Favorable Attributes

of Alkaline-Surfactant-Polymer Flooding
Shunhua Liu, SPE, Rice University; Danhua Leslie Zhang, SPE, Intertek Westport; Wei Yan, SPE, Bechtel; and
Maura Puerto, George J. Hirasaki, SPE, and Clarence A. Miller, SPE, Rice University
Summary
A laboratory study of the alkaline-surfactant-polymer (ASP) pro-
cess was conducted. It was found from phase-behavior studies that
for a given synthetic surfactant and crude oil containing naph-
thenic acids, optimal salinity depends only on the ratio of the
moles of soap formed from the acids to the moles of synthetic
surfactant present. Adsorption of anionic surfactants on carbonate
surfaces is reduced substantially by sodium carbonate, but not by
sodium hydroxide. The magnitude of the reduction with sodium
carbonate decreases with increasing salinity.
Particular attention was given to a surfactant blend of a pro-
poxylated sulfate having a slightly branched C
1617
hydrocarbon
chain and an internal olefin sulfonate. In contrast to alkyl/aryl
sulfonates previously considered for EOR, alkaline solutions of
this blend containing neither alcohol nor oil were single-phase
micellar solutions at all salinities up to approximately optimal
salinity with representative oils. Phase behavior with a west Texas
crude oil at ambient temperature in the absence of alcohol was
unusual in that colloidal material, perhaps another microemulsion
having a higher soap content, was dispersed in the lower-phase
microemulsion. Low interfacial tensions existed with the excess oil
phase only when this material was present in sufficient amount in
the spinning-drop device. Some birefringence was observed near
and above optimal conditions. While this phase behavior is some-
what different from the conventional Winsor phase sequence,
overall solubilization of oil and brine for this system was high,
leading to low interfacial tensions over a wide salinity range and to
excellent oil recovery in both dolomite and silica sandpacks. The
sandpack experiments were performed with surfactant concentra-
tions as low as 0.2 wt% and at a salinity well below optimal for the
injected surfactant. It was necessary that sufficient polymer be
present to provide adequate mobility control, and that salinity be
below the value at which phase separation occurred in the poly-
mer/surfactant solution.
A 1D simulator was developed to model the process. By cal-
culating transport of soap formed from the crude oil and injected
surfactant separately, it showed that injection below optimal sa-
linity was successful because a gradient in local soap-to-surfactant
ratio developed during the process. This gradient increases robust-
ness of the process in a manner similar to that of a salinity gradient
in a conventional surfactant process. Predictions of the simulator
were in excellent agreement with the sandpack results.
Background
Although both injection of surfactants and injection of alkaline
solutions to convert naturally occurring naphthenic acids in crude
oils to soaps have long been suggested as methods to increase oil
recovery, key concepts such as the need to achieve ultralow inter-
facial tensions and the means for doing so using microemulsions
were not clarified until a period of intensive research between
approximately 1960 and 1985 (Reed and Healy 1977; Miller and
Qutubuddin 1987; Lake 1989). Most of the work during that period
was directed toward developing micellar-polymer processes to re-
cover residual oil from sandstone formations using anionic surfac-
tants. However, Nelson et al. (1984) recognized that in most cases
the soaps formed by injecting alkali would not be at the optimal
conditions needed to achieve low tensions. They proposed that a
relatively small amount of a suitable surfactant be injected with the
alkali so that the surfactant/soap mixture would be optimal at
reservoir conditions. With polymer added for mobility control, the
process would be an alkaline-surfactant-polymer (ASP) flood. The
use of alkali also reduces adsorption of anionic surfactants on
sandstones because the high pH reverses the charge of the posi-
tively charged clay sites where adsorption occurs.
The initial portion of a Shell field test, which did not use
polymer, demonstated that residual oil could be displaced by an
alkaline-surfactant process (Falls et al. 1994). Several ASP field
projects have been conducted with some success in recent years in
the US (Vargo et al. 2000; Wyatt et al. 2002). Pilot ASP tests in
China have recovered more than 20% OOIP in some cases, but the
process has not yet been applied there on a large scale (Chang
et al. 2006).
Nevertheless, important aspects of the ASP process remain
incompletely understood. One, which we address in this paper, is
how to make surfactant and soap propagate in such a way as to
maintain ultralow tension. Another is that application of surfactant
processes, including ASP, to carbonate reservoirs received little
attention until the last few years, probably owing to concern that
the main surfactants being considered (e.g., alkyl/aryl sulfonates)
would form calcium and magnesium sulfonates that would either
precipitate or partition into the oil phase. An exception was the
work of Adams and Schievelbein (1987), who found from labo-
ratory experiments and two well pair tests that oil could be dis-
placed in a carbonate reservoir using a mixture of petroleum sul-
fonates and alkyl ether sulfates or alkyl/aryl ether sulfates.
Carbonate reservoirs are typically mixed-wet and often frac-
tured as well. As a result, considerable effort has been directed
toward promoting spontaneous imbibition of aqueous solutions by
adding surfactants to alter wettability. Standnes and Austad (2003)
suggested using cationic surfactants to promote desorption of acids
from carbonate rock surfaces, making the rock more water-wet.
Others have investigated the effectiveness of various surfactants in
altering wettability (Spinler et al. 2000; Chen et al. 2001; Xie et al.
2005). Hirasaki and Zhang (2004) showed that if sodium carbonate
was used as the alkali and injected with a suitable anionic surfac-
tant, the usual positive charge of carbonate rocks could be re-
versed, with the result that surfactant adsorption was greatly de-
creased and oil-wet surfaces were modified to intermediate wet.
They found that a significant amount of oil could be recovered
from an initially mixed-wet carbonate core placed in an imbibition
cell containing a suitable aqueous solution of surfactant, sodium
carbonate, and sodium chloride. The wettability modification al-
lowed the surfactant solution to enter, and the resulting low inter-
facial tension reduced capillary forces to the point that oil rose to
the top of the core, where it was released. No oil was recovered
when a sodium chloride solution was used instead. They proposed
that such alkaline-surfactant solutions could be injected into frac-
tured carbonate formations to increase recovery. Mohanty and co-
workers (Seethepali et al. 2004; Adibhatla et al. 2005) pursued a
similar approach experimentally and performed simulations of
how such a process would perform for field conditions.
Scope of Paper
In this paper, we present laboratory results on phase behavior,
interfacial tensions, adsorption, and oil displacement in unconsoli-
Copyright 2008 Society of Petroleum Engineers
This paper (SPE 99744) was accepted for presentation at the 2006 SPE/DOE Symposium
on Improved Oil Recovery, Tulsa, 2226 April, and revised for publication. Original manu-
script received for review 20 February 2006. Revised manuscript received 2 May 2007.
Paper peer approved 16 May 2007.
