US3753594A - Method of producing hydrocarbons from an oil shale formation containing halite - Google Patents

Method of producing hydrocarbons from an oil shale formation containing halite Download PDF

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US3753594A
US3753594A US00075037A US3753594DA US3753594A US 3753594 A US3753594 A US 3753594A US 00075037 A US00075037 A US 00075037A US 3753594D A US3753594D A US 3753594DA US 3753594 A US3753594 A US 3753594A
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halite
oil shale
formation
fluid
oil
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US00075037A
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T Beard
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Shell USA Inc
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Shell Oil Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/006Combinations of processes provided in groups C10G1/02 - C10G1/08
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/17Interconnecting two or more wells by fracturing or otherwise attacking the formation
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/28Dissolving minerals other than hydrocarbons, e.g. by an alkaline or acid leaching agent
    • E21B43/281Dissolving minerals other than hydrocarbons, e.g. by an alkaline or acid leaching agent using heat

Abstract

A method of producing hydrocarbons and optionally halite from a subterranean oil shale formation containing zone(s) of halite, by penetrating said formation with at least one borehole and leaching or dissolving the halite from the formation with a solvent fluid so as to form a cavern(s) and/or interconnected cavities, followed by fracturization and/or rubblization of the oil shale surrounding the caverns or cavities, and thereafter injecting into the fracturized and/or rubblized zones, a pyrolyzing fluid to effect insitu hydrocarbon recovery therefrom.

