SPE 113469

A Systematic Laboratory Approach to Low-Cost, High-Performance

Chemical Flooding
Adam K. Flaaten, SPE, Quoc P. Nguyen, SPE, Gary A. Pope, SPE, and Jieyuan Zhang
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
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Abstract
We present a systematic study of laboratory tests of alternative chemical formulations for a chemical flood design and
application. Aqueous and microemulsion phase behavior tests have previously been shown to be a rapid, inexpensive and
highly effective means to select the best chemicals and minimize the need for relatively expensive core flood tests.
Microemulsion phase behavior testing was therefore conducted using various combinations of surfactants, co-solvents and
alkalis with a particular crude oil and reservoir conditions of interest. Branched alcohol propoxy sulfates and internal olefin
sulfonates showed high performance in these tests, even when mixed with both conventional and novel alkali agents.
Systematic screening methods helped tailor and fine-tune chemical mixtures to perform well under the given design
constraints. The best chemical formulations were validated in core flood experiments, and compared in terms of both oil
recovery and surfactant retention in cores. Each of the four best formulations tested in core floods gave nearly 100% oil
recovery and very low surfactant adsorption. The two formulations with conventional and novel alkali agents gave almost
zero surfactant retention. In standard practice, soft water must be used with alkali, but we show how ASP flooding can be
used in this case even with very hard, saline brine.

Introduction
Many mature reservoirs under water flood have low economic production rates despite having as much as 50 - 75% of the
original oil still in place. These reservoirs are viable candidates for chemical enhanced oil recovery (EOR) that uses both
surfactant to reduce oil-water interfacial tension (IFT) and polymer to improve sweep efficiency. However, designing these
aqueous chemical mixtures is complex, and must be tailored to the reservoir rock and fluid (i.e. crude oil and formation
brine) properties of the application. A strategic design methodology can help provide a low cost, well-performing chemical
formulation, even for challenging and problematic reservoir properties. Additionally, furthering laboratory and field-testing
in this area contributes to an expanding research database to help broaden reservoir types that can become candidates for
routine chemical EOR application.
This paper describes a systematic laboratory approach to low cost, high performance chemical flooding, and explores
novel approaches to alkali-surfactant-polymer (ASP) flooding in reservoirs containing very hard, saline brines. The design
strategy first uses microemulsion phase behavior experiments to quickly select and optimize concentrations of injected
chemicals. Assessment of formula optimization strategies are carried out through varying surfactant-to-co-surfactant ratio,
reducing co-solvent concentration, reducing total surfactant concentration, selecting a suitable alkali, and utilizing formation
brine in the injection mixture. Formulations performing well in phase behavior are validated in core flood experiments that
adhere to necessary design criteria such as pressure and salinity gradients, surfactant adsorption, and capillary effects.
We illustrate the application of our design approach in prepared Berea sandstone cores previously water flooded with very
hard, saline brine, and show how ASP flooding can use some of the same brine in the chemical formulation. Conventional
ASP flooding requires soft water that may not always be available, and softening hard brines can be very costly or infeasible
in many cases depending on the location and other factors. These new results demonstrate high tolerance to both salinity and
hardness of the high performance surfactants, and how novel alkalis, in particular sodium metaborate, can provide similar
benefits in such harsh environments as sodium carbonate has shown in environments without divalent cations. This
experimental success begins to vastly increase the range of conditions for economical enhanced oil recovery using chemicals.

2 SPE 113469
Background
The early success of a systematic laboratory approach to low-cost, high performance chemical flooding depends on the
efficiency of designing a formula for core flood injection in accordance with sound evaluation criteria. A general, three-stage
procedure has been developed previously to screen hundreds of potential chemicals (i.e. surfactant, co-surfactant, co-solvent,
alkali, polymer, and electrolytes), and arrive at a mixture having good recovery of residual oil in cores (Jackson, 2006; Levitt,
2006; Levitt et al., 2006). The first stage uses a chemical EOR database developed from previous research to select a list of
surfactants and other chemicals showing previous experimental and/or field success, and having crude oil, brine, and
reservoir properties similar to that being tested. The second stage screens and optimizes chemical concentrations in an
aqueous mixture through assessing microemulsion phase behavior performance with crude oil. Prior knowledge of how
chemical components interact with each other provides a design pathway that helps to minimize experimental time and cost
(Flaaten, 2007). The third stage tests these formulations in core flood experiments, aiming to merely validate and fine-tune
the few well-designed mixtures.
Mobilizing residual oil in cores is understood to occur when a surfactant solution replaces the water flood brine, and
reduces the interfacial tension (IFT) between the residual oil and aqueous phase (Stegemeier, 1976). Well performing
surfactants commonly lower the IFT to 10
-3
dynes/cm, compared to an oil-water IFT around 30 dynes/cm. Such a low IFT
nearly eliminates the capillary forces that originally trapped the residual oil, causing the oil to mobilize. Therefore, a major
objective of early-stage phase behavior experiments is to obtain chemical mixtures that demonstrate low IFT, and several
studies have shown relationships between microemulsion phase behavior and IFT (Levitt et al., 2006; Winsor, 1954; Healy et
al., 1976; Huh, 1979; Nelson and Pope, 1978; Pope et al., 1979; Bourrel and Schechter, 1988; Aoudia et al., 1995).
The interactions of an aqueous phase containing surfactant with a hydrocarbon phase will, under some conditions,
produce a microemulsion containing surfactant, water, and oil. Windsor (1954) characterized these microemulsions as Type I
(oil solubilized in water), Type II (water solubilized in oil), and Type III (middle phase, often assumed to be bicontinuous,
and may be in equilibrium with excess oil and water phases). Systematically varying one of several different parameters has
shown transitioning (i.e. shifting) from a lower- to upper-phase (i.e. Type I to Type III to Type II) microemulsion (or vice
versa) (Winsor, 1954; Huh, 1979; Bourrel and Schechter, 1988; Aoudia et al., 1995; Green and Willhite, 1998). For anionic
surfactants (e.g. sulfates, sulfonates), parameters relate to surfactant structure (alkyl chain length, number of propylene oxide
(PO) and ethylene oxide (EO) groups), crude oil (aromaticity, equivalent alkane carbon number (EACN)), and the aqueous
mixture (electrolyte strength (i.e. salinity), co-solvent concentration) (Huh, 1979; Aoudia et al., 1995).
Healy et al. (1976) quantified phase transitioning by incrementally varying electrolyte strength in different pipettes
containing oil and aqueous surfactant phases. Volumes of oil (V
o
) and/or water (V
w
) solubilized in the microemulsion phase
were measured at each increment, normalized to the total pure surfactant volume (V
s
) present, and plotted as oil and water
solubilization ratios (V
o
/V
s
and V
w
/V
s
, respectively) versus electrolyte strength. All surfactant was assumed to partition into
the microemulsion phase. Two solubilization curves were fitted to the oil and water data, and the intersection point
represented a Type III microemulsion with an optimal solubilization ratio (
*
) and optimal salinity (S
*
) value.
The relationship between IFT and solubilization ratio was observed and empirically correlated by Healy et al. (1976) and
others, and even used in simulation models (Pope et al., 1979). Huh (1979), however, first established a theoretical
proportionality between IFT () and optimal solubilization ratio (
*
), with C around 0.3 dynes/cm:
( )
C
2
*
=

