Note: Descriptions are shown in the official language in which they were submitted.
33~;
OIL RECOVER~ MET~IOD USING IN SITU-PARTITIONING
SURFACTANT FLOOD S~STEMS
. .
Backgrou d of~~h_ Inventi~n
This invention relates to recovery of oil from a subterranean reser-
voir through the use of surfactant 100ding.
It has long been known that the primary recovery of oil from a sub-
terranean formation leaves a substantial amount of the initial oil still in
the formation. This has led ~o the use of what is commonly referred to as
secondary recovery or water flooding wherein a fluid such as brine is injected
into a well to force the oil from the pores of the reservoir toward a recovery
well. However, this technique also leaves substantial amounts of oil in the
reservoir because of the inability of the water to wet the oil and the capil-
lary retention of the oil. Accordingly, it has been suggested to use a sur-
factant in the water flooding processes. It has been found that the use of
surfactants can reduce the interfacial tension between the oil and the water
to such an extent that substantially increased quantities of oil can be dis-
placed.
However, there are other variables involved in addition to the wet-
ting ability of the water, and in fact conventional surfactan~ flooding tech-
niques also leave substantial amounts of oil in place.
Further efforts to better remove residual oil from subterranean
deposLts have focused on the use of microemulsions. In accordance with this ;~`
technique, a microemulsion is prepared by mixing oil with brine and surface-
active agents. Some systems are capable of achieving good results in removing
oil from the pores of a subterranean formation. However, there is an obvious
drawback to any system for recovering oil which involves the injection of oil
which has already been recovered back into the groundO ~nother drawback is
high surfactant usage due to adsorption of the surfactant on formation rock.
Summary of_~he Inve ion
It is an object of this invention ~o achieve recovery of oil in a
manner comparable to that obtained using microemulsions but without the affir~
mative introduction of oil back into the ground;
/ ~ :
~7334~;
It is another object o~ this invention to reduce the adsorption of
the surface-active components of surfactant flood systems on formation rock.
It is a further ob~ect of this invention to tailor a surfactant
flooding system to the particular character-Lstics oi the oil ~eing recovered,
and
It is yet a further ob~ect of this invention to sweep residual oil
from the pores of a subterranean formation by means of a multiphase bank
formed in situ.
In accordance with this invention, samples of oil from the reservoir
to be flooded are mixed with brine and a series of sulfonate surfactants hav-
ing an average equivalent weight within the range of 375 to 500 and a series
of cosurfactants having solubility in water within the range of 0.5 to 20
grams per 100 grams of water. Thereafter a brine-surfactant-cosurfactant sys-
tem corresponding to one of those which formed a multiphase system on mixing
is introduced into the formation where a multiphase bank is formed in situ.
Descri~tibn f the Drawings
In the drawing~ forming a part hereof there is shown in bar graph
form the composition of a mixture of oil and a surfactant system on initial
contact and after the mixture has reached equilibrium.
Description of the Preferred Embodlments
The surfactant to be used in this invention is a petroleum sulfonate
having an average equivalent weight within the range of 375 to 500 preferably
about 400-425 more p~eferably 407-417. These sulfonates are well kno~n in the
art and are sometimes referred to as alkyl aryl sulfonates. They are also
sometimes referred to as petroleum mahogany sulfonates, Generally, these sul-
fonates contain one monovalent cation, which may be any of the alkali metals
or the ammonium ion. These sulfonates can be produced in the manner known in
the art by the treatment of appropriate oil feedstocks with sulfuric acid and
then neutralizing with an alkali metal or ammonium hydroxide. The equivalent
weights referred to are, as noted, average equivalent weights and ~here may
be present sîgnificant amounts of sulfonates ha~ing an equivalent weight as
low as 200 and as high as 650.
- 2 -
~ ~q ~ 3~ 6
While it is an object of this invention to achieve the advantages
of microemuls~on flood techniques without the injection of additional oil~
this is not to preclude the possibility of a small amount of unreacted oil
being unavoidably present in the sulfonate. The sulfonate surfactant is used
in an amount within the range of 3 to 12 preferably 4 to 8 weight percent
based on the weight of water.
