The subject application is related to U.S. Provisional Application Ser. No. 61/426,340, filed Dec. 22, 2010. This application is also related to U.S. application Ser. No. 13/335,409, entitled “In-Situ Kerogen Conversion and Recovery” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,525, entitled “In-Situ Kerogen Conversion and Product Isolation” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,607, entitled “In-Situ Kerogen Conversion and Upgrading” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,673, entitled “In-Situ Kerogen Conversion and Recycling” filed Dec. 22, 2011, and U.S. application Ser. No. 13/335,290, entitled “Preparation and Use of Nano-Catalysts for In-Situ Reaction with Kerogen” filed Dec. 22, 2011. The contents of all of these related applications are incorporated herein by reference in their entirety.
If proponents of Hubbert peak theory are correct, world oil production will soon peak, if it has not done so already. Regardless, world energy consumption continues to rise at a rate that outpaces new oil discoveries. As a result, alternative sources of energy must be developed, as well as new technologies for maximizing the production and efficient consumption of oil. See T. Mast, Over a Barrel: A Simple Guide to the Oil Shortage, Greenleaf Book Group, Austin, Tex., 2005.
A particularly attractive alternative source of energy is oil shale, the attractiveness stemming primarily from the fact that oil can be “extracted” from the shale and subsequently refined in a manner much like that of crude oil. Technologies involving the extraction, however, must be further developed before oil shale becomes a commercially-viable source of energy. See J. T. Bartis et al, Oil Shale Development in the United States: Prospects and Policy Issues, RAND Corporation, Arlington, Va., 2005.
The largest known deposits of oil shale are found in the Green River Formation, which covers portions of Colorado, Utah, and Wyoming. Estimates on the amount of recoverable oil from the Green River Formation deposits are as high as 1.1 trillion barrels of oil—almost four times the proven oil reserves of Saudi Arabia. At current U.S. consumption levels (˜20 million barrels per day), these shale deposits could sustain the U.S. for another 140 years (Bartis et al.) At the very least, such shale resources could moderate the price of oil and reduce U.S. dependence on foreign oil.
Oil shale typically consists of an inorganic component (primarily carbonaceous material, i.e., a carbonate), an organic component (kerogen) that can only be mobilized by breaking the chemical bonds in the kerogen, and frequently a second organic component (bitumen). Thermal treatment can be employed to break (i.e., “crack”) the kerogen into smaller hydrocarbon chains or fragments, which are gas or liquids under retort conditions, and facilitate separation from the inorganic material. This thermal treatment of the kerogen is also known as “thermal upgrading” or “retorting,” and can be done at either the surface or in situ, where in the latter case, the fluids so formed are subsequently transported to the surface.
In some applications of surface retorting, the oil shale is first mined or excavated, and once at the surface, the oil shale is crushed and then heated (retorted) to complete the process of transforming the oil shale to a crude oil—sometimes referred to as “shale oil.” See, e.g., Shuman et al., U.S. Pat. No. 3,489,672. The crude oil is then shipped off to a refinery where it typically requires additional processing steps (beyond that of traditional crude oil) prior to making finished products such as gasoline, lubricant, etc. Note that various chemical upgrading treatments can also be performed on the shale prior to the retorting, See, e.g., So et al., U.S. Pat. No. 5,091,076.
A method for in situ retorting of carbonaceous deposits such as oil shale has been described in Kvapil et al., U.S. Pat. No. 4,162,808. In this method, shale is retorted in a series of rubblized in situ retorts using combustion (in air) of carbonaceous material as a source of heat.
The Shell Oil Company has been developing new methods that use electrical heating for the in situ upgrading of subsurface hydrocarbons, primarily in subsurface formations located approximately 200 miles (320 km) west of Denver, Colo. See, e.g., Vinegar et al., U.S. Pat. No. 7,121,342; and Berchenko et al., U.S. Pat. No. 6,991,032. In such methods, a heating element is lowered into a well and allowed to heat the kerogen over a period of approximately four years, slowly converting (upgrading) it into oils and gases, which are then pumped to the surface. To obtain even heating, 15 to 25 heating holes could be drilled per acre. Additionally, a ground-freezing technology to establish an underground barrier around the perimeter of the extraction zone is also envisioned to prevent groundwater from entering and the retorting products from leaving. While the establishment of “freeze walls” is an accepted practice in civil engineering, its application to oil shale recovery still has unknown environmental impacts. Additionally, the Shell approach is recognized as an energy intensive process and requires a long timeframe to establish production from the oil shale.
In view of the aforementioned limitations of the above methods, simpler and more cost-effective methods of extracting and upgrading kerogen from a subsurface shale formation would be extremely useful.
The present invention is directed to processes for preconditioning a subsurface shale formation comprising kerogen and an extractible organics component. In one embodiment the process comprises (a) providing a first hydrocarbon solvent to the subsurface shale formation comprising kerogen and an extractible organics component; (b) at least partially solubilizing at least a portion of the extractible organics component in the first hydrocarbon solvent; and (c) removing the first solvent containing the extractible organics component from the subsurface shale formation.
In another embodiment, the process for preconditioning a subsurface shale formation comprising kerogen and an extractible organics component comprises (a) providing a first hydrocarbon solvent to the subsurface shale formation comprising kerogen and an extractible organics component; (b) at least partially solubilizing at least a portion of the extractible organics component in the first hydrocarbon solvent; (c) removing the first solvent containing the extractible organics component from the subsurface shale formation; (d) providing a second solvent to the subsurface shale formation comprising kerogen and an extractible organics component; (e) at least partially solubilizing at least a portion of the first hydrocarbon solvent in the second solvent; and (f) removing the second solvent containing the first hydrocarbon solvent from the subsurface shale formation.
Among other factors, these processes are based on the discovery that to more easily access the kerogen in oil shale, it is helpful to first remove the extractible organics component from the subsurface shale formation. The extractible organics component can be isolated and upgraded to produce useful products. The presently disclosed processes are more environmentally benign, more economical, and more efficient in producing commercial products and in providing access to kerogen.
Introduction
Subsurface shale formations contain kerogen and an extractible organics component in an inorganic matrix.
This extractible organics component is at least partially soluble in an organic solvent. In contrast, the kerogen is not soluble in organic solvent. The extractible organics can exist as an oily layer on the kerogen and removing the extractible organics increases the accessible surface area of the kerogen and makes the kerogen more accessible to fluids and catalysts.
Kerogen is a particularly attractive alternative source of hydrocarbons for energy. By making the kerogen more accessible to fluids and catalysts, kerogen derived hydrocarbonaceous products can be more readily removed from the subsurface shale formation. After removal of extractible organics, the kerogen can be more readily accessed for removal using methods including thermal treatments or heating. After removal of extractible organics, the kerogen can also be upgraded in-situ creating mobile kerogen based products as described in U.S. application Ser. No. 13/335,409, entitled “In-Situ Kerogen Conversion and Recovery” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,525, entitled “In-Situ Kerogen Conversion and Product Isolation” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,607, entitled “In-Situ Kerogen Conversion and Upgrading” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,673, entitled “In-Situ Kerogen Conversion and Recycling” filed Dec. 22, 2011, and U.S. application Ser. No. 13/335, 290, entitled “Preparation and Use of Nano-Catalysts for In-Situ Reaction with Kerogen” filed Dec. 22, 2011. The contents of all of these applications are incorporated herein by reference in their entirety.
Preconditioning the subsurface shale formation by removing at least a portion of the extractible organics component makes these processes for obtaining hydrocarbons from kerogen more efficient and higher yielding.
The present invention is directed to methods of preconditioning the subsurface shale formation by removing at least a portion of the extractible organics component. Preconditioning a subsurface shale formation by removing at least a portion of the extractible organics assists in making the kerogen more accessible. The kerogen is more accessible for contacting with reactive fluids, catalysts, and heat treatments. In addition, the extractible organics component can be isolated as a hydrocarbon product.
The present methods utilize in-situ extraction of the extractible organics component using liquid phase chemistry at ambient temperatures and pressures for the subsurface shale formation. Therefore, the processes are more environmentally benign, more economical, and more efficient in producing commercial products.
Definitions
In accordance with this detailed description, the following abbreviations and definitions apply. It must be noted that as used herein, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a hydrocarbon solvent” includes a plurality of such.