(1)
Estimating IFT from Eq. 1 is much quicker than direct measurement (e.g. with spinning drop tensiometer) and sufficiently
accurate for screening purposes; some direct measurements though are performed on final solutions for validation.
Emulsions will equilibrate (or coalesce) to a stable, microemulsion phase over an equilibration/coalescence time period.
Fast equilibration indicates a beneficial, low viscosity microemulsion. Lengthy or hindered coalescence occurs when
macroemulsions, gels, liquid crystals, etc. are present, and screening for fast equilibration will remove these undesirable
formulations (Nelson et al., 1984). Because microemulsions are thermodynamically stable, the coalesced volume at
equilibrium should be constant indefinitely given no external perturbations or temperature and/or pressure changes. Highly
viscous microemulsions are also undesirable, and differ from macroemulsions in being ultra-fine, dispersed oil or water
droplets. Viscous microemulsions correlate with high surfactant retention, and transport poorly through porous media under
low pressure gradients (Levitt et al., 2006).
Chemical flooding in cores selects and validates well performing formulations from phase behavior experiments for
consistency of performance in cores. Core flood performance can be evaluated on residual oil recovery, surfactant retention,
pressure gradient, salinity gradient, and chemical cost, and acceptable values are obtained prior to recommending a candidate
formula for upscale simulation and a field-scale chemical flood.
Residual oil recovery in the core still depends on the formulation tested in phase behavior to maintain low IFT conditions,
helping to mobilize the residual oil target trapped by pore-scale capillary forces (Levitt, 2006). The capillary number, N
c
, is a
non-dimensional ratio of viscous forces (represented by the permeability (k) and viscous potential gradient ( ) product) to
capillary forces (represented by IFT ()):
SPE 113469 3
c
k
N

=

(2)
Empirical data for different porous media has shown a reduction of residual oil correlates to an increase in capillary number
(Delshad et al., 1986). Residual oil first mobilizes upon reaching a critical capillary number, and can all mobilized with a
capillary number several orders of magnitude greater. A surfactant-based chemical flood reducing IFT from 30 to 10
-3

dynes/cm commonly achieves capillary numbers representing zero residual oil (Shen et al, 2006).
Pressure drop and surfactant retention are necessary design considerations in core floods. A 1 psi/ft pressure gradient is
common for field-scale water flooding, with frontal velocity generally around 1 ft/day. A similar pressure gradient is
necessary for chemical flooding, and low microemulsion viscosity helps achieve this. Additionally, surfactant retention
values less than 0.2 mg surfactant / g rock are recommended to reduce surfactant costs, and low microemulsion viscosity and
alkali presence has been shown to help in this.
Salinity gradient design is important in any chemical flood, but in our application it needed special attention due to the
very hard, high salinity formation brine in the reservoir. From phase behavior experiments, microemulsions can have two
different interfaces: an oil-microemulsion and/or a water-microemulsion interface, each with different IFT values. A Type III
microemulsion specifically at optimal salinity is unique and favorable because both interfaces have equal and low IFT.
Salinity greater than optimal lowers oil-microemulsion IFT, and can trap surfactant in the residual microemulsion in Type II
conditions with a greater water-microemulsion IFT reducing oil mobilization. Salinity less than optimal lowers water-
microemulsion IFT keeping surfactant in a lower phase microemulsion and increasing oil-microemulsion IFT.. Designing
chemical flood to stay at optimum salinity is difficult for a variety of reasons such as changes in calcium concentration due to
cation exchange, mixing due to crossflow, even changes in pressure and many other variables. Pope et al. (1979) found a
negative salinity gradient offers a more robust chemical flood design. With a negative salinity gradient, initial reservoir water
existing at a Type II salinity step down to a surfactant slug at optimal salinity, followed by another step down to a polymer
drive at Type I salinity. This salinity gradient significantly increases the chances of low IFT, Type III conditions somewhere
in the mixing zone (Levitt et al., 2006). A polymer drive of salinity near the Type I/Type III boundary can give prolonged
Type III conditions, but decreasing the salinity in the polymer drive well into the Type I region adds robustness to the design.
Therefore, design of the salinity gradient is based on desired risk-to-reward.

Experimental Description
Chemicals and Fluids. Two surfactants were chosen for our low temperature, light oil application. Levitt et al. (2006)
showed good performance in a low-temperature (< 60 C), light oil core flood from an alcohol propoxy sulfate surfactant C
16-
17
7POSO
4
-
containing a C
16-17
branched alcohol hydrophobe, seven propylene oxide (PO) groups, and a sulfate group.
Sulfate surfactants hydrolyze at temperatures above about 60 C, and therefore similar sulfonate surfactants are used. Levitt et
al. (2006) found the best results when mixing the propoxy sulfate with C
15-18
IOS, an internal olefin sulfonate (IOS) having a
twin-tailed hydrophobe and sulfonate group.
A primary surfactant is directly involved in microemulsion formation, while co-surfactant improves the action of the
primary surfactant (Nelson et al., 1984). A co-solvent acts to prevent gel formation and reduce equilibration time among
other benefits, and is often needed to make the surfactant compatible with polymer in the aqueous slug (Pope et al., 1982).
Alkali agents can enable in-situ soap generation from crude oil components, can hasten microemulsion
equilibration/coalescence (with or without soap formation), and can lower surfactant adsorption in cores (Jackson, 2006).
Polymer provides viscosity for mobility control in a reservoir flood, and electrolytes provide adjustment to optimal salinity
(i.e. low IFT), and a negative salinity gradient (lower salinity in the polymer drive compared to the surfactant slug) for a more
efficient, robust chemical flood (Pope et al., 1979).

Primary and Co-surfactants C
16-17
Alcohol Propoxy Sulfate (APS), C
15-18
Internal Olefin Sulfonate (IOS). Stepan
Chemical Company provided their Petrostep S1 as a primary surfactant, a commercially available alcohol propoxy sulfate
(APS). Shell Chemical Companys Neodol 67 formed the hydrophobe, a C
16-17
branched (~1.5 methyl groups along carbon
chain) alcohol. Stepan propoxylated the hydrophobe with about 7 PO groups, and sulfated with sulfur trioxide or sulfamic
acid. Stepan also provided their Petrostep S2 as a co-surfactant, a commercially available internal olefin sulfonate (IOS). A
C
15-18
internal olefin hydrophobe supplied by Shell was manufactured by olefin metathesis (i.e. ethylene oligomerization).
Stepan sulfonated the olefins, resulting in a proportion of alkene and hydroxyl alkane sulfonates (~60:40 mixture), each with
several isomers depending the double-bond positioning in the olefin. Further description of both surfactants can be referred to
in Levitt et al. (2006).

Co-solventsSec-Butanol (SBA), Iso-Butanol (IBA). Co-solvents are frequently small carbon chain (C
3
to C
5
) alcohol
molecules that act at oil-water interfaces of microemulsion droplets, between oriented surfactant hydrophobes, to reduce
microemulsion viscosity, gel formation, and coalescence time (Sanz and Pope, 1995). Co-solvents equally soluble in oil and
water phases (i.e. neutral partition coefficient) act at the phase interfaces. For our low temperature, light oil application, sec-
butanol (SBA) and iso-butanol (IBA) have both showed good performance. This paper shows only experimental results with
SBA; however, in our recent work we prefer using IBA for its low-cost advantage. Co-solvents can have disadvantages in
4 SPE 113469
both decreasing optimal solubilization ratio (i.e. increasing IFT) and increasing chemical costs. The phase behavior testing
performed sought the lowest possible concentration of alcohol, and good performance was shown with complete elimination
of alcohol.

