U.S. patent number 3,700,280 [Application Number 05/138,379] was granted by the patent office on 1972-10-24 for method of producing oil from an oil shale formation containing nahcolite and dawsonite.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to Michael N. Papadopoulos, Russell C. Ueber.
United States Patent |
3,700,280 |
Papadopoulos , et
al. |
October 24, 1972 |
METHOD OF PRODUCING OIL FROM AN OIL SHALE FORMATION CONTAINING
NAHCOLITE AND DAWSONITE
Abstract
A new and improved method of recovering hydrocarbons and
dawsonite decomposition products from a subterranean oil shale
formation containing substantial amounts of nahcolite and dawsonite
comprising penetrating said formation with at least one well
borehole and forming a cavern therein. A hot fluid is circulated in
the upper region of the cavern to effect formation of carbon
dioxide by decomposition of the nahcolite and dawsonite thereby
causing pressure build-up resulting in fracturization and/or
rubbling and enlargement of the cavern, thereafter injecting
simultaneously or sequentially into the upper region of the cavern
a cooling liquid, and into the rubblized zone a kerogen-pyrolyzing
fluid to recover hydrocarbons and final by recovering dawsonite
decomposition products by suitable means such as solution
mining.
Inventors: |
Papadopoulos; Michael N.
(Lafayette, CA), Ueber; Russell C. (Houston, TX) |
Assignee: |
Shell Oil Company (New York,
NY)
|
Family
ID: |
22481748 |
Appl.
No.: |
05/138,379 |
Filed: |
April 28, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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835323 |
Jun 23, 1969 |
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Current U.S.
Class: |
299/5; 166/307;
166/271; 423/206.2; 166/272.2 |
Current CPC
Class: |
E21B
43/2405 (20130101); E21B 43/281 (20130101) |
Current International
Class: |
E21B
43/28 (20060101); E21B 43/16 (20060101); E21B
43/24 (20060101); E21B 43/00 (20060101); E21b
043/24 (); E21b 043/28 () |
Field of
Search: |
;166/266,269,270,271,272,303,307 ;299/4,5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wolfe; Robert L.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of copending
application, Ser. No. 835,323, filed June 23, 1969 and now
abandoned.
Claims
I claim as my invention
1. A method of producing hydrocarbons and dawsonite decomposition
products from a subterranean oil shale formation containing rich
deposits of nahcolite and dawsonite comprising the steps of:
a. penetrating at least one well borehole into an underground
nahcolite-dawsonite oil shale formation;
b. injecting a nahcolite leaching solution to create a cavern;
c. circulating a hot fluid along the cavern roof to release carbon
dioxide from the nahcolite and dawsonite and thereby increasing the
volume of the cavern by effecting rubbling;
d. injecting a cool fluid along the enlarged cavern roof while
injecting a kerogen-pyrolyzing fluid into the oil shale rubble and
recovery hydrocarbons therefore; and
e. recovering water insoluble dawsonite decomposition products.
2. The method of claim 1 wherein the leaching solution in step (b)
is hot water and the hot fluid in step (c) is steam.
3. The method of claim 1 wherein the decomposed dawsonite is
recovered by solution mining.
4. The method of claim 3 wherein the decomposed dawsonite is
essentially analcite.
5. A method of producing hydrocarbons and analcite from an
underground oil shale formation rich in nahcolite and dawsonite
comprising the steps of:
a. penetrating at least one well borehole into an underground oil
shale formation rich in nahcolite and dawsonite;
b. leaching a portion of the nahcolite with hot water to create a
cavern;
c. circulating steam along the roof of cavern to release carbon
dioxide from the nahcolite and dawsonite the latter being converted
to analcite to enlarge the cavern vertically and rubble the oil
shale;
d. injecting a cooling fluid along the roof of the cavern;
e. injecting steam into the rubbled oil shale and recovering
hydrocarbons therefrom; and
f. recovering analcite by solution mining.
Description
BACKGROUND OF THE INVENTION
This invention relates to the recovery of hydrocarbons and
dawsonite decomposition products from an underground oil shale
formation containing nahcolite and dawsonite deposits by creating a
cavern in said formation, decomposing the nahcolite and dawsonite
to form carbon dioxide to effect pressure build-up and
fracturization and/or rubbling of the oil shale, in-situ recovering
hydrocarbons by means of a kerogen-pyrolyzing fluid and finally
recovering the dawsonite decomposition product by solution mining
or other suitable means.
Description of the Prior Art
The use of various techniques both nuclear and non-nuclear to
fracture, rubblize or break-up or fragment underground oil shale
formations so as to form a fractured formation or a chimney or
cavern filled with rubble or fragmented oil shale to facilitate
shale oil recovery from such fractured, fragmented oil shale areas
by in-situ pyrolysis is well known in the art. Although some oil
shale formations are known to contain nahcolite and dawsonite,
their recovery in conjunction with insitu pyrolysis of shale oil
recovery has not been thought feasible in the past because of the
thermal decomposition of the nahcolite and dawsonite and in the
case of the latter the formation of insoluble oxides and/or silica
complexes of aluminum. Therefore, attempts to recover dawsonite
from subterranean oil shale formations containing rich zones of
nahcolite and dawsonite has not been attempted except with respect
to shallow deposits from which the minerals are mined and processed
at surface locations.