5 March 2008 SPE Journal
dated sandpacks for an ASP process using a novel surfactant, a
propoxylated sulfate having a slightly branched C
1617
hydrocar-
bon chain. The propylene oxide provides increased tolerance to
salt and divalent ions. The branched hydrocarbon chain, recently
developed by Shell Chemical with Procter and Gamble (Scheibel
2004), mitigates the formation of liquid crystalline phases in the
absence of oil, thereby permitting surfactant injection as a single-
phase micellar solution at ambient temperature with no added al-
cohol or oil below or at optimal salinity for many oils. In contrast,
alkyl/aryl sulfonates considered previously for EOR exhibited liq-
uid crystal formation well below and at optimal salinity in the
absence of substantial amounts of alcohol or oil. Moreover, the
long hydrocarbon chain and the attached PO chain allow this new
surfactant to have high oil solubilization and hence low interfacial
tensions over a wide range of conditions. It is studied in combi-
nation with an internal olefin sulfonate (IOS-15-18), which is more
hydrophilic and can be used to adjust optimal salinity of the mix-
ture, and with sodium carbonate as the alkali and partially hydro-
lyzed polyacrylamide as the polymer. Recovery of 98% of residual
crude oil having a viscosity of 19 cp was observed in a vertical
dolomite sandpack at ambient temperature using a surfactant slug
of 0.5 PV containing 0.2 wt% surfactant. Similar excellent recov-
ery was also seen in a silica sandpack. A 1D finite-difference
simulator, which tracked transport of soap and injected surfactant
separately, gave predictions in good agreement with the experi-
mental results in both cases. A gradient in soap-to-surfactant ratio
in the direction of flow develops with ultralow tensions being
achieved near the value of this ratio corresponding to optimal
conditions at formation salinity. This gradient acts to make the
process more robust in a manner similar to a salinity gradient in a
conventional surfactant EOR process. The simulations indicate
that another important factor leading to the high recovery observed
in the sandpack experiments is the unusually wide range of con-
ditions for which low interfacial tensions were found in the labo-
ratory experiments.
A process using mixtures of the same two surfactants and the
same polymer but with added alcohol and no alkali has been de-
veloped in parallel by Levitt et al. (2006) for recovery of another
crude oil from dolomite cores.
Experimental
Crude oil samples MY3 and MY4 from a west Texas field were
used. Both came from the same well, and have very similar prop-
erties. API gravity is 28, and acid number is reported to be 0.20 mg
KOH/g. Water was deionized with a conductivity of 47 mS/cm.
Anhydrous sodium carbonate powder (99.8% purity with 0.005%
calcium), NaCl (certified for biological work), and CaCl
2
2H
2
O
(ACS certified) were all obtained from Fisher Scientific. A par-
tially (2530%) hydrolyzed polyacrylamide Flopaam 3330S with a
molecular weight of approximately 8 million was obtained from
SNF Floerger. The two surfactants studied were ammonium C
1617
7PO sulfate (hereafter shortened to N67) supplied by Stepan and
sodium C
1518
internal olefin sulfonate (hereafter IOS) supplied by
Shell. Table 1 lists key abbreviations used in this paper.
Surfactant adsorption was measured on calcite and dolomite.
Calcite powder (SOCAL31) was acquired from Solvay Perfor-
mance Chemicals. Its surface area determined by BET adsorption
was 17.9 m
2
/g. Dolomite powder (Carl Pool Products) was also
used for some experiments. Surface area was 1.7 m
2
/g. The initial
surfactant concentration in aqueous solution was fixed, and calcite
or dolomite was added in increments with equilibrium surfactant
concentration determined after each addition. Potentiometric titra-
tion (Metrhom Titrino Model 716, from Brinkman Instruments)
with hyamine 1622 (benzethonium chloride, from Gallord-
Schlesinger Industries) was used for this purpose. The adsorption
density was calculated by mass balance.
Surfactant solutions and oils were mixed at a specific water/oil
ratio (WOR) in glass vials or pipettes. They were first shaken well
by hand for 1 minute, then mixed on a rotating shaker for 24 hours.
Afterward, they were put in an upright position and allowed to settle.
Interfacial tensions were determined using a University of
Texas Model 300 Spinning Drop Tensiometer equipped with a
video camera (JEM6222, Javelin) and a video micrometer (VIA-
100, Boecheler).
Dolomite sand (Unimin Corporation) and silica sand (US Silica
Ottawa Foundry) were used for the sandpack experiments. Fluids
were injected with an ISCO injection pump Model 2350. A pres-
sure transducer was placed at the inlet to determine the pres-
sure drop across the sandpack, the outlet of which was at atmo-
spheric pressure.
Phase Behavior of Oil-Free Surfactant Solutions
Effect of Salt. Fig. 1 shows the phase behavior at ambient tem-
perature of aqueous solutions containing 3 wt% (active) of mix-
tures of N67 and IOS as a function of added NaCl for a fixed 1
wt% concentration of Na
2
CO
3
, but no alcohol at ambient tempera-
ture. IOS exhibits precipitation above 4 wt% NaCl. In contrast, no
precipitation occurs and a surfactant-rich liquid phase less dense
than brine forms as NaCl content increases for solutions containing
N67 and its mixtures having up to 75% IOS. The line is drawn for
conditions where separation of a second bulk phase was seen. The
solutions appeared cloudy at salinities slightly below the line, in-
dicating that some small droplets of the new phase were present.
The phase transition occurs at higher salinities as IOS is initially
added to N67, reaching a maximum near 8 wt% NaCl for a 1/1
blend. For the 4/1 mixture of N67/IOS, which we shall call the NI
blend, it occurs at approximately 6 wt% NaCl. For N67 alone, but
not for the mixtures, some cloudiness was observed in initially
clear solutions after several months even at low salinities (data
points with additional +). The transition at high IOS contents be-
tween formation of the second liquid phase and precipitation
(dashed line in Fig. 1) was not studied, as these compositions are
of little interest for purposes of the present paper.
The significance of Fig. 1 is that N67/IOS mixtures can be
injected as a single-phase micellar solution of relatively low vis-
cosity at ambient temperature at salinities approaching or in some
cases even exceeding optimal salinity for many oils without addi-
tion of alcohol or oil, a situation rarely found for petroleum sul-
fonate and synthetic sulfonate systems considered previously for
EOR. Injection of a single-phase solution is important because
Fig. 1Effect of added NaCl on phase behavior of 3 wt% solu-
tions of N67/IOS mixtures containing 1 wt% Na
2
CO
3
. (See Table
1 for the definition of N67 and IOS as well as for other abbre-
viations in later figures.)
6 March 2008 SPE Journal
formation of precipitate, liquid crystal, or a second liquid phase
can lead to nonuniform distribution of injected material and non-
uniform transport owing to phase trapping or different mobilities
of coexisting phases.
For example, optimal conditions for the NI blend with 1 wt%
Na
2
CO
3
and MY4 crude oil occur at salinities up to approximately
5 wt% NaCl (see Fig. 2, which is discussed later). Thus, the entire
optimal curve for NI blend is below the phase separation point of
Fig. 1 for the oil-free solution. For comparison, optimal salinity in
Healy and Reeds classic study with a synthetic C
12
orthoxylene
sulfonate, tertiary amyl alcohol, and a mixture of refined oils oc-
curred at 1.5 wt% NaCl (Reed and Healy 1977). However, the
oil-free surfactant/alcohol/brine mixtures were dispersions of the
lamellar liquid crystalline phase or a single lamellar phase for
solutions containing 04 wt% NaCl (Miller et al. 1986). The lamel-
lar phase consists of multiple stacked surfactant bilayers. The
branched nature of the N67 and IOS hydrocarbon chains is an
important factor in inhibiting liquid crystal formation. Straighter
chains can pack more easily into compact surfactant aggregates,
such as bilayers.