As used herein, the terms “hydrocarbon” or “hydrocarbonaceous” or “petroleum” are used interchangeably to refer to material originating from oil shale, coal, tar sands, crude oil, natural gas or biological processes. Carbon and hydrogen are major components of hydrocarbons; minor components, such as oxygen, sulfur and nitrogen may also occur in some hydrocarbons. The hydrocarbon fraction includes both aliphatic and aromatic components. The aliphatic component can further be divided into acyclic alkanes, referred to as paraffins, and cycloalkanes, referred to as naphthenes. A paraffin refers to a non-cyclic, linear (normal paraffin) or branched (iso-paraffin) saturated hydrocarbon. For example, a C8 paraffin is a non-cyclic, linear or branched hydrocarbon having 8 carbon atoms per molecule. Normal octane, methylheptane, dimethylhexane, and trimethylpentane are examples of C8 paraffins. A paraffin-rich feed comprises at least 10 wt %, at least 20 wt % or even at least 30 wt % paraffins. For example, a C8 rich paraffinic feedstock contains at least 10 wt % C8 hydrocarbons.
As disclosed herein, boiling point temperatures are based on the ASTM D-2887 standard test method for boiling range distribution of petroleum fractions by gas chromatography, unless otherwise indicated. The mid-boiling point is defined as the 50% by volume boiling temperature, based on an ASTM D-2887 simulated distillation.
As disclosed herein, carbon number values (i.e., C5, C6, C8, C9 and the like) generally refers to a number of carbon atoms within a molecule. Carbon number ranges as disclosed herein (e.g., C8 to C12) refer to molecules having a carbon number within the indicated range (e.g., between 8 carbon and 12 carbon atoms), including the end members of the range. Likewise, an open ended carbon number range (e.g., C35+) refers to molecules having a carbon number within the indicated range (e.g., 35 or more carbon atoms), including the end member of the range. As described herein, carbon number distributions are determined by true boiling point distribution and gas liquid chromatography.
The term “surface facility” as used herein is any structure, device, means, service, resource or feature that occurs, exists, takes place or is supported on the surface of the earth. The kerogen products that are generated in the process disclosed herein are recovered in surface facilities and upgraded or transported for upgrading.
“Shale,” as defined herein, generally refers to “oil shale” and is a general term applied to a group of rocks rich enough in organic material (called kerogen) to yield petroleum upon pyrolysis and distillation. Such shale is generally subsurface and comprises an inorganic (usually carbonate) component or matrix in addition to the kerogen component.
A “subsurface shale formation,” as defined herein, is an underground geological formation comprising (oil) shale. The subsurface shale formation comprises kerogen and an extractible organics component in an inorganic matrix.
A “low-permeability hydrocarbon-bearing formation,” as defined herein, refers to formations having a permeability of less than about 10 millidarcies, wherein the formations comprise hydrocarbonaceous material. Examples of such formations include, but are not limited to, diatomite, coal, tight shales, tight sandstones, tight carbonates, and the like.
“Kerogen,” as defined herein and as mentioned above, is an organic component of shale. On a molecular level, kerogen comprises very high molecular weight molecules that are generally insoluble by virtue of their high molecular weight and likely bonding to the inorganic component or matrix of the shale. In a geologic sense, kerogen is a precursor to crude oil. Kerogen is typically identified as being one of five types: Type I, Type II, Type II-sulfur, Type III, or Type IV, based on its C:H:O ratio and sulfur content, the various types generally being derived from different sources of ancient biological matter.
“Kerogen-based” and “kerogen-derived” are terms used herein to denote a molecular product or intermediate derived from kerogen, such derivation requiring a chemical modification of the kerogen, and the term being exclusive of derivations carried out over geologic timescales.
“Extractible organics” are organic components of the subsurface shale formation that are at least partially soluble in an organic solvent. In contrast, the kerogen is not soluble in organic solvent. This organic component that is at least partially soluble is referred to herein as “extractible organics”. This extractible organic component includes what is commonly referred to as “bitumen”. The extractable organic component is a solid or semi-solid material that is soluble or at least partially soluble in an organic solvent. As such, the extractable organic component can be removed by extraction using an organic solvent. Extraction of the extractable organic component makes the kerogen more accessible. In the present methods, extraction of the extractable organic component makes the kerogen more accessible to the metal for reaction to create mobile kerogen-based product.
The term “aqueous fluid” as used herein refers to any water containing fluid, such as, municipal water; surface water, including from a lake, sea, ocean, river, and/or stream; formation water; water associated with industrial activity; or mixtures thereof.
The term “formation fluid” or “formation water” as used herein refers to the fluid, typically, water or aqueous fluid that is naturally occurring in a geological formation, such as the subsurface shale formation, or in a subsurface aquifer. The amount (or presence) of formation water in the formation, and the amount (or presence) of formation water in contact with the kerogen in the formation, depends on a number of factors, including the depth of the subsurface shale formation or the kerogen deposit that is within at least a portion of the subsurface shale formation. The naturally occurring formation water may contain dissolved alkali materials from naturally occurring deposits in the environment of the subsurface shale. In some cases, formation water is present in the formation prior to the start of the process for extracting a kerogen-based product from a subsurface shale formation.
A “surfactant” as used herein refers to any substance that reduces surface tension of a liquid, or reduces interfacial tension between two liquids, or between a liquid and a solid, or facilitates the dispersion of an organic material into an aqueous solution.
A “dense phase fluid,” as defined herein, is a non-gaseous fluid. Such dense phase fluids include liquids and supercritical fluids (SCFs). The dense phase fluid can be any such fluid that suitably provides for increased accessibility of the kerogen to a fluid—typically due to fracturing and/or rubblizing of the shale in which the kerogen resides.
A “supercritical fluid” or a “fluid at supercritical conditions” as used herein, is any substance at a temperature and pressure above its thermodynamic critical point. Supercritical fluids can be regarded as “hybrid solvents” with properties between those of gases and liquids, i.e., a solvent with a low viscosity, high diffusion rates and no surface tension. The most common are carbon dioxide (CO2) at supercritical conditions and water at supercritical conditions. For example, the critical temperature of CO2 is 31.1° C., and the critical pressure of CO2 is 72.9 atm (7.39 MPa).
The term “mechanical stress,” as used herein, refers to structural stresses within the shale formation that result from pressure variations within the formation. Such stress can lead to fracturing and/or rubblization of the shale formation.
The term “thermal stress,” as used herein, refers to structural stresses within the shale formation that result from thermal variations. Such thermal stresses can induce internal mechanical stresses as a result of differences in thermal coefficients of expansion among the various components of the shale formation. Like mechanical stress mentioned above, thermal stress can also lead to fracturing and/or rubblization of the shale formation.
The term “fracturing,” as used herein, refers to the structural degradation of a subsurface shale formation as a result of applied thermal and/or mechanical stress. Such structural degradation generally enhances the permeability of the shale to fluids and increases the accessibility of the kerogen component to such fluids. The term “rubblization,” as used herein, is a more extensive fracturing process yielding fracture planes in multiple directions that generate shale derived “rubble.”
The term “cracking,” as mentioned in the background section and as used herein, refers to the breaking of carbon-carbon bonds in the kerogen so as to yield species of lower molecular weight. “Retorting,” provides thermal cracking of the kerogen. “Upgrading,” provides cracking of the kerogen, but can involve a thermal or chemical upgrading agent. Accordingly, the term “thermal upgrading” is synonymous with the term “retorting.”
The term “in situ,” as used herein refers to the environment of the subsurface shale formation. The processes as disclosed herein involve in situ liquid phase extractions.
The term “commercial petroleum-based products,” as used herein, refers to commercial products that include, but are not limited to, gasoline, aviation fuel, diesel, lubricants, petrochemicals, and the like. Such products can also include common chemical intermediates and/or blending feedstocks.
“Optional” or “optionally” means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where the event or circumstance occurs and instances in which it does not.
The present invention is generally directed to methods for extracting an extractible organics component from a subsurface shale formation comprising kerogen and an extractible organics component in an inorganic matrix. The methods include the steps of providing a first hydrocarbon solvent to the subsurface shale formation comprising kerogen and an extractible organics component; at least partially solubilizing at least a portion of the extractible organics component in the first hydrocarbon solvent; and removing the first solvent containing the extractible organics component from the subsurface shale formation.
In certain embodiments, the methods comprise using one solvent, and in other embodiments two solvents are used. In embodiments in which two solvents are used, one solvent can be used primarily for solubilizing the extractible organics component and the second solvent can be used primarily for at least partially solubilizing and removing the first hydrocarbon solvent containing the extractible organics. As such, the second solvent can be used to assist in flushing the first solvent from the subsurface shale formation.
