SPE/DOE 12702

SPE/DOE
Society 01
Petroleum Engln .. rs
u.s. Depertment
01 Energy
A Study of the Relationship Between
Surfactant/Oil/Brine System Phase Behavior
and Chemical Flood Recovery in Short Cores
by S.S. Ashrawi, Texaco Inc.
Member SPE-AIME
Copyright 1984 Society of Petroleum Engineers of AIME
This paper was presented at th.e SPE/DOE F ~ u r t h Symposium on Enhanced Oil Recovery held in Tulsa, OK, April 15-18, 1984. The material is subject to
correction by the author. Permission to copy IS restricted to an abstract of not more than 300 words. Write SPE, 6200 North Central Expressway, Drawer
64706, Dallas, Texas 75206 USA. Telex 730989 SPEDAL.
ABSTRACT
This study correlates the phase behavior of
surfactant/oil/brine systems with their chemical
flood performance in short cores. The study focuses
on the influence of two important system composi-
tion variables: viz. the brine salinity and the
nominal equivalent weight of a petroleum sulfonate
blend. Furthermore, it investigates the influence
of the addition of an alkylether sulfate in terms
of optimal salinities, increased salinity tolerance
and tertiary recovery efficiency.
The oil displacement experiments employ a very
fast, near-continuous, constant salinity flooding
process in 3-inch long Berea cores, using a micro-
wave instrument to determine the oil saturations.
A typical turn-around time for a flooding experi-
ment was seven hours.
Tertiary oil recovery contours are developed
in a brine salinity-surfactant equivalent weight
space. The region of highest tertiary oil recovery
in that space closely matched the region in which
equilibrium three-phase systems existed. Optimal
salinities and equivalent weights, as defined by
the chemical flood with the lowest final oil satu-
ration, were obtained with excellent resolution.
More significantly, they closely matched those
optimal values obtained under equilibrium
conditions from time-consuming solubilization
parameter measurements.
The addition of the alkylether sulfate
solubilizer had the effects of increasing the
optimal salinity, and significantly broadening the
three-phase region as well as the region of high
tertiary oil recovery. This broadening effect
caused a lower resolution in the determination of
optimal system variables. In the presence of the
solubilizer, a close correspondence between the
three-phase region and the region of optimum oil
recovery was also observed.
References.and illustrations at end of paper.
311
This study introduces a rapid and meaningful
technique to determine the EOR potential of sur-
factants and surfactant formulations. Applica-
tions of the results of this work include:
the rapid screening of surfactants for enhanced
oil recovery processes in specific rock
matrices, the design and optimization of
surfactant formulations and the quality control
of plant-manufactured surfactants and field-
blended surfactant formulations.
INTRODUCTION
The screening and selection of surfactant
candidates for possible use in a chemical flood-
ing operation is a multi-tiered process,
governed by both economic and technical con-
siderations. From an economic poiI" ~ view,
surfactant cost and availability are the two
major considerations. From a technical point of
view, it is generally recognized that a proposed
surfactant or surfactant formulation should, as
a minimum requirement, be able to reduce the
tension, under field conditions, between the
injected solution and the oil in place. This
reduction in the tension should be sufficient to
either eliminate or significantly reduce the
capillary forces which have trapped the oil in
the formation.
In addition to tension reduction, a number
of other criteria are taken into account in the
process of selecting, designing and optimizing a
surfactant system. Surfactant loss, due to
adsorption onto the rock or due to other
retention mechanisms such as phase entrapment
during a chemical flood, should be minimized
because it can otherwise be detrimental to the
efficacy of the injected formulation. The
stability and effectiveness of the surfactant
should be ascertained in brines with the
salinities and divalent cation concentrations
likely to be encountered in the formation in
question. Furthermore, the potential for the
chromatographic separation, during the flooding
process, of the various _ components of a
2
A STUDY OF THE RELATIONSHIP BETWEEN SURFACTANT/OIL/BRINE SYSTEM
PHASE BEHAVIOR AND CHEMICAL FLOOD RECOVERY IN SHORT CORES SPE 12702
commercial surfactant, or a blend of synthetic
surfactants should be closely examined because it
may be significant enough to reduce the
effectiveness of the surfactant formulation.
Laboratory core floods have generally been
used to determine the effectiveness of a given
surfactant formulation in displacing oil from a
given rock matrix. There are two major problems
associated with laboratory core floods. The first
is related to the availability of representative
core material from a given formation. The second
arises from the lengthy turn-around time of a
single core flood, which, for a l-ft core at a flow
rate of 1 ft/day, is approximately four to five
days. These two problems place severe limitations
on the number of core floods that may be conducted
in the process of surfactant screening and
formulation optimization. Thus, there has
always been the need to develop a rapid, accurate
and meaningful oil displacement test in a rock
matrix, in order to decrease the number of
necessary long linear floods, or alternatively, to
allow for a larger number of screening floods
within a given time constraint.
A number of tools for the investigation,
development and optimization of surfactant systems
for chemical flooding have been presented in the
literature. Schechter, Wade and co-workers
l
-
4
developed the Equivalent Alkane Carbon Number
(EACN) concept to model crude oils and to locate
interfacial tension minima by varying the salinity
and other solution composition parameters. Healy,
5-8
Reed and co-workers introduced the notion of the
Optimal Salinity ( C ~ ) as that salinity which
minimized the height of the multiphase region.