Separation of a surfactant-rich liquid on increasing salinity in
this anionic surfactant system is similar to that seen in nonionic
surfactant solutions as temperature is raised above the cloud point.
In both cases, phase separation, which is thought to involve ag-
gregation of or network formation by micelles, takes place as the
surfactant is made less hydrophilic.
Effects of Propylene Oxide, Calcium, and Polymer. In addition
to the effect of hydrocarbon chain branching discussed previously,
the presence of an ethylene oxide and/or propoxylene oxide chain
in such anionic surfactant systems seems to promote formation of
a surfactant-rich liquid instead of lamellar phase. For instance, a
straight-chain C
1213
ethoxylated sulfate having three ethylene ox-
ide groups exhibited formation of a second liquid phase at 30C
upon adding 12.5 wt% NaCl (Mori et al. 1990). Similar behavior
was seen for a 1:1 blend of a similar surfactant and a propoxylated
sulfate having an iso-C
13
hydrophobe (Zhang 2006) (TC blend, see
Table 1). Phase separation in this latter case occurred at 5% NaCl
(with 1% Na
2
CO
3
present). Optimal salinities for these surfactants
with representative oils are higher than the respective phase sepa-
ration salinities. For instance, Fig. 2 shows an optimal salinity of
approximately 12 wt% NaCl for the TC blend itself with MY4
crude (i.e., at low soap-to-surfactant ratios). The TC blend could,
in principle, be used in alkaline/surfactant processes for this crude
oil if injected at salinities where it remains a micellar solution, as
shown by Hirasaki and Zhang (2004). However, the NI blend is
preferable in this case as its optimal salinity is not as far above that
of the naphthenic soaps but is still above field salinity. As a result,
optimal conditions and hence low interfacial tensions are less sen-
sitive to changes in the soap-to-surfactant ratio for the NI blend, as
shown by the lower slope of its curve in Fig. 5.
As indicated previously,, such behavior is different from that of
petroleum and other alkyl/aryl sulfonates, where addition of NaCl
typically produced separation of the lamellar liquid crystalline
phase at salinities well below optimal conditions for representative
oils. Similar behavior with dispersions of the lamellar phase ap-
pearing well below optimal salinity in the absence of alcohol and
oil was also observed for an iso-C
13
propoxylated, ethoxylated
sulfate (Ghosh 1985). This surfactant was studied by Exxon for use
in high-salinity reservoirs. Apparently, the branched hydrophobes
of N67 and IOS produced more resistance to formation of surfac-
tant bilayers than the iso-C
13
hydrophobe.
Fig. 3 shows behavior when CaCl
2
is added to 0.5 wt% mix-
tures of the two surfactants with 2 wt% NaCl present, but no
Na
2
CO
3
. A solid precipitate is observed for IOS alone and for the
mixture containing 80% IOS for CaCl
2
concentrations exceeding
approximately 0.1 and 0.25 wt%, respectively. Except when IOS
content falls below 10%, tolerance to calcium ions is approxi-
mately 1 wt% CaCl
2
for mixtures having higher contents of N67.
For these mixtures, separation of a viscous, surfactant-rich phase
denser than brine occurs at high concentrations of CaCl
2
.
As in petroleum sulfonate systems, addition of a high molecular
weight polymer can cause phase separation. Fig. 4 shows that
increasing NaCl content from 2 to 4 wt% produces phase separa-
tion in a solution containing 0.5 wt% NI blend, 1 wt% Na
2
CO
3
and
0.5 wt% Flopaam 3330S, a partially hydrolyzed polyacrylamide.
Larger micelles are expected at the higher salinity, which promotes
separation into surfactant-rich and polymer-rich phases. Formation
of molecular complexes between the anionic surfactant and an-
ionic polymer are unlikely owing to electrical repulsion.
Phase Behavior With Oil
Importance of Soap-to-Surfactant Ratio. Fig. 5 shows variation
of phase behavior with NaCl concentration for alcohol-free solu-
tions containing 0.2 wt% (active) NI blend and 1 wt% Na
2
CO
3
Fig. 2Optimal salinity as a function of soap-surfactant ratio
for NI and TC surfactant blends with MY4 crude oil.
Fig. 3Effect of added CaCl
2
on phase behavior of 0.5 wt% solu-
tions of N67/IOS mixtures containing 2 wt% NaCl but no Na
2
CO
3
.
Fig. 4Phase separation caused by increasing NaCl content for
aqueous solution of 0.5 wt% NI blend, 1 wt% Na
2
CO
3
, and 0.5
wt% polymer.
7 March 2008 SPE Journal
mixed with MY4 crude oil at a water-to-oil (WOR) ratio of 3 and
stored at ambient temperature for 40 days. From the reported acid
number of this crude oil (0.2 mg KOH/g), soap-to-surfactant ratio
was calculated to be 0.35, assuming that pH is high enough to
saponify virtually all the acid. Its appearance seems to be that of a
conventional Winsor I, III, II microemulsion sequence (Reed and
Healy 1977) with some remaining emulsion that has not yet coa-
lesced. We argue in the following that the situation is in actuality
more complex. We will use the term optimal salinity to designate
that point at which the solubilization ratios (V
o
/V
s
) and (V
w
/V
s
) of
oil and water to surfactant are equal.
Results for several such salinity scans (Zhang 2006) showed
that, if the effect of the soap was ignored, optimal salinity was a
function of both surfactant concentration of the solution and WOR.
Each salinity scan had a fixed soap-to-surfactant ratio. Fig. 2
shows that results for the various scans can be collapsed onto a
single curve depicting optimal salinity as a function of soap-to-
surfactant ratio for both the NI and TC blends. At large and small
values of this ratio, optimal salinity approaches those of the soap
alone (approximately 0.5% NaCl) and surfactant alone (5% and
12% NaCl for NI and TC blends respectively), both in addition to
1 wt% Na
2
CO
3
. For the TC blend, data points at different values
of WOR are explicitly shown, although both WOR and surfactant
concentration were also varied for the NI blend. The optimal sa-
linity of the soap formed from a crude oil is usually below field
salinity. In this case, the surfactant chosen for an ASP flood should
have its optimal salinity above the field value. Such a choice will
facilitate development of a gradient in soap-to-surfactant ratio
passing through the low-tension region, as discussed next.
