US3554283A - Situ recovery of petroleumlike hydrocarbons from underground formations - Google Patents
Situ recovery of petroleumlike hydrocarbons from underground formations Download PDFInfo
- Publication number
- US3554283A US3554283A US686285A US3554283DA US3554283A US 3554283 A US3554283 A US 3554283A US 686285 A US686285 A US 686285A US 3554283D A US3554283D A US 3554283DA US 3554283 A US3554283 A US 3554283A
- Authority
- US
- United States
- Prior art keywords
- shale
- hydrocarbon
- petroleumlike
- hydrocarbons
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title abstract description 15
- 238000005755 formation reaction Methods 0.000 title description 14
- 238000011084 recovery Methods 0.000 title description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 19
- 238000004880 explosion Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 2
- 239000011800 void material Substances 0.000 abstract description 10
- 230000035699 permeability Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000005474 detonation Methods 0.000 abstract 1
- 239000011435 rock Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004058 oil shale Substances 0.000 description 5
- 239000002360 explosive Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- -1 oil Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/263—Methods for stimulating production by forming crevices or fractures using explosives
- E21B43/2635—Methods for stimulating production by forming crevices or fractures using explosives by means of nuclear energy
Definitions
- This invention relates to an improvement in the recovery of gas, oil, and other petroleumlike hydrocarbon energy bearing compositions from subsurface shale or like formations and, more specifically, to a methodfor increasing the permeability and porosity of the shale or like strata to aid recovery of the hydrocarbons.
- Hydrocarbon containing geological formations e.g., oil containing shale, kerogen rock, or the like are relatively common, and are typically found beneath relatively thick overburden formation(s) of earth, cap rock or the like. Despite their relatively high incidence, extraction of the desired substances has been limited.
- One method for recovering the oil or other desired hydrocarbon is to mine the oil-containing shale, or kerogen rock. After transportation to a suitable refinery, the relatively compact rock material is first fractured to increase its rate of subjection to reaction. Oil is then recovered from the crushed shale, as by employing a retorting .operation such as is described in L. P. Evans U.S. Pat. No. 3,281,349 issued Oct. 25, i966.
- a retorting .operation such as is described in L. P. Evans U.S. Pat. No. 3,281,349 issued Oct. 25, i966.
- a mining technique is most often not economically competitive with alternative sources of the particular hydrocarbon.
- in situ recovery of the oil, gas or other mineral has been suggested. Essentially this compriseseffecting an underground explosion to fracture the pertinent shale strata, thereby coincidentally creating a cavity about the fractured shale to serve for underground retorting.
- the use of nuclear devices has been contemplated for the requisite explosive.
- the desired hydrocarbon is removed by any one of several known methods.
- the hydrocarbon may be removed via an outlet conduit responsive to heated gas, brine, or the like being drivenunder pressure into the cavity via an inlet conduit.
- an ignited combustible gas may be driven down the inlet conduit.
- the above and other in situ processes will efficiently recover the desired hydrocarbon only from the shale structure which has been increased in permeability and porosity responsive to the nuclear explosion(s). More specifically, the retorting or other product extraction process can operate only on the exposed surfaces and fissures in the fractured shale which has such characteristics. For prior art explosion methods, this is limited to the shale directly fractured by the nuclear or other explosive device, and the shale structure immediately surrounding the resulting cavity. Accordingly, a relatively limited amount of useful shale structure is prepared by each explosion. 1
- a void is created in the oil shale strata by any conventional method, for example by boring into the formation and exploding a conventional, or relatively small nuclear device at the bottom of such bore.
- the depth of the void is determined by the thickness and density of the overburden, and by the thickness of the oil shale formation.
- the bore hole is redrilled into the void and a second nuclear explosive inserted therein.
- the void is then filled. either in toto or to a substantial degree, with a liquid. preferably serving as a carrier for selected additives.
- a liquid preferably serving as a carrier for selected additives.
- an acidic water solution may be employed.
- the nuclear device is exploded to produce a subsurface cavity substantially larger than the initial void.
- the cavity includes therein a great amount of oil shale, kerogen rock or the like which was fractured by the second explosion, and which is thus characterized by many crevices and fissures, thereby exhibiting a relatively high permeability and porosity.
- oil shale structure surrounding the cavity is also characterized by an increased permeability and porosity. These characteristics are imparted by the blast directly, and substantially magnified in scope by the penetration of the acid solution into the shale structure.
- the acid attacks the shale, decomposing a portion thereof, and also causing apertures and fissures therein to effect the desired increased characteristics.