Description

United States Patent 1 [111 3,753,594
Beard Aug. 21, 1973 METHOD OF PRODUCING 3,510,167 5/1970 Carmody 299/4 HYDROCARBONS FROM AN 01L SHALE 3,502,372 3/1970 Prats 299/5 FORMATION CONTAINING HALITE Thomas N. Beard, Denver, Colo.
Assignee: Shell Oil Company, New York, N.Y.
Filed: Sept. 24, 1970 Appl. No; 75,037
Related US. Application Data Continuation-impart of Ser. No. 770,964, Oct. 28, 1968, abandoned.
Inventor:
US. Cl. 299/4, 166/271 Int. Cl E2lb 43/28 Field of Search 299/4, 5; 166/259,
References Cited UNITED STATES PATENTS 12/1969 Prats 166/251 Primary Examiner-Robert L. Wolfe Attorney-George G. Pritzker and Harold L. Denkler ABSTRACT A method of producing hydrocarbons and optionally halite from a subterranean oil shale formation containing zone(s) of halite, by penetrating said formation with at least one borehole and leaching or dissolving the halite from the formation with a solvent fluid so as to form a cavern(s) and/or interconnected cavities, followed by fracturization and/or rubblization of the oil shale surrounding the caverns or cavities, and thereafter injecting into the fracturized and/or rubblized zones, a pyrolyzing fluid to effect insitu hydrocarbon recovery therefrom.
5 Claims, 2 Drawing Figures "E IL-ul: -1,
Patented Aug. 21, 1973 lOb INVENTOR:
N. BEARD 1 M HIS AG NT FIG.2
METHOD OF PRODUCING HYDROCARBONS FROM AN OIL SHALE FORMATION CONTAINING I-IALITE CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of copending application Ser. No. 770,964, filed Oct. 28, 1968 and now abandoned.
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the recovery of hydrocarbons and optionally halite from underground oil shale formations containing halite deposits. More particularly, it relates to hydrocarbon recovery by in-situ thermal fluid extraction of oil shale within a fracturized and/or rubblized portion of a subterranean oil shale formation in and around a cavern and/or interconnected cavities formed by leaching or dissolving, e.g., solution mining of the halite therefrom.
2. Description of the Prior Art Large deposits of oil in the form of oil shale are found in various sections of the United States, particularly in Colorado and surrounding states and Canada. Various methods of recovery of oil from these shale deposits have been proposed and the principal difficulty with these methods is their high cost which renders the recovered oil too expensive to compete with petroleum crudes recovered by more conventional methods. Mining the oil shale and removing the oil therefrom by above-ground retorting in furnaces presents a disposal and pollution problem and also such processes are also generally commercially uneconomical. In-situ retorting to convert the oil shale to recover the oil contained therein is made difficult because of the non-permeable nature of the oil shale. The art discloses various means of improving oil recovery of oil from oil shale such as described in U.S. Pat. Nos. 3,400,762 or 3,437,378 or 3,478,825 and particularly various means of increasing permeability of oil shale formations as described in U.S. Pat. Nos. 3,273,649 or 3,481,398 or 3,502,372, or copending application Ser. No. 839,350, filed July 7, 1969. Although these references are directed to an advancement of the art, the basic technique for recovering oil from oil shale still requires rubblization techniques such as by means of explosive devices, e.g., nuclear energy which is expensive, difficult to control and presents a radioactive contamination problem all of which are very undesirable.
OBJECTS OF THE INVENTION It is an object of this invention to provide an improved method for recovering hydrocarbons from a halite containing oil shale formation by leaching or dissolving the halite such as by solution mining so as to form a cavern and/or interconnected cavities within the oil shale formation.
It is a further object of the invention to effect rubblization and/or fracturization of the halite leached oil shale formation surrounding the cavern and/or cavities so as to form a permeable zone thereby enhancing insitu thermal fluid extraction (pyrolysis) of hydrocarbons therefrom.
Still another object of this invention is to effect insitu pyrolysis to produce hydrocarbons from oil shale subjected to leaching, rubblization and fracturization as indicated in the previous two paragraphs, and subsequently recovering the hydrocarbons by suitable means.
Still another object of the present invention is to recover watersoluble minerals from a rich halite containing oil shale formation that may be removed during the leaching and/or solution mining, rubblization and/or fracturization, and/or pyrolysis processes.
Still another object of the present invention is to sequentially and/or simultaneously recover halite and hydrocarbons from halite containing oil shale formations that may be removed during the leaching and/or solution mining, rubblization and/or fracturization and/or pyrolysis processes.
Other objects of the invention will be apparent from the following description.-
SUMMARY OF THE INVENTION The present invention is directed to recovery of hydrocarbons and optionally halite from a halite containing oil shale formation by the following steps: (1) subjecting a rich halite zone(s) of an oil shale formation to a leaching, dissolving or solution mining process so as to remove the halite, thereby creating porosity to allow for thermal expansion of the oil shale and establish communication through the treated zone(s), (2) effecting in said leached zone(s) rubblization and/or fracturization so as to form zone(s) of rubblized and/or fractured oil shale with large surface area for more efficient heat treatment by in-situ thermal fluid extraction (pyrolysis) and (3) injecting into the rubblized and/or fracturized oil shale zone(s) a pyrolyzing fluid to effect hydrocarbon recovery.