AlkaliSodium Carbonate (Na
2
CO
3
) and Sodium Metaborate (NaB(OH)
4
. Alkali agents increase injection fluid pH,
offering benefits of soap generation in reactive crude oils, and decreased adsorption of anionic surfactant on rock surfaces
(Nelson et al., 1984; DOE, 2005). In situ saponification essentially provides free chemicals to reduce IFT, while low
adsorption maintains surfactant slug propagation through the reservoir (Nelson and Pope, 1978; Falls, 1992; Zhang and
Hirasaki, 2006). Sodium carbonate (Na
2
CO
3
), a conventional alkali, offers additional advantages of reducing co-solvent
requirements, aiding polyacrylamide (polymer) hydration, and speeding microemulsion equilibration time and phase
separation to mobilize oil quicker (Jackson, 2006; Nelson et al., 1984; Wellington and Richardson, 1997; Labrid, 1991).
Sodium metaborate (NaB(OH)
4
) was tested as an alternative, novel alkali. Like all other alkali metal borates, monomeric
borate ion (B(OH)
4
-
) is strongly hydrolyzed to form polymeric borate ions when its concentration and solution pH change
(Ingri, 1963). It is a classic alkaline buffer in detergent formulations, with pH determined principally by the acid-to-base ratio
as shown by Eq. 3:
( )
( )
+ 3
a
-
4
B OH
H K
B OH
= (3)
Infrared and ion exchange studies indicate the presence of B
4
O
5
(OH)
5
-
for pH within the range of 9.2-10.5 and B(OH)4-
at higher pH (Filippova et al., 1975). This implies that metaborate could be synthesized from the significantly less expensive
sodium tertraborate (i.e. Borax) and sodium hydroxide. Multivalent cations such as Ca
2+
and Mg
2+
could be complexed with
borate ions, monovalent electrolytes, and divalent ion sequestrants to increase their effective solubility in an aqueous phase.
Our current work has shown that borate ions at first form an amorphous precipitate with calcium and/or magnesium that
dissolves as the divalent ion concentration increases. We also found that sodium metaborate could tolerate as high as 6000
ppm Ca
2+
and Mg
2+
, which is much higher than sodium carbonate. Moreover, Zhang et al. (2008) shows sodium metaborate
to significantly outperform sodium carbonate and sodium hydroxide in enhanced imbibition experiments in silica and
carbonate rocks.

Polymer. The addition of a high molecular weight water-soluble polymer to a chemical EOR solution increases the
viscosity of the injected solution, the chemical slug. This increase in viscosity is needed to off set the increase in the water
relative permeability that occurs when the IFT is reduced by 1000s of fold. Higher viscosity (low mobility ratio) also
increases the sweep efficiency in a reservoir by preventing an unstable displacement (fingering), channeling due to layering
and other heterogeneities, and by passing among other mechanisms. For these and other reasons, polymer is needed in both
the slug and the polymer drive pushing the slug. Oil recovery in the field has been shown to increase in portion to the amount
of polymer used up to very high concentrations and pore volumes. Thus, the use of co-solvents to co-solubilize the surfactant
and polymer is often (but not always) essential.
Hydrolyzed polyacrylamides (HPAMs) are a common, inexpensive class of polymers containing long, flexible structures
(Sorbie, 1991; Lake, 1989; Wreath, 1989). The length of the polymer structure can be selected based on reservoir
permeability and other rock characteristics such as pore structure but generally lower permeability means a lower molecular
weight polymer must be used. Flopaam 3330S HPAM polymer was used for the aqueous stability and core flood
experiments. The polymer is 30% hydrolyzed, with a molecular weight of 8 million Daltons. A concentrated polymer stock
solution was prepared with 5000 ppm polymer and 1000 ppm NaCl, mixed for more than 24 hours, and filtered through a 1.2
m filter. Proper hydration was determined through calculating the filtration ratio (FR) comparing the time to filter equal
volumes of polymer solution near the beginning (20 to 40 mL) and end (80 to 100 mL) of filtration:
80 100mL
20 40mL
t
FR
t

(4)
A polymer solution hydrated sufficiently generally has a filtration ratio less than 1.2.

Electrolytes, dilute formation brine, and crude oil. Hard, saline synthetic formation brine (SFB) that mimicked actual
reservoir formation brine contained 156,525 mg/L total dissolved solids (TDS) (from Na
+
, Ca
++
, Mg
++
, and Cl
-
), with 8,667
mg/L being divalents (Ca
++
and Mg
++
) (Table 1). The SFB was diluted with deionized water to a varying degree for some
phase behavior and core flood experiments, and is referred to as simply hard brine. Soft brine containing varying
concentrations of sodium chloride (NaCl) was also used in experiments. Electrolyte concentrations of hard and soft brines
were measured as mg/L TDS and mg/L NaCl, respectively, where the TDS has the same proportions of ions as the SFB. The
crude oil used was a light, West Texas crude from a sandstone reservoir at a reservoir temperature of 52 C. Table 2 shows
density and viscosity measurements of both the crude oil and SFB.

SPE 113469 5
Table 1Composition of Synthetic Formation Brine
Ion Na
+
Ca
++
Mg
++
Cl
-
TDS
mg / L 51288 6648 2019 96570 156525


Table 2Density and Viscosity Crude Oil and Synthetic
Formation Brine Measured at Reservoir Temperature (52 C)

Crude Oil
Synthetic Formation
Brine
Density, g/cc 0.8 1.098
Viscosity, cp (at 11 sec
-1
) 1.96 0.73

Aqueous and microemulsion phase behavior. Fisherbrand standard 5 mL borosilicate serological pipettes with 5 mm
inner diameter and 0.1 mL markings held dispensed aqueous and oil volumes for the phase behavior experiments. Two
milliliters of aqueous volume in each pipette contained concentrated stock solutions of surfactants and co-solvent mixed with
alkali and hard or soft brine. Each phase behavior experiment used an array of pipettes with incremental electrolyte
differences to obtain microemulsion data versus electrolyte concentration.
Prior to adding crude oil to pipettes, an aqueous stability assessment determined the clarity and homogeneity of all
dispensed aqueous solutions. After dispensing in each tube, aqueous volumes were agitated and settled for one hour, and
aqueous stability was assessed by visually inspecting any cloudiness and/or phase separation. In addition, identical aqueous
volumes containing polymer were frequently prepared in 10 mL glass vials to assess aqueous stability with polymer.
Aqueous stability is important to ensure a stable surfactant slug for injection, one where surfactant and polymer are
compatible with electrolyte concentration at optimal salinity. An experiment containing any phase separation or precipitation
in the aqueous phase at and slightly beyond optimal salinity fails this screening. After assessing aqueous stability, 1 mL of
crude oil was added to pipettes, and pipettes were heat-sealed, cooled, and slowly inverted 12 times to allow oil and aqueous
phase mixing. Pipettes were then incubated in a convection oven at reservoir temperature, and fluid interfaces recorded over
time. While measuring interfaces, pipettes were tilted to visual inspect and screen against interface in-fluidity,
macroemulsion and gel presence, and/or high microemulsion viscosity. Pipettes having free flowing interfaces without gel or
macroemulsion had aqueous-microemulsion and/or microemulsion-oil phase interfaces measured over time, interpolated to
the nearest 0.01 mL using pipette markings. Oil and aqueous phase volumes could then be calculated with time and salinity to
obtain optimal salinity, optimal solubilization ratio, and equilibration time values.
A common testing strategy is to use coarse salinity increments between pipettes to initially identify the optimal salinity
region, then use an additional test with finer increments to focus in on this region for more accurate assessment. However, to
be considered for core flood, phase behavior mixtures at or near optimal salinity had to pass several screening criteria:
visually appear gel and macroemulsion free, and show low viscosity, free-flowing interfaces; have a solubilization ratio
greater or equal to 10 (IFT 0.003 dynes/cm); have quick equilibration/coalescence time (< 7 days); have a clear,
homogeneous, and aqueous stable mixture.