The cosurfactant can be any alcohol, amide, amine, ester, aldehyde
or ketone containing 1-20 carbon atoms and having a solubility in water within
the range of 0.5 to 20, preferably 2 to 10 grams per 100 grams of water. Pre-
ferred mater~als are the C4 to C7 alkanols or mixtures thereof~ Most preferredare C4 and C5 alcohols having a solubility within the above range. Isobutyl
alcohol with a solubility of 9.5 grams per 100 grams of water is particularly
suitable. Other preferred cosurfactants include secondary butyl alcohol,
n-butyl, n-amyl and isoamyl alcohol. Alcohols such as isopropyl~ which are
known in the art to be useful in surfactant-flooding systems generally, are
not suitable for use in this invention because of the undesirably high solu-
bility in water which requires going to extremely high salt concentration
and/or extremely high sulfonate equivalent weight to give an operable system
which is not desirable. The cosurfactant is utilized in an amount within the
range of about 1 to 12, preferably 3-~ weight percent based on the weight of
water.
The brine constitutes 85 to 95 weight percent of the total compo-
sition including brine, surfactant, and cosurfactant. The brine is made up of
water and an electrolyte which is generally predominantly sodium chloride.
The electrolyte is present in the water in an amount within the range of 250
to 100,000, preferably 2,000 to 50,000, parts per million total dissolved
solids (TDS). In systems using lower average equivalent weight sulfonates
(below about 435) and/or more soluble cosurfactants (more than 5 gll00 g water)
10,000 to 50,000, preferably 15,000 to 30,000 TDS may be more desirable.
Other electrolytes which may be used or which may be present in minor amounts
346
in combination with the sodium chloride include potassium chloride, calcium
chloride, magnesium chloride, sodium sulfate, ammonium chloride, and the like.
Large amounts of divalent ions are undesirable.
The small scale partitioning step can be carried out in several
ways. The variables in the in situ-partitioning surfactant flood system
include the nature of the surfactant, its concentration, the nature of the
cosurfactant, its concentration, and the nature and eoncentration of the
brine. These variables are all inter-related such that some co~binations of
ingredients and concentrations can achieve the benefits of in situ-partition-
ing which other closely related combinations will not. Hence, a series ofsolutions can be prepared wherein one or more ingredients or their concentra-
tions is kept constant while the remaining ingredients and concentrations are
varied. In practice, availability or cost considerations will cause one or
more ingredients or their concentrations to be relatively fixed and thus the
series will contain variations of the other ingredients to define the desir-
able partitioning system.
The surfactant solutions to be contacted with the crude oil should
be stable, that is, they should be homogeneous and preferably clear solutions.
Such stability is desirable for convenience in storage and handling and sta-
bility at temperatures of the formation is particularly desirable.
About 1-3 parts, generally about 2 parts, of surfactant solution
and about 1 part of crude oil, by weight, are equilibrated by any suitable
means such as vigorous shaking, vigorous stirring, and the like. The crude
oil should be representative of the formation into which the surfactant system
will be injected. However, for convenience, the gaseous or easily volatili~-
able components of the crude, which might interfere with the small scale par-
~itioning step, may have been removed. The temperature of the equilibration
should approximate the temperature of the formation.
The resulting equilibrated mixture is then allowed to stand undis-
turbed for about 6-24 hours (or less if partitioning occurs sooner) to deter-
~334 E;
mine its partitioning effectiveness. The temperature of the mixture during
this period should also approximate the temperature of the formation to be
treated.
Partitioning is considered to have occurred if (1) the equilibrated
and settled mixture separates into 2 or more phases, and (2) an oil-rich
microemulsion phase which contains at least 85% and preferably at least 95%
of the petroleum sulfonate surfactant is present as one of the phases.
In practice, the partitioning surfactant solutions will separate
into a lower aqueous phase which is predominantly brine and which contains
some of the cosurfactant but very little of the petroleum sulfonate surfactant.
This aqueous phase is generally in contact with the upper oil-rich and sur-
factant-rich microemulsion phase. The microemulsion phase generally contains
substantial amounts of oil and brine with some cosurfactant. Most importantly,
almost all of the petroleum sulfonate surfactant will have partitioned itself
into this oil-rich microemulsion phase.