When two solvents are used, the solvents can be the same or different. In certain embodiments, the two solvents are different. In embodiments using two solvents, the methods comprise providing a first hydrocarbon solvent to the subsurface shale formation comprising kerogen and an extractible organics component; at least partially solubilizing at least a portion of the extractible organics component in the first hydrocarbon solvent; removing the first solvent containing the extractible organics component from the subsurface shale formation; providing a second solvent to the subsurface shale formation comprising kerogen and an extractible organics component; at least partially solubilizing at least a portion of the first hydrocarbon solvent in the second solvent; and removing the second solvent containing the first hydrocarbon solvent from the subsurface shale formation.
The methods rely on the extractible organics component being at least partially soluble in the hydrocarbon solvent. Among other factors, these processes are based on the discovery that the shale formation comprises both kerogen component and an extractible organics component. These processes are also based on the discovery that to more easily access the kerogen in oil shale, it is helpful to first remove the extractible organics component from the subsurface shale formation. Preconditioning a subsurface shale formation by removing at least a portion of the extractible organics assists in making the kerogen more accessible for contacting with reactive fluids, catalysts, and heat treatments. In addition, the extractible organics component can be isolated as a hydrocarbon product.
After extraction, the extractible organics component can be isolated and upgraded to produce useful products. The presently disclosed processes are more environmentally benign, more economical, and more efficient in producing commercial products and in providing access to kerogen.
The subsurface shale formation is accessed from the surface through at least one well. In general, the well will be cased, at least for a portion of its distance. Specifications for drilling access wells into a subsurface shale formation are known. In most applications of the invention, multiple wells will be provided into the subsurface shale formation, the well pattern based on recognized principles for this application. In some embodiments, a portion of the wells are employed as injection wells for passing solvents or fluids from the surface to the formation, and a portion of the wells are employed as production wells for withdrawing solvents or fluids from the formation to the surface. Each of the multiple wells may be used successively as an injection well and a production well, depending on the needs of the process. In an alternative, each well may be prepared and managed optimally as either an injection well or a production well. Specifications of each well for preparing and using the well as an injection well and/or a production well can readily be developed by one of skill in the art.
In the present methods, the hydrocarbon solvent may be provided and withdrawn using these wells. The hydrocarbon solvent can be any solvent in which the organics component is at least partially soluble. Suitable or exemplary solvents for extracting the extractible organics include 2-methyltetrahydrofuran, tetrahydrofuran, dichloromethane, chloroform, methanol, ethanol, acetone, carbon disulfide, benzene, toluene, xylene, pyridine, n-methyl-2-pyrrolidone (NMP), cyclopentyl methyl ether (CPME), ethyl lactate, dibasic esters (DBE), propylene carbonate, dimethyl carbonate, CO2, CO2 at supercritical conditions, and mixtures thereof. In certain embodiments, environmentally benign or green solvents are utilized.
Certain embodiments of the present methods involve using one hydrocarbon solvent, a first solvent, and certain embodiments involve using two hydrocarbon solvents, a first solvent and a second solvent. These solvents can be the same or different. In certain embodiments, the first solvent can be selected from the group consisting of 2-methyltetrahydrofuran, tetrahydrofuran, dichloromethane, chloroform, acetone, carbon disulfide, benzene, toluene, xylene, pyridine, n-methyl-2-pyrrolidone (NMP), cyclopentyl methyl ether (CPME), ethyl lactate, dibasic esters (DBE), propylene carbonate, dimethyl carbonate, CO2, CO2 at supercritical conditions, and mixtures thereof. In certain embodiments, the second solvent can be selected from the group consisting of methanol, ethanol, acetone, CO2, CO2 at supercritical conditions, and mixtures thereof. In some embodiments the second solvent is a fluid at supercritical conditions.
In one embodiment of the methods disclosed herein, the first solvent is 2-methyltetrahydrofuran and the second solvent is ethanol or CO2 at supercritical conditions.
In the present methods, the solvent is provided to the formation and the extractible organics are absorbed into the solvent. The hydrocarbon solvent can be contacted with the extractible organics on the surface of the kerogen by circulating the solvent through the formation. Providing the solvent can generally be described as flowing the solvent through the formation, where it can be active (e.g., pumping) and/or passive. The solvent contacts the extractible organics component and at least a portion of the extractible organics component is dissolved or partially solubilized therein.
The step of extracting the organics component involves contacting the organics component with a hydrocarbon solvent and then removing the solvent containing the organics component from the subsurface shale formation. The step of extracting the organics component generally does not involve a chemical modification of the extractible organics component or the kerogen.
In the present methods, at least a portion of the extractible organics component is removed using the hydrocarbon solvent. After at least a portion of the extractible organics component is solubilized into the solvent, the solvent is removed from the formation. The step of removing the solvent containing the extractible organics component can generally be described as flowing the solvent containing the extractible organics component out of the subsurface formation, where it can be active (e.g., pumping) and/or passive.
The extractible organics can be isolated from the solvent at a surface facility. Product can be separated from the solvent flowing or pumped out of the formation using solvent extractions or by physical means, such as, for example, liquid-liquid separation, distillation, membrane separation, thermal separation processes, chromatography and the like. In one embodiment, the extractible organics component has a higher boiling point than the hydrocarbon solvent so the hydrocarbon solvent and extractible organics component can be separated based on these differing boiling points by distillation techniques and the like. The solvents can be recycled to the formation and re-circulated through the formation.
In some embodiments, hydrocarbon products are isolated and then upgraded (thermally and/or chemically) in a surface facility to provide commercial products. Such surface upgrading can be intermediate to subsequent refining.
In some embodiments, the above-described method may involve one or more additional steps which serve to sample and subsequently analyze the hydrocarbon solvent during the extraction process. Such sampling and analysis can have a direct bearing on the techniques employed in the subsequent steps. In certain embodiments, the first solvent can be analyzed for the extractible organics component. A predetermined content of extractible organics component can be set by one of ordinary skill in the art. As long as the first solvent contains the predetermined amount of extractible organics component or more, additional first solvent can be utilized to continue to remove extractible organics. When the amount of extractible organics component falls below the predetermined amount, extraction with the first solvent can be ceased.
As described, in certain embodiments two hydrocarbon solvents are utilized. When two solvents are used in the methods, the second solvent can be provided to the subsurface shale formation to remove at least a portion of the first hydrocarbon solvent from the subsurface shale formation and then the second solvent can be removed from the subsurface shale formation. When a second solvent is used, the first solvent should be miscible with the second solvent and the second solvent should be more miscible with the solvents to be used in the processes for mobilizing products from the kerogen. For example, typically the solvents used for mobilizing products from the kerogen are aqueous based or aqueous compatible. In these methods, the first solvent can be selected to best solubilize at least a portion of the extractible organics component and the second solvent can be chosen so that it is more compatible with the solvents for mobilizing a kerogen-based product. The extractible organics component may also be at least partially soluble in the second solvent. However, in certain embodiments, the second solvent is used primarily to solubilize and remove the first solvent containing extractible organics component, not to directly remove extractible organics component. Sampling and analysis of the first solvent can assist in determining when to switch from using the first solvent to the second solvent. In certain embodiments, when the amount of extractible organics component falls below the predetermined amount, extraction with the first solvent can be ceased and second solvent can be provided to the subsurface shale formation.
Embodiments using two solvents may be particularly useful in methods for creating a mobile kerogen-based product as described in U.S. application Ser. No. 13/335,409, entitled “In-Situ Kerogen Conversion and Recovery” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,525, entitled “In-Situ Kerogen Conversion and Product Isolation” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,607, entitled “In-Situ Kerogen Conversion and Upgrading” filed Dec. 22, 2011; U.S. application Ser. No. 13/335,673, entitled “In-Situ Kerogen Conversion and Recycling” filed Dec. 22, 2011, and U.S. application Ser. No. 13/335,290, entitled “Preparation and Use of Nano-Catalysts for In-Situ Reaction with Kerogen” filed Dec. 22, 2011. The contents of all of these applications are incorporated herein by reference in their entirety.
In embodiments using two solvents, the process comprises providing a first hydrocarbon solvent to the subsurface shale formation comprising kerogen and an extractible organics component; at least partially solubilizing at least a portion of the extractible organics component in the first hydrocarbon solvent; removing the first solvent containing the extractible organics component from the subsurface shale formation; providing a second solvent to the subsurface shale formation comprising kerogen and an extractible organics component; at least partially solubilizing at least a portion of the first hydrocarbon solvent in the second solvent; and removing the second solvent containing the first hydrocarbon solvent from the subsurface shale formation. As described, the first solvent is chosen by one of ordinary skill in the art for solubilizing the extractible organics component and the second solvent is selected such that it is miscible with the first solvent and more compatible with the solvents for mobilizing a kerogen-based product. As such, the second solvent can be used to flush the first solvent from the formation.