Special Features of Phase Behavior. Observation over time of
the samples below optimal salinity in Fig. 5 revealed that drops or
particles of material less dense than the lower-phase microemul-
sion rose to the oil-microemulsion interface over time. As a result,
a thin layer of a colloidal dispersion formed, as shown in more
detail in Fig. 6 for a similar sample with 2 wt% NaCl, but with 23
days settling. As demonstrated in the following section, the mate-
rial in this colloidal dispersion is essential for achieving interfacial
tensions (IFT) that are very low in the Winsor I region. It is not
simply a collection of drops having the same composition as the
crude oil that have not yet coalesced with the excess oil phase,
because such drops would not affect IFT. The low density of the
dispersed material suggests a higher ratio of oil to brine than in the
lower phase. The volume of this dispersion increases with increas-
ing salinity below optimal salinity for the scan at WOR3 shown
in Fig. 5. Moreover, its volume was significantly greater for the
same surfactant concentration at WOR1, which contained more
soap and less surfactant. This latter result suggests that the dis-
persed material has a higher soap-to-surfactant ratio than the lower
phase and hence is more lipophilic than the lower phase, with the
capability of solubilizing more oil but less brine.
The nature of the colloidal dispersion discussed previously for
underoptimum samples remains under investigation. Its dispersed
material may be a second microemulsion, which, because it is
more lipophilic than the lower-phase microemulsion, would have
a lower IFT than the lower-phase microemulsion with excess oil.
The existence of two microemulsions in equilibrium is possible for
mixtures of surfactants very different in structure and in hydro-
philic/lipophilic properties, as is the case here. Low IFT between
the microemulsion phases would contribute to ease of dispersion
of one in the other. Such behavior represents a deviation from the
classical Winsor I behavior of a single microemulsion plus excess
oil for underoptimum conditions.
As shown in the following, optimal salinity for the salt scan of
Fig. 5, as defined by conditions for equal solubilization of oil and
brine, is approximately 3.5% NaCl. Fig. 7, the same scan as seen
when the samples are placed between perpendicularly oriented
Fig. 7Salinity scan of Fig. 5 viewed between perpendicularly
oriented polarizers.
Fig. 5Salinity scan for 0.2% NI blend, 1% Na
2
CO
3
with MY4
crude oil for WOR=3 after settling time of 28 days at 25C.
x=wt.% NaCl.
Fig. 6View of dispersion region near interface for sample from
salinity scan of Fig. 5 except after 23 days settling.
8 March 2008 SPE Journal
sheets of polarizing material, shows that slightly below optimal
salinity at 3.2% NaCl the lower phase becomes birefringent. Nev-
ertheless, it behaves as a Newtonian fluid with a low viscosity of
approximately 1.1 mPas (1.1 cp), according to our measurements
using a cone and plate viscometer. Its interface with oil is mobile
when the pipette is tilted and IFT is ultralow, as discussed next.
For overoptimum conditions, a thin birefringent layer exists above
the excess brine. It is separated from the uppermost phase, which
is presumably an oil-continuous microemulsion, by a dispersion of
the birefringent and microemulsion phases.
Equal oil and brine solubilization corresponds to conditions
when surfactant films have no tendency to curve toward either an
oil-continuous or brine-continuous configuration and thus is fa-
vorable for formation of the lamellar liquid crystalline phase,
which consists of many parallel surfactant bilayers and exhibits
birefringence. In view of its low overall surfactant concentration
and viscosity, the birefringent region seen at 3.2% NaCl in Fig. 7
is likely a dispersion of the lamellar phase in a water-continuous
microemulsion. That the dispersion has not separated after 40 days
indicates that the two phases have nearly equal densities. At higher
salinities, the thin birefringent region is probably a lamellar phase.
Interfaces in these overoptimum samples remained mobile after
40 days.
Coexistence of a lamellar phase and a microemulsion has pre-
viously been observed at relatively low surfactant concentrations
when alcohol concentration or temperature in certain microemul-
sions containing anionic surfactant fell below values needed to
obtain the usual Winsor phase behavior with no liquid crystal
(Hackett and Miller 1988). The Winsor sequence can be obtained
in alkaline systems with N67 and MY4 by adding alcohol (Zhang
2006), but interfacial tensions are expected to rise with increasing
alcohol content.
Solubilization Ratios. A solubilization ratio (V
o
/V
s
) can be cal-
culated as the ratio of the volume of solubilized oil to the volume
of surfactant present (excluding soap) for the underoptimum
samples. The volume of solubilized oil is the difference between
the volume of the initial oil in the sample and that of the excess oil
phase after equilibration. It represents a composite value for the
combined lower phase microemulsion and surfactant-containing
phase in the dispersion. As Fig. 8 shows, values of (V
o
/V
s
) increase
from approximately 7 at 2% NaCl to approximately 20 at 3.4%
NaCl, just below optimal salinity. Similar values were found for a
scan with 0.5 wt% NI blend, except that the salinities were higher
with optimal salinity of approximately 4.5% NaCl because the
soap-to-surfactant ratio was smaller. Above optimal salinity, a
similar procedure can be used to obtain an overall (V
w
/V
s
), as
shown in Fig. 8. At salinities well below or above optimal, the
combination of low solubilization and some emulsion precluded
determination of solubilization ratios from phase volumes.
Huh (1979) proposed for classical Winsor III behavior that
solubilization ratios for the microemulsion phase and interfacial
tensions of the microemulsion with excess oil and brine phases
were related as follows:

mo
= cV
o
V
s

2
,
mw
= cV
w
V
s

2
, . . . . . . . . . . . . . . . . (1)
where c is a constant for each system. He found that results avail-
able for EOR systems at that time were consistent with these
expressions for values of c near 0.3 mN/m. Using the first of these
equations with c0.3 mN/m and with (V
o
/V
s
) from Fig. 8 to
estimate IFT below optimal salinity and similarly for (V
w
/V
s
)
above optimal salinity, we obtain the predicted behavior of IFT
shown in Fig. 9. Near optimal salinity where the two curves of Fig.
8 cross, an estimate of both solubilization ratios is 50, which would
lead to the lowest tensions, as indicated by the dip in the curve in
Fig. 9 representing the correlation predictions. The experimental
interfacial tensions shown are discussed in the next section.
We note that some surfactant-oil-brine systems form highly
viscous phases or emulsions, which would be unfavorable for
EOR. As indicated both by the rather mobile nature of the inter-
faces in scans such as that of Fig. 5 and by the results of the
sandpack experiments described next, formation of highly viscous
material does not appear to be a problem in the present system with
proper process design.
Interfacial Tension
A key requirement of alkaline/surfactant processes is achieving
ultralow interfacial tensions. If such tensions correlate with opti-
mal phase behavior and high solubilization as in previous EOR
work, they must depend on the soap-to-surfactant ratio, according
to Fig. 2. Because the amount of soap present for a given volume
of crude oil is dictated by its acid number, relatively low surfactant
concentrations are required if quantities of soap and surfactant are
to be comparable for experiments such as those of the preceding
section. As a result, volumes of some surfactant-containing phases
are small and, as indicated previously, they sometimes occur as
dispersions. These factors make it challenging to obtain reproduc-
ible measurements of interfacial tension.
For the scan of Fig. 5 with 0.2 wt% NI blend, it was found that
below optimal salinity, measured tensions between the lower phase
and excess oil depended on the settling time between the end of the
mixing process and the sampling of the lower phase (well below
the interface) and excess oil. Fig. 10 shows that for the sample
containing 2 wt% NaCl, low tensions (i.e., those below 0.01 mN/
m) were achieved only for settling times of approximately 4 hours
or less. These results suggest that low tensions were not obtained
once most of the colloidal material dispersed in the lower phase
had risen to the vicinity of the interface and thus was not sampled.