These workers demonstrated that C ~ , which is
obtained from equilibrium phase volume measurements
as the salinity where the solubilization parameter
for oil in the microemulsion (V /V) equals the
o s
solubilization parameter for water in the
microemulsion (V /V ), corresponded closely to the
.w s
salinity at which the tension between the
microemulsion and the excess oil phase equals the
tension between the microemulsion and the excess
brine phase. They further demonstrated a close
correspondence between C ~ and the optimal salinity
for oil recovery by immiscible microemulsion banks
in 4-ft linear core floods. Nelson and
co-workers
9
,10 used equilibrium phase data to
develop the Salinity Requirement Diagram - which
depicts the dependence on surfactant concentration
of the midpoint salinity (related to C ) and the
~
salinity range over which Type III systems exist.
The Salinity Requirement Diagram was shown to
provide insight into the performance of slug
chemical flooding processes and, therefore, to be
useful in the design of chemical flooding systems.
It is quite clear that investigative tools
such as EACN, the Optimal Salinity or the Salinity
Requirement Diagram are very helpful in reducing
the number of long linear core floods that are
312
necessary for a more complete surfactant system
optimization procedure. Common to these tools
or approaches is the reasonable notion that a
laboratory core flood, under normal reservoir
flow rates, can be viewed as an equilibrium
process, or a series of local equilibrium
processes. In fact, the meaningfulness and
validity of these tools are established by
relating the results of the equilibrium
measurements involved therein to the results
obtained under the dynamic conditions of a core
flood. However, equilibrium interfacial tension
and phase behavior measurements are not without
problems. They can be quite time-consuming, due
to the fact that equilibration times may range
from a few days to a few months. They can also
be quite tedious. Furthermore, these approaches
do not allow for rock/fluid interactions in a
significant portion of the screening and
optimization procedure. Therefore, the question
of a rapid, accurate and meaningful oil
displacement test in a rock matrix still needs
to be addressed.
A quick and accurate oil displacement test
requires that it be conducted at high flow rates
in short cores, and that the oil/brine satura-
tions in the core be determined accurately and
reproducibly. Large errors can be obtained when
material balance calculations are applied to
floods in short cores. The noninvasive
determination of the oil/brine saturation in a
core offers a much higher degree of accuracy and
reproducibility. Recently, a number of micro-
wave absorption spectrometers have been
11-14
developed for the routine monitoring of
oil/brine saturation distributions during
flooding experiments in field and laboratory
cores, having cylindrical, rectangular and slab
geometries. One of these spectrometer
assemblies was also adapted for saturation
measurements in very short cores.
This report presents the results of a
large number of oil displacement experiments
which employed a very fast, near-continuous,
constant-salinity flooding procedure in 3-inch
long Berea cores, using the aforementioned
microwave instrument to determine the oil/brine
saturations. The report also correlates these
results with the phase behavior of the
surfactant/oil/brine systems in question. The
result is a demonstration of a rapid and
meaningful technique for the determination of
the EOR potential of surfactants and surfactant
formulations.
MATERIALS
The chemicals used in this study were:
deionized water which was filtered through a 0.2
vm filter capsule; Certified A.C.S. sodium
chloride; n-decane, 99+% mol purity; 2-propanol,
Certified A.C.S. Spectranalyzed; sec-butanol,
Certified 99.6% mol purity; l-pentanol, 99% mol
purity; two petroleum sulfonates and a
solubilizer which are described next.
SPE 12702
SAMIR S. ASHRAWI
3
The two petroleum sulfonates used were Witco
TRS-40 and TRS-18. The TRS-40 was reported to have
a nominal equivalent weight of 343. and to contain
41.4% wt active sulfonate. The TRS-18 was reported
to have a nominal equivalent weight of 510. and to
contain 61.7% wt active sulfonate. The solubilizer.
LN-60COS. was a specialty batch manufactured by
Texaco. It is an alkylether sulfate. with a
C
12
-C
14
parent alcohol and an average of six
ethylene oxide units. It had a nominal equivalent
weight of 554. and contained 58.5% wt active
sulfated material. The petroleum sulfonates and
the solubilizer were neither de-oiled nor purified
in any fashion. All calculations and preparations
were based on the nominal equivalent weights and
activities.
The Bere,a cores were rectanguLar pieces
with cross-sectional dimensions of 1. 6 cm x 1. 9
cm. They were cut to a length of 3 inches and
fired at ,800°F for 24 hours.
EXPERIMENTAL PROCEDURES
Phase Behavior Experiments
The phase qehavior data presented here were
obtained from phase volume on
equilibrated samples. The samples represent
points on three compositional space grids.
scanning the two compositional variables. brine
salinity and the nominal equivalent weight of
the petroleum sulfonate blend. at three
solubilizer concentrations. No attempt was made
to determine the global phase behavior of any of
the systems.
The procedure for sample preparation was as
follows. Aqueous surfactant solutions. having a
fixed (0.025 N) overall concentration of
petroleum sulfonate blend + solubilizer. were
prepared in brines' of various salinities.
Solution stability was noted and recorded.
