U.S. patent number 3,802,508 [Application Number 05/148,202] was granted by the patent office on 1974-04-09 for in situ recovery of oil from tar sands using water-external micellar dispersions.
This patent grant is currently assigned to Marathon Oil Company. Invention is credited to Joe T. Kelly, deceased, Fred H. Poettmann.
United States Patent |
3,802,508 |
Kelly, deceased , et
al. |
* April 9, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
IN SITU RECOVERY OF OIL FROM TAR SANDS USING WATER-EXTERNAL
MICELLAR DISPERSIONS
Abstract
Hydrocarbon from subsurface tar sands having an injection means
in fluid communication with a production means is recovered by
first heating the tar sands, then injecting a water-external
micellar dispersion into the tar sands, and thereafter displacing
the dispersion toward the production means and recovering the
hydrocarbon through the production means. The tar sands are heated
to a temperature sufficiently high to cause the incoming micellar
dispersion to become heated to a temperature of at least about
100.degree.F upon entering the tar sands. The micellar dispersion
can be preceded by a slug of hot water which can optionally have a
pH greater than about 7. Also, the micellar dispersion can have a
pH of about 7-14 and preferably a temperature up to about
100.degree.F. The micellar dispersion contains hydrocarbon,
surfactant, aqueous medium, and optionally cosurfactant and/or
electrolyte.
Inventors: |
Kelly, deceased; Joe T. (late
of Littleton, CO), Poettmann; Fred H. (Littleton, CO) |
Assignee: |
Marathon Oil Company (Findlay,
OH)
|
[*] Notice: |
The portion of the term of this patent
subsequent to March 14, 1989 has been disclaimed. |
Family
ID: |
26845637 |
Appl.
No.: |
05/148,202 |
Filed: |
May 28, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
888897 |
Dec 29, 1969 |
3637018 |
|
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Current U.S.
Class: |
166/272.3 |
Current CPC
Class: |
E21B
43/20 (20130101); C09K 8/592 (20130101); E21B
43/24 (20130101) |
Current International
Class: |
C09K
8/58 (20060101); E21B 43/24 (20060101); E21B
43/16 (20060101); E21B 43/20 (20060101); C09K
8/592 (20060101); E21b 043/24 () |
Field of
Search: |
;166/272,271,273,274,302 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wolfe; Robert L.
Attorney, Agent or Firm: Herring; Joseph C. Willson, Jr.;
Richard C. Hummel; Jack L.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of our copending application titled
"In Situ Recovery of Oil from Tar Sands Using Water-External
Micellar Dispersions," Ser. No. 888,897, filed Dec. 29, 1969 and
now U.S. Pat. No. 3,637,018.
Claims
What is claimed is:
1. A process of recovering hydrocarbon from sub-surface tar sands
having at least one injection means in fluid communication with at
least one production means, comprising heating the tar sands to a
temperature sufficient to heat an incoming water-external micellar
to a temperature above about 100.degree.F. by the time the micellar
dispersion travels about 7.5 to about 15 feet into the tar sands,
injecting the water-external micellar dispersion into the tar
sands, displacing the micellar dispersion toward the production
means and recovering hydrocarbon through said production means.
2. The process of claim 1 wherein the water phase of the micellar
dispersion has a pH within the range of about 7 to about 14.
3. The process of claim 1 wherein a slug of water at a temperature
above 100.degree.F. precedes the injection of the micellar
dispersion.
4. The process of claim 3 wherein the pH of the water is above
about 7.
5. The process of claim 1 wherein the micellar dispersion is
comprised of hydrocarbon, surfactant, and aqueous medium.
6. The process of claim 5 wherein the micellar dispersion contains
cosurfactant, electrolyte or cosurfactant and electrolyte.
7. The process of claim 1 wherein the temperature of the micellar
dispersion is above about ambient temperature and below about
100.degree.F.
8. The process of claim 1 wherein steam is injected to heat the tar
sands before the micellar dispersion is injected.
9. The process of claim 1 wherein a mobility buffer is injected
after the micellar dispersion.
10. The process of claim 1 wherein an aqueous drive material is
used to displace the micellar dispersion toward the production
means.