A protocol given in Appendix A was developed to assure that
enough of the dispersed material was initially present in the lower-
phase sample to achieve low tensions but not so much as to ob-
scure the oil drop during the spinning-drop measurement, when the
dispersed material collects in the form of a cloud of small droplets
or particles near the larger drop of excess oil. An example of the
latter effect is shown in Fig. 11, where the oil drop at the far left
is almost invisible in the cloud. Some aspects of the protocol such
Fig. 8Solubilization ratios for salinity scan of Fig. 5. Fig. 9Interfacial tensions for salinity scan of Fig. 5 as pre-
dicted from solubilization ratios of Fig. 7 and as measured ex-
perimentally.
9 March 2008 SPE Journal
as the rotation, settling, and pre-equilibration times of Steps 2, 3,
and 6 are specific for this system, but the basic procedure should
be useful in other systems with similar behavior.
With this protocol, tensions below 0.01 mN/m were obtained
over a wide salinity range both above and below optimal for the
scan containing 0.2 wt% NI blend, as shown in Fig. 12. Agreement
with the solubilization ratio correlation is good except at 3.6%
3.8% NaCl (Fig. 9), where measured tensions are higher but still
low enough (near 0.001 mM/m) to mobilize oil and prevent trap-
ping. If soap were included with the surfactant in calculating the
solubilization ratios, the latter would be somewhat smaller and IFT
predictions of the correlation would be somewhat larger and closer
to the data in this salinity range.
Fig. 12 further emphasizes that low tensions are not seen if the
dispersed material is absent, owing either to long settling times or
to its complete removal after being concentrated near the axis of
the tube in the spinning-drop device before adding an oil drop. The
two lower curves show that Step 6 of the protocol, pre-
equilibration of oil drop and aqueous phase in the spinning drop
tube before spinning, may not be required to achieve the equilib-
rium IFT value. However, the time of spinning required to reach
the same constant IFT can be much longeras much as 8 hours
without Step 6 at the lower salinities (see Fig. 13).
For a salt scan identical to that of Fig. 5 but with no sodium
carbonate present (and hence minimal soap), less colloidal disper-
sion was seen. Moreover, IFT values were below 0.01 mN/m over
a much narrower range of NaCl concentrations, as the comparison
of Fig. 14 shows. This result indicates that the wide range of low
tensions with alkali present is a consequence of formation of naph-
thenic soaps.
Adsorption
Figs. 15 and 16 show adsorption isotherms of N67 and IOS on
calcite powder for solutions containing no NaCl and either 0% or
1% Na
2
CO
3
. Adsorption is approximately 0.0035 and 0.007 mmol/
m
2
in the plateau region for the respective surfactants in the ab-
sence of Na
2
CO
3
, corresponding to 0.47 and 0.23 nm
2
/molecule,
assuming a uniform monolayer. The latter number (for IOS) is
close to the area of a single straight hydrocarbon chain. Because
this surfactant consists of a mixture of molecules with the sul-
fonate group located at various places along the hydrocarbon
chain, the adsorbed molecules are twin-tailed. As a result, their
area per molecule should be approximately twice that of a single
chain, and it seems likely that an adsorbed bilayer exists in the
plateau region. Bilayers often form for adsorption of surfac-
tant ions on surfaces of opposite charge at concentrations near
and above the critical micelle concentration (CMC) because they
expose a polar surface, which has a low free energy with the
aqueous phase. The arrangement of adsorbed molecules for N67 is
not clear.
The plateau region for each surfactant represents concentra-
tions well above the CMC, where micelle composition is constant
even for these commercial surfactants with numerous individual
species because virtually all the surfactant is present in the mi-
celles. The plateau region extends to lower surfactant concentra-
tions for the more lipophilic N67 owing to its lower CMC.
Figs. 15 and 16 show the amount adsorbed per unit area be-
cause it is a fundamental property and can be converted to the
amount adsorbed for a rock sample of known mass by measuring
the pore area per unit mass of the sample. With the BET method,
we found that the surface areas of two dolomite cores from a west
Texas formation were 0.13 and 0.21 m
2
/g. Based on the average of
these values and Fig. 15, adsorption of N67 for this formation
would be approximately 0.04 and 0.45 mg/g with and without
sodium carbonate.
The most striking feature of Figs. 15 and 16 is the large reduc-
tion in adsorption produced by addition of Na
2
CO
3
more than an
order of magnitude for N67 and several-fold for IOS. This behav-
ior is similar to that reported previously for the TC blend of an-
Fig. 11View of cloud of dispersed material nearly obscuring
drop at far left, but not at right, during spinning-drop experiment.
Fig. 12IFT for salinity scan of Fig. 5 with different settling
times and procedures.
Fig. 13More rapid achievement of low IFT is possible when
Step 6 of the protocol (Appendix A) is followed.
Fig. 10Dependence of IFT on settling time of sample at 2 wt%
NaCl from salinity scan of Fig. 5.
10 March 2008 SPE Journal
ionic surfactants mentioned previously and occurs for the same
reason: Carbonate is a potential determining ion, which reverses
the charge of the calcite surface from positive to negative, leading
to repulsion of anionic surfactant ions (Hirasaki and Zhang 2004).
Hydroxide is not a potential determining ion for carbonate sur-
faces, and using NaOH instead of Na
2
CO
3
as the alkali produced
no significant change in adsorption of the TC blend (Fig. 17).
While the results of Fig. 17 are for dolomite powder, a series of
experiments with the TC blend showed that the adsorption per unit
area was nearly the same for calcite and dolomite powders.
Fig. 18 shows adsorption isotherms of the NI blend on calcite
at different NaCl concentrations with and without 1 wt% Na
2
CO
3
.
In the absence of NaCl, adsorption is comparable to that of N67
alone. As NaCl concentration increases, the beneficial effect of
Na
2
CO
3
is reduced, presumably because the screening effect of the
additional electrolyte decreases electrostatic repulsion between
surfactant ions in solution and the calcite surface. Nevertheless,
Na
2
CO
3
reduces adsorption by more than a factor of three for 3
wt% NaCl. Additional experiments showed that only 0.10.2 wt%
Na
2
CO
3
was sufficient to produce the same decreases in adsorp-
tion as those shown in Fig. 18 for 1 wt% Na
2
CO
3
.
ASP Forced Displacement Experiments
An ASP process was conducted at ambient temperature using up-
ward flow in a vertical, 35-darcy dolomite sandpack 1 ft long and
1 in. in diameter. After the sandpack was saturated with 2 wt%
NaCl brine, MY4 crude oil (viscosity 19 mPas or 19 cp) was
injected. Then, the sandpack was aged in an oven at 60C for 60
hours to alter wettability of the dolomite. Waterflooding at ambient
temperature with 3.2 PV of 2% NaCl brine reduced oil saturation
from 98% to 18%.