Formulations which exhibited phase separation
were not included in either the phase behavior
or the flooding experiments. The alcohol type
and concentration were kept constant at 1.0%
sec-butanol and 0.5% l-pentanol throughout the
study. These alcohols were selected because of
their influence on macroemulsion stability and
the phase behavior of surfactant/oil/brine
systems. Their relative concentrations were not
rigorously selected. In order to scan the
equivalent weight of the petroleum sulfonate
blend. similar solutions were prepared at fixed
brine salinities. but with a variable
TRS-40:TRS-18 molar ratio ranging between 90:10
and 10:90. Fixed volumes of the aqueous
solutions and n-decane were then placed in 25 mL
serological pipets whose tips had been sealed. The
aqueous solution to n-decane ratio was 3:1. chosen
to closely correspond to the residual oil
saturation after water flooding (Sorw) in the
flooding experiments. The pipets were then
torch-sealed at the top. tumbled end-on-end at 4
rpm in an air bath for 12 hours. and then left
to stand upright in a 27°C air bath for
equilibration. Clear excess phases. clean
interfaces and constant phase volumes were
313
presumed to indicate complete equilibration.
Samples in the three-phase region tended. in
general. to equilibrate more rapidly than others.
which still had some unbroken emulsions in the
excess brine and/or oil phases.
Flooding Experiments
Flooding experiments were conducted in
short rectangular Berea cores. which were mounted
with microwave absorber rods and potted in
plastic barrels according to a previously
11
described procedure Measurement of the brine
saturations was done with a 24.125 GHz microwave
spectrometer which has been described in detail
by Brost and Davis
ll
Because only short cores
were used in this study. no scanning was
necessary to determine the saturation profile in
the core. Only one measurement was required to
determine the brine saturation after each step in
the flooding experiment. Therefore. the
microwave source and detector were rigidly
mounted on Lucite blocks in a box. into which the
short core barrel can be locked in place for the
duration of the experiment.
A flooding experiment involved the
following steps. The clean evacuated core was
first rapidly saturated with deionized water.
This step was initially used to determine the
porosity of the core. and routinely used to
determine the permeability of the core to water.
The core was then saturated with an aqueous
2-propanol solution to a constant microwave
reading in order to check the calibration of the
core. This was followed with the injection of
several pore volumes of deionized water. Next
the core was saturated with a brine of the given
salinity. X % NaCl. The core was then flooded
with n-decane at the rate of 360 ft/day. to a
constant microwave reading which is equivalent to
initial oil saturation (S .). Next. the core was
01
flooded at a rate of 90 ft/day with the same brine
(X % NaCl). to a constant microwave reading which
is equivalent to residual oil saturation after
water flooding (Sorw). The core was then
flooded. at a rate of 10 ft/day. with 1.0 pore
volume of a surfactant solution. prepared in a
brine of the same salinity (X % NaCl) according
to the procedure described in the preceding
section. Finally. the core was flooded at a rate
of 20 ft/day. with a brine of the same salinity
to a constant microwave reading which is
equivalent to the residual oil saturation after
chemical flooding (S ). The final brine drive
orc
invariably used between 1.25 and 1.75 pore
volumes of fluid. During each step of the
flooding procedure. pressure readings were taken
from an in-line pressure gauge placed just prior
to the entry port of the core. The floods were
conducted at ambient temperature which varied by
1 or 2 degrees during an experiment. but which
ranged between 23°C and 27°C during the course of
the study. The core was cleaned with a series of
solvents. dried and evacuated overnight. The
total turn-around time for the flooding and
cleaning operations was approximately seven
hours.
4
A STUDY OF THE RELATIONSHIP BETWEEN SURFACTANT/OIL/BRINE SYSTEM
PHASE BEHAVIOR AND CHEMICAL FLOOD RECOVERY IN SHORT CORES SPE 12702
In order to convert the readings taken after
each step in the flooding pr9cedure to Microwave
Equivalent Oil Saturation (MES) values, a
calibration curve was needed f8r each core.
Calibration was done with aqueous 2-propanol
solutions as described previouslyll. Typical
calibration curves are shown in Figure 1. It was
noted by Brost and Davis
ll
that the K-Band MES
o
values are fortuitously very similar
fraction 2-propanol in rectangular cores
to weight
and up to
3 3
0.7 cm /cm. In this study, the instrumental
response to n-decane under conditions necessary to
rigorously establish the same similarity was not
determined. Our use of the 2-propanol calibration
curve to report MESo values is valid, however, for
purposes of comparison and discrimination between
the different injection fluids that were studied.
RESULTS AND DISCUSSION
This study was divided into two parts. The
first part investigated the influence of the brine
salinity and the nominal equivalent weight of the
petroleum sulfonate blend on the phase behavior and
chemical flood recovery efficiency of formulations
that contained the two commercial petroleum
sulfonates. The second part extended the
investigation to include the influence of an
alkylether sulfate solubilizer on these systems.
Alkylether sulfate solubilizers contain a nonionic
and an anionic moiety in their hydrophilic part.
This character endows them with a tolerance for
high brine salinities and hardness
15
-
l8
while
circumventing the potential problem of
chromatographic separation in anionic/nonionic
surfactant mixtures. They were included in this
study so that an understanding of their
interactions with petroleum sulfonates may be
developed and in order to be able to conduct the
experiments at salinities of field relevance. In
both parts, the influence of the brine salinity and
the nominal equivalent weight of the petroleum
sulfonate blend was investigated by a scanning
procedure. The influence of the solubilizer was
investigated by studying the systems at two
solubilizer concentrations covering the range of
economic interest.