11. A process of recovering hydrocarbon from sub-surface tar sands
having at least one injection means in fluid communication with at
least one production means, comprising:
1. heating the tar sands to a temperature sufficient to heat an
incoming water-external micellar dispersion to a temperature above
about 100.degree.F by the time the front portion of the dispersion
has traveled about 7.5 to about 15 feet in the tar sands,
2. injecting about 1 to about 30 percent formation pore volume of
the water-external micellar dispersion into the tar sands,
3. thereafter, injecting about 5 to about 75 percent formation pore
volume of a mobility buffer into the tar sands,
4. and then injecting sufficient drive material to displace the
micellar dispersion and mobility buffer toward the production means
and recovering hydrocarbon through the production means.
12. The process of claim 11 wherein the micellar dispersion is at a
temperature above about ambient temperature and less than about
100.degree.F.
13. The process of claim 11 wherein up to about 100 percent
formation pore volume of an aqueous preslug at a temperature above
100.degree.F. is injected into the tar sands before the micellar
dispersion is injected.
14. The process of claim 13 wherein the pH of the aqueous preslug
is about 7 to about 14.
15. The process of claim 11 wherein the micellar dispersion is
comprised of hydrocarbon, surfactant, and aqueous medium.
16. The process of claim 15 wherein the micellar dispersion
contains cosurfactant, electrolyte, or cosurfactant and
electrolyte.
17. The process of claim 15 wherein the surfactant is petroleum
sulfonate.
18. The process of claim 11 wherein the mobility buffer is an
aqueous solution containing a mobility reducing agent.
19. The process of claim 11 wherein the drive material is
aqueous.
20. The process of claim 11 wherein the pH of the water phase of
the micellar dispersion is about 7 to about 14.
21. The process of claim 11 wherein steam is injected to heat the
reservoir before the micellar dispersion is injected.
22. The process of claim 11 wherein the micellar dispersion
contains about 2 to about 50 percent by volume hydrocarbon, about
40 to about 95 percent by volume aqueous medium, at least about 4
percent by volume surfactant, and about 0.01 to about 20 percent by
volume cosurfactant and about 0.001 to about 5 percent by weight of
electrolyte.
23. The process of claim 22 wherein the surfactant is petroleum
sulfonate.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the recovery of hydrocarbon from tar
sands by an in-situ process using a water-external micellar
dispersion. The tar sands are first heated, then the micellar
dispersion (contains hydrocarbon, surfactant, and aqueous medium)
is injected and displaced through the tar sand formation.
2. Description of the Prior Art
Tar sands, also known as oil sands and bituminous sands, are sands
that contain a very viscous hydrocarbon. One of the largest
deposits is the Athabasca sands found in Northern Alberta, Canada.
The appearance of such sands is generally asphaltic, due to the
viscous hydrocarbon. Oil or hydrocarbon from tar sands is
substantially more viscous than crude oil obtained from the normal
oil-bearing subterranean formation.
It is known in the prior art that hydrocarbon from tar sands can be
recovered by first flooding with steam and then following this
steam flood with an aqueous solution of sodium hydroxide. The
sodium hydroxide slug aids in emulsification of the oil in the tar
sands.
U. S. Pat. No. 2,882,973 to Doscher et al. teaches the use of an
aqueous solution containing a nonionic surface-active agent and
optionally a neutral salt, the solution at a pH of at least 12.
Examples of useful nonionic surfactants include oil-soluble
monohydric alcohols, oil-soluble dihydric alcohols, and oil-soluble
alcohols containing substituents such as ether and/or ester groups.
The nonionic surfactant is present in sufficient concentration to
effect instantaneous or spontaneous emulsion of the oil or tarry
material present in tar sands and to maintain it in the emulsified
state. Concentrations of 0.1-5 percent by weight are effective for
this purpose. The high pH is obtained by adding alkali metal
hydroxide or ammonia.
U. S. Pat. No. 3,375,870 to Satter et al. teaches an in situ
process for recovering hydrocarbon from tar sands by heating the
tar sands to a temperature above 300.degree.F., then using
"recognized recovery methods" to recover the hydrocarbon. Examples
of such processes are waterflooding, steam injection, forward
combustion and gas injection.
Also, combustion processes have been used to recover the oil. Air
in injected into the tar sand reservoir and the hydrocarbon and air
combusted. The fire front distills the oil ahead of it, fuel for
the fire is mostly coke deposited by the destructive
distillation.