In some instances of a partitioned surfactant system, depending upon
the nature and concentration of the ingredients, the microemulsion phase can
be in contact with an upper oil phase. The oil phase is almost completely
oil with very minor amounts of any of the ingredients of the original surfac-
tant solution.
By subjecting a given surfactant solution or a series of surfactantsolutions to the above-described partitioning procedure, the surfactant solu-
tions which are capable of partitioning in situ can be identified. Thus, the
present inven~ion provides a method to selec~, optimize, or monitor surfactant
solutions for use in surfactant flood operations.
The surfactant system of this invention is injected into an injection
well or wells in a manner well known in the art in water-flooding operations.
On contacting of the oil in the formation, a three-phase bank is formed in
situ comprising (1) a leading phase of said reservoir oil containing a small
amount of said cosurfactant, (2) a middle microemulsion phase comprising (a)
~ 3 3'~
oil from said reservoir and (b) water, surfactant and cosurfactant from said
injected surfactant system, said surfactant being at a substantially higher
concentration in said middle phase than in said injected surfactant system;
and (3) a trailing phase comprising the majority of sa;d water from said
injected surfactant system, a portion of said cosurfactant from said injected
surfactant system and a minor portion of said surfactant from said injected
surfactant system. In the actual formation, the variations in structure are
such that the middle and trailing phases do not necessarily remain in the
middle and end, respectively, in all places at all times but rather the mul-
tiple phases may manifest themselves on a microscopic level, i.e., within
individual pores or small structures. The figure shows a typical example of
the formation of a three-phase bank, the data incorporated into FIGURE 1 hav-
ing been obtained from a laboratory experiment wherein crude oil was mixed
with the indicated surfactant system.
A mobility buffer is injected behind the surfactant system. Examples
of useful mobility buffers include aqueous and non-aqueous fluids containing
mobility-reducing agents such as high molecular weight partially hydrolyzed
polyacrylamides, polysaccharides, soluble cellulose ethers, and the like.
The mobility buffer comprises 50 to 20,000, preferably 200 to 5,000, parts
per million of said mobility reducing agent in said fluid. The mobility
bufEer can be graded, that is, its concentration can be relatively high at
the leading edge and relatively low at the trailing edge. For instance, the
mobility buffer can start at 2500 ppm PAM and end at 250 ppm. These mobility
buffers are known in the art.
Finally, a drive fluid is injected behind the mobility buffer to
force oil contalned in the reservoir toward a recovery well. The drive mate-
rlal can be aqueous or non-aqueous and can be liquid, gas or a combination of
the two. Generally, it is formation water or water sImilar thereto. When a
hard brine is the drive liquid, it can be beneEicial to precede the brine with
a slug of relatively fresh water.
-- 6 --
~O~f3346
It is preferred, although not essential to the inventlon, that the
surfactant system be preceded by a preflush solution. Such preflush oper-
ations are known in the art and can be carried out utilizing a brine compat-
ible with the surfactant system, such as one containing 2~000 to 50,000 parts
per million TDS, predominantly sodium chloride. A brine solu~ion of the type
used to make up the surfactant system is particularly suitable.
The preflush if employed will generally be utilized in an amount
within the range of 0.01 to 2.0) preferably 0~25 to 1 pore volume, based on
the pore volume of the total formation being treated. The surfactant system
is injected in an amount within the range of about 0.001 to 1.0, preferably
0.01 to 0O25 pore volume based on the pore volume of the total formation being .-
treated.
The mobility buffer is injected in an amount within the range of
about 0.001 to 1.0, preferably 0.01 to 0.25 pore volume, based on the pore
volume of the total formation. The drive fluid is simply injected until all
feasible recovery of the oil has been made.
The invention is effective in oil-wet reservoirs where tertiary
recovery is inherently difficult and is extremely effective in recovery of
oil from water-wet sandstone reservoirs. Also, because of the extremely low
adsorption of the sulfonate on the rock, the invention is of great advantage
in flooding dolomite reservoirs.