- the relevant substance i.e., the oil contained within the shale formation
- inlet and outlet conduits may be drilled into the cavity and heated gases, steam, brine or the like may be driven into the cavity to effect underground retorting in the known manner to drive the oil fraction out of the cavity via the outlet conduit. Since more of the oil-containing structure is made porous in accordance with the principles of the present invention, an increased hydrocarbon yield will result from any given size explosion.
- the water or other liquid will absorb and moderate the principal radioactive byproducts of the nuclear explosion. Accordingly, the radioactivity of the resulting oil or other desired product is maintained at a relatively low level. Further, the vaporized liquid may be recovered in part after the explosion to comprise a commercially salable chemical product.
- additional additives may be included in the aqueous or other solution for special purposes and effects.
- catalyst(s) to aid in the recovery process- may be employed.
- additives which attach the shale formation to generate a retort aiding gas pressure may be utilized.
- An improved method for extracting petroleumlike hydrocarbons from subsurface rocklike formations including the steps of forming a void space in the hydrocarbon-containing rock formation, inserting a liquid state noncombustible aqueous acidic solution in said void space, inserting a nuclear device in said void space, and exploding said nuclear device in said liquid containing void, said liquid being operative for absorbing radioactive byproducts from said explosion step and for vaporizing and penetrating into the surrounding rocklike formation to increase the explosive effect of said nuclear explosion and, further, for increasing the hydrocarbon productive effect of said explosion by chemical action over an ex tended time period.
- a method as in claim 1 further comprising the step of boring inlet and outlet conduits into. the cavity resulting from said nuclear explosion, and retorting the hydrocarbon-containing materials included in said cavity by inserting a heated, pressurized fluid in said inlet conduit and extracting said hydrocarbon from said outlet conduit.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A void in a petroleumlike hydrocarbon-containing geological formation is filled with an acidic solution, and a nuclear device is exploded therein. The detonation fractures the surrounding shale structure, and the solution penetrates into the hydrocarbon shale in and about the resulting cavity, increasing its porosity and permeability. The desired hydrocarbon may then be removed by conventional methods, as by in situ retorting.
Description
l 6 (3"3 07 o XR inventor Alvin Abrams Woodmere, Long Island, N.Y. Appl. No. 686,285 Filed Nov. 28, 1967 Patented Jan. 12, 1971 Assignee Irradiation Controls Inc.,
New York, N.Y.,
a corporation of New York SlTU RECOVERY OF PETROLEUMLIKE HYDROCARBONS FROM UNDERGROUND FORMATIONS 2 Claims, No Drawings US. Cl 166/247, 166/272, 166/307 Int. Cl E2lb 43/26, E21 b 43/27 Field of Search 166/36, 42,
[56] References Cited UNITED STATES PATENTS Re2 1 ,356 211940 Pitzer l66/42X 2,676,662 4/1954 Ritzmann 166/36 3,024,840 3/1962 Allen 166/1 1 3,113,620 12/1963 Hemminger.. 166/11 3,342,257 9/1967 Jacobs et al. l66/36X 3,404,919 10/1968 Dixon 166/36X Primary Examiner-Stephen J. Novosad A ttorney Davis, Hoxie, Faithfull and Hapgood SITU RECOVERY OF PETROLEUMLIKE HYDROCARBONS FROM UNDERGROUND FORMATIONS DISCLOSURE OF INVENTION This invention relates to an improvement in the recovery of gas, oil, and other petroleumlike hydrocarbon energy bearing compositions from subsurface shale or like formations and, more specifically, to a methodfor increasing the permeability and porosity of the shale or like strata to aid recovery of the hydrocarbons.
Hydrocarbon containing geological formations, e.g., oil containing shale, kerogen rock, or the like are relatively common, and are typically found beneath relatively thick overburden formation(s) of earth, cap rock or the like. Despite their relatively high incidence, extraction of the desired substances has been limited. I
One method for recovering the oil or other desired hydrocarbon is to mine the oil-containing shale, or kerogen rock. After transportation to a suitable refinery, the relatively compact rock material is first fractured to increase its rate of subjection to reaction. Oil is then recovered from the crushed shale, as by employing a retorting .operation such as is described in L. P. Evans U.S. Pat. No. 3,281,349 issued Oct. 25, i966. However, because of the requisite operations of mining, transporting, fracturing, and retorting theshale, and disposing of the overburden, such a mining technique is most often not economically competitive with alternative sources of the particular hydrocarbon. I
To obviate many of the difficulties associated with mining, in situ recovery of the oil, gas or other mineral has been suggested. Essentially this compriseseffecting an underground explosion to fracture the pertinent shale strata, thereby coincidentally creating a cavity about the fractured shale to serve for underground retorting. Recently, the use of nuclear devices has been contemplated for the requisite explosive. After such explosion(s), the desired hydrocarbon is removed by any one of several known methods. For example, the hydrocarbon may be removed via an outlet conduit responsive to heated gas, brine, or the like being drivenunder pressure into the cavity via an inlet conduit. Alternatively, an ignited combustible gas may be driven down the inlet conduit.