SUMMARY OF THE INVENTION
Applicant has discovered a novel method of recovering oil from tar
sands by injecting a water-external micellar dispersion into heated
subsurface tar sands and displacing the dispersion toward a
production means in fluid communication with the tar sands. The
heated tar sands should have sufficient enthalpy or heat to raise
the temperature of the micellar dispersion to at least
100.degree.F. upon entering the tar sands, e.g. the dispersion
should be heated to at least 100.degree.F. by the time the front
portion of the dispersion is introduced about 7.5 - 15 feet into
the tar sands. The water-external micellar dispersion contains
hydrocarbon, surfactant, and aqueous medium and can have a pH of
about 7-14, the higher pH aids in emulsification of the oil. The
micellar dispersion can be preceded by a hot water flood, the water
flood can be at a pH greater than 7. In addition, the micellar
dispersion can be followed by a mobility buffer and this, in turn,
followed by a drive material, e.g. drive water. The mobility buffer
acts to impart a more stable flow to the process.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The water-external micellar dispersion is comprised of hydrocarbon,
surfactant, and aqueous medium. Optionally, alcohol and/or
electrolyte can be incorporated. Examples of useful volume amounts
include about 2 to about 50 percent hydrocarbon, about 40 to about
95 percent aqueous medium, at least about 4 percent surfactant,
about 0.01 to about 20 percent cosurfactant, and about 0.001 to
about 5 percent by weight of electrolyte. In addition, the
dispersion can contain other additives such as corrosion inhibiting
agents, bactericides, sequestering agents, etc.
Examples of useful hydrocarbons include crude oil, partially
refined fractions thereof, e.g. side cuts from crude columns, crude
column overheads, gas oils, kerosene, heavy naphthas, naphthas,
straight-run gasoline, liquefied petroleum gases, etc.; and refined
fractions thereof including propane, pentane, decane, dodecane,
aryl compounds such as benzene, naphthalene, anthracene, and
substituted products thereof. Also, the hydrocarbon can be a
synthesized hydrocarbon. In addition, the unsulfonated hydrocarbon,
e.g., heavy vacuum gas oils in petroleum sulfonates is also
useful.
The aqueous medium can be soft, brackish, or a brine water.
Preferably, the water is soft but it can contain small amounts of
salts which are compatible with the ions within the tar sands.
The surfactant can be anionic, cationic, and nonionic. Examples of
useful surfactants include those found in U.S. Pat. No. 3,254,714
to Gogarty et al. Especially useful surfactants are the petroleum
sulfonates, also known as alkyl aryl naphthenic sulfonates.
Preferred petroleum sulfonates include those having an average
equivalent weight of about 350 to about 525 and more preferably
about 390 to about 460. The sulfonate is preferably one containing
a monovalent cation. Mixtures of different surfactants as well as
mixtures of low, medium, and high average equivalent weight
surfactants or sulfonates are useful.
The cosurfactant (also known as semi-polar organic compound and
cosolubilizer) can have limited water solubility. Preferably, the
water solubility of the cosurfactant is about 0.1 to about 20
percent or more and more preferably about 1 to about 5 percent at
ambient temperature. Examples of useful cosurfactants include
alcohols, amino compounds, esters, aldehydes, ketones and like
compounds containing one to about 20 or more carbon atoms and more
preferably about 3-16 carbon atoms. Specific examples of useful
alcohols include isopropanol, n- and isobutanol, the amyl alcohols
such as n-amyl alcohol, 1- and 2-hexanol, 1- and 2-octanol, decyl
alcohols, alkaryl alcohols, and alcoholic liquors such as fusel
oil. The alcohols can be primary, secondary, and tertiary alcohols.
Preferably, the concentrations within the dispersions are about
0.01 to about 5 percent and more preferably about 0.1 to about 3 by
volume. Mixtures of two or more different cosurfactants are
useful.
The electrolyte useful in the water-external micellar dispersions
include inorganic bases, inorganic acids, and inorganic salts;
organic bases, organic acids, and organic salts, which are either
weakly or strongly ionized. Preferably the electrolytes are
inorganic bases, inorganic acids, and inorganic salts, e.g. sodium
hydroxide, sodium chloride, sodium sulfate, hydrochloric acid,
sulfuric acid, sodium nitrate, ammonium hydroxide, etc. Examples of
other useful electrolytes are found in U.S. Pat. No. 3,330,343 to
Tosch et al. Preferably, the electtolyte is one that will yield a
high pH, e.g., sodium or ammonium hydroxide and like materials.