The first solvent can be sampled and analyzed for the extractible organics component. Techniques for sampling and analysis are well known to one of ordinary skill in the art and can readily be selected. Analysis techniques include gas chromatography, mass spectrometry, and the like. Sampling and analysis can be used to assist in determining when to switch from using the first solvent to the second solvent. A predetermined content of extractible organics component can be set by one of ordinary skill in the art. As long as the first solvent contains the predetermined amount of extractible organics component or more, additional first solvent can be utilized to continue to remove the extractible organics component. When the amount of extractible organics component falls below the predetermined amount, extraction with the first solvent can be ceased and the second solvent can be provided to the formation. The second solvent can be used to solubilize and remove the first solvent from the formation.
After being withdrawn from the formation, the first and second solvents can be recycled to and recirculated through the subsurface formation so that less total volume of solvent is needed for the present methods.
The present methods utilize in-situ extraction of the extractible organics component using liquid phase chemistry at ambient temperatures and pressures for the subsurface shale formation. Providing the solvent and contacting it with the extractible organics component are generally conducted at or near natural formation temperature. In embodiments, providing the solvent and solubilizing the extractible organics component occurs at a temperature below pyrolysis temperature of the kerogen. In embodiments, this occurs at a temperature in the range of between 0° C. and 200° C. In one embodiment, this occurs at temperatures of 20° C. to 150° C. In some such embodiments, this occurs at a temperature in one of the following ranges: between 20° C. and 150° C.; between 20° C. and 100° C.; or between 25° C. and 75° C.
In a non-limiting specific example, providing the solvent and contacting it with the extractible organics component is conducted at a temperature of less than 50° C. above the natural formation temperature. The natural formation temperature, as used herein, is the temperature of the subsurface shale formation, in the region of the kerogen, prior to human intervention with or in the formation. Methods for determining a natural formation temperature are well known to those of skill in the art. Pyrolysis temperature, as used herein, is the temperature at which the kerogen thermally decomposes without the intervention of a catalytic or chemical agent. In the methods herein, the contacting occurs at a temperature below a pyrolysis temperature of the kerogen.
In some embodiments, the present methods are conducted under conditions in which no added heat is supplied to the formation fluid and/or to the subsurface shale in contact with the formation fluid. In some embodiments, if heat is supplied, it can be supplied by recirculating heating fluids. As such, no oxidative heating is used. The method as disclosed herein occurs at temperature below pyrolysis temperature of the kerogen.
Generally, the method is also conducted at or above natural formation pressure (i.e., the pressure of the subsurface shale formation in the region that includes the kerogen and extractible organics component). Methods for determining the formation pressure and the formation fracture pressure are known. In some such embodiments, the pressure can be up to 1000 psig; or up to 750 psig; or up to 500 psig; or even up to 250 psig above the initial formation pressure. The natural formation pressure, as used herein, is the pressure of the subsurface shale formation, in the region of the kerogen, prior to human intervention with or in the formation. Methods for determining a natural formation pressure are known.
Increasing Accessibility
The above-mentioned method may further comprise steps of increasing accessibility of the kerogen and extractible organic component to the hydrocarbon solvent prior to providing the solvent to the subsurface shale. The step of increasing the accessibility of the subsurface shale may include a variety of techniques and/or technologies such as, but not limited to, explosive fracturing, hydraulic fracturing, thermal fracturing, propellants, and the like. Generally, any method of fracturing and/or rubblizing regions of the shale formation, so as to render the shale more permeable to fluids, is suitable. Such fracturing and/or rubblizing can also involve chemicals reactive to, e.g., at least part of the inorganic shale component.
In some embodiments, the step of increasing accessibility includes the sub-steps of: drilling a cased injection well into the subsurface shale formation comprising the subsurface shale; pressurizing the injection well with an aqueous fluid or water at pressures greater than the formation pressure, so as to create fractures and other voids in the formation.
In some embodiments, the step of increasing accessibility includes the sub-steps of: drilling a cased injection well into the subsurface shale formation comprising the subsurface shale; pressurizing and subsequently sealing the injection well with a dense phase fluid to provide a pressurized well; and rapidly de-pressurizing the pressurized well to reach a steady state reduced pressure. In some such embodiments, the sub-steps of pressurizing and de-pressurizing are repeated until an equilibrium pressure is reached.
The dense phase fluid can be any such fluid that suitably provides for increased accessibility of the kerogen and extractible organics component to a fluid or solvent—typically due to fracturing and/or rubblizing of the shale in which the kerogen and organic component resides. In some embodiments, the dense phase fluid comprises a component selected from the group consisting of carbon dioxide (CO2), nitrogen (N2), liquid natural gas (LNG), ammonia (NH3), carbon monoxide (CO), argon (Ar), liquefied petroleum gas (LPG), hydrogen (H2), hydrogen sulfide (H2S), air, C1 to C20 hydrocarbons (including, but not limited to, ethane, propane, butane, and combinations thereof), and the like.
In some embodiments, the pressure in the pressurized well exceeds the fracture pressure of the subsurface shale formation. Such formation fracture pressure could be ascertained beforehand, for example—thereby helping to direct the choice of variable parameters used in this step.
In some embodiments, the dense phase fluid is absorbed by the kerogen and the kerogen subsequently swells, and wherein the swollen kerogen expands the subsurface shale formation and creates mechanical stresses leading to subsequent fracturing and/or rubblization of the formation. In some such embodiments, the mechanical stresses created during the pressurizing and depressurizing sub-steps enhance fracturing and/or rubblization of the subsurface shale formation.
In some embodiments, the pressurizing and depressurizing sub-steps create thermal and/or mechanical stresses in the subsurface shale formation. In some such embodiments, the kerogen at least partially delaminates from the inorganic component of the shale as a result of the thermal stresses.
In some embodiments, explosives are added to the dense phase fluid to enhance rubblization and fracturing of the formation. Examples of such explosives include, but are not limited to, strongly oxidizing species, nitro-containing species (e.g., trinitrotoluene, nitroglycerine), thermite mixtures, and the like. The dense phase fluids to which such explosives can be added include, but are not limited to, carbon dioxide (CO2), nitrogen (N2), liquid natural gas (LNG), ammonia (NH3), carbon monoxide (CO), argon (Ar), liquefied petroleum gas (LPG), hydrogen (H2), hydrogen sulfide (H2S), air, C1 to C20 hydrocarbons (including, but not limited to, ethane, propane, butane, and combinations thereof), and the like.
Other Preconditioning Treatments
The above-mentioned method also may also comprise other preconditioning treatments. These treatments may include techniques such as, but not limited to, acidifying the inorganic matrix, oxidizing the kerogen, removing water from the formation, circulating a solvent to swell the kerogen, and combinations thereof. Generally, any method that makes the kerogen and/or extractible organic component more accessible is suitable.
According to the present methods, the kerogen in the subsurface shale formation can be preconditioned by any one, or a combination or all of the above described preconditioning processes. If a combination or all of the above described preconditioning processes are utilized, the preconditioning processes can be performed in any order desired. If a combination of preconditioning processes are utilized which involve the use of a solvent or fluid, the same solvent or fluid can advantageously be utilized for the various preconditioning treatments. For example, if a combination of acidifying the inorganic matrix and contacting the kerogen with a swelling agent are utilized, then ethanol, CO2, CO2 at supercritical conditions, or combinations thereof can advantageously be utilized for both preconditioning processes.
Products
The extractible organics can be isolated as hydrocarbon products from the solvents removed from the formation (e.g., by flowing or pumping) and can be recovered as a syncrude or a syncrude product. The products can be separated from the solvent by distillation, extraction and/or other separation techniques at a surface facility. In one embodiment, the extractible organics component has a higher boiling point than the hydrocarbon solvent so the hydrocarbon solvent and extractible organics component can be separated based on these differing boiling points by distillation techniques and the like. The products comprise primarily paraffins, including n-paraffins and isoparaffins. The syncrude is a suitable feedstock for refining, petrochemical and power generating facilities. The products can be transported by pipeline or shipped in tankers, either by tanker or ship.
In further embodiments, the products are upgraded to yield one or more commercial petroleum-based products. Various techniques common in the industry (e.g., hydroprocessing, hydrogenation, saturation, hydrotreating, hydrocracking, isomerization, fluid catalytic cracking, thermal cracking, esterification, oligomerization, reforming, alkylation, denitrification and desulfurization) may be employed to obtain a desired commercial product. Such upgrading is largely dependent on the nature of the product derived from the extractible organics component and the commercial product desired.