Next, the ASP slug (0.5 PV) containing 0.2 wt% NI blend, 1
wt% Na
2
CO
3
, 2 wt% NaCl, and 0.5 wt% (5,000 ppm) Flopaam
3330S was injected at an interstitial velocity of 14 ft/day, followed
by 1.0 PV of a drive with no surfactant or alkali but with the same
NaCl and polymer concentrations and approximately the same
viscosity (45 mPas or 45 cp) as the slug. The relatively high
polymer concentration and viscosity of both slug and drive were
used owing to the high viscosity of the crude oil. It bears emphasis
that the injected NaCl concentration of 2 wt% was well below the
optimal salinity of 5 wt% for the NI blend alone with this crude
oil (Fig. 2).
The two series of photos in Fig. 19 illustrate the formation and
propagation of the oil bank and the effluent samples. Fig. 20 shows
cumulative recovery of the waterflood residual oil. The oil bank
broke through at approximately 0.8 PV and surfactant at 0.99 PV
(based on the first observation of a colored microemulsion con-
taining solubilized oil instead of transparent brine in the effluent).
The process recovered 98% of the residual oil with 80% as clean
oil. The small amount of oil solubilized in the aqueous effluent was
not measured and hence not included in these numbers.
Fig. 21 shows that the pressure drop across the sandpack in-
creased steadily during injection of the first pore volume of vis-
cous slug and drive fluid, then remained nearly constant at 2.8 psi
(19 kPa). That is, no highly viscous phases or emulsions developed.
A similar ASP flood was performed in a vertical silica sand-
pack of the same dimensions. Permeability was 40 darcies, and
less water was injected, so that remaining oil after waterflooding
was 25% PV. Otherwise, the procedure and solution compositions
were the same as previously described, except that the sandpack
was not subjected to aging and the surfactant concentration in the
slug was 0.5 wt% NI blend. Figs. 22 and 23 show photographs of
Fig. 15Adsorption of N67 on calcite powder (17.85 m
2
/g) with
and without 1 wt% Na
2
CO
3
and with no NaCl.
Fig. 16Adsorption of IOS on calcite powder (17.85 m
2
/g) with
and without 1 wt% Na
2
CO
3
and with no NaCl.
Fig. 17Adsorption of TC blend on dolomite powder, compar-
ing NaOH and Na
2
CO
3
as source of alkali.
Fig. 14IFT for salt scan of Fig. 5 with and without Na
2
CO
3
.
11 March 2008 SPE Journal
the sandpack during the flood and cumulative oil recovery, respec-
tively. Both development and propagation of the oil bank and
recovery of 98% of the oil remaining after waterflooding at ap-
proximately 1.3 PV fluid injected are similar to the results for the
dolomite sandpack, as is the pressure history (not shown). Surfac-
tant broke through slightly earlier at 0.9 PV.
Another ASP flood in a similar silica sandpack was made with
the same procedure and compositions, except that NaCl content of
the brine was 4 wt% instead of 2 wt%. As Fig. 24 shows, consid-
erable oil traveled behind the oil bank, which was much less dis-
tinct than in Fig. 22. Moreover, pressure drop rose to 25 psi (172
kPa), nearly an order of magnitude greater than before Fig. 24. The
high pressure drop indicates that a highly viscous phase or emul-
sion was present, presumably owing to separation of the surfac-
tant slug into polymer-rich and surfactant-rich phases at this sa-
linity (shown in Fig. 4). As Fig. 25 shows, the pressure drop rose
sharply as the concentrated polymer phase was displaced by the
polymer drive.
Simulation
A 1D, two-phase, multicomponent finite-difference simulator was
developed to model the ASP process and was applied for flooding
with the NI blend. Naphthenic acids in the oil are assumed to be
completely converted to soap once the alkali front arrives. Along
the optimal salinity curve of Fig. 2, the partition coefficient be-
tween oil and water phases is taken as unity for both soap and
surfactant and interfacial tension is assumed to be 0.001 mN/m.
The IFT data of Fig. 12, showing low IFTs over a wide range of
salinities at a soap-to-surfactant ratio of 0.35, were used in gener-
ating the IFT contour plot of Fig. 26 (see Appendix B for details).
Values of IFT from Fig. 26 at this soap-to-surfactant ratio shown
in Fig. 12 are conservative at low (<2%) and high (>4%) NaCl
concentrations, where solubilization ratios could not be determined
accurately to confirm the low values of IFT measured. Both soap
and surfactant are assumed to partition strongly into the aqueous
and oil phases, respectively, at salinities somewhat below and
above optimal. Fractional-flow curves for oil and aqueous phases
were calculated as a function of IFT and viscosities of the phases,
taking into account changes in residual oil saturation and shape of
the relative permeability curves which occur as IFT is reduced. A
horizontal displacement was assumed, and surfactant adsorption
and longitudinal dispersion were incorporated into the simulator
(Hirasaki et al. 2005). Simulation parameters used to obtain the
results described in the next paragraph are shown in Table 2. They
are basically those for the ASP floods described previously. Fur-
ther details on the simulations are given in Appendix B.
An important feature of the simulator is its ability to follow
transport of injected surfactant and soap generated from the oil
separately, so that the ratio of their concentrations and hence IFT
Fig. 18Adsorption of NI blend on calcite as a function of NaCl
content with and without 1 wt% Na
2
CO
3
.
Fig. 20Measured and predicted cumulative oil recovery for
ASP flood in dolomite sandpack.
Fig. 21Time-dependence of pressure drop during ASP flood
in dolomite sandpack.
Fig. 19Photos showing behavior during ASP flood of dolomite
sandpack (flow upward).
12 March 2008 SPE Journal
can be calculated as a function of position and time. For instance,
the three plots on the left side of Fig. 27 show soap and surfactant
concentrations, their ratio, IFT, and oil saturation as a function of
position after injection of the 0.5 PV slug during the dolomite
sandpack simulation. A gradient in the soap-to-surfactant ratio
exists, with large values corresponding to overoptimum conditions
ahead of the low-tension region and small values corresponding to
underoptimum conditions behind it. When ultralow tensions exist
over a broad range of conditions, as in Fig. 26, the region of such
tensions in Fig. 27 has a substantial length in the direction of flow.
This region propagates along the sandpack, leaving very little re-
sidual oil. Because any trapping behind the oil bank occurs for
underoptimum conditions, the particularly wide region of low IFT
for such conditions shown in Fig. 26 is important for achieving
high oil recoveries.
Another simulation was performed with a hypothetical nar-
rower low-IFT region. The same optimal contour as in Fig. 26 was
assumed with the same IFT of 0.001 mN/m. However, the contours
for 0.01 mN/m for a soap-to-surfactant ratio of 0.35 were taken at
NaCl concentrations of 3.4 and 3.6%, instead of 2.0 and 4.0% as
in Fig. 26. As shown on the right side of Fig. 26, total oil recovery
is reduced from 95 to 62% of the waterflood residual oil even
though the minimum interfacial tension is the same. The reason is
that once the soap-to-surfactant ratio drops below that correspond-
ing to the minimum IFT, the soap begins to transfer from the oil
into the aqueous phase. If the latter travels faster than the
oil, soap-to-surfactant ratio of the solution in contact with the
trailing oil falls rapidly, leading to a rise in IFT and oil trapping.