-Petroleum Sulfonate Studies
The Microwave Equivalent Oil Saturation (MESo)
values at initial (S i)' water flood (S ) and
o orw
chemical flood (Sorc) conditions for a sample
series of constant salinity floods, which scanned
the salinity range of 0.1 to 1.5 wt % NaCl, are
plotted as a function of flood salinity in Figure
2a. The petroleum sulfonate blend in these floods
had a nominal equivalent weight of 410. In most of
these floods, stable microwave r.eadings were
obtained after injecting 1.25-1.75 pore volumes of
the drive brine. In the floods with salinities
higher than 0.8 wt % NaCl, the readings did not
stabilize, even after injecting 4 or 5 pore volumes
of the drive brine. However, the prolonged
injection increased the recovery efficiency by a
314
few percentage points only. The measured
pressures during these drives were significantly
higher than those associated with the drives in
the other floods. The higher pressures may be
associated with the in situ formation of viscous
macroemulsions. This assumption is consistent
with our observations on the relative stability
of the macroemulsions that formed when the
surfactant formulations in question were
equilibrated with n-decane in the phase behavior
experiments.
As can be seen from Figure 2a, the microwave
equivalent S . and S values stayed fairly
01. orw
constant over the salinity range investigated.
The average S . value was 0.591 ± 0.008 V /V ,
01. P
while the average S value was 0.255 ± 0.010
orw
V/V. Because the small variations in these
p
flood salinities would have a very small effect
on the absorption coefficient (see Reference 11),
these results essentially reflect the reproduci-
bility of the measurement. The S orc values go
through a distinct minimum at a flood salinity of
0.3 wt % NaCl, at which the recovery efficiency
was 74.5%. Recovery efficiency (E
R
) values,
defined as (S - S ) /S ,are plotted as a
orw orc orw
function of flood salinity in Figure 3. The
recovery efficiency values are very well
resolved, down to 0.05 wt % NaCl difference in
flood salinity. This reflects the discriminating
ability of the technique employed in this study,
and further documents the significant role that
salinity plays in determining chemical flood
performance. An optimal salinity is thus clearly
defined at the minimum S orc or the maximum ER
values, under the stated experimental conditions.
The phase behavior optimal salinity for the
same surfactant formulation was determined at a
water to oil ratio (WOR) of 3:1, using the
definition of Healy and Reed
7
,19. Oil and brine
solubilization parameters at the different
salinities were determined from phase volume
measurements, ignoring the presence of alcohols
for the sake of These solubilization
parameters are plotted as a function of brine
salinity in Figure 2b. The phase behavior
optimal salinity is thus determined to be 0.4 wt
% NaCl, which is in fairly good agreement with
that defined by maximum oil recovery. It is
important here to emphasize that the flow rates
during these laboratory core floods were 10
ft/day for the surfactant and 20 ft/day for the
drive, which is much higher than normal reservoir
or conventional laboratory core flood flow rates.
In order to establish that the flooding
procedure employed here does in fact yield
results' that reflect the ultimate recovery
potential of a given formulation, a number of
floods were conducted at three different
salinities, using 1. 0, 1. 5, 2.0 and 2.5 pore
volumes of the surfactant solution. The results,
which are plotted in Figure 4 as ER versus
SPE 12702
SAMIR S. ASHRAWI
5
surfactant pore volume, clearly show that the
ultimate recovery potential of a given formula-
tion was indeed determined by simply using 1.0 pore
volume of surfactant injection.
A series of constant salinity floods were
conducted to scan the nominal equivalent weight
of the petroleum sulfonate blend in the surfac-
tant formulation. The brine salinity in these
floods was fixed at 0.3 wt % NaCl. The resulting
microwave equivalent S ., Sand S values are
01 orw orc
plotted as a function of the nominal equivalent
weight of the petroleum sulfonate blend in Figure
Sa. The microwave equivalent S oi and S orw values
remained fairly constant. The average S oi value
was 0.591 ± 0.005 V/V , while the average S was
p orw
0.263 ± 0.005 V/V. This is a clear demonstration
p
of the consistency and reproducibility of the
measurement. The microwave equivalent S orc was
very well resolved and showed a distinct minimum ac
a nominal equivalent weight of 410. This is the
optimum equivalent weight as determined by the
flooding experiments. The resolution of Sorc
values obtained here points to the potential
application of this rapid flooding technique in
insuring that the proper sulfonate equivalent
weight specifications have been met. The oil and
brine solubilization parameters were also
calculated from phase volume measurements on
samples that scanned the nominal equivalent weight
of the petroleum sulfonate blend at a WOR of 3: 1
and under the same salinity and alcohol conditions
used in the core floods. The results are shown in
Figure 5b. The optimum equivalent weight found at
equal oil and brine solubilization parameters was
41S.