In the examples which follow, a mid~continent crude oil was used to
demonstrate the process of the present invention. This crude oil i8 described
as follows:
-Crude Oil Analysis Summary
General Crude Tests
Type-Base Intermediate
Gravity~ API at 60F. 39.1
Pour Test, F. +20
Sulfur, % 0~15
Hydrogen Sulfide negative
107;~3'~S
Crude Oil Analysis'Summa~y (Continued)
Yields~ Hempel)
Gasolin :' (4Q8F. '-EP
Percent 30.9
Octane No. - Research (Clear) 41.4
Octane No. - Research (~3 ml TEI,) 71.7
Kerosene:
Percent 16.8
Gravity 41.9
'Total'Gas Oil~ % 26.5
Still'Residue
Percent 25.3
Gravity 21.1
Carbon Residue, % 3.5
Vacuum Gas Oil Characterization:
% C 10.82
% CNA 19.32
SCF 11.54
VGC 0.8395
EXAMPLE I
A surfactant solution was prepared containing 92.0 percent brine,
5.0 percent petroleum sulfonate surfactant and 3.0 percent isobutyl alcohol
cosurfactant, by weight. The brine was essentially a fresh water (about 600
ppm TDS) to which had been added 15,000 ppm ~aCl. The sulfonate surfactant
was a sodium petroleum sulfonate ~itco Petronate TRS 10-410) which had a ~;
relatively narrow molecular weight distribution and an average equivalent
weight of 417. This commercial material contained about 62 weight percent
active material, about 34~ unsulfonated oil and about 4 weight percent water.
It has 0.5 percent inorganic salts, mostly sodium sulfate and sodium sulfite.
The pH is relatively high, a solution thereof in water has a pH of 8-10.
The surfactant solution was prepared by simple mixing at 120F. It
was a clear, essentially colorless solution and was stable in that it did not
separate into phases.
A 50 g portion of this solution was then equilibrated with 25 g of
the crude oil described above by vigorously shaking in a graduated cylinder.
The mixture was allowed to stand undisturbed overnight at 120F.
This system separa~ed into 3 phases. The bottom phase was a clear
40.8 g solutlon containing 97.9 percent brine, 2.1 percent lsobutyl alcohol
1C~73346
and 0.04 percent sulfonate, by weight. The middle phase was a 15.9 g micro-
emulsion containing 47.9 percent oilS 39.1 percent brine, 9.5 percent sulfo-
nate and 3.5 percent isobutyl alcohol, the oil being the continuous phase.
The 18.3 g upper phase was essentially oil containing 0.8 percent isobutyl
alcohol.
This equilibration test is diagrammatically shown in FIGURE 1. The
surfactant system is considered to have partitioned in that: three phases
were observed to form; an oil-rich microemulsion phase over an essentially
clear aqueous phase was present; and, most importantlyS the sulfonate surfac-
had partitioned itself almost completely (about 99%) in~o the microe~ulsionphase where it is less susceptible to loss by adsorption on formation surfaces.
In other related runs using this partitioning procedure and using
these same surfactant solution ingredients, it was found that the volume of
the microemulsion phase (middle phase) was always proportional to the sulfo-
nate concentration in the original aqueous surfactant solution. This indi-
cates that the sulfonate concentration in the microemulsion phase, which will
form in situ in the formation, tends to remain constant regardless~of the
volume of the microemulsion phase. Thus, in a formation where adsorption
slowly decreases the amount of sulfonate in the system, the volume of the
microemulsion phase should shrink as petroleum sulfonate is lost to the rock.
However, the ability of the microemulsion phase to displace oil should remain
constant since lts composition does not change appreciably.
EXAMPLE II
In a manner similar to that of Example I, a series of surfactant
solutions was prepared, each containing a petroleum sulfonate surfactant, an
alcohol cosurfactant and a brine. Both the nature and the concentration of
these ingredients were varied to provide a number of different solutions.
The sulfonate surfactants employed were closely related sodium
petroleum sulfonates (Witco) but which varied in average equivalent weight.
These included equivalent weights of 350~TRS-50); 407(TRS-10~395);
417(TRS-10-410); 450(TRS-16); and 494(TRS-18).