If the region of ultralow tension is of considerable length, trapping
is reduced.
Good mobility control is also essential for process success.
Even with the broad region of ultralow tension of Fig. 26, recovery
falls from 95 to 86% if viscosity of the aqueous phase decreases
from 40 to 24 mPa s (40 to 24 cp) for this viscous oil (19 mPa s
or 19 cp).
Figs. 20 and 23 show that the simulator was able to match well
the cumulative oil recovery curves of the sandpack experiments
described above for both dolomite and silica sand. Parameters
were adjusted slightly from those of Table 1 as required to be
consistent with the conditions of the experiments (e.g., measured
viscosities of the fluids, surfactant concentration, and residual oil
saturation after waterflooding).
Conclusions
1. Use of Na
2
CO
3
as the alkali in ASP processes can substantially
reduce adsorption of anionic surfactants on carbonate surfaces,
Fig. 23Measured and predicted cumulative oil recovery for
ASP flood in silica sandpack.
Fig. 24Photos showing behavior during unsuccessful ASP
flood of silica sandpack where phase separation caused by
polymer has occurred (flow upward).
Fig. 25Time-dependence of pressure drop during unsuccess-
ful ASP flood of silica sandpack where phase separation
caused by polymer has occurred.
Fig. 22Photos showing behavior during ASP flood of silica
sand pack (flow upward).
13 March 2008 SPE Journal
especially at low salinities. No significant reduction was seen
when NaOH was used instead.
2. For a given synthetic surfactant and crude oil containing naph-
thenic acids, optimal salinity for alkaline conditions was found
to depend only on the soap-to-surfactant ratio for the range of
conditions studied.
3. Experiments at ambient temperature with a blend of a propoxy-
lated sulfate with a slightly branched C
1617
hydrophobe and an
internal olefin sulfonate but with no alcohol have exhibited:
a. Surfactant/alkali/brine solutions containing no oil that remain
single-phase micellar solutions with increasing salinity until
salinity reaches or exceeds optimal for representative oils, in
contrast to most surfactants such as alkyl/aryl sulfonates in-
vestigated previously for EOR.
b. Phase behavior with a crude oil for alkaline conditions and
low-surfactant concentrations that has the appearance of the
usual Winsor I, III, II sequence with some emulsion that has
not yet coalesced. However, colloidal material, perhaps an-
other microemulsion having a high soap content, is dispersed
in the lower-phase microemulsion for underoptimum condi-
tions. Solubilization parameters are high over a wide range of
salinities. No highly viscous emulsions or gels were ob-
served, although some birefringence was seen near and above
optimal salinity.
c. Interfacial tensions below 0.01 mN/m over a wide range of
salinities both below and above optimal provided that enough
of the dispersed colloidal material is present in the sample
used for the measurement. The experimental range of IFT
below 0.01 mN/m is in reasonable agreement with that pre-
dicted by Huhs correlation based on the measured solubili-
zation ratios.
d. 98% recovery of residual oil in ASP sandpack experiments
for both dolomite and silica sands with the polymer being a
partially hydrolyzed polyacrylamide and with surfactant con-
centrations in the slug as low as 0.2 wt%. Injection salinity
was well below optimal for the synthetic surfactant alone,
thereby avoiding phase separation in the presence of polymer.
4. A 1D numerical simulator was developed to model the ASP
process. It predicted oil recovery curves in agreement with those
of the sandpack experiments. By calculating transport of in-
jected surfactant and soap formed from the crude oil separately,
the simulations indicate that a gradient in soap-to-surfactant
ratio develops with conditions shifting from overoptimum near
the rear of the oil bank to underoptimum behind the main dis-
placement front. The wide range of low tensions found for the
surfactant blend used was found to be an important factor con-
tributing to the high recovery predictions.
Nomenclature
c constant in Huhs correlation
E
j
saturation exponent of phase j in relative permeability
calculation
K partition coefficient
k
o
rj
relative permeability of phase j
k
o
ro
endpoint permeability of oil
k
o
rw
endpoint permeability of water
S
j
saturation of phase j
S
jR
educed saturation of phase j
S
1r
residual saturation of aqueous phase
S
2r
residual saturation of oleic phase
V
o
volume of excess oleic phase
V
s
volume of surfactant phase
V
w
volume of excess water phase

mo
solubilization ratio between microemulsion and excess oil

mw
solubilization ratio between microemulsion and excess water
Acknowledgments
This research was supported by DOE grant DE-FC26-03NT15406
and by the Consortium on Processes in Porous Media at Rice
University. We gratefully acknowledge Shell Chemical and Stepan
for supplying surfactants, Gary Pope and members of his group at
the University of Texas for useful interaction, and Brent Biseda for
performing some of the adsorption experiments.
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Appendix AProtocol for IFT Measurements
With Dispersion Present
1. Mix the crude oil with the alkaline surfactant solution.
2. Rotate the mixture for 24 hours.
3. After settling the mixture for 4 hours, withdraw samples of
oleic and aqueous phases into different syringes.
4. Because the samples in the syringes may continue to settle,
shake them before the spinning-drop measurement, so that they
can be considered as the same samples that were obtained after 4
hours settling.
5. Before the spinning-drop measurement, centrifuge the aque-
ous phase in the spinning tube. Then remove some of the dispersed
material by syringe, because the sample will be too dark if too
much of it remains. The remaining dispersion should have a vol-
ume slightly less than that of the excess oil drop that is subse-
quently added to the spinning-drop tube.
6. Let the oil drop settle in the vertically-oriented tube for some
time (12 hours), so that the dispersed material can equilibrate
with the oil and the lower-phase microemulsion.
7. Begin the spinning-drop measurement and measure IFT.
Appendix BAdditional Information
on Simulator
Fractional Flow. The fractional-flow curve is a function of re-
sidual saturations and relative permeabilities, which are deter-
mined by IFT. For residual saturations, we calculate them from Eq.
B-1, which is similar to the approach used by Pope and Nelson
(1978):
S
1r
= 0, S
2r
= 0 when IFT 0.005 mNm
S
1r
= 0.3
*
1 + log
10
IFT2.3
S
2r
= 0.3
*
1 + log
10
IFT2.3
when 0.005 dynecm IFT 1 mNm, . . . . . . . . . . . . . . . . (B-1)
Fig. 27Spatial distribution of soap and surfactant concentra-
tions; their ratio, IFT, and oil saturation after injection of 0.5 PV
ASP slug for wide and narrow regions of low IFT.
15 March 2008 SPE Journal
S
1r
= 0.3, S
2r
= 0.3 when IFT 1 mNm,
where S
1r
is the residual saturation of aqueous phase, and S
2r
is the
residual saturation of oleic phase.