The halite and hydrocarbons may be recovered sequentially or simultaneously and if the latter, the two products can be separated by suitable means such as settling or solvent extraction above ground. The oil shale formation may contain more than one zone of rich halite which zones may be separated by impermeable oil shale layers of several feet to several hundred feet and each of these halite layers or zones can be leached or dissolved or solution mined in accordance with the process of the present invention.
The first or initial step should be so designed to create a cavern or interconnecting cavities in the halite bed(s) or zone(s) by dissolving, leaching or solution mining techniques through at least one borehole penetrating said formation. Leaching can be effected by cold or hot aqueous solutions either at atmospheric or elevated pressures. When hot solutions are used such as hot water and/or steam, more rapid dissolution is effected to produce void spaces in the oil shale formation thereby providing and enhancing well communication, space for thermal expansion of the shale, and greater surface contact with subsequent pyrolyzing fluid.
If necessary, fracturing the formation either before or after leaching by conventional means such as hydrofracturing, explosive means, nuclear means, etc., may be desirable. The leaching solutions can contain chemical agents to enhance dissolution of the minerals.
Leaching or solution mining of the halite can be accomplished by a suitable solution mining technique such as described in U.S. Pat. Nos. 2,618,475; 3,387,888; 3,393,013; 3,402,966; 3,236,564; 3,510,167 or Canadian patents 832,828 or 832,276 or as described in copending application Ser. No. 2,765, filed Jan. 14, 1970. Spalling and rubbling can be accomplished by the method described in US. Pat. No. 3,478,825 or by other means such as by hydraulic explosive, nuclear, electrical means. Preferably rubblization is accomplished by hot fluid circulation through two caverns causing the two walls to spall and fracture. ln-situ thermal recovery of oil can be effected by a pyrolyzing fluid such as steam and/or hot water or solvent extraction means.
The circulation of a pyrolyzing fluid not only effects oil recovery but also effects thermal rubblirig and/or fracturization. Also, if the pyrolyzing fluid such as steam is used to extract and recover oil, more halite may be dissolved perpetuating the process.
The term pyrolyzing fluid is used to refer to a liquid or gas which by means of thermal, chemical and/or solvent action, interacts with the kerogen components of an oil shale to produce and entrain hydrocarbon such as oil. Such a fluid can be comprised of hot fluids such as hot water or steam or mixtures of hot water and steam, hot hydrocarbons and/or mixtures of such fluids with chemicals such as acids, e.g., I-ICl and/or organic solvents, benzene, toluene, cumene, phenol, etc. The kerogen pyrolyzing fluid can be heated by surface or borehole-located heating devices. The kerogenpyrolyzing fluid can advantageously comprise or contain a solvent for the halite, such as a steam condensate, havinga temperature such as of at least lOF, such as from about 450F to above about l,500F and preferably from about 550F to 1,000F. Where the kerogen-pyrolyzing fluid contains or forms aqueous components, its circulation through the treated oil shale formation can enlarge the cavern, by solution mining the soluble minerals, while shale oil is being produced. Also, simultaneously or sequentially, pyrolyzing and oil extracting fluids can be used such as steam followed by a solvent such as phenol or benzene.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a vertical sectional view, partly diagrammatic, of an embodiment of the invention showing a formation penetration by more than one well; and
FIG. 2 is a sectional view of an embodiment of the invention, the formation being penetrated by a single well.
DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. I of the drawing, a plurality of well boreholes are shown penetrating into a subterranean oil shale formation 9 which contain rich zones of halite 10, 10a and 10b. An injection well borehole 11 is shown extending into oil shale formation 9 and rich halite zone(s) 10 or multizones such as 100 and 10b that are located within the oil shale formation 9 and are also encountered by well borehole 12. Well boreholes 11 and 12 are illustrated by having casings 13 through 14, respectively, cemented in place in their respective boreholes by suitable sealants 15 through 16, respectively. Although only a single injection well borehole 1 1 and a single production well borehole 12 have been illustrated, obviously various combinations of one or more injection and production wells may be provided by one skilled in the art.