The results of the two flooding scans
discussed above were' combined with the results of
other similar scans in order to develop a contour
map of the recovery efficiency of TRS-40/TRS-lS
blends under the stated experimental conditions, in
the composition space defined by the brine salinity
and the equivalent weight of the petroleum
sulfonate blend. The resulting contour map is
shown in Figure 6. The recovery efficiency is
highly sensitive to the two composition variables:
salinity and surfactant equivalent weight.
Recoveries higher than SO% were obtained in only a
very small region of the composition space, while
some steep gradients were encountered outside of
that region. High recovery efficiencies (E
R
~ 60%)
occupy a narrow ridge region of the composition
space. This region defines optimum compositions of
the surfactant formulation. The general orienta-
tion of this region is not unexpected. An increase
in the brine salinity and an increase in the
equivalent weight both contribute to an increased
lipophilicity of the surfactant system. Therefore,
in order to maintain a balanced system and a high
recovery efficiency, high equivalent weight sur-
factant blends are required with low salinity
brines, and lower equivalent weight surfactant
blends are required with higher brine salinities.
315
The boundaries of the three-phase region in
this composition space have been superimposed on
the recovery efficiency contour map in Figure 6.
At low salinities and equivalent weights,
brine-continuous microemulsions, in equilibrium
with excess oil, were observed. At higher
salinities and equivalent weights, oil-continuous
microemulsions, in equilibrium with excess brine,
were observed. There is a close correspondence
between the region where equilibrium three-phase
systems were observed, and the region of high
recovery efficiencies obtained in 3-inch long
cores at very high flow rates.
The results presented in this section
demonstrate a rapid, accurate and discriminating
flooding technique. The meaningfulness of this
technique derives from correlating its dynamic
results with optimum phase behavior conditions,
which are recognized as a necessary but not
sufficient requirement for the successful
displacement of oil from a rock matrix.
Petroleum Sulfonate/Solubilizer Studies
Using surfactant formulations which
contained TRS-40, TRS-lS and the solubilizer
LN-60COS at a fixed overall concentration of
0.025 N, several constant-salinity floods were
conducted to scan the brine salinity up to 15 wt
% NaCl and to scan the range of petroleum
sulfonate blend equivalent weight. The same
alcohol types and concentrations were used as in
the previous floods. The two solubilizer
concentrations investigated were 17 and 25 mol %
of the total blend.
As an example, Figure 7 shows the microwave
equivalent S values obtained with three sets
orc
of salinity scan floods, in which the petroleum
sulfonate blend had an equivalent weight of 410.
These scans were terminated when phase separation
was observed in solutions with high brine
salinities. Average microwave equivalent Soi and
S values are given in Table 1. Two observa-
orw
tions can
performance
solubilizer.
(i.e., where
be made regarding the recovery
of formulations containing the
First, the optimal salinities
is lowest) for these formula- S
orc
tions are higher than that of the formulation
which contained no solubilizer. Second, the
range of salinities over which good recoveries
(Le., low S values) were obtained is
orc
dramatically increased in the presence of the
solubilizer. Unfortunately, this meant that the
instrumental resolution of peak recoveries and
optimal conditions was diminished.
It was noted earlier that higher pressures
were observed during floods with salinities
greater than O.S wt % NaCl for the systems
containing no solubilizer. It is noted here that
higher pressures were also observed at salinities
greater than 4 wt % NaCl for the systems contain-
ing 17 mol % solubilizer, and at salinities
greater than 5 wt % NaCl for the systems
containing 25 mol % solubilizer. These higher
6
A STUDY OF THE RELATIONSHIP BETWEEN SURFACTANT/OIL/BRINE SYSTEM
PHASE BEHAVIOR AND CHEMICAL FLOOD RECOVERY IN SHORT CORES SPE 12702
pressures were associated with extended oil
production times (i.e., unstable microwave
readings) and may also be related to the in situ
formation of viscous macroemulsions.
Figures 8 and 9 are contour maps of the
recovery efficiencies (E
R
) of these surfactant/
solubilizer systems at 17 and 25 mol % solubilizer
content, respectively. The contour maps are
plotted in the compositional space which is defined
by the brine salinity and the nominal equivalent
weight of the petroleum sulfonate blend in the
formulation. The results of a total of 105
constant salinity floods were used in developing
these maps. The observed boundaries of the
three-phase regions in this composition space have
been superimposed on both maps.
A comparison between these two ER contour maps
and the one shown in Figure 6, for the petroleum
sulfonate blends alone, reveals the following
observations:
1. There is a close correspondence between
the location of the three-phase region and
that of the high recovery efficiency
region in both low and high salinity
brines. Thus, the viability of the
experimental technique and approach used
in this study is extended to conditions of
relevance to field situations.
2. The region of the compositional space over
which high recoveries (E
R
> 60%) and
three-phase systems were obtained was
tremendously enlarged in the presence of
the solubilizer. The enlargement occurred
with respect to both variables defining
the compositional space. This suggests
that the impact of chromatographic
separation of petroleum sulfonate
components in solubilized systems may not
be as crucial as it is in petroleum
sulfonate surfactant formulations.
3. Optimal recoveries and. optimum phase
behavior conditions in the presence of the
solubilizer were obtained at significantly
higher salinities. The associated shift
to higher petroleum sulfonate equivalent
weights is relatively smaller.
4. The movement of the "center" of the region
of very high recoveries with increasing
solubilizer content is precisely what one
would expect from a knowledge of the
relative hydrophilic/lipophilic character
of the products used in this study.