Core preparation. Berea sandstone cores were initially drilled and cut to about 30 cm in length and 5 cm in diameter, then
dried and weighed. Air permeability was measured at the inlet, outlet, and middle of the bare, dry cores, and cores with low
permeability regions or high permeability anisotropy were discarded. Plastic end pieces were then fastened with quick-curing
epoxy; after curing the core was placed in a thin, 6.5 cm diameter lexan tube, and the annular space filled with slow-curing
epoxy. After the epoxy hardened, two holes were drilled 10 cm from each face to serve as pressure taps, and nylon flow lines
were epoxied into these holes. Valves were then fitted to all flow channels, and the core pressure tested to 100 psi in a water
bath to check and repair air leaks. Air was then evacuated with a vacuum pump, the core flooded with CO
2
to displace
residual air, and the CO
2
evacuated. Cores were then saturated with SFB.
A sequence of pre-chemical floods (brine, oil, and water floods) provided core data and residual oil saturation for
chemical flood design and oil recovery. Several pore volumes of SFB were flooded at a constant rate until reaching a
constant pressure drop across the core, which allowed the absolute permeability with respect to SFB to be calculated. Filtered
(1.2 m) crude oil was flooded from the top of the vertical oriented core at a high pressure gradient (20 to 50 psi/ft) until
constant pressure drop was reached, and no further brine was recovered. SFB then water flooded the core at a frontal velocity
(1 to 2 ft/day) similar to field-scale water flooding until no further oil was recovered. Oil and water flood data provided end-
point relative oil permeability and residual water saturation values, and end-point relative water permeability and residual oil
saturation values, respectively.

Core flood design. Chemical flood experiments were designed with several simple calculations using core parameters
measured and calculated from the brine, oil, and water flood experiments. The several estimated design parameters included:
an injected fluid viscosity for efficient displacement of mobilized residual oil, the expected pressure drop given polymer
permeability reduction, and the injection salinity of the polymer drive for a robust salinity gradient.
6 SPE 113469
The mobility (
i
) of a fluid is the ratio of a fluids effective permeability (k
i
) to its viscosity (
i
), and defined as:
i
i
i
k
=

(5)
A ratio of the displacing and displaced fluid mobilities can characterize the displacement efficiency, given by a dimensionless
ratio called the mobility ratio, M:
displacing
displaced
M

=

(6)
where a mobility ratio less than or equal to one indicates favorable displacement (Lake, 1989). For each core flood
experiment fluid mobilities and their corresponding mobility ratio were calculated using end-point relative permeability
values. Mobility values calculated from oil (
o
) and water (
w
) flood data were used to estimate an apparent viscosity (
app
)
necessary in injection fluids for favorable displacement (i.e. M < 1) and mobility control, which is estimated as the inverse of
the total relative mobility (
rel
):
( ) ( )
1 1
app rel o w

= = + (7)
Experimental data plots of polymer concentration versus measured viscosity in brines were used to select an appropriate
polymer concentration for desired viscosity in both the surfactant slug and polymer drive. The electrolyte concentration in the
surfactant slug was at or near the optimal salinity obtained from solubilization plots. The electrolyte concentration used in
the polymer drive was 60% that used in the surfactant slug in order to create a robust negative salinity gradient in the core.
Surfactant slug and polymer drive viscosities were verified prior to injection using a couette-type viscometer to ensure
that they exceed the calculated apparent viscosity. Measured viscosity values can then be used to estimate a pressure drop
expected during the chemical flood. A pressure drop ratio between estimated chemical flood and actual water flood pressure
drops is equal to the inverse ratio their mobility values:
slug rw k slug
wf wf
wf slug slug wf
P k R
k
P k

= =

(8)

Effluent Collection, Preparation, and Analysis. Effluent samples collected throughout a chemical flood have compositions
dependent on their time of recovery, which also determines what analysis techniques are used to further characterize them. A
list of the chronology of effluent collected and the analyses performed on them is provided below:
1. Formation Brine Recovery
The first effluent is a pure aqueous phase consisting mostly of recovered formation brine, and is characterized by its
conductivity and percent dilution relative to SFB.
2. Oil Bank Recovery
Effluent can contain as much as 50% oil, which visibly appears as a pure phase. Measurements are taken of the oil
volume and volume fraction, and the aqueous phase conductivity.
3. Early Post - Surfactant Breakthrough
Effluent contains microemulsion and/or emulsion, indicating the presence of surfactant. Some samples are heated to
break the emulsion accurately measure the oil volume, with the remaining aqueous phase measured for conductivity.
Other effluent samples are used to measure their surfactant concentration using HPLC analysis.
4. Late Microemulsion
Recovered microemulsion will contain a decreasing proportion of oil as the polymer drive progresses, and a core
flood is considered complete when relatively clear, microemulsion-free polymer is recovered. Samples are still
analyzed for conductivity, surfactant concentration, and possible oil volume.


Phase Behavior Results: Formula Selections and Optimization for Core Floods
Chemical Formula Design. Chemical mixtures containing surfactants, co-solvent, hard or soft brine, and/or alkali were
tested in phase behavior experiments to optimize the composition of the chemical slug and polymer drive.. Early phase
behavior experiments contained 2 wt% total surfactant concentration, between 0.5 to 2 wt% co-solvent, and soft brine, and
used coarse salinity increments between pipettes to narrow in on an optimal salinity range. Later phase behavior experiments
used optimization and fine-tuning of alternative formulations, and provided solutions for four well-performing for core
floods. The laboratory approach used for formulation screening and optimization included: varying surfactant-to-co-
surfactant ratio, reducing co-solvent concentration, reducing total surfactant concentration, adding alkali, and maximizing the
concentration of electrolyte.