The products can be used, for example, in the production of fuels, lubricant and lubricant base oils, polymers, pharmaceuticals, solvents, petrochemicals and food additives. The products can be upgraded and optionally used with additives, and/or other base oils, to make a finished lubricant. The finished lubricants can be used in passenger car motor oils, industrial oils, and other applications. When used for passenger car motor oils, base oils meet the definitions of the current version of API Base Oil Interchange Guidelines 1509.
In embodiments, at least some of the products are used as feedstocks to make lubricants and distillate fuels. These distillate fuels generally boil in the range of about C5-700° F. (121°-371° C.) as determined by the appropriate ASTM test procedure. The term “distillate fuel” is intended to include gasoline, diesel, jet fuel and kerosene boiling range fractions. The kerosene or jet fuel boiling point range is intended to refer to a temperature range of about 280°-525° F. (138°-274° C.) and the term “diesel boiling range” is intended to refer to hydrocarbon boiling points of about 250°-700° F. (121°-371° C.). Gasoline or naphtha is normally the C5 to 400° F. (204° C.) endpoint fraction of available hydrocarbons. The boiling point ranges of the various product fractions recovered in any particular refinery or synthesis process will vary with such factors as the characteristics of the source, local markets, product prices, etc. Reference is made to ASTM standards D-975, D-3699-83 and D-3735 for further details on kerosene, diesel and naphtha fuel properties.
Exemplary Processes
In an exemplary process illustrated in
The hydrocarbon solvent enters the subsurface shale formation as solvent 15 and contacts the kerogen and extractible organics present in the subsurface shale formation in step 20. In step 20 at least a portion of the extractible organics component is at least partially solubilized in the hydrocarbon solvent 25. The solvent containing the extractible organics component 25 is produced to the surface in step 30. In one embodiment, multiple fluid batches of hydrocarbon solvent are provided to the subsurface shale formation. The timing of each solvent addition depends, at least in part, on the progress of the solubilizing the extractible organics component and the content of extractible organics solubilized in the hydrocarbon solvent produced to the surface.
The solvent containing the extractible organics component produced at the surface is treated in step 40 for isolation and recovery of hydrocarbons 45. Optionally, when the solvent containing extractible organics is treated and a hydrocarbon product is isolated, solvent also can be isolated and then the solvent can be recycled to the process. In the illustrative process shown in
An alternative exemplary process is illustrated in
The first hydrocarbon solvent enters the subsurface shale formation as solvent 15 and contacts the kerogen and extractible organics present in the subsurface shale formation in step 20. In step 20 at least a portion of the extractible organics component is at least partially solubilized in the first hydrocarbon solvent 25. The first hydrocarbon solvent containing the extractible organics component 25 is produced to the surface in step 30. In one embodiment, multiple fluid batches of first hydrocarbon solvent are provided to the subsurface shale formation. The timing of each solvent addition depends, at least in part, on the progress of the solubilizing the extractible organics component and the content of extractible organics solubilized in the hydrocarbon solvent produced to the surface.
The first hydrocarbon solvent containing the extractible organics component produced at the surface is treated in step 40 for isolation and recovery of hydrocarbons 45. Optionally, when the first hydrocarbon solvent containing extractible organics is treated and a hydrocarbon product is isolated, solvent also can be isolated and then the solvent can be recycled to the process. In the illustrative process shown in
When the amount of extractible organics component solubilized in the first solvent produced at the surface falls below a predetermined amount, addition of first hydrocarbon solvent 5 can be ceased. Sampling and analysis of the first solvent containing extractible organics component produced at the surface can be performed by techniques well known to those of skill in the art.
At a determined time, a second hydrocarbon solvent 4 is passed to the subsurface shale formation comprising kerogen and an extractible organics component in step 12 via a (e.g., injection) well that has been drilled to penetrate the subsurface formation to provide access to the kerogen within the formation. Two different injection wells (as illustrated) may be used or the same injection well may be used.
The second hydrocarbon solvent enters the subsurface shale formation as solvent 14 and contacts the kerogen, extractible organics present in the subsurface shale formation, and first hydrocarbon solvent present in the formation in step 21. In step 21 at least a portion of the first hydrocarbon solvent present in the formation is at least partially solubilized in the second hydrocarbon solvent 26. The second hydrocarbon solvent containing the first hydrocarbon solvent 26 is produced to the surface in step 31. In one embodiment, multiple fluid batches of second hydrocarbon solvent are provided to the subsurface shale formation. The timing of each solvent addition depends, at least in part, on the progress of the solubilizing the first solvent, the progress of solubilizing the extractible organics component, the content of first hydrocarbon solvent in the formation, and the content of extractible organics solubilized in the hydrocarbon solvent produced to the surface.
The second hydrocarbon solvent containing the first hydrocarbon solvent produced at the surface is treated in step 41 for recovery of the two hydrocarbon solvents 4 and 5 and any hydrocarbon product from the extractible organics component 45. The hydrocarbon solvents 4 and 5 can be recycled to the formation.
Variations
A variation (i.e., alternate embodiment) on the above-described process is the application of some or part of such above-described methods to alternative sources, i.e., low-permeability hydrocarbon-bearing (e.g., oil and gas) formations, in situ coal, in situ heavy oil, in situ oil sands, and the like. General applicability of at least some of the above-described invention embodiments to any hydrocarbon-bearing formation exists. Surface processing applications may include upgrading of oil shale, coal, heavy oil, oil sands, and other conventional oils with asphaltenes, sulfur, nitrogen, etc.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of the invention. Other objects and advantages will become apparent to those skilled in the art from a review of the preceding description.
