrolyte Concentration, ppm NaCl
S
o
l
u
b
i
l
i
z
a
t
i
o
n

R
a
t
i
o
,

c
c
/
c
c
Without
co-solvent
With
co-solvent

Fig. 5Effect of co-solvent on the solubilization ratios for crude # 2 with 2% C
20-24
IOS.
10 SPE 113432
C
oi l
/ C
surfactant
N
a
2
C
O
3
(
p
p
m
)
0
10,000
20,000
30,000
40,000
50,000
60,000
0 50 100 150 200 250 300
Type I
Type III
Type II
C
oi l
/ C
surfactant
N
a
2
C
O
3
(
p
p
m
)
0
10,000
20,000
30,000
40,000
50,000
60,000
0
10,000
20,000
30,000
40,000
50,000
60,000
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Type I
Type III
Type II

Fig. 6Activity map of Crude # 5 at five ratios of oil and surfactant.
0%
20%
40%
60%
80%
100%
0%
20%
40%
60%
80%
100%
0.0 0.5 1.0 1.5 2.0
Pore Volumes
T
o
t
a
l

O
i
l

R
e
c
o
v
e
r
e
d
0.0
0.2
0.4
0.6
0.8
1.0
O
i
l

C
u
t
% Recovery
Oil Cut
% Recovery
Oil Cut

Fig. 7Oil recovery from core flood example 1.
SPE 113432 11

0
2
4
6
8
10
0.0 0.4 0.8 1.2 1.6 2.0
Pore Volumes
P
r
e
s
s
u
r
e

D
r
o
p

(
p
s
i
)
Whole (0-150 psi)
In (0-5 psi)
Mid (0-30 psi)
Out (0-5 psi)

Fig. 8Pressure drop data for core flood 1.
0%
20%
40%
60%
80%
100%
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
T
o
t
a
l

O
i
l

R
e
c
o
v
e
r
e
d
0
2
4
6
8
10
12
p
H
% Recovery
Oil Cut
pH

Fig. 9Oil recovery for core flood example 2.