SPE 113469 7
Varying SurfactanttoCo-Surfactant Ratio. The ratio of C
16-17
7POSO
4
-
to C
15-18
IOS surfactant concentrations was
systematically varied at 1:1, 5:3, 3:1, 7:1, and only C
16-17
7POSO
4
-
, with 2 wt% total surfactant concentration used for these
experiments. Additionally, between 1 and 2 wt% co-solvent was used to help microemulsion equilibration, with differences
in co-solvent due to previous research showing higher co-solvent requirements needed for higher proportions of C
16-17
7PO
SO
4
-
. Table 3 shows the results of testing different surfactant-co-surfactant ratios. All ratios show sufficiently high (i.e. >10)
solubilization ratios at optimal salinity to give ultra-low IFT except for the very viscous microemulsion produced when no
co-surfactant was used. Table 3 also shows that increasing surfactant to- co-surfactant ratio decreased optimal salinity, from
72,200 to 21,500 mg/L NaCl for a 1:1 to 7:1 ratio, respectively. Therefore, the surfactant ratio can be varied to modify
optimal salinity to a value most suitable for reservoir conditions given that all ratios showed good solubilization and phase
behavior. The equilibration time showed no noticeable trend, even though solutions with more co-solvent were expected to
equilibrate faster.

Table 3Effects of SurfactanttoCo-Surfactant Ratio on Phase Behavior Using Soft Brine
Surfactant Co-surfactant Ratio Co-solvent
Optimal
Salinity, S*
C
16-17
7PO-
SO
4
-
(wt%)
C
15-18
IOS
(wt%)
surf :
co-surf
SBA (wt%)
Optimal
Solubilization
Ratio, * (cc/cc)
Eq. Time at
S* (days)
mg/L NaCl
1.0 1.0 1 : 1 1 13 21 72200
1.25 0.75 5 : 3 1 15 5 53750
1.5 0.5 3 : 1 1 13 5 36860
1.75 0.25 7 : 1 2 17 21 21500
2.0 0 2 very viscous >55 very viscous

Reducing Co-solvent. Reducing co-solvent concentration reduces overall chemical costs, and should be minimal while
maintaining performance and aqueous stability. The SBA concentration was varied from 0.5 to 2 wt% for 1:1, 5:3, and 3:1
surfactant to- co-surfactant ratios, and the results are shown in Table 4. A co-solvent concentration of 0.5 wt% SBA showed
the highest solubilization with the 5:3 ratio; however, sufficiently high solubilization ratio (> 10) occurred for all
experiments. Only 1:1 and 5:3 ratios were possible though at the lowest co-solvent concentration because higher ratios
showed viscous behavior. Experiments with low co-solvent did show higher equilibration times compared to using more co-
solvent; however, visual observation of low co-solvent tests still showed fluid interfaces, and these formulations were
deemed suitable. Additionally, low surfactant to- co-surfactant ratios were desired because they could withstand higher
concentrations of NaCl.

Table 4Effects of Co-Solvent Concentration on Phase Behavior Using Soft Brine
Co-Solvent Surfactant Co-surfactant Ratio
Optimal
Salinity, S*
wt% SBA
C
16-17
- 7PO-
SO
4
-
(wt%)
C
15-18
IOS
(wt%)
surf :
co-surf
Optimal
Solubilization
Ratio, (cc/cc)
Equilibration.
Time at S*
(days) mg/L NaCl
1.0 1.0 1 : 1 16 21 75250 0.5
1.25 0.75 5 : 3 18 21 53750
1.0 1.0 1 : 1 13 21 72180
1.25 0.75 5 : 3 15 5 53750
1
1.5 0.5 3 : 1 13 5 36860
1.5 1.5 0.5 3 : 1 17 21 35320
1.25 0.75 5 : 3 13 5 49150 2
1.75 0.25 7 : 1 17 21 21500

Reducing Total Surfactant Concentration. Reducing total surfactant concentration in phase behavior helps understand
microemulsion performance with varying concentration. Table 4 shows results for 0.5, 1, and 2 wt% total surfactant
concentrations for surfactant to co-surfactant ratios of 3:1, 5:3, and 1:1. Co-solvent concentration was varied proportionally
with surfactant concentration as well. The results show that good solubilization was maintained as surfactant concentration
decreased for all surfactant ratios. Both equilibration time and optimal salinity showed slight decreases with decreasing
surfactant concentration. Because lower surfactant concentrations maintained performance with more free-flowing interfaces,
they were preferred. It is important to understand that chemical flooding depends on the total mass of surfactant in a chemical
flood, proportional to the slug size times its concentration, which satisfies surfactant adsorption (actually retention) in the
reservoir. Because mixtures here performed well regardless of surfactant concentration, a small, concentrated surfactant slug
should perform as well as a larger, dilute slug, as long as the total amount of surfactant is the same.

8 SPE 113469
Table 5Effects of Surfactant Concentration on Microemulsion Phase Behavior Using Soft Brine
Surfactant Co-surfactant Ratio Co-solvent
Optimal
Salinity, S*
Total
Surfactant
(wt%)
C
16-17
- 7PO-
SO
4
-
(wt%)
C
15-18
IOS (wt%)
surf :
co-surf
SBA (wt%)
Optimal
Solubilization
Ratio, (cc/cc)
Eq. Time at
S* (days)
mg/L NaCl
1.5 0.5 3 : 1 1.5 16.5 21 35325
1.0 1.0 1 : 1 0.5 16 21 75255
2
1.25 0.75 5 : 3 0.5 18 21 53750
0.75 0.25 3 : 1 0.75 15 3 35325
0.50 0.50 1 : 1 0.25 16 15 73720 1
0.625 0.375 5 : 3 0.25 18 - 53750
0.25 0.25 1 : 1 0.125 18 3 66040
0.5
0.3125 0.1875 5 : 3 0.125 15 15 47610

Alkali Effects and Selection. The effect of sodium carbonate and sodium metaborate alkali chemicals were tested on
several surfactant concentrations, and an alkali concentration from 0.5 to 1 wt% was determined sufficient to provide suitable
pH and satisfy alkali consumption in the core. Alkali, however, was found to improve the fluidity of the microemulsion, and
several experiments were performed at low surfactant concentration without any co-solvent. Table 6 compares phase
behavior results with and without alkali using hard and soft brines, and displays experiments with no co-solvent and low
surfactant concentration. When soft brine was used, the solubilization ratio remained constant at 19, and the optimal salinity
remained within a 53000 to 60000 mg/L range. Using hard brine gave an acceptable, but lower solubilization when sodium
metaborate was used, and the optimal salinity decreased from 36000 to 29740 mg/L TDS for alkali and no alkali
experiments, respectively. Equilibration time data was not gathered for all experiments, but all microemulsions were very
fluid, and of low viscosity. Therefore, adding alkali did not significantly affect performance, and eliminating co-solvent gave
good results. However, it is important to realize that co-solvent may be crucial for most crude oils, with this one being the
exception.

Table 6Effects of Conventional and Novel Alkali Using Both Hard Synthetic Formation Brine or Soft Brine
Surfactant Co-surfactant Ratio Co-solvent
Optimal
Salinity, S*
Alkali / wt%
C
16-17
- 7PO-
SO
4
-
(wt%)
C
15-18
IOS
(wt%)
surf :
co-surf
SBA (wt%)
Optimal
Solubilization
Ratio, (cc/cc)
Eq. Time at
S* (days)
mg/L
Hard or soft
brine
0.25 0.25 1 : 1 0 19 - 58360 Soft
None
0.25 0.25 1 : 1 0 18 > 14 29740 Hard
Na2CO3 / 1 wt% 0.25 0.25 1 : 1 0 19 28 53750 Soft
0.25 0.25 1 : 1 0 12 21 36000 Hard Na
2
B
2
O
5
(OH)
4
/
1 wt% 0.25 0.25 1 : 1 0 19 - 59900 Soft

Formation Brine Utilization. In many reservoirs under water flood, produced formation brine is used as the injection
fluid where other fresh or saline water sources may be unavailable or uneconomical. The utilization of some or all the
formation brine as the aqueous phase during field injection can minimize disposal and/or softening costs, or the cost of
drilling into alternate aquifers. To utilize the most formation brine in a surfactant slug, the optimal salinity must be high.
Table 6 shows phase behavior results that compared the optimal salinity values of both hard and soft brines for experiments
with and without alkali. The alternative alkali sodium metaborate was used with hard brine as the conventional sodium
carbonate would form precipitates with the high Ca
++
concentration of the hard brine. As mentioned previously, using hard
brine versus soft brine decreased the optimal salinity of respective ions nearly in half for experiments with and without
metaborate. Therefore, one economic trade-off when utilizing formation brine is that incurring softening costs can utilize
twice the amount of produced water and decrease disposal costs.