:~0~3346
The alcohols included in the series varied in ~heir solubility in
water as follows:
Alcohol SolubilitY~ g/100 g H20
isopropyl (IPA) 00
n-butyl (NBA) 7.9
isobutyl (IBA) 9.5
t~butyl (TBA) 0~
sec-butyl (SBA) 12O5
isoamyl (IAA) 2.9
10Each of these solutions was prepared by simple mixing at 120F.
Some combinations of ingredients were unstable in that they did not remain
homogeneous but most formed clear, essentially colorless solutions.
Each of these solutions was then subjected to the partitioning test
described in Example I. The results of these tests are shown in Table I. . .
-- 10 --
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-- 13 --
.. .... .. . . ...
~L07334~6
The first seven runs show that with a low equivalent weight sulfo-
nate partitioning did not occur even when using alcohols such as n-butyl
alcohol and sec-butyl alcohol, which are of the proper solubility.
Runs 8-19 utili2ing a sulfonate of the proper equivalent weight
shows the dependency of partitioning upon the type of alcohol. For instance,
runs 8 and 10 show that with alcohols such as isopropyl alcohol and tert-butyl
alcohol which have high solubility in water, partitioning did not occur, hence,
the preferred range for the solubility of the alcohol of 2 to 10 grams per
100 grams of water. In Run 12 sec-butyl alcohol having a solubility outside
the preferred range was borderline showing no partitioning in this test but
showing a partitioning into two phases in later run 42.
~ un 18 shows that in this system with only 10,000 parts per million
sodium chloride, partitioning did not occur, thus showing the advantage for
the preferred range of total dissolved solids of 15,000 to 25,000 in systems
using a sulfonate toward the low end of the desired range of equivalent
Neight. ~owever, as can be seen from Run 50, partitioning into at least two
phases can occur with a concentra~ion of sodiu~ chloride of 10,000, hence the
broader range for total dissolved solids content of 2,000 to 50jO00. As can
be seen comparing runs 18 or 37 and 50, increasing the equivalent weight of
the sulfonate allows the use of less salt and as little as 250 parts per
million can be used, hence, the broad range of 250 to 100,000 TDS.
Runs 30 and 31 show the desirability of the preferred range of
cosurfactant of 2 to 4 percent as 1 percent failed to give partitioning in
this test, although in test 48, 1 percent was shown to be borderline, hence
the broad range of 1 to 10 percent.
The significant feature is that by utilizing a sulfonate surfactant
having an equivalent weight within the range of 375 to 500 and preparing only
a few samples utilizing alcohols having solubility within the range of about
0.5 to 20 grams per hundred grams of water, the optimum partitioning system
for a given type of oil can be determined easlly. Alternatively, a given
!
~Oq334~;
alcohol having a solubility within the range set out hereinabove can be util~
ized and a series of samples prepared utilizing sulfonates of varying equiva-
lent weights within the range of 375 to 500.
Thereafter9 a large quantity of a surfactant solution for field use
comprising the desired sulfonate, cosurfactant, and the brine can be prepared
corresponding to that which gave good partitioning in the preliminary ~est.
As has been noted hereinabove, surfactant flooding is well known as
is the principle behind it, to wit: reduction of surface tension so as to
remove the oil from the pores. However, the instant invention represents a
radical departure from this known technology in that the difference between
the partitloning and non-partitioning systems is not a function of how much
the surface tension is lowered. Rather, the instant invention represents a
three-fold advance in the art in that it makes possible the use of simple lab-
oratory technlque to determine the outcome of the system, it provides for
forming a three-phase system in situ, thus avoiding the disadvantage of con-
ventional microemulsion systems which require pumping part of the oil which
has been recovered back into the system, and as will be noted hereinbelow, it
surprisingly provides for more economical operation due to a reduced loss of
surfactant as the water flood bank proceeds through the reservoir.
~0 EXAMPLE III
In this series of runs, 0.1 pore volume slugs of six different sur-
factant systems were injected into 3-foot water-wet Berea cores containing
waterflood residual crude oil. The surfactant systems were similar in compo-
sition but 3 gave partitioning results while the other 3 did not partition
when subjected to the ~est of Exa~ple I. One of the surfactant systems was
tested twice, each time in a different core.