Number | Name | Date | Kind |
---|---|---|---|
1269747 | Bogers | Jun 1918 | A |
2969226 | Huntington | Jan 1961 | A |
3001775 | Allred | Sep 1961 | A |
3001776 | Poollen et al. | Sep 1961 | A |
3017168 | Carr | Jan 1962 | A |
3061009 | Shirley | Oct 1962 | A |
3076762 | Dill | Feb 1963 | A |
3127935 | Poettmann et al. | Apr 1964 | A |
3136361 | Marx | Jun 1964 | A |
3139928 | Broussard | Jul 1964 | A |
3205942 | Sandberg | Sep 1965 | A |
3233158 | Baker | Dec 1965 | A |
3228468 | Nichols | Jan 1966 | A |
3241611 | Dougan | Mar 1966 | A |
3280910 | Crider | Oct 1966 | A |
3285335 | Reistle, Jr. | Nov 1966 | A |
3292699 | Slusser et al. | Dec 1966 | A |
3322194 | Strubhar | May 1967 | A |
3342258 | Prats | Sep 1967 | A |
3342261 | Bond | Sep 1967 | A |
3346044 | Slusser | Oct 1967 | A |
3349848 | Burgh | Oct 1967 | A |
3358756 | Vogel | Dec 1967 | A |
3362471 | Slusser et al. | Jan 1968 | A |
3382922 | Needham | May 1968 | A |
3398793 | Milton, Jr. | Aug 1968 | A |
3400762 | Peacock et al. | Sep 1968 | A |
3434757 | Prats | Mar 1969 | A |
3437378 | Smith | Apr 1969 | A |
3442789 | Zimmerman, Jr. | May 1969 | A |
3455383 | Prats et al. | Jul 1969 | A |
3468376 | Bramhall | Sep 1969 | A |
3474863 | Deans et al. | Oct 1969 | A |
3478825 | Closmann | Nov 1969 | A |
3480082 | Gilliland | Nov 1969 | A |
3481398 | Prats | Dec 1969 | A |
3489672 | Schuman | Jan 1970 | A |
3499490 | Needham et al. | Mar 1970 | A |
3500913 | Closmann et al. | Mar 1970 | A |
3502372 | Prats | Mar 1970 | A |
3503868 | Shields | Mar 1970 | A |
3504747 | Fitch et al. | Apr 1970 | A |
3513913 | Bruist | May 1970 | A |
3515213 | Prats | Jun 1970 | A |
3521709 | Needham | Jul 1970 | A |
3537528 | O'Brien et al. | Nov 1970 | A |
3548938 | Parker | Dec 1970 | A |
3554283 | Abrams | Jan 1971 | A |
3561532 | Roberts et al. | Feb 1971 | A |
3565171 | Closmann | Feb 1971 | A |
3578080 | Closmann | May 1971 | A |
3593789 | Prats | Jul 1971 | A |
3593790 | Herce | Jul 1971 | A |
3601193 | Grady | Aug 1971 | A |
3661423 | Garret | May 1972 | A |
3666014 | Beard | May 1972 | A |
3700280 | Papadopoulos et al. | Oct 1972 | A |
3766982 | Justheim | Oct 1973 | A |
3779601 | Beard | Dec 1973 | A |
3804169 | Closmann | Apr 1974 | A |
3804172 | Closmann et al. | Apr 1974 | A |
3882941 | Pelofsky | May 1975 | A |
3950029 | Timmins | Apr 1976 | A |
3994343 | Cha et al. | Nov 1976 | A |
4005752 | Cha | Feb 1977 | A |
4008761 | Fisher et al. | Feb 1977 | A |
4008762 | Fisher et al. | Feb 1977 | A |
4018280 | Daviduk et al. | Apr 1977 | A |
4026360 | Drinkard | May 1977 | A |
4027731 | Smith et al. | Jun 1977 | A |
4027917 | Bartel et al. | Jun 1977 | A |
4029360 | French | Jun 1977 | A |
4036299 | Cha et al. | Jul 1977 | A |
4045313 | Yen et al. | Aug 1977 | A |
4061190 | Bloomfield | Dec 1977 | A |
4065183 | Hill et al. | Dec 1977 | A |
4067390 | Camacho et al. | Jan 1978 | A |
4072350 | Bartel et al. | Feb 1978 | A |
4076312 | Cha et al. | Feb 1978 | A |
4082145 | Elkington | Apr 1978 | A |
4082146 | Compton et al. | Apr 1978 | A |
4083604 | Bohn et al. | Apr 1978 | A |
4084640 | Allred | Apr 1978 | A |
4091869 | Hoyer | May 1978 | A |
4105072 | Cha | Aug 1978 | A |
4108760 | Williams et al. | Aug 1978 | A |
4109718 | Burton | Aug 1978 | A |
4126180 | Cha | Nov 1978 | A |
4130474 | Anthony | Dec 1978 | A |
4140180 | Bridges et al. | Feb 1979 | A |
4144935 | Bridges et al. | Mar 1979 | A |
4147388 | French | Apr 1979 | A |
4147389 | Bartel et al. | Apr 1979 | A |
4148358 | Compton | Apr 1979 | A |
4148359 | Laumbach et al. | Apr 1979 | A |
4151068 | McCollum et al. | Apr 1979 | A |
4156461 | Cha | May 1979 | A |
4158467 | Larson et al. | Jun 1979 | A |
4162808 | Kvapil et al. | Jul 1979 | A |
4166721 | Cha | Sep 1979 | A |
4167291 | Ridley | Sep 1979 | A |
4169506 | Berry | Oct 1979 | A |
4176882 | Studebaker et al. | Dec 1979 | A |
4181177 | Compton | Jan 1980 | A |
4184547 | Klass et al. | Jan 1980 | A |
4189376 | Mitchell | Feb 1980 | A |
4191251 | Cha | Mar 1980 | A |
4192381 | Cha | Mar 1980 | A |
4192552 | Cha | Mar 1980 | A |
4193451 | Dauphine | Mar 1980 | A |
4202412 | Ruskin | May 1980 | A |
4218309 | Compton | Aug 1980 | A |
4227574 | Cha | Oct 1980 | A |
4239283 | Ridley | Dec 1980 | A |
4239284 | Ridley et al. | Dec 1980 | A |
4243100 | Cha | Jan 1981 | A |
4246965 | Cha | Jan 1981 | A |
4265307 | Elkins | May 1981 | A |
RE30738 | Bridges et al. | Sep 1981 | E |
4324292 | Jacobs et al. | Apr 1982 | A |
4328863 | Berry | May 1982 | A |
4347118 | Funk et al. | Aug 1982 | A |
4359246 | Ricketts | Nov 1982 | A |
4366986 | Bohn et al. | Jan 1983 | A |
4374545 | Bullen et al. | Feb 1983 | A |
4376034 | Wall | Mar 1983 | A |
4378949 | Miller | Apr 1983 | A |
4379591 | Tassoney | Apr 1983 | A |
4379593 | Weichman | Apr 1983 | A |
4384614 | Justheim | May 1983 | A |
4389300 | Mitchell | Jun 1983 | A |
4396491 | Stiller et al. | Aug 1983 | A |
4401162 | Osborne | Aug 1983 | A |
4401163 | Elkins | Aug 1983 | A |
4401551 | Mitchell | Aug 1983 | A |
4408665 | Dougan | Oct 1983 | A |
4423907 | Ridley | Jan 1984 | A |
4424121 | Choi et al. | Jan 1984 | A |
4425220 | Kestner | Jan 1984 | A |
4425967 | Hoekstra | Jan 1984 | A |
4435016 | Wissenberg et al. | Mar 1984 | A |
4436344 | Forgac et al. | Mar 1984 | A |
4437519 | Cha et al. | Mar 1984 | A |
4441985 | Burchfield et al. | Apr 1984 | A |
4444258 | Kalmar | Apr 1984 | A |
4449586 | Urban et al. | May 1984 | A |
4452689 | Russum | Jun 1984 | A |
4454915 | York et al. | Jun 1984 | A |
4457365 | Kasevich et al. | Jul 1984 | A |
4457374 | Hoekstra et al. | Jul 1984 | A |
4458757 | Bock et al. | Jul 1984 | A |
4458944 | Fernandes | Jul 1984 | A |
4470459 | Copland | Sep 1984 | A |
4481099 | Mitchell | Nov 1984 | A |
4483398 | Peters et al. | Nov 1984 | A |
4485869 | Sresty et al. | Dec 1984 | A |
4487260 | Pittman et al. | Dec 1984 | A |
4491514 | Siskin et al. | Jan 1985 | A |
4495056 | Venardos et al. | Jan 1985 | A |
4502942 | Lee et al. | Mar 1985 | A |
4531783 | Ricketts | Jul 1985 | A |
4532991 | Hoekstra et al. | Aug 1985 | A |
4533181 | Ricketts | Aug 1985 | A |
4552214 | Forgac et al. | Nov 1985 | A |
4584088 | McCollum et al. | Apr 1986 | A |
4595056 | Zahradnik et al. | Jun 1986 | A |
4637464 | Forgac et al. | Jan 1987 | A |
4640352 | Vanmeurs et al. | Feb 1987 | A |
4691773 | Ward et al. | Sep 1987 | A |
4695373 | Ho | Sep 1987 | A |
4698149 | Mitchell | Oct 1987 | A |
4703798 | Friedman | Nov 1987 | A |
4705108 | Little et al. | Nov 1987 | A |
4718439 | Gorra et al. | Jan 1988 | A |
4737267 | Pao et al. | Apr 1988 | A |
4798668 | Ho | Jan 1989 | A |
4856587 | Nielson | Aug 1989 | A |
4856589 | Kuhlman et al. | Aug 1989 | A |
4886118 | Van Meurs et al. | Dec 1989 | A |