For the relative permeability, we calculate as follows:
S
jR
=
S
j
S
jr

1 S
1r
S
2r

j = 1, 2 . . . . . . . . . . . . . . . . . . . . . . . (B-2)
k
rj
= k
rj
o
S
jR
Ej
j = 1, 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (B-3)
k
r1
o
= k
rw
o
+ 1 k
rw
o
0.3 S
2r
0.3
k
rw
o
is endpoint permeability of water . . . . . . . . . . . . . . . . . . (B-4)
k
r2
o
= k
ro
o
+ 1 k
ro
o
0.3 S
1r
0.3
k
ro
o
is endpoint permeability of oil . . . . . . . . . . . . . . . . . . . . . (B-5)
Ej = 1.0 when IFT 0.005 mNm
Ej = 1.5 + 16
*
log
10
IFT
when 0.005 mNm IFT 1 mNm . . . . . . . . . . . . . . . . . . . (B-6)
Ej = 1.5 when IFT 1 mNm
At high IFT, these parameters are for a water-wet system.
Interfacial Tension and Partitioning. Fig. 25 was constructed as
follows: Based on the lowest measured IFT in Fig. 12, IFT was
taken to be 0.001 mN/m along the entire curve for the NI blend
given in Fig. 2, showing dependence of optimal salinity on soap/
surfactant ratio. For a soap/surfactant ratio of 0.35, where optimal
salinity is approximately 3.5% NaCl, the point in the underopti-
mum region on the IFT contour for 0.01 mN/m was estimated to
be at 2.0% NaCl, using the data of Fig. 12. This choice is conser-
vative because IFT values near 0.01 mN/m were seen at even
lower salinities, according to Fig. 12. However, emulsions present
at these low salinities prevented confirmation of the low tensions
by solubilization ratio measurements. In the overoptimum region,
IFT was taken to be 0.01 mN/m at 4.0% NaCl for the same soap/
surfactant ratio. Here too, the choice is conservative because mea-
sured IFT values were near 0.01 mN/m at higher salinities, but
emulsions precluded estimates of solubilization parameter. For the
same soap/surfactant ratio, IFT was taken to be 0.1 mN/m at 0.5%
and 5.0% NaCl. In view of Fig. 12 these choices are also conser-
vative. Simulation results were insensitive to the exact location of
the 0.1 mN/m IFT contours. Points on the IFT contours for other
soap/surfactant ratios were located by assuming that a particular
IFT (e.g., 0.01 mN/m) was the same percentage below (or above)
the optimal value as when the ratio was 0.35.
The partition coefficient K between oil and aqueous phases for
the soap/surfactant mixture was calculated by the following em-
pirical method.
Above Optimal Salinity. K 0.01
*
100
R
where R =
Salinity
Optimal Salinity
Below Optimal Salinity. K 1(0.01
*
100
R
)
where R =
Optimal Salinity
Salinity
.
Clearly, K1 at optimal salinity as required. Recovery pre-
dicted by the simulator was found to be relatively insensitive to the
detailed expression for calculating K except that numerical insta-
bilities were encountered if K varied too rapidly near optimal
conditions.
Numerical Details. Table 2 indicates that a value of dt/dx of 0.05
was used. This value is the largest where stability could be main-
tained during the finite-difference calculations with minimal nu-
merical dispersion. For dt/dx0.1, sometimes there was an insta-
bility problem. Similarly, the choice of 100 gridblocks reflects the
smallest number for which the solution does not change signifi-
cantly with an increasing number of gridblocks.
The surfactant breakthrough curve was determined for 1D non-
adsorbing tracer experiments in dolomite sandpacks with a differ-
ent but similar anionic surfactant mixture. When the simulator was
used to match the results, a Peclet number of 500 was obtained. A
similar value was found for experiments where surfactant was
present in addition to the tracer.
SI Metric Conversion Factors
cp 1.0* E03 Pas
psi 6.894 757 E+00 kPa
*Conversion factor is exact.
Shunhua Liu is a PhD candidate in chemical engineering at
Rice University. His research interests include surfactant sci-
ence, enhanced oil recovery, and numerical simulations. He
holds BS and MS degrees from Tsinghua University, China, both
in chemical engineering. Danhua Leslie Zhang joined Intertek
Westport Technology Center in January 2007 after a year with
Halliburton. Her research interests include formation evalua-
tion, enhanced oil recovery, fracturing fluid formulation, and
rheology. She holds a BS degree in chemical engineering from
Tianjin University, China, and a PhD degree in chemical engi-
neering from Rice University. Wei Yan held industrial positions
for 7 years in China before coming to the US, and is now a
process engineer with Bechtel (IPSI) in Houston. He holds a BS
degree in chemical engineering from Tianjin University, China,
and a PhD degree in chemical engineering from Rice Univer-
sity. Maura C. Puerto is a Complimentary Visiting Scholar at
Rice University. She retired from ExxonMobil as a Research As-
sociate after more than 25 years of service in the Reservoir
Division. She is known as an expert in application of surfactants
to processes involving flow through porous media and is skilled
in the area of designing laboratory coreflood testing and his-
tory matching the results by simulation. Before joining Exxon in
1974, she was employed in quality control and product devel-
opment for Almay Hypoallergenic Cosmetics and was techni-
cal director of the cosmetic branch at the Cuban Institute of
Soap and Cosmetics. In 1996, she received, based on her work
on CO
2
solubility in LVP solvents for aerosols, the Quality Award
from Exxon Chemicals for turning environmental regulations
into opportunities. Since her retirement from Exxon, she has
participated on a part-time basis in research on enhanced oil
recovery and aquifer remediation at Rice. She holds a chemi-
cal engineering degree from Oriente University in Cuba. She
was the recipient in 1980 of the SPE Cedric K. Ferguson Award,
George J. Hirasaki had a 26-year career with Shell Develop-
ment and Shell Oil Companies before joining the Chemical
Engineering faculty at Rice University in 1993. At Shell, his re-
search areas were reservoir simulation, enhanced oil recovery,
and formation evaluation. At Rice, his research interests are in
NMR well logging, reservoir wettability, enhanced oil recovery,
gas hydrate recovery, asphaltene deposition, emulsion coa-
lescence, and surfactant/foam aquifer remediation. He was
the 1999 recipient of the Society of Core Analysts Technical
Achievement Award, and is a member of the National Acad-
emy of Engineers. He holds a BS degree in chemical engineer-
ing from Lamar University and a PhD degree in chemical en-
gineering from Rice University. He received the SPE Lester Uren
Award in 1989, and was named an Improved Oil Recovery
Pioneer at the 1998 SPE/DOR IOR Symposium. Clarence A.
Miller is Louis Calder Professor of Chemical and Biomolecular
Engineering at Rice University and a former chairman of the
department. Before coming to Rice University, he taught at
Carnegie-Mellon University. He has been a Visiting Scholar at
Cambridge University, the University of Bayreuth (Germany),
and the Delft University of Technology (Netherlands). His re-
search interests center on emulsions, microemulsions, and
foams and their applications in detergency enhanced oil re-
covery and aquifer remediation. He is coauthor of the book
Interfacial Phenomena, the second edition of which was re-
cently published by CRC Press. He holds BS and PhD degrees
from Rice University and the University of Minnesota, both in
chemical engineering.
16 March 2008 SPE Journal