Fluid communication between well boreholes l1 and 12 (FIG. 1) and the zones rich in halite therebetween may be established by solution mining a cavern or cavities 23, through the soluble mineral zones. Communication can be enhanced by means of conventional hydraulic, electric, and/or explosive fracturing tech niques, all well known in the art. Where, for example, subterranean stresses in and around soluble mineral zones 10, 10a, and 10b are conducive to the formation of horizontal fractures, the fluid communication between well boreholes 11 and I2 and the halite can be established by a conventional hydraulic fracturing technique. Referring to FIG. 1, after fluid communication has been established between a pair of wells, aqueous leaching or solution mining liquid is injected through tubing 17 down well borehole 11, out through perforations l8 opposite any or all of the soluble beds through the bed 10, 10a and/or 10b up borehole 12 through tubing via perforation 19 creating a leached cavern 23. The aqueous liquid may comprise water and/or steam or aqueous solutions of acid or acidforming materials and is circulated at pressures either above or below the over-burden pressure. The circulating aqueous liquid dissolves the halite which is recovered from the fluid flowing out of well borehole 12, for example, by conventional evaporation and/or precipitation procedures.
Fluid communication can also be established in one borehole between at least two spaced portions of the well borehole and the halite (as for example, in FIG. 2 communication is through the tubing strings, the ends of which are open to the halite and some distance apart). Thus, a single well may be utilized by a dual zone completion arrangement as shown in FIG. 2 such that fluids can be injected at one point of the well and produced from another point of the same well. In FIG. 2, the wellbore is 26, the casing is 27, the sealant is 28, within the casing are the injection tubing string 29 and production tubing string 30, the borehole 26 penetrates oil 0shale formation 9 with halite zone(s) 10 or multizones 10a and 10b.
Fracturing pressures are generated within the oil shale formation 9 while lower pressures are maintained within the cavern 23 which is formed within oil shale formation 9 by the removal of the halite. These pressures are preferably generated by merely circulating hot fluid through cavern 23. As the walls of the cavern(s) 23 (23a FIG. 2) are heated kerogen is pyrolyzed within the cavern walls and the pressures of the pyrolysis products increase until portions of the walls are spalled into the cavern 23 creating a rubblized zone 24 (240 FIG. 2) and surrounding fracture area 25 (25a FIG. 2).
Alternatively, fracturization and/or rubblization can be accomplished by conventional means such as hydraulic, explosive means and the like. To provide additional void space, if necessary, further leaching can be conducted.
Finally, a kerogen-pyrolyzing fluid such as steam is circulated from well borehole 11 (FIG. 1) through the rubblized zone 24 and fractured zone 25 of oil shale formation 9 and out of well borehole l2. Hydrocarbon materials are then recovered from the heated fluid circulating out of well borehole 12 by means well known in the art. Removal of hydrocarbons from the oil shale provides additional void space enlarging the original rubblized zone, perpetrating the process. Similar techniques can be applied to single wells as shown in FIG. 2.
Conventional equipment and techniques, such as heating means, pumping means, separators and heat exchangers may be used for pressurizing, heating, injecting, producing and separating components of the heated fluid circulating through the oil shale formation 9. The production of the fluid may be aided by downhole pumping means, not shown, or restricted to the extent necessary to maintain the selected pressure within the oil shale formation 9.
The fluid circulated through rubblized zone 24 and fractured zone 25 (FIG. 1) to recover oil shale from oil shale formation 9 may comprise any heated gas, liquid or steam. Oil shale reactive properties may also be imparted to the circulating fluid as discussed hereinabove.
Where the oil shale formation contains a zone rich in halite in which zone the halite occur in the form of adjacent but discrete nodules or lenses 31, or the like, the present process is applied as described above. In this situation, the caverns comprise a network of relatively small cavities that are interconnected by fractures.
It is understood that various changes in the detailed described to explain the invention can be made by persons skilled in the art within the scope of the invention as expressed in the appended claims.
I claim as my invention:
1. A method of producing hydrocarbons from a subterranean oil shale formation having halite containing zones therein comprising the steps of:
a. penetrating a well borehole into the halite zone of the oil shale formation;
b. injecting water down the well borehole and into the halite containing zone to leach and withdraw halite thereby creating voids and cavities in the formation;
c. injecting a non-combustible pyrolyzing fluid into the leached voids and cavities to effect extraction of hydrocarbons from the oil shale; and
d. recovering the hydrocarbons from treatment (0) above ground.
2. The method of claim 1 wherein the pyrolyzing fluid comprises steam having a temperature sufficient to thermally fracture oil shale adjacent the leached voids and cavities.
3. The method of claim 1 wherein at least two wells penetrate the formation one of which functions as an injection well and one as a production well.
4. The method of claim 2 wherein the halite is removed by steam used also to effect hydrocarbon recovcry.
5. The method of claim 4 wherein the halite and hydrocarbon are recovered simultaneously.