Specifically, the "center" moves towards
higher salinities and higher petroleum
sulfonate equivalent weights. Because the
solubilizer LN-60COS is quite hydrophilic,
as may be surmised from its high optimal
salinity (see Figure 10), the balance of
the formulation has to be corrected in the
direction which increases the lipophili-
city of the system. That correction is
achieved by increasing both the brine
salinity and the equivalent weight of the
petroleum sulfonate blend.
316
5. The general orientation of the high
recovery region and the three-phase
region in the presence or absence of the
solubilizer follows an expected trend.
In order to maintain high recoveries, an
increase in the salinity must be
balanced by an appropriate decrease in
the equivalent weight of the petroleum
sulfonate. Together with observation
No.4, this observation suggests that,
in a core flood that uses a surfactant
mixture, surfactant composition
gradients as well as salinity gradients
may be necessary to maintain the system
in the optimum region for the longest
period.
6. Sharp gradients in the recovery
efficiency contours are observed in the
presence and absence of the solubilizer.
For the systems that contain the
solubilizers, however, the ER gradients
may not be particularly detrimental
since the region of very high recoveries
is quite large.
It is important to note here that the
increased optimal salinity and salinity tolerance
associated with the presence of the solubilizer
were not accompanied by a decrease in the
solubilization parameters. Figures 10 and 11 are
plots of the optimal salinity, the width of the
three-phase region in salinity units and the
solubilization parameters at optimum as a
function of the mole fraction of the solubilizer
in a petroleum sulfonate/solubilizer system,
wherein the equivalent weight of the petroleum
sulfonate was fixed at 410. Recovery efficiency
values are also noted in Figure 10. We have
previously observed diminished solubilization
with increased optimal salinities and salinity
tolerance in petroleum sulfonate systems.
Finally, a quantitative comparison of the
optimal salinities obtained from equilibrium
phase behavior data and those obtained from
core flooding experiments is in order. Figure 12
depicts this comparison. There is a close
correspondence between the two optimum
parameters. However, it must be emphasized that
the accuracy with which the optimal salinity by
either method could be determined, decreases as
the value of the optimal salinity increases.
This is because the higher optimal salinities
were associated with broader three-phase and
high recovery regions.
CONCLUSIONS
Based on the results of the experiments
described in this work, the following conclusions
can be made:
1. The phase behavior and the recovery
efficiency in short Berea cores of
petroleum sulfonate systems are very
sensitive to the brine salinity and the
equivalent weight of the sulfonate
blend.
SPE 12702 SAMIR S. ASHRAWI 7
2. The solubilizer LN-60COS increases the
salinity tolerance of petroleum sulfonate
formulations in terms of both the optimal
salinity and the width of the salinity
range over which optimum phase behavior
conditions and oil recoveries are
obtained.
3. The solubilizer LN-60COS decreases the
sensitivity of phase behavior and recovery
efficiencies of petroleum sulfonate
systems to the equivalent weight of the
sulfonate blend in these systems. This
conclusion has implications in terms of
the ability of the solubilizer to reduce
the adverse effects of the chromatographic
separation of sulfonate components in a
reservoir.
4. There is a close correspondence between
optimum equilibrium phase behavior
conditions and optimum oil recovery in
near-continuous, constant salinity floods
conducted at high flow rates in 3-inch
long Berea cores. This conclusion holds
for petroleum sulfonate systems as well as
for petroleum sulfonate/solubilizer
systems.
5. A rapid, accurate and meaningful oil
displacement test in a specific rock
matrix has been demonstrated. The
techniques involved therein may be applied
in the areas of surfactant screening,
design and optimization for EOR purposes.
They may also be applied in evaluating
plant-manufactured surfactants and field-
blended surfactant formulations for
meeting specific guidelines.
NOMENCLATURE
C ~ - Phase behavior optimal salinity, % NaCl
EACN - Equivalent Alkane Carbon Number
MES
o
S
orc
S
orw
v
- Chemical flood recovery efficiency
- Permeability to water, millidarcy
- Microwave Equivalent Oil Saturation,
3 3
cm /cm
- Initial oil saturation before water
flood, cm
3
/cm
3
- Residual oil saturation
flood, cm
3
/cm
3
- Residual oil saturation
flood, cm
3
/cm
3
3
- Volume of fluid, cm
after chemical
after water
V /V - Oil solubilization parameter in
o s 3 3
microemulsion, cm Icm 3
V
P
- Pore volume of a core, cm
V Iv - Water solubilization parameter in
w s
. 1 . 3/ 3
m1croemu S10n, cm cm
WOR - Water to oil ratio
317
ACKNOWLEDGEMENT
The author wishes to acknowledge Texaco Inc.
for permission to publish this work. The author
would also like to acknowledge the many helpful
discussions with Dr. L. A. Davis and the expert
technical assistance of U. K. Kaliher and M. N.
Dinh.
REFERENCES
1. Cayias, J. L., Schechter, R. S. and Wade,
Low
351-357
2.
3.
4.
5.
6.
7.
8.
9.