However, the above and other in situ processes will efficiently recover the desired hydrocarbon only from the shale structure which has been increased in permeability and porosity responsive to the nuclear explosion(s). More specifically, the retorting or other product extraction process can operate only on the exposed surfaces and fissures in the fractured shale which has such characteristics. For prior art explosion methods, this is limited to the shale directly fractured by the nuclear or other explosive device, and the shale structure immediately surrounding the resulting cavity. Accordingly, a relatively limited amount of useful shale structure is prepared by each explosion. 1
1 It is therefore an object of the present invention to provide.
an improved method for removing hydrocarbons from subsurface geological deposits.
More specifically, it is an object of the present invention to increase the permeability and porosity of hydrocarbon energy containing shale or like formations such that a relatively large product recovery can be had responsive to each subsurface strata-fracturing explosion.
The above and other objects of the present invention are realized in an illustrative improvedmethod for the recovery of a desired hydrocarbon, e.g., oil, from subsurface formations. A void is created in the oil shale strata by any conventional method, for example by boring into the formation and exploding a conventional, or relatively small nuclear device at the bottom of such bore. The depth of the void is determined by the thickness and density of the overburden, and by the thickness of the oil shale formation.
The bore hole is redrilled into the void and a second nuclear explosive inserted therein. The void is then filled. either in toto or to a substantial degree, with a liquid. preferably serving as a carrier for selected additives. As discussed hereinafter, an acidic water solution may be employed.
The nuclear device is exploded to produce a subsurface cavity substantially larger than the initial void. The cavity includes therein a great amount of oil shale, kerogen rock or the like which was fractured by the second explosion, and which is thus characterized by many crevices and fissures, thereby exhibiting a relatively high permeability and porosity.
In addition, the oil shale structure surrounding the cavity is also characterized by an increased permeability and porosity. These characteristics are imparted by the blast directly, and substantially magnified in scope by the penetration of the acid solution into the shale structure. The acid attacks the shale, decomposing a portion thereof, and also causing apertures and fissures therein to effect the desired increased characteristics.
The relevant substance, i.e., the oil contained within the shale formation, is extracted by any prior'art method. For example, inlet and outlet conduits may be drilled into the cavity and heated gases, steam, brine or the like may be driven into the cavity to effect underground retorting in the known manner to drive the oil fraction out of the cavity via the outlet conduit. Since more of the oil-containing structure is made porous in accordance with the principles of the present invention, an increased hydrocarbon yield will result from any given size explosion.
It is noted at this point that the water or other liquid will absorb and moderate the principal radioactive byproducts of the nuclear explosion. Accordingly, the radioactivity of the resulting oil or other desired product is maintained at a relatively low level. Further, the vaporized liquid may be recovered in part after the explosion to comprise a commercially salable chemical product.
Also, additional additives may be included in the aqueous or other solution for special purposes and effects. For example, catalyst(s) to aid in the recovery process-may be employed. Also, additives which attach the shale formation to generate a retort aiding gas pressure may be utilized. 1
In addition, the above-described process may be repeated several times to continuously enlarge the cavity, with additional prepared shale material being produced with each explosion. i
It is to be understood that the above-described method is only illustrative of the principles of the present invention. Numerous modifications and adaptions thereof may be readily devised by those skilled in the art without departing from the principles of the present invention. For example, in addition to oil shale or kerogen rock, the invention is applicable to tar sands, oil sands, bituminous limestone, peat and anthracite coal formations, and the like.
1. An improved method for extracting petroleumlike hydrocarbons from subsurface rocklike formations including the steps of forming a void space in the hydrocarbon-containing rock formation, inserting a liquid state noncombustible aqueous acidic solution in said void space, inserting a nuclear device in said void space, and exploding said nuclear device in said liquid containing void, said liquid being operative for absorbing radioactive byproducts from said explosion step and for vaporizing and penetrating into the surrounding rocklike formation to increase the explosive effect of said nuclear explosion and, further, for increasing the hydrocarbon productive effect of said explosion by chemical action over an ex tended time period.
2. A method as in claim 1 further comprising the step of boring inlet and outlet conduits into. the cavity resulting from said nuclear explosion, and retorting the hydrocarbon-containing materials included in said cavity by inserting a heated, pressurized fluid in said inlet conduit and extracting said hydrocarbon from said outlet conduit.