4888031 | Martens | Dec 1989 | A |
4895206 | Price | Jan 1990 | A |
4926941 | Glandt et al. | May 1990 | A |
5020596 | Hemsath | Jun 1991 | A |
5058675 | Travis | Oct 1991 | A |
5060726 | Glandt et al. | Oct 1991 | A |
5091076 | So | Feb 1992 | A |
5236039 | Edelstein et al. | Aug 1993 | A |
5255742 | Mikus | Oct 1993 | A |
5297626 | Vinegar et al. | Mar 1994 | A |
5338442 | Siskin et al. | Aug 1994 | A |
5404952 | Vinegar et al. | Apr 1995 | A |
5411089 | Vinegar et al. | May 1995 | A |
5433271 | Vinegar et al. | Jul 1995 | A |
5843311 | Richter et al. | Dec 1998 | A |
6056057 | Vinegar et al. | May 2000 | A |
6079499 | Mikus et al. | Jun 2000 | A |
6102122 | de Rouffignac | Aug 2000 | A |
6279653 | Wegener et al. | Aug 2001 | B1 |
6547957 | Sudhakar et al. | Apr 2003 | B1 |
6702016 | de Rouffignac et al. | Mar 2004 | B2 |
6715549 | Wellington et al. | Apr 2004 | B2 |
6719047 | Fowler et al. | Apr 2004 | B2 |
6722431 | Karanikas et al. | Apr 2004 | B2 |
6729395 | Shahin, Jr. et al. | May 2004 | B2 |
6769483 | de Rouffignac et al. | Aug 2004 | B2 |
6769486 | Lim et al. | Aug 2004 | B2 |
6782947 | de Rouffignac et al. | Aug 2004 | B2 |
6877555 | Karanikas et al. | Apr 2005 | B2 |
6880633 | Wellington et al. | Apr 2005 | B2 |
6889769 | Wellington et al. | May 2005 | B2 |
6890424 | Wilde | May 2005 | B1 |
6896053 | Berchenko et al. | May 2005 | B2 |
6902004 | de Rouffignac et al. | Jun 2005 | B2 |
6915850 | Vinegar et al. | Jul 2005 | B2 |
6918442 | Wellington et al. | Jul 2005 | B2 |
6923257 | Wellington et al. | Aug 2005 | B2 |
6932155 | Vinegar et al. | Aug 2005 | B2 |
6951247 | de Rouffignac et al. | Oct 2005 | B2 |
6951248 | Conaway et al. | Oct 2005 | B2 |
6953087 | de Rouffignac et al. | Oct 2005 | B2 |
6964300 | Vinegar et al. | Nov 2005 | B2 |
6991032 | Berchenko | Jan 2006 | B2 |
6991033 | Wellington et al. | Jan 2006 | B2 |
6991036 | Sumnu-Dindoruk et al. | Jan 2006 | B2 |
6994160 | Wellington et al. | Feb 2006 | B2 |
6994169 | Zhang et al. | Feb 2006 | B2 |
6997518 | Vinegar et al. | Feb 2006 | B2 |
7004251 | Ward et al. | Feb 2006 | B2 |
7011154 | Maher et al. | Mar 2006 | B2 |
7013972 | Vinegar et al. | Mar 2006 | B2 |
7032660 | Vinegar et al. | Apr 2006 | B2 |
7051811 | de Rouffignac et al. | May 2006 | B2 |
7055600 | Messier et al. | Jun 2006 | B2 |
7073578 | Vinegar et al. | Jul 2006 | B2 |
7077198 | Vinegar et al. | Jul 2006 | B2 |
7086465 | Wellington et al. | Aug 2006 | B2 |
7090013 | Wellington | Aug 2006 | B2 |
7091460 | Kinzer | Aug 2006 | B2 |
7096942 | de Rouffignac et al. | Aug 2006 | B1 |
7100994 | Vinegar et al. | Sep 2006 | B2 |
7114566 | Vinegar et al. | Oct 2006 | B2 |
7121342 | Vinegar et al. | Oct 2006 | B2 |
7344889 | Kelemen et al. | Mar 2008 | B2 |
7416022 | Maguire | Aug 2008 | B2 |
7441603 | Kaminsky et al. | Oct 2008 | B2 |
7484561 | Bridges | Feb 2009 | B2 |
7500517 | Looney et al. | Mar 2009 | B2 |
7510000 | Pastor-Sanz et al. | Mar 2009 | B2 |
7540324 | de Rouffignac et al. | Jun 2009 | B2 |
7543638 | Goodman | Jun 2009 | B2 |
7549470 | Vinegar et al. | Jun 2009 | B2 |
7556096 | Vinegar et al. | Jul 2009 | B2 |
7559368 | Vinegar et al. | Jul 2009 | B2 |
7562707 | Miller | Jul 2009 | B2 |
7584789 | Mo et al. | Sep 2009 | B2 |
7604052 | Roes et al. | Oct 2009 | B2 |
7631690 | Vinegar et al. | Dec 2009 | B2 |
7635023 | Goldberg et al. | Dec 2009 | B2 |
7669657 | Symington et al. | Mar 2010 | B2 |
7712528 | Langdon et al. | May 2010 | B2 |
7735935 | Vinegar et al. | Jun 2010 | B2 |
7789164 | Looney et al. | Sep 2010 | B2 |
7841407 | Wellington et al. | Nov 2010 | B2 |
7841408 | Vinegar | Nov 2010 | B2 |
7845411 | Vinegar et al. | Dec 2010 | B2 |
7849922 | Vinegar et al. | Dec 2010 | B2 |
7857056 | Kaminsky et al. | Dec 2010 | B2 |
7862705 | Dana et al. | Jan 2011 | B2 |
7866386 | Beer et al. | Jan 2011 | B2 |
7906014 | Dana et al. | Mar 2011 | B2 |
7942203 | Vinegar et al. | May 2011 | B2 |
7950453 | Farmayan et al. | May 2011 | B2 |
7967974 | Dana et al. | Jun 2011 | B2 |
7980312 | Hill et al. | Jul 2011 | B1 |
20010030145 | Conaway | Oct 2001 | A1 |
20020029882 | de Rouffignac et al. | Mar 2002 | A1 |
20020033253 | de Rouffignac et al. | Mar 2002 | A1 |
20020033256 | Wellington et al. | Mar 2002 | A1 |
20020033257 | Shahin, Jr. et al. | Mar 2002 | A1 |
20020036084 | Vinegar et al. | Mar 2002 | A1 |
20020036089 | Vinegar et al. | Mar 2002 | A1 |
20020038705 | Wellington et al. | Apr 2002 | A1 |
20020038709 | Wellington et al. | Apr 2002 | A1 |
20020038710 | Maher et al. | Apr 2002 | A1 |
20020038711 | de Rouffignac et al. | Apr 2002 | A1 |
20020040173 | de Rouffignac et al. | Apr 2002 | A1 |
20020040778 | Wellington et al. | Apr 2002 | A1 |
20020040779 | Wellington et al. | Apr 2002 | A1 |
20020040780 | Wellington et al. | Apr 2002 | A1 |
20020040781 | Keedy et al. | Apr 2002 | A1 |
20020045553 | Vinegar et al. | Apr 2002 | A1 |
20020046832 | Zhang et al. | Apr 2002 | A1 |
20020046837 | Wellington et al. | Apr 2002 | A1 |
20020046838 | Karanikas et al. | Apr 2002 | A1 |
20020049360 | Wellington et al. | Apr 2002 | A1 |
20020050352 | Wellington et al. | May 2002 | A1 |
20020050357 | Wellington et al. | May 2002 | A1 |
20020052297 | de Rouffignac et al. | May 2002 | A1 |
20020053429 | Stegemeier et al. | May 2002 | A1 |
20020053431 | Wellington et al. | May 2002 | A1 |
20020053435 | Vinegar et al. | May 2002 | A1 |
20020056551 | Wellington et al. | May 2002 | A1 |
20020056552 | Wellington et al. | May 2002 | A1 |
20020057905 | Wellington et al. | May 2002 | A1 |
20020062052 | de Rouffignac et al. | May 2002 | A1 |
20020062961 | Vinegar et al. | May 2002 | A1 |
20020066565 | de Rouffignac et al. | Jun 2002 | A1 |
20020076212 | Zhang et al. | Jun 2002 | A1 |
20020084074 | de Rouffignac et al. | Jul 2002 | A1 |
20020096320 | Wellington et al. | Jul 2002 | A1 |
20030040441 | Miller et al. | Feb 2003 | A1 |
20030062164 | Wellington et al. | Apr 2003 | A1 |
20030079877 | Wellington et al. | May 2003 | A1 |
20030098149 | Wellington et al. | May 2003 | A1 |
20030098605 | Vinegar et al. | May 2003 | A1 |
20030102125 | Wellington et al. | Jun 2003 | A1 |
20030102130 | Vinegar et al. | Jun 2003 | A1 |
20030116315 | Wellington et al. | Jun 2003 | A1 |
20030130136 | de Rouffignac et al. | Jul 2003 | A1 |
20030137181 | Wellington et al. | Jul 2003 | A1 |
20030141067 | de Rouffignac et al. | Jul 2003 | A1 |
20030142964 | Wellington et al. | Jul 2003 | A1 |
20030146002 | Vinegar et al. | Aug 2003 | A1 |
20030155111 | Vinegar et al. | Aug 2003 | A1 |
20030173072 | Vinegar et al. | Sep 2003 | A1 |
20030173080 | Berchenko et al. | Sep 2003 | A1 |
20030173081 | Vinegar et al. | Sep 2003 | A1 |
20030173082 | Vinegar et al. | Sep 2003 | A1 |
20030183390 | Veenstra et al. | Oct 2003 | A1 |
20030196789 | Wellington et al. | Oct 2003 | A1 |
20030196810 | Vinegar et al. | Oct 2003 | A1 |