A number of proposals have been made in the art to recover
dawsonite from oil shale above ground by subjecting an oil shale
previously retorted above ground to a leaching process using an
aqueous solution of sodium carbonate and sodium hydroxide and
subsequently precipitating the dawsonite with carbon dioxide in
order to recover dawsonite. In U.S. Pat. No. 3,502,372 in-situ
recovery of oil and dawsonite from subterranean rubblized oil shale
formation is described using a combination of a pyrolysis and
solution mining technique involving forming a fracture-permeated
zone within a subterranean oil shale formation, prior to such
treatment.
The above-ground retorting techniques for recovering oil and
dawsonite are outside the scope of the present invention, and are
undesirable and unsuitable for carrying out the process of the
present invention since the process results in the formation of
large amounts of insoluble materials which are undesirable and
difficult to handle making these operations costly and
unattractive. The process described in U.S. Pat. No. 3,502,372 is
more attractive and less costly than an above-ground retorting
technique but tends to cause a formation of some insoluble products
and a failure to recover a significant proportion of the
dawsonite.
OBJECTS OF THE INVENTION
It is an object of this invention to provide an improved method for
recovering hydrocarbons and dawsonite decomposition products from
underground oil-shale formations containing nahcolite-dawsonite
deposits.
Still another object of this invention is to decompose the
nahcolite and dawsonite of an underground oil-shale formation rich
in these minerals to carbon dioxide to aid in the fracturing and
rubbling of the formation; insitu recovering hydrocarbons therefrom
by means of a kerogen-pyrolyzing fluid and finally recovering the
insoluble complexes of aluminum from the decomposed dawsonite.
Still another object of this invention is to circulate a hot fluid
preferably along the roof of the cavern to effect formation of
carbon dioxide by decomposing the nahcolite and dawsonite to cause
enlargement of the cavern and fracturization and/or rubbling of the
oil-shale therein, cooling the roof or upper portion of the cavern
to terminate this process; injecting a kerogen-pyrolyzing fluid
into the rubbled oil shale to effect recovery of hydrocarbons
therefrom and finally recovering the dawsonite decomposition
products containing water insoluble aluminum complexes.
Still another object of this invention is that the cavern in the
oil shale formation containing the nahcolite-dawsonite zones is
formed by leaching a portion of the nahcolite and thereafter
forming carbon dioxide by decomposing the remaining nahcolite and
dawsonite by means of a hot fluid such as steam.
Still another object of this invention is that the
kerogen-pyrolyzing fluid to effect hydrocarbon recovery from the
oil shale and the cooling fluid used to prevent vertical migration
of the cavern roof can be circulated through the cavern
sequentially or simultaneously.
SUMMARY OF THE INVENTION
These and other objects are preferably accomplished by forming a
cavern preferably one which is generally horizontally controlled in
a subterranean oil shale-bearing formation that is impermeable and
contains a significant proportion of nahcolite and dawsonite below
its upper boundary region and providing fluid communication between
the earth surface and the cavern. Hot fluid is injected and
circulated through the cavern in its upper region and should
preferably be in contact with the roof thereof at a temperature
sufficient to cause decomposition of the nahcolite and dawsonite
and form carbon dioxide and water thereby causing a high pressure
build-up within portions of the cavern and cause fracturing and
rubbling of the roof of the cavern. As the volume of the hot fluid
within the cavern increases, the paths of fluid flow within the
cavern are preferably adjusted to keep the hot fluid in contact
with the upward migrating roof of the cavern. The fluid circulation
is continued for a time sufficient to enlarge the cavern by a
significant amount. The cavern roof is cooled prior to its
migration above a selected depth, such as an upper boundary region
of the normally impermeable hydrocarbon-bearing formation, by
displacing a cooling fluid into contact therewith. Relatively cool
fluid is maintained in contact with the roof of the enlarged cavern
while circulating a kerogen-pyrolyzing fluid through the
hydrocarbon-bearing material within the cavern to recover
hydrocarbons therefrom and finally solution mining to recover the
dawsonite decomposition products.
The process of this invention is particularly applicable to various
subsurface oil shale formations, such as in the Green River
formation in the Colorado area of the United States, containing
rich deposits of nahcolite and dawsonite. The nahcolite and
dawsonite are apt to occur within an oil shale formation in the
form of beds, lenses, nodules, loads, veins, or the like, having
sizes ranging from microscopic particles to layers that are many
feet in thickness and many miles in extent. Dawsonite is
particularly apt to occur in the form of microscopic particles in
amounts of up to about 10 or 12 percent by weight of the oil shale
while the nacholite can vary in amounts of 5-40percent.