W. H.: "Modeling Crude Oils for
Interfacial Tension," SPEJ, 16,
(1976). --
Cayias, J. L., Schechter, R. S. and Wade,
W. H.: "The Utilization of Petroleum
Sulfonates for Producing Low Interfacial
Tensions Between Hydrocarbon and Water," J.
ColI. Interface Sci., 21, 31-38 (1977).
Cash, L., Cayias, J. L., Fournier, G.,
McAllister, D., Scharz, T., Schechter, R. S.
and Wade, W. H.: "The Application of Low
Interfacial Tension Scaling Rules to Binary
Hydrocarbon Mixtures," J. ColI. Interface
Sci., 21, 39-44 (1977) .
Morgan, J. C., Schechter, R. S., and Wade,
W. H.: "Recent Advances in the Study of Low
Interfacial Tensions," in Improved Oil
Recovery by Surfactant and Polymer Flooding,
Shah, D.O., and Schechter, R. S., editors;
Academic Press Inc., N.Y., 1977.
Healy, R. N. and Reed, R. L.: "Physico-
chemical Aspects of Microemulsion Flooding,"
Soc. Pet. Eng. J. (Oct. 1974) 491-501;
Trans., AIME, Vol. 257.
Healy, R. N., Reed, R. L. and Carpenter,
C. W.: "A Laboratory Study of Microemulsion
Flooding," Soc. Pet. Eng. J. (Feb. 1975)
87-103; Trans., AIME, Vol. 259.
Healy, R. N. Reed, R. L. and Stenmark,
D. G.: "Multiphase Microemulsion Systems,"
Soc. Pet. Eng. J. (June 1976) 147-160;
Trans., AIME, VoL 261.
Healy, R. N. and Reed, R. L.: "Immiscible
Microemulsion Flooding," Soc. Pet. Eng. J.
(April 1977) 129-139.
Nelson, R. C. and Pope,
Relationships in Chemical
Pet. Eng. J. (Oct. 1978)
AIME, Vol. 265.
G. A.: "Phase
Flooding," Soc.
325-338; Trans.
10. Nelson, R. C.: "The Salinity Requirement
Diagram--A Useful Tool in Chemical Flooding
Research and Development," SPE paper 8824,
presented at the First Joint SPEIDOE
Symposium on Enhanced Oil Recovery at Tulsa,
Oklahoma, April 20-23, 1980.
8
A STUDY OF THE RELATIONSHIP BETWEEN SURFACTANT/OIL/BRINE SYSTEM
PHASE BEHAVIOR AND CHEMICAL FLOOD RECOVERY IN SHORT CORES SPE 12702
11. Brost. D. F. and Davis. L. A.: "Determination
of Oil Saturation Distributions in Field Cores
by Microwave Spec troscopy." SPE paper 10.110.
presented at the 56th Annual Fall Technical
Conference and Exhibition of the SPE of AIME.
at San Antonio. Texas. October 5-7. 1981.
12. Haskin. H. K. and Davis. L. D.: "A Comparison
of Laboratory Linear and Pattern Flow Chemical
Floods Using a Volumetric Linear Scaling
Concept for Oil Saturation Distributions." SPE
paper 10.197. presented at the SPE-AIME 56th
Annual Fall Technical Conference and
Exhibition. at San Antonio. Texas.
October 5-7. 1981.
13. Haskin. H. K. and Davis. L. A.: "Multiple
Slug Scaling of Linear and Pattern Laboratory
Chemical Floods." SPE paper 10.715. presented
at the SPE/DOE 3rd Joint Symposium on Enhanced
Oil Recovery. at Tulsa. Oklahoma. April 4-7.
1982.
14. Davis. L. A.: "Computer-Controlled Measurement
of Laboratory Areal Flood Saturation
Distributions." SPE paper 12.037. presented at
the SPE-AIME 58th Annual Technical Conference
and Exhibition. at San Francisco. California.
October 5-8. 1983.
15. Flournoy. K. H .• Cardenas. R. L .• Haferkamp.
G. L. and Shupe. R. D.: "Surfactant Oil
Recovery Process Usable in Formations
Containing Water Having High Concentrations of
Polyvalent Ions Such as Calcium and
Magnesium." U.S. Patent No. 3.811.505 (May
1974).
16. Flou"noy. K. H .• Maddox. J .• Jr. and Tate.
J. F.: "Oil Recovery Processes Usable in
Formations Containing Water Having High
Concentrations of Polyvalent Ions." U.S.
Patent No. 3.858.656 (Dec. 1973).
17. Maddox. J .• Jr. and Shupe. R. D.: "Surfactant
Oil Recovery Processes Usable in High
Temperature. High Salinity Formations." U. S.
Patent No. 4.077.471 (March 1978).
18. Dycus. D. W .• Malmberg. E. W. and Wilchester.
H. L.: "Oil Recovery Using Aqueous Surfactant
Compositions." U. S. Patent No. 3.827.497
(Feb. 1973) and "Surfactant Compositions
Useful in Oil Recovery Processes." U.S. Patent
No. 3.890.239 (Feb. 1973).
19. Reed. R. L. and Healy. R. N.. "Some
Physicochemical Aspects of Microemulsion
Flooding: A Review" in Improved Oil Recovery
by Surfactant and Polymer Flooding. Shah. D.
o. and Schechter. R. S .• editors; Academic
Press. Inc .• N.Y .• 1977.