Claims (1)
- 2. A method as in claim 1 further comprising the step of boring inlet and outlet conduits into the cavity resulting from said nuclear explosion, and retorting the hydrocarbon-containing materials included in said cavity by inserting a heated, pressurized fluid in said inlet conduit and extracting said hydrocarbon from said outlet conduit.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68628567A | 1967-11-28 | 1967-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3554283A true US3554283A (en) | 1971-01-12 |
Family
ID=24755685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US686285A Expired - Lifetime US3554283A (en) | 1967-11-28 | 1967-11-28 | Situ recovery of petroleumlike hydrocarbons from underground formations |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3554283A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8701788B2 (en) | 2011-12-22 | 2014-04-22 | Chevron U.S.A. Inc. | Preconditioning a subsurface shale formation by removing extractible organics |
| US8839860B2 (en) | 2010-12-22 | 2014-09-23 | Chevron U.S.A. Inc. | In-situ Kerogen conversion and product isolation |
| US8851177B2 (en) | 2011-12-22 | 2014-10-07 | Chevron U.S.A. Inc. | In-situ kerogen conversion and oxidant regeneration |
| US8992771B2 (en) | 2012-05-25 | 2015-03-31 | Chevron U.S.A. Inc. | Isolating lubricating oils from subsurface shale formations |
| US9033033B2 (en) | 2010-12-21 | 2015-05-19 | Chevron U.S.A. Inc. | Electrokinetic enhanced hydrocarbon recovery from oil shale |
| US9181467B2 (en) | 2011-12-22 | 2015-11-10 | Uchicago Argonne, Llc | Preparation and use of nano-catalysts for in-situ reaction with kerogen |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE21356E (en) * | 1936-03-10 | 1940-02-13 | Method of and means for treating wells | |
| US2676662A (en) * | 1949-05-17 | 1954-04-27 | Gulf Oil Corp | Method of increasing the productivity of wells |
| US3024840A (en) * | 1958-06-16 | 1962-03-13 | Texaco Inc | In situ combustion |
| US3113620A (en) * | 1959-07-06 | 1963-12-10 | Exxon Research Engineering Co | Process for producing viscous oil |
| US3342257A (en) * | 1963-12-30 | 1967-09-19 | Standard Oil Co | In situ retorting of oil shale using nuclear energy |
| US3404919A (en) * | 1966-05-04 | 1968-10-08 | Nuclear Proc Corp | Method of creating large diameter boreholes using underground nuclear detonations |
-
1967
- 1967-11-28 US US686285A patent/US3554283A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE21356E (en) * | 1936-03-10 | 1940-02-13 | Method of and means for treating wells | |
| US2676662A (en) * | 1949-05-17 | 1954-04-27 | Gulf Oil Corp | Method of increasing the productivity of wells |
| US3024840A (en) * | 1958-06-16 | 1962-03-13 | Texaco Inc | In situ combustion |
| US3113620A (en) * | 1959-07-06 | 1963-12-10 | Exxon Research Engineering Co | Process for producing viscous oil |
| US3342257A (en) * | 1963-12-30 | 1967-09-19 | Standard Oil Co | In situ retorting of oil shale using nuclear energy |
| US3404919A (en) * | 1966-05-04 | 1968-10-08 | Nuclear Proc Corp | Method of creating large diameter boreholes using underground nuclear detonations |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9033033B2 (en) | 2010-12-21 | 2015-05-19 | Chevron U.S.A. Inc. | Electrokinetic enhanced hydrocarbon recovery from oil shale |
| US8839860B2 (en) | 2010-12-22 | 2014-09-23 | Chevron U.S.A. Inc. | In-situ Kerogen conversion and product isolation |
| US8936089B2 (en) | 2010-12-22 | 2015-01-20 | Chevron U.S.A. Inc. | In-situ kerogen conversion and recovery |
| US8997869B2 (en) | 2010-12-22 | 2015-04-07 | Chevron U.S.A. Inc. | In-situ kerogen conversion and product upgrading |
| US9133398B2 (en) | 2010-12-22 | 2015-09-15 | Chevron U.S.A. Inc. | In-situ kerogen conversion and recycling |
| US8701788B2 (en) | 2011-12-22 | 2014-04-22 | Chevron U.S.A. Inc. | Preconditioning a subsurface shale formation by removing extractible organics |
| US8851177B2 (en) | 2011-12-22 | 2014-10-07 | Chevron U.S.A. Inc. | In-situ kerogen conversion and oxidant regeneration |
| US9181467B2 (en) | 2011-12-22 | 2015-11-10 | Uchicago Argonne, Llc | Preparation and use of nano-catalysts for in-situ reaction with kerogen |
| US8992771B2 (en) | 2012-05-25 | 2015-03-31 | Chevron U.S.A. Inc. | Isolating lubricating oils from subsurface shale formations |
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