Examples of useful water-external micellar dispersions are taught
in U.S. Pat. Nos. 3,506,071 and 3,506,070, to Jones.
Preferably, the pH of the micellar dispersion is above 7 and more
preferably about 10-14. The desired pH can be obtained by adding
the appropriate electrolyte to obtain the desired pH, e.g. NaOH,
NH.sub.4 OH, etc.
The temperature of the micellar dispersion can be from below about
ambient temperature up to about 100.degree.F., more preferably it
is closer to 100.degree.F. Heating the micellar dispersion to above
ambient temperature before injecting it into the injection means
can be accomplished using conventional heating equipment. Also, the
enthalpy or heat potential of the subterranean conditions can be
used advantageously to heat the micellar dispersion as it
progresses down the well bore before entering the tar sand.
The tar sand formation is heated before the dispersion is injected
therein. The enthalpy or heat within the formation should be
sufficiently high to cause the incoming micellar dispersion to
become heated to at least 100.degree.F. as it enters the formation,
e.g. the front portion should be at least 100.degree.F. by the time
it travels about 7.5-15 feet into the formation. Temperatures up to
the flash point of components within the micellar dispersion are
useful within the formation. Methods of heating the formation are
known in the art, e.g., steam flooding, in situ combustion,
injecting heated fluids, etc.
The components of the micellar dispersion are designed to obtain a
stable dispersion at the high temperature within the reservoir. For
example, increasing the aromaticity of the hydrocarbon, increasing
the electrolyte content, increasing the molecular weight of the
surfactant and/or cosurfactant, etc. are methods useful to obtain
dispersions stable at high temperatures. Specific methods of
increasing the thermostability range to higher temperatures are
taught in U.S. Pat. Nos. 3,493,048 to Jones, 3,493,047 to Davis et
al, 3,495,660 to Davis et al, 3,500,912 to Davis et al, and
3,508,611 to Davis et al. The dispersion is made up on the surface
so that it will be stable at formation temperatures, i.e., the
surface mixture may not be thermodynamically stable at surface
temperature, but at formation temperature, it will be a stable
micellar dispersion.
The water-external micellar dispersion can be preceded by a water
slug. The water slug is at a temperature greater than 100.degree.F.
and more preferably above 150.degree.F. Also, the pH of the
pre-water slug can be adjusted to about 7-14. High pHs aid in the
emulsification of the oil. The high pH can be obtained by adding
water-soluble bases, e.g. NaOH, etc. Volume amounts up to about 1
pore volume and greater are useful as a preslug.
The mobility, i.e., the effective mobility of the micellar
dispersion flowing in the tar sands, can be adjusted, e.g.,
decreased, to give a more stable fluid flow to reduce or inhibit
fingering. Such can be obtained by adjusting the components within
the micellar dispersion to obtain a desired viscosity. However, it
will generally be desired to design the mobility to be about equal
to or greater than that of the formation fluids flowing in front of
the dispersion.
The micellar dispersion can be followed by a drive material.
Optionally, a mobility buffer can be injected behind the micellar
dispersion and this, in turn, followed by the drive material.
Examples of useful mobility buffers include aqueous and nonaqueous
fluids containing mobility reducing agents such as high molecular
weight, partially hydrolyzed polyacrylamides, polysaccharides,
polyisobutylenes, etc. Generally, any mobility reducing agent is
useful as long as it is compatible with the dispersion and the tar
sands and does effectively reduce the mobility of the aqueous or
nonaqueous mobility buffer slug flowing in the tar sands.
As mentioned previously, the micellar dispersion can be followed by
a drive material. The drive material can be aqueous or nonaqueous
and can be liquid, gas, or a combination of the two. Preferably it
is an aqueous drive material. The drive material can contain ions
but such ions are preferably compatible with the ions within the
subterranean formation.
Formation pore volumes of about 1 to about 30 percent of more of
the water-external micellar dispersion are useful with this
invention. More preferably, about 1 to about 10 percent formation
pore volume is useful. The mobility buffer can be in amounts of up
to about 5 to about 75 percent or more formation pore volume.
It is not intended that the invention be limited by the specifics
taught above. Rather, all equivalents obvious to those skilled in
the art are intended to be included within the scope of the
invention as defined within the specification and appended
claims.
* * * * *