Claims (4)

  1. 2. The method of claim 1 wherein the pyrolyzing fluid comprises steam having a temperature sufficient to thermally fracture oil shale adjacent the leached voids and cavities.
  2. 3. The method of claim 1 wherein at least two wells penetrate the formation one of which functions as an injection well and one as a production well.
  3. 4. The method of claim 2 wherein the halite is removed by steam used also to effect hydrocarbon recovery.
  4. 5. The method of claim 4 wherein the halite and hydrocarbon are recovered simultaneously.
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804169A (en) * 1973-02-07 1974-04-16 Shell Oil Co Spreading-fluid recovery of subterranean oil
US3880238A (en) * 1974-07-18 1975-04-29 Shell Oil Co Solvent/non-solvent pyrolysis of subterranean oil shale
US3888307A (en) * 1974-08-29 1975-06-10 Shell Oil Co Heating through fractures to expand a shale oil pyrolyzing cavern
US3915234A (en) * 1974-08-28 1975-10-28 Cities Service Res & Dev Co In situ production of hydrocarbon values from oil shale using H{HD 2{B S and CO{HD 2{B
US4059308A (en) * 1976-11-15 1977-11-22 Trw Inc. Pressure swing recovery system for oil shale deposits
US4065183A (en) * 1976-11-15 1977-12-27 Trw Inc. Recovery system for oil shale deposits
US4083604A (en) * 1976-11-15 1978-04-11 Trw Inc. Thermomechanical fracture for recovery system in oil shale deposits
US4264104A (en) * 1979-07-16 1981-04-28 Ppg Industries Canada Ltd. Rubble mining
US4279444A (en) * 1980-01-07 1981-07-21 Occidental Oil Shale, Inc. Jetting out weak areas for forming an in situ oil shale retort
US4545891A (en) * 1981-03-31 1985-10-08 Trw Inc. Extraction and upgrading of fossil fuels using fused caustic and acid solutions
US5059307A (en) * 1981-03-31 1991-10-22 Trw Inc. Process for upgrading coal
US5085764A (en) * 1981-03-31 1992-02-04 Trw Inc. Process for upgrading coal
US20070137852A1 (en) * 2005-12-20 2007-06-21 Considine Brian C Apparatus for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
US20070137858A1 (en) * 2005-12-20 2007-06-21 Considine Brian C Method for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
WO2010096855A1 (en) * 2009-02-25 2010-09-02 Peter James Cassidy Oil shale processing
US20160251947A1 (en) * 2015-02-27 2016-09-01 Schlumberger Technology Corporation Methods of Modifying Formation Properties
US10012064B2 (en) 2015-04-09 2018-07-03 Highlands Natural Resources, Plc Gas diverter for well and reservoir stimulation
US10344204B2 (en) 2015-04-09 2019-07-09 Diversion Technologies, LLC Gas diverter for well and reservoir stimulation
US10982520B2 (en) 2016-04-27 2021-04-20 Highland Natural Resources, PLC Gas diverter for well and reservoir stimulation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3481398A (en) * 1967-02-28 1969-12-02 Shell Oil Co Permeabilizing by acidizing oil shale tuffaceous streaks in and oil recovery therefrom
US3502372A (en) * 1968-10-23 1970-03-24 Shell Oil Co Process of recovering oil and dawsonite from oil shale
US3510167A (en) * 1968-08-19 1970-05-05 Hardy Salt Co Methods of solution mining

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3481398A (en) * 1967-02-28 1969-12-02 Shell Oil Co Permeabilizing by acidizing oil shale tuffaceous streaks in and oil recovery therefrom
US3510167A (en) * 1968-08-19 1970-05-05 Hardy Salt Co Methods of solution mining
US3502372A (en) * 1968-10-23 1970-03-24 Shell Oil Co Process of recovering oil and dawsonite from oil shale