The 7 Berea cores used in this series were very similar and had
similar propertiesO Their specific permeabilities to water were 500-600 md,
their permeabilities to b~ine at residual oil saturation were 26-36 md, and
the saturations after waterflood varied only from 0.360 to 0.393.
-`15 -
10733~;
Each of the cores was saturated with a synthetic formation brine,
flooded with the previously described crude oil, then flooded with the forma-
tion brine to residual oil saturation, The cores were then preflushed with 1
pore volume of the same brine (about 15,000 ppm in fresh water) used later in
the surfactant systems. This preflush was followed by a 0.1 pore volume plug
of the indicated surfactant system, 1.0 pore volume of a 2000 ppm polyacryl-
amide (Betz Hi-Vis) in fresh water mobility buffer and one final pore volume
of fresh water driving fluid (one core received only 0.12 pore volume driving
fluid~. The rate was maintained at 0.8 feet per day during each sur~actant
flood. The results are shown hereinbelow in Table II.
Another showing of all of this data is that increasing salt concen-
tration is equivalent to raising the equivalent weight of the sulfonate or
decreasing the solubility of the alcohol. Thus, if the salt concentration is
constant and the equivalent weight of the sulfonate is increased, a more solu-
ble alcohol must be used to compensate, or if the alcohol solubility is con-
stant and a higher equivalent weight sulfonate is used, then the concentration
of the salt must be decreased. Similarly, if the equivalent weight of the
sulfonate is constant and a more soluble alcohol is used, the concentration of
the salt must be increased, or if the salt concentrativn is constant and a
more soluble alcohol is used, then a higher equivalent weight sulfonate must
be used, Finally if the equivalent weight of the sulfonate is constant and
the concentration of the salt is increased, then a more soluble alcohol must
be used, or if the alcohol solubility is constant and a higher salt concentra-
tion is used a lower equivalent weight sulfonate must be used~
3346
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-- 17 --
~ ~ .
33~6
Disregarding run 57 which may be low for other reasons, a comparison
of the remaining six runs shows an average oil recovery of about 85 percent for
the non-partitioning systems and 90 percent for the partitionlng systems.
While this shows an advantage for the partitioning systems, it i8 believed to
be within the limits of experimental error~ One reason the percent recovery
of oil does not distinguish significantly between partitioning and non-parti-
tioning systems is that the cores utilized were too short for the amount of
surfactant solution used to clearly show an advantage for the partitioning
systems.
The significant feature which is shown by the data is the adsorption
of sulfonate. The adsorption of sulfonate in the partitioning systems was
about 400 pounds per acre-foot, which is about half the average of 800 pounds
per acre-foot adsorption shown for the non-partitioning systems. Thus, it can
be seen that under actual field conditions the non-partitionin~ system would
lose sufficient sulfonate to be rendered ineffective much sooner than would
the partitioning system for a given amount of sulfonate used.
EXAMPLE IV
Cut Bank crude oil from the Southwest Cut Bank Sand Unit, Glacier
County, Montana, was used in this example. Sulfonate used was 5 percent of a
sulfonate ha~ing an average molecular weight of 424. The brine was Cut Bank
in~ection water having 7,000 parts per million total dissolved solids which
were almost entirely sodium chloride. The alcohol was 1-1/2 percent of a
mixture of 45 percent normal amyl and 55 percent isoamyl alcohol. Thus, the
composition was 5 percent sulfonate, 1-1/2 percent cosurfactant, 0.7 percent
solids and 92,8 percent water.
This surfactant system on equilibration with the crude oil parti-
tioned into two phases and was stable at 95F, the temperature of the formation
where this crude was obtained, This surfactant system was used in a core,
injecting 0.075 pore volume and 92 percent recovery of the oil was obtained.
This shows that with higher equivalent weight sulfonate and less soluble
alcohols the concentration of the salt can go down.
- 18 -
~0~33~6
While this invention has been described in detail for the purpose
of illustration, it is not to be construed as limited thereby but i5 intended
to cover all changes and modifications within the spirit and scope thereof.
- 19 ~