The present process provides a means for enlarging a permeable zone
within a normally impermeable oil shale by circulating a hot fluid
such as hot water, steam, mixtures thereof or non-aqueous fluids to
effect decomposition of the nahcolite and dawsonite present therein
to carbon dioxide at a temperature between about 300.degree. F and
about 1,500.degree. F, preferably between 350.degree. F and
750.degree. F. The invention also provides a means for terminating
the enlargement of the permeable zone at a selected depth and
avoiding the danger of extending fractures to surface or subsurface
locations that would create a danger or disadvantage by means of
cooling fluids. It further provides a procedure that generates
significant amounts of carbon dioxide as a circulating fluid which
also has a significant stripping action on the hydrocarbon
materials released from the heated oil shale by a kerogen
pyrolyzing fluid which may be an aqueous or non-aqueous pyrolyzing
fluid or by use of hydrocarbon extracting materials such as phenols
etc. Oil shale begins to release hydrocarbons at significant rates
at temperatures from about 400.degree. F and preferably between
550.degree. and 750.degree. F. In the presence of carbon dioxide,
the hydrocarbons released from the oil shale by a pyrolyzing fluid
such as steam tend to be entrained and transported in the form of
vapors. This provides both an economy in the recovery of
hydrocarbon products and their upgrading. The utilization of the
carbon dioxide and water that are generated in-situ can be used as
a part of the hot fluid that is circulated along the cavern roof to
cause vertical expansion of the cavern within a subterranean oil
shale and results in a significant increase in the amount of shale
oil recovered.
The recovery of dawsonite decomposition products can be finally
recovered by solution mining using an aqueous fluid preferably
containing a chelating agent.
The chelating agents useful as additives in the aqueous alkaline
fluid of this invention can include any organic chelating agent
capable of chelating with the aluminum or other prevalent metallic
compounds present in the oil shale and forming soluble compounds in
the aqueous solution and include nitrogen-containing carboxylic
acids and amine or metallic salts thereof such as amino-, imino-,
nitrilo-, carboxylic acids and salts thereof such as described in
U.S. Pats. Nos. 2,631,978; 2,959,547; 3,256,196 and 3,409,551 and
include amino carboxylic acids, e.g., ethylene diamine tetraacetic
acid and salts thereof methyl iminodiacetric acid, nitroacetic
acid, phenyl iminodiacetic acid, 1, 2-diamino cyclohexane
tetraacetic acid of which preferred are the amine and alkali metal
(sodium) salts of ethylene diamine tetraacetic acid, e.g., di-,
tri- and tetrasodium ethylene diamine eteraacetate (Na.sub.2 -,
Na.sub.3, or Na.sub.4 EDTA), 1, 2-diamino cyclohexane tetraacetic
acid and mixtures thereof.
The presence of the chelating agent in the aqueous alkaline
solutions aids in the recovery of dawsonite decomposition products
which are substantially insoluble aluminum compounds, such as
analcite.
SPECIFIC EMBODIMENT OF THE INVENTION
The procedural steps in carrying out the process of the present
invention are essentially as follows:
1. establishing at least one well borehole into a
nahcolite-dawsonite rich oil-shale formation;
2. forming a cavern therein by leaching a portion of the nahcolite
with an aqueous fluid such as water which may be cool or hot,
preferably the latter;
3. circulating a hot fluid such as hot water and/or steam in the
upper region and preferably along the cavern roof to effect
decomposition of the nahcolite and dawsonite to carbon dioxide and
water insoluble products of dawsonite such as insoluble oxides and
silicates complexes of aluminum such as analcite to effect
enlargement of the cavern by upward migration of the cavern roof as
well as fracturization and/or rubbling;
4. circulating sequentially or simultaneously a cooling fluid such
as hydrogen along the cavern roof and a kerogen pyrolyzing fluid
such as steam and/or solvents such as benzene phenol, etc. through
the rubbled oil shale to effect hydrocarbon recovery; and
5. solution mining to recovery the aluminum complexes from
dawsonite.
EXAMPLE
Into an oil-shale formation rich in nahcolite and dawsonite a well
was completed at below about 2000 feet and a portion of the
nahcolite bed was water leached to form a cavern. Steam was
injected along the cavern roof to decomposition the nahcolite and
dawsonite to form carbon dioxide thereby building up pressure and
cause upward migration of the cavern roof and oil shale rubbling.
The dawsonite is essentially converted to water insoluble complexes
of aluminum such as analcite. A cooling fluid hydrogen is
thereafter circulated along the cavern roof to prevent further
upward roof migration while steam is injected into the oil shale
rubble to effect hydrocarbon recovery thereafter.
After the hydrocarbons such as oil have been recovered a basic
solution containing a chelating agent such as an alkali metal salt
of ethylene diamine tetraacetic acid, e.g., Na.sub.4 EDTA (the
sodium salt of ethylenediaminetetraacetic acid) or Na salt of 1,
2-diamino cyclohexane tetraacetic acid is injected into the treated
oil recovery zone of the shale formation preferably at a
temperature of from about 100.degree. F to about 500.degree. F to
effect recovery of analcite.
The foregoing description of the invention is merely intended to be
explanatory thereof. Various changes in the details of the
described method may be made within the scope of the appended
claims without departing from the spirit of the invention.
* * * * *