Formulations for Core floods. Four well performing chemical formulations were selected for four different core flood
experiments based on the phase behavior results. Surfactant-to-co-surfactant ratios of 1:1 and 5: 3 worked well for low co-
solvent requirements, and both ratios maintained performance at low surfactant concentrations. A starting point for the first
core flood formulation was a 5:3 ratio of 1 wt% total surfactant, 0.25 wt% co-solvent, no alkali, and soft brine, which is
similar to a successful formulation (3:1 ratio, 1 wt% surfactant, 1 wt% co-solvent) used by Levitt et al (2006). The other three
formulations favored a 1:1 ratio, low surfactant concentration of 0.5 wt%, and no co-solvent, which performed well in phase
behavior experiments. These formulations contained soft brine with 1 wt% sodium carbonate, and hard brine with no alkali
and 0.75 wt% sodium metaborate. Table 7 lists these formulations used in core flood experiments D-2 to D-8, with their
phase behavior solubilization and optimal salinity. Note that the polymer concentration added to complete the SP or ASP slug
is not indicated in Table 7. Solubilization ratio data for all four formulations can be seen in Figs. 1 through 4.

SPE 113469 9
Table 7Four Surfactant-Alkali Formulations Selected for Core Flood Experiments Showing Good Phase Behavior Performance
Surfactant Co-surfactant Ratio Co-solvent Alkali (wt% active)
Optimal
Salinity, S*

C
16-17
- 7PO-
SO
4
-
(wt%)
C
15-18
IOS
(wt%)
surf :
co-surf
SBA (wt%) Na
2
CO
3
Na
2
B
2
O
5
(OH)
4

Optimal
Solubilization
Ratio, (cc/cc) mg/L
Hard or
Soft Brine
D 2 0.625 0.375 5 : 3 0.25 - - 16 49500 Soft
D 5 0.25 0.25 1 : 1 - - - 18 30000 Hard
D 7 0.25 0.25 1 : 1 - - 0.75 17 34000 Hard
D 8 0.25 0.25 1 : 1 - 1 - 19 47500 Soft

Core Flood Results: Validation of Promising Chemical Formulations
Core flood results. Core flood experiments were a means to validate whether a promising chemical formulation that
performed well in phase behavior experiments were capable of recovering residual oil in cores with low surfactant retention.
All core flood experiments showed significant residual oil recovery without a preflood despite the high salinity contrast at the
displacement front of the surfactant slug with initial SFB saturation. Table 8 lists dimension, permeability, and saturation
core property data measured or calculated during core preparation and pre-flood (SFB flood, oil flood, water flood)
experiments. Core data shows some differences despite Berea sandstone being used for all experiments. Absolute
permeability ranged from 200 to 1000 md, while relative oil and water permeabilities ranged from 0.458 to 0.623 and 0.065
to 0.119, respectively. However, residual oil saturation was similar for all cores (from 0.286 to 0.324) prior to chemical
flooding, and its recovery was a major focus of the experiments.

Table 8Measured Core Properties
D - 2 D 5 D - 7 D - 8
Mass (dry core only) M (g) 1248 1254 1244
Total Length L (cm) 30.4 29.7 29.7 29.8
Diameter D (cm) 5.1 5.1 5.1 5.1
Pore Volume PV (mL) 126.7 105 107 97
Mass,
Dimensions
Porosity 0.204 0.175 0.175 0.16
Air (dry, bare core) k
air
(md) 815 700.5 313.4 1179
Absolute (SFB) k
br
(md) 603 714.2 200.2 1004
Relative oil (end-point) k
ro
0.623 0.458 0.608 0.539
Permeability
Relative water (end-point) k
rw
0.119 0.065 0.1 0.102
initial water S
wi
0.706 0.714 0.707 0.676
Residual water S
wr
0.39 0.42 0.37 0.28
initial oil S
oi
0.61 0.58 0.63 0.72
Saturation
Residual oil S
or
0.294 0.286 0.293 0.324

Surfactant slug and polymer drive. Table 9 lists the chemical formulations for the surfactant slug and polymer drive
solutions used in the four core floods. The surfactant slug is based of the phase behavior data discussed previously in Table 7,
except that polymer has been added to provide sufficient viscosity. The polymer drive solution, compared to the surfactant
slug, contains about 60% of the electrolyte concentration and the same concentration of polymer. Table 10 contains viscosity
measurements of these injection fluids prior to injection, and compares them to calculated apparent viscosity required for
each core. The viscosity of all injection fluids was 2 to 5 times the apparent viscosity, which is acceptable for favorable
displacement. Viscosity was also used to estimate an expected pressure drops around 1 to 2 psi/ft using a polymer
permeability reduction factor, R
k
, of 1.5.

Injection rates and volumes. Injection rates and volumes of the surfactant slug and polymer drive are displayed in Table
10. The target injection rate was around 2 ft/day, but varied depending on the absolute permeability of a core. Experiment D-
2 and D-5 were at or near the target rate, and contained permeability of 603 md and 714 md, respectively. Experiment D-7
injected a lower rate of 1.6 ft/day due to a 313 md permeability, and D-8, with a permeability of 1179 md, injected at a higher
rate of 2.4 ft/day. All core floods injected a 0.3 pore volume surfactant slug, with a polymer drive volume of 1.7 to 2.3 pore
volumes depending on completion of microemulsion recovery.

10 SPE 113469
Table 9Chemical Formulations for the Surfactant Slug and Polymer Drive
D - 2 D - 5 D 7 D - 8
C
16-17
- 7PO - SO
4
-
(wt%) 0.625 0.25 0.25 0.25
C
15-18
IOS (wt%) 0.375 0.25 0.25 0.25
Surfactants
Ratio (surf. - co-surf.) 5 : 3 1 : 1 1 : 1 1 : 1
co-solvent SBA (wt%) 0.25 - - -
Na
2
CO
3
(wt%) - - - 1
Alkali
Na
2
B
2
O
4
8H2O (wt% active) - - 0.75 -
Polymer Flopaam S3330 (ppm) 2000 2500 2100 1500
Hard Brine (mg/L TDS) - 34740 38640 -
Surfactant
Slug
Electrolyte
Soft Brine (mg/L NaCl) 49500 - - 51970
Polymer Flopaam S3330 (ppm) 2000 2500 2100 1500
Hard Brine (mg/L TDS) - 15650 23480 -
Polymer Drive
Electrolyte
Soft Brine (mg/L NaCl) 32710 - - 34090