SI METRIC CONVERSION FACTORS
*
ft x 3.048 E - 01 = m
OF (OF - 32)/1.8
*
in. x 2.54
E + 00 : cm
*
* mL x 1.0 E + 00
Conversion factdr is exact.
= cm
3
TABLE I
MICROWAVE EQUIVALENT OIL SATURATIONS
AT INITIAL AND WATER FLOOD CONDITIONS
Formulations Containing
LN-60COS
mol %
0
17
25
Average S .
V/V Ol
p
0.594 ± 0.008
0.597 ± 0.008
0.613 ± 0.014
318
Average S
V/V orw
p
0.255 ± 0.10
0.302 ± 0.007
0.272 ± 0.020
III
"
.,j
<J)
z
0
0..
<J)
W
Ir

z
w
::E

Ir

<J)


-25
-35
-45
-55
0- INITIAL CALIBRATION
k
w
=519 mD
e- CALIBRATION AFTER 21
kw"197mD
2 - PROPANOL WE I GHT FRACTION
Fig. 1-Typical 2-propanol core calibration curves.
FLOODS
0.8 • .--------------__
0.6 W' •••••
5"
NEAR-CONTINUOUS FLOODS
3- in BEREA CORES
,..
u
z
w
C3

IL
w
>-
Ir
W
>
0
U
w
Ir
PS EW=410
0.' 1.0
FLOOD SALINITY, % NoCI BRINE SAL INITY, % NoCI
Fig. 2-Effect of salinity on (a) MESo values and (b)
solubilization parameters.
O.B r----------------------------------,
0.7
0.6
0.5
0.4
0.3
0.2
0.1
NEAR-CONTINUOUS FLOODS
3-IN BEREA CORES
PS EW=410

FLOOD SALINITY. % NaCI
Fig. 3-Effect of flood salinity on recovery efficiency.
2.r---------------,
0.8 r--------------,
0.6
0.2
. . ..... .
NEAR·CONTINUOUS FLOODS
3-in BEREA CORES
SALINITY: 0.3% NaCI
5"
s.,.

NOMINAL EO. WT. OF SURFACTANT
__ L_ ____ J_ ____ _L ____
'40 '80 420 460
NOMINAL EO. WT. OF SURFACTANT
Fig. 5-Effect of petroleum sulfonate blend equivalent weight
on (a) MESo values and (b) solubilization parameters.
Fig. 6-Recovery efficiency contour map for TRS-40fTR8-18 blends.
I.'
...
>
.....
>
o
en
w
::!E
0.3 ~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~
0.2
0.1
o
o
mol "10 LN-60COS
..... __ ..:::0__ _
• ___ JI. __ _
25
.. -------
2 3 4 5 6
FLOOD SALINITY, % NaCI
Fig. 7-Etfect of salinity on Sore for TRS-40fTRS-18/LN-60COS systems.
\l
z
;!.
>-
~
';;;;
-'
..
'"
10.0...----.--,.,.,....,oc---::=---------,
380 420 460 500
NOMINAL EQ. WT. OF TRS-40/TRS-18 BLEND
Fig. 9-ER contour map for TRS-40fTRS-18 blends with 25 mol%
LN-60COS.
15,----------------------------------,
u
0
z
1ft
,: 10
!:
z
..J
..
U)
..J
..
:::;
j:
0..
0
c
8
..J
LL
..J
5
..
u
:E
w
J:
0
NEAR-CONTINUOUS FLOODS
3-io BEREA CORES
PS EW=410
0.2 0.4. O.S 0.8
MOLE FRACTION OF LN-SOCOS
1.0
Fig. 10-Effect of LN-60COS on chemical flood optimal salinity of TRS40fTRS-18/LN-60CQS
SV!UAml'l
7 8
U
" z
,e
.
)o!"
I-
Z
..J
«
CI)
..J
«
::!E
l-
lL
0
a::
0
~
:I:
1&.1
a!
1&.1
CI)
«
:I:
IL
12
10
8
6
4
2
u
0
z
1ft
,:
I-
c
~
Z
0
"
UJ
0::
w
U)
..
J:
0..
I
W
W
0::
J:
I-
1 0 ~ ~ - 1
RECOVERY EFFICIENCY
CONTOURS
'i:
z 6
380 420 460 500
NOMINAL EO. WT. OF TRS-40/TRS-18 BLEND
Fig. 8-ER contour map for TRS-40ffRS-18 blends with 17 mol% LN-BOCOS.
25 ~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - , 2 5
20
20
-
15
15
10 10
5
5
o 1!::=--______ -1... __________ L-________ ..J 0
o 0.1 0.2 0.3
MOLE FRACTION OF LN-60COS
,.,
~
....
,.,
E
"
i
::l
:::;
j:
0..
0
I-
..
>w
~
Fig. 11-Effect of LN-60COS on the width or tne three-phase region and solubilization parameters at
optimal salinity.


EQUAL OPTIMAL SALINITIES

NEAR-CONTINUOUS FLOODS
3-ln BEREA CORES
2 4 6 8 10
CHEMICAL FLOOD OPTIMAL SALINITY, % NaCI
Fig. 12-Correlation between chemical flood and phase behavior optimal salinities.
12
SPE127
02
.-

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