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804169A (en) * 1973-02-07 1974-04-16 Shell Oil Co Spreading-fluid recovery of subterranean oil
US3880238A (en) * 1974-07-18 1975-04-29 Shell Oil Co Solvent/non-solvent pyrolysis of subterranean oil shale
US3915234A (en) * 1974-08-28 1975-10-28 Cities Service Res & Dev Co In situ production of hydrocarbon values from oil shale using H{HD 2{B S and CO{HD 2{B
US3888307A (en) * 1974-08-29 1975-06-10 Shell Oil Co Heating through fractures to expand a shale oil pyrolyzing cavern
US4059308A (en) * 1976-11-15 1977-11-22 Trw Inc. Pressure swing recovery system for oil shale deposits
US4065183A (en) * 1976-11-15 1977-12-27 Trw Inc. Recovery system for oil shale deposits
US4083604A (en) * 1976-11-15 1978-04-11 Trw Inc. Thermomechanical fracture for recovery system in oil shale deposits
US4264104A (en) * 1979-07-16 1981-04-28 Ppg Industries Canada Ltd. Rubble mining
US4279444A (en) * 1980-01-07 1981-07-21 Occidental Oil Shale, Inc. Jetting out weak areas for forming an in situ oil shale retort
US4545891A (en) * 1981-03-31 1985-10-08 Trw Inc. Extraction and upgrading of fossil fuels using fused caustic and acid solutions
US5059307A (en) * 1981-03-31 1991-10-22 Trw Inc. Process for upgrading coal
US5085764A (en) * 1981-03-31 1992-02-04 Trw Inc. Process for upgrading coal
US20080163895A1 (en) * 2005-12-20 2008-07-10 Raytheon Company Method of cleaning an industrial tank using electrical energy and critical fluid
US8096349B2 (en) 2005-12-20 2012-01-17 Schlumberger Technology Corporation Apparatus for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
US20070137852A1 (en) * 2005-12-20 2007-06-21 Considine Brian C Apparatus for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
US7461693B2 (en) 2005-12-20 2008-12-09 Schlumberger Technology Corporation Method for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
US20090114384A1 (en) * 2005-12-20 2009-05-07 Schlumberger Technology Corporation Method for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
US9187979B2 (en) 2005-12-20 2015-11-17 Schlumberger Technology Corporation Method for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
US7875120B2 (en) 2005-12-20 2011-01-25 Raytheon Company Method of cleaning an industrial tank using electrical energy and critical fluid
US20070137858A1 (en) * 2005-12-20 2007-06-21 Considine Brian C Method for extraction of hydrocarbon fuels or contaminants using electrical energy and critical fluids
US8590620B2 (en) 2009-02-25 2013-11-26 Peter James Cassidy Oil shale processing
US20110186296A1 (en) * 2009-02-25 2011-08-04 Peter James Cassidy Oil shale processing
US8967261B2 (en) 2009-02-25 2015-03-03 Peter James Cassidy Oil shale processing
WO2010096855A1 (en) * 2009-02-25 2010-09-02 Peter James Cassidy Oil shale processing
US20160251947A1 (en) * 2015-02-27 2016-09-01 Schlumberger Technology Corporation Methods of Modifying Formation Properties
US10012064B2 (en) 2015-04-09 2018-07-03 Highlands Natural Resources, Plc Gas diverter for well and reservoir stimulation
US10344204B2 (en) 2015-04-09 2019-07-09 Diversion Technologies, LLC Gas diverter for well and reservoir stimulation
US10385257B2 (en) 2015-04-09 2019-08-20 Highands Natural Resources, PLC Gas diverter for well and reservoir stimulation
US10385258B2 (en) 2015-04-09 2019-08-20 Highlands Natural Resources, Plc Gas diverter for well and reservoir stimulation
US10982520B2 (en) 2016-04-27 2021-04-20 Highland Natural Resources, PLC Gas diverter for well and reservoir stimulation

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