Table 10Design Calculations and Measurements, and Chemical Flood Injection, Recovery, and Pressure Data

D 2 D - 5 D - 7 D 8
Surfactant slug viscosity (cp) at 11 sec
-1
10.9 6.5 4 5.21
Polymer drive viscosity (cp) at 11 sec
-1
8.7 8.88 5.2 6.8
Calculated apparent viscosity (cp) 2.08 3.1 2.24 2.41
Design
Calculations,
Measurements
Estimated pressure drop (psi) 2.13 1.19 1.07 1.43
(mL/hr) 11.2 9 7.2 9.6
Flow rate
(ft/d) 2.1 2 1.6 2.4
Surfactant slug size (PV) 0.3 0.3 0.3 0.3
Injection
Data
Polymer drive size (PV) 2.3 1.7 1.7 2
Oil Bank breakthrough (PV) 0.3 0.3 0.3 0.35
Surfactant Breakthrough (PV) 0.83 0.9 0.83 0.5
Oil Recovery (%) 97 84 96 97
Recovery
Data
Surfactant Retention (mg/g) 0.24 0.11 - 0.07
2.5 2.05 5.9 0.75
Max pressure drop (psi) at PV
at 0.4 at 0.5 at 0.9 at 0.5
Max pressure drop (psi) at 1 ft/D 1.19 1.03 3.7 0.31
Average polymer pressure drop (psi) 1.6 1.5 3.8 0.68
Pressure Data
polymer perm reduction ratio, Rk 1.60 2.26 3.39 1.60

Pressure Drop. Figures 13 through 16 show the pressure drop across the whole core versus pore volumes injected for
each chemical flood, and Table 10 displays measured and calculated pressure data. The maximum pressure drop was
generally reached after 0.4 to 0.5 pore volumes of fluid were injected, corresponding to the beginning of oil recovery.
Experiment D-7 containing sodium metaborate had a delayed pressure maximum at 0.9 PV, but also experienced a local
pressure maximum around 0.4 PV as well. Core floods also showed pressure to level off at different times, which did not
correlate to how long the microemulsion recovery time was. Experiment D-8 using sodium carbonate showed the lowest
pressure drop profile, therefore the sodium carbonate likely contributed to low microemulsion viscosity.
The pressure drop measured at the final steady state condition was used to estimate the polymer permeability, assuming
only the polymer solution was present. Actual values were generally less than less than those estimated, except compared to a
higher pressure drop for D-7. During the epoxy process, some epoxy seeped under the inlet end-cap of the core, and the core
end was drilled through the tubing to allow fluid flow. Therefore, the inlet had a higher pressure drop than the other
experiments. Calculated polymer permeability reduction was near the assumed design value of 1.5 for experiments D-2 and
D-4, and much different that the 2.26 and 3.39 calculated for D-5 and D-7. Measured maximum pressure drops were
normalized to the flow rate to estimate the maximum pressure drop per 1 ft/day flow rate. In all floods except D-7, these were
at or lower than typical, field-scale water flood values of 1 psi / ft/day. Experiment D-7 containing sodium metaborate was
almost four times higher than the target, but still acceptable for a field-scale flood.

SPE 113469 11
Oil Recovery. Figures 5 through 8 show plots of oil cut and cumulative oil recovery versus pore volumes injected for
each core flood experiment. Residual oil recovery was around 97% for both core floods D-7 and D-8 containing alkali, and
flood D-2 without alkali containing soft brine. Core flood D-5 without alkali containing hard formation brine had less
recovery at 84%. All core floods showed oil bank recovery to begin after 0.3 pore volumes of injection, and three of four
showed surfactant breakthrough at 0.8 to 0.9 pore volumes. Core flood D-8 showed early surfactant breakthrough at 0.5 pore
volumes and microemulsion recovery to end latest at 2.2 pore volumes; however most residual oil was still recovered.
Experiment D-2 showed the most desirable recovery pattern, with nearly 90% of recovery occurring within 1 PV of injection,
mostly during oil bank production. Experiments D-5 had 60% of its 84% recovery during oil bank production, while D-7 had
less than 40% of its 96% recovery from its oil bank.

Salinity Gradient. The aqueous phase in many of the recovered effluent samples was measured for conductivity using an
Orion 5-star benchtop conductivity meter. Figures 9 through 12 plot the measured effluent conductivity versus injected pore
volumes, with conductivity represented as salinity in terms of mg/L TDS. In all core floods, early effluent was nearly all
SFB, decreasing to a salinity indicative of surfactant slug salinity (i.e. near optimal salinity) around surfactant breakthrough,
and polymer drive salinity after long injection times. Oil mobilization begins when salinity decreases to Type III conditions,
otherwise surfactant can be trapped as a Type II microemulsion phase. Additional surfactant could be mobilized when
salinity reached the Type I region, as shown in Fig. 10 with the additional surfactant recovery peak. Initial recovery of the oil
bank can have a Type II salinity because oil has been pushed ahead of the mobilization front into more saline conditions. In
all core floods, oil recovery began around injection of 0.3 pore volumes, with effluent salinity ranging from 100,000 to
150,000 mg/L TDS, far from the 30,000 to 60,000 mg/L TDS range of the Type III / Type II boundaries (Figs. 9 through 12).
Effluent contained Type III salinity during microemulsion production after surfactant breakthrough.
Remaining in Type III salinity conditions for a longer injection period is most favorable, indicating a prolonged period of
low IFT. The polymer drive should have a salinity low enough for surfactant to quickly transition into the Type III region,
and to eventually transition into the Type I region. For all core floods, effluent reached a Type III salinity after about one
pore volume, and remained there for at least 0.5 pore volumes. Experiments D-7 and D-8 remained in the Type III region for
the duration of the flood, resulting in significant slower oil recovery and more oil recovery as emulsion and/or microemulsion
after surfactant breakthrough (Figs. 7 and 8). A slightly lower salinity in the polymer drive would have been more favorable.

Surfactant Recovery. Surfactant concentration in the effluent samples was measured using HPLC analysis. Figures 9
through 12 show the measured surfactant concentrations for each core flood. The beginning of surfactant recovery
corresponds with surfactant breakthrough, and lasted for 0.9 to 1.7 pore volumes depending on the core flood. Surfactant
retention is calculated as the difference between total surfactant injected and recovered, normalized to the dry rock mass.
Total surfactant recovery is estimated as the area under the surfactant recovery curve. Figure 9 shows a smooth surfactant
recovery curve having a single peak for experiment D-2. For this core flood, approximately 69 mg of the 380 mg surfactant
injected was recovered, and therefore 311 mg of surfactant, or 0.24 mg surfactant per gram rock, was retained in the rock.
Similar measurement for experiments D-5 and D-8 show a retention of around 0.1 mg /g. Surfactant recovery for experiment
D-7 containing sodium metaborate was not measured, and therefore a surfactant retention could not be calculated.

Conclusions
This paper describes a systematic laboratory approach to chemical flooding that successfully tested and optimized chemical
formulations using fast, inexpensive phase behavior experiments, and validated their ability to recover almost 100% of the
water flood residual oil from cores. The success of this simple and fast laboratory approach was based on several decades of
theoretical and practical research, and recent laboratory successes in the laboratory using the high performance surfactants
Petrostep S1 (C
16-17
7PO SO
4
-
) and Petrostep S2 (C
15-18
IOS) provided by Stepan Chemical Co. A mixture of these two
surfactants consistently showed good performance in microemulsion phase behavior experiments, even with hard, saline
brines.
Properly selected, high-performance surfactants and well designed core floods showed high oil recovery and low
surfactant retention in a hard, saline environment without the need for a preflood. The high salinity mixing between the brine
and surfactant slug at the displacement front did not hinder the oil recovery process, and shows very clearly the robustness of
a chemical flood with a properly designed salinity gradient.
Metaborate was tested as an alternative alkali since it can tolerate high concentrations of calcium ions. This allowed us to
mix the ASP slug using hard brine rather than soft brine. This novel formulation was tested in a core flood and 96% of the
water flood residual oil saturation was recovered. This is a very significant development with a high potential to decrease the
cost of ASP enhanced oil recovery since soft water may be unavailable and hard brines can be expensive to soften.

Acknowledgements
The authors would like to acknowledge the companies that provided expertise, financial support, and materials for this work.
Chevron Corporation and Cano Petroleum have provided funding, materials and field data. Stepan, Harcros, Shell Chemical
and Sasol provided surfactant samples and helpful information about them including some new surfactants first tested at The
University of Texas at Austin. SNF Floerger provided the polymer samples and helpful information about their polymers. We
12 SPE 113469
would also like to thank the 18 companies who participate in the Chemical EOR JIP in the Center for Petroleum and
Geosystems Engineering (CPGE) (www.cpge.utexas.edu) at The University of Texas at Austin for both the real world
knowledge they share with students and faculty and the research funding that makes this work possible. We thank laboratory
assistants Cody Cox, Anna Pham, and Katherine Tanner for their help with laboratory experiments and data analysis. We also
acknowledge staff, technicians, and resources at the CPGE.


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SPE 113469 13


























Fig. 1Oil and water solubilization data using soft brine used in core flood D-2 (55 days).




























Fig. 2Oil and water solubilization data using hard formation brine used in core flood D-5 (28 days).




0
10
20
30
40
15000 25000 35000 45000
Hard Brine (mg/L TDS)
S
o
l
u
b
l
i
z
a
t
i
o
n

R
a
t
i
o

(
c
c
/
c
c
)
Temp = 52 C
Oil Solubilization Ratio
Water Solubilization Ratio
0
20
40
60
42500 47500 52500 57500
Soft Brine (mg/L NaCl)
S
o
l
u
b
l
i
z
a
t
i
o
n

R
a
t
i
o

(
c
c
/
c
c
)
Temp = 52 C
Oil Solubilization Ratio
Water Solubilization Ratio
14 SPE 113469



























Fig. 3Oil and water solubilization data using metaborate in hard brine used in core flood D-7(28 days).



























Fig. 4Oil and water solubilization data using sodium carbonate in soft brine used in core flood D-8. (28 days).




0
10
20
30
40
37500 42500 47500 52500 57500 62500
Soft Brine (mg/L NaCl)
S
o
l
u
b
l
i
z
a
t
i
o
n

R
a
t
i
o

(
c
c
/
c
c
)
Temp = 52 C
Oil Solubilization Ratio
Water Solubilization Ratio
0
10
20
30
40
20000 25000 30000 35000 40000 45000
Hard Brine (mg/L TDS)
S
o
l
u
b
l
i
z
a
t
i
o
n

R
a
t
i
o

(
c
c
/
c
c
)
Temp = 52 C
Oil Solubilization Ratio
Water Solubilization Ratio
SPE 113469 15



























Fig. 5Oil cut and cumulative oil recovery for core flood D-2.




























Fig. 6Oil cut and accumulated recovery cores for core flood D-5.



0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.5 1.0 1.5 2.0
Pore Volumes
F
r
a
c
t
i
o
n
Cumulative Oil Recovery
Oil Cut
OIL BANK
0
0.2
0.4
0.6
0.8
1
0.0 0.5 1.0 1.5 2.0
Pore Volumes
F
r
a
c
t
i
o
n
Oil Cut
Cumulative Oil Recovery OIL BANK
16 SPE 113469



























Fig. 7Oil cut and accumulated recovery cores for core flood D-7.




























Fig. 8Oil cut and accumulated recovery cores for core flood D-8.



0
0.2
0.4
0.6
0.8
1
0.0 0.5 1.0 1.5 2.0
Pore Volumes
F
r
a
c
t
i
o
n
Oil Cut
Cumulative Oil Recovery OIL BANK
0
0.2
0.4
0.6
0.8
1
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
F
r
a
c
t
i
o
n
Oil Cut
Cumulative Oil Recovery OIL BANK
SPE 113469 17




























Fig. 9Produced surfactant and salinity concentrations for core flood D-2.




























Fig. 10Surfactant effluent and dilution ratio curves for core flood D-5.


0
50000
100000
150000
0 0.5 1 1.5 2
Pore Volumes
S
a
l
i
n
i
t
y
,

m
g
/
L

T
D
S
0
1000
2000
3000
S
u
r
f
a
c
t
a
n
t

C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
TYPE II
TYPE III
TYPE I
Surfactant
Concentration
Salinity
0
50000
100000
150000
0 0.5 1 1.5 2
Pore Volumes
S
a
l
i
n
i
t
y
,

m
g
/
L

T
D
S
0
500
1000
1500
S
u
r
f
a
c
t
a
n
t

C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
TYPE II
TYPE III
TYPE I
Surfactant
Concentration
Salinity
18 SPE 113469




























Fig. 11Surfactant effluent and dilution ratio curves for core flood D-7.




























Fig. 12Surfactant effluent and dilution ratio curves for core flood D-8.


0
50000
100000
150000
0 0.5 1 1.5 2
Pore Volumes
S
a
l
i
n
i
t
y
,

m
g
/
L

T
D
S
TYPE II
TYPE III
TYPE I
Salinity
0
50000
100000
150000
0 0.5 1 1.5 2
Pore Volumes
S
a
l
i
n
i
t
y
,

m
g
/
L

T
D
S
0
1000
2000
3000
S
u
r
f
a
c
t
a
n
t

C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
TYPE II
TYPE III
TYPE I
Salinity
Surfactant
Concentration
SPE 113469 19




























Fig. 13Measured pressure data for core flood D-2.





























Fig. 14Measured pressure data for core flood D-5.

0
1
2
3
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
P
r
e
s
s
u
r
e

D
r
o
p
,

p
s
i
Surfactant
Slug
Polymer Drive
0
1
2
3
0.0 0.5 1.0 1.5 2.0
Pore Volumes
P
r
e
s
s
u
r
e

D
r
o
p
,

p
s
i
Surfactant
Slug
Polymer Drive
20 SPE 113469




























Fig. 15Measured pressure data for core flood D-7.




























Fig. 16Measured pressure data for core flood D-8.
0
2
4
6
8
0.0 0.5 1.0 1.5 2.0
Pore Volumes
P
r
e
s
s
u
r
e

D
r
o
p
,

p
s
i
Surfactant
Slug
Polymer Drive
0
0.5
1
1.5
2
0.0 0.5 1.0 1.5 2.0
Pore Volumes
P
r
e
s
s
u
r
e

D
r
o
p
,

p
s
i
Surfactant
Slug
Polymer Drive