20030201098 | Karanikas et al. | Oct 2003 | A1 |
20030205378 | Wellington et al. | Nov 2003 | A1 |
20030213594 | Wellington et al. | Nov 2003 | A1 |
20040015023 | Wellington et al. | Jan 2004 | A1 |
20040020642 | Vinegar et al. | Feb 2004 | A1 |
20040149433 | McQueen | Aug 2004 | A1 |
20050252656 | Maguire | Nov 2005 | A1 |
20050269091 | Pastor-Sanz et al. | Dec 2005 | A1 |
20070012598 | Rendall | Jan 2007 | A1 |
20070023186 | Kaminsky et al. | Feb 2007 | A1 |
20070193743 | Harris et al. | Aug 2007 | A1 |
20070209799 | Vinegar et al. | Sep 2007 | A1 |
20070221377 | Vinegar et al. | Sep 2007 | A1 |
20070284107 | Crichlow | Dec 2007 | A1 |
20080006410 | Looney et al. | Jan 2008 | A1 |
20080017549 | Kennel et al. | Jan 2008 | A1 |
20080023197 | Shurtleff | Jan 2008 | A1 |
20080059140 | Salmon et al. | Mar 2008 | A1 |
20080087427 | Kaminsky et al. | Apr 2008 | A1 |
20080087428 | Symington et al. | Apr 2008 | A1 |
20080116694 | Hendershot | May 2008 | A1 |
20080164030 | Young | Jul 2008 | A1 |
20080173450 | Goldberg et al. | Jul 2008 | A1 |
20080207970 | Meurer et al. | Aug 2008 | A1 |
20080257552 | Shurtleff et al. | Oct 2008 | A1 |
20080283241 | Kaminsky et al. | Nov 2008 | A1 |
20080290719 | Kaminsky et al. | Nov 2008 | A1 |
20080314593 | Vinegar et al. | Dec 2008 | A1 |
20090014179 | Mango | Jan 2009 | A1 |
20090014181 | Vinegar et al. | Jan 2009 | A1 |
20090050319 | Kaminsky et al. | Feb 2009 | A1 |
20090078415 | Fan et al. | Mar 2009 | A1 |
20090101346 | Vinegar et al. | Apr 2009 | A1 |
20090133935 | Kinkead | May 2009 | A1 |
20090200022 | Bravo et al. | Aug 2009 | A1 |
20090200023 | Costello et al. | Aug 2009 | A1 |
20090242196 | Pao | Oct 2009 | A1 |
20090250381 | Fan et al. | Oct 2009 | A1 |
20090313772 | Talley | Dec 2009 | A1 |
20100032171 | Bali et al. | Feb 2010 | A1 |
20100056404 | Talley | Mar 2010 | A1 |
20100126727 | Vinegar et al. | May 2010 | A1 |
20100173806 | Fan et al. | Jul 2010 | A1 |
20100181231 | Gurin | Jul 2010 | A1 |
20100200232 | Langdon et al. | Aug 2010 | A1 |
20100200234 | Mango | Aug 2010 | A1 |
20100218945 | Sadok | Sep 2010 | A1 |
20100270015 | Vinegar et al. | Oct 2010 | A1 |
20100270038 | Looney et al. | Oct 2010 | A1 |
20100282460 | Stone et al. | Nov 2010 | A1 |
20100288028 | Carbonell et al. | Nov 2010 | A1 |
20100319909 | Symington et al. | Dec 2010 | A1 |
20110000825 | McGrady et al. | Jan 2011 | A1 |
20110049016 | McGrady et al. | Mar 2011 | A1 |
20110062057 | Duyvesteyn | Mar 2011 | A1 |
20110088904 | De Rouffignac et al. | Apr 2011 | A1 |
20110146982 | Kaminsky et al. | Jun 2011 | A1 |
20110174496 | Burnham et al. | Jul 2011 | A1 |
20110180262 | O'Dowd | Jul 2011 | A1 |
20110186296 | Cassidy | Aug 2011 | A1 |
20110290490 | Kaminsky et al. | Dec 2011 | A1 |
20110303413 | Fairbanks et al. | Dec 2011 | A1 |
Number | Date | Country |
---|---|---|
WO2005010320 | Feb 2005 | WO |
WO2010-093785 | Aug 2010 | WO |
WO2011007172 | Jan 2011 | WO |
Entry |
---|
U.S. Appl. No. 13/481,303, filed May 25, 2012, entitled “Isolating Lubricating Oils from Subsurface Shale Formations”. |
U.S. Appl. No. 13/491,925, filed Jun. 8, 2012, entitled “Soluble Acids from Naturally Occurring Aqueous Streams”. |
U.S. Appl. No. 13/335,409, filed Dec. 22, 2011, entitled “In-Situ Kerogen Conversion and Recovery”. |
U.S. Appl. No. 13/335,525, filed Dec. 22, 2011, entitled “In-Situ Kerogen Conversion and Product Isolation”. |
U.S. Appl. No. 13/335,607, filed Dec. 22, 2011, entitled “In-Situ Kerogen Conversion and Product Upgrading”. |
U.S. Appl. No. 13/335,673, filed Dec. 22, 2011, entitled “In-Situ Kerogen Conversion and Recycling”. |
U.S. Appl. No. 13/335,290, filed Dec. 22, 2011, entitled “Preparation and Use of Nano-Catalyst for In Situ Reaction with Kerogen”. |
U.S. Appl. No. 13/335,864, filed Dec. 22, 2011, entitled “Kerogen Conversion in a Subsurface Shale Formation with Oxidant Regeneration”. |
U.S. Appl. No. 13/335,907, filed Dec. 22, 2011, entitled “Electrokinetic Enhanced Hydrocarbon Recovery from Oil Shale”. |
PCT International Search Report and Written Opinion, International Application No. PCT/US2012/070690, dated Apr. 26, 2013. |
US 6,595,286, Jul. 22, 2003, Fowler et al., (Withdrawn). |
Vandenbrouck, M. et al., “Kerogen origin, evolution and structure”, Organic Geochemistry 38:719-833 (2007). |
Philp, R.P. et al., “Saponification of the Insoluble Organic Residues from Oil Shales, Algal Oozes, and Algae”, Energy Sources 4(2):113-123 (1978). |
Huseby, B. and Ocampo, R, “Evidence for porphyrins bound, via ester bonds, to the Messel oil shale kerogen by selective chemical degradation experiments”, Geochimica et Cosmochimica Acta 61(18):3951-3955 (1997). |
Amblès, A., et al., “Ester- and ether bond cleavage in immature kerogens”, Org. Geochem 24(6/7):681-690 (1996). |
McGowan, C.W., et al., “A Comparison of the Dissolution of Model Compounds and the Kerogen of Green River Oil Shale by Oxidation with Perchloric Acid—A Model for the Kerogen of the Green River Oil Shale”, Fuel Processing Technology 10:195-204 (1985). |
McGowan, Chris W., “The Oxidation of Green River Oil Shale with Perchloric Acid—Part I—The Reaction of Green River Oil Shale with Perchloric of Varying Concentration and Boiling Point”, Fuel Processing Technology 10:169-179 (1985). |
McGowan, Chris W., et al., “The Role of Ether Oxygen and Carbon Double Bonds as Linkages During the Dissolution of Kerogens with Perchloric Acid” ACS Fuel 42(1):172-175 (Spring 1997). |
Boucher, Raymond J., et al., “Molecular characterization of kerogens by mild selective chemical degradation—ruthenium tetroxide oxidation”, Fuel 70:695-708 (1991). |
Robinson, W.E., et al., “Constitution of Organic Acids Prepared from Colorado Oil Shale”, Industrial and Engineering Chemistry 48(7):1134-1128 (1956). |
Philp, R.P. and Yang, E., “Alkaline Potassium Permanganate Degradation of Insoluble Organic Residues (Kerogen) Isolated from Recently-Deposited Algal Mats” Energy Sources 3(2):149-161 (1997). |
Robinson, W.E., et al., “Alkaline Permanganate Oxidation of Oil-Shale Kerogen”, Industrial and Engineering Chemistry 45(4):788-791 (1953). |
Djuricic, M., et al., “Organic acids obtained by alkaline permanganate oxidation of kerogen from the Green River (Colorado) shale”, Geochimica et Cosmochimica Acta 35:1201-1207 (1971). |
Young, D.K. and Yen, T.F., “The nature of straight-chain aliphatic sstructures in Green River kerogen”, Geochimica et Cosmochimica Acta 41:1411-1417 (1977). |
Amblès, A., et al., “Nature of Kerogen from Green River Shale based on the Charactyer of the Products of a Forty-Step Alkaline Permanganate Oxidation”, Adv. Org. Geochem 554-560 (1981). |
Vitorović, D., et al., “Improvement of kerogen structural interpretations based on oxidation products isolated from aqueous solutions”, Advances in Organic Geochemistry 10:1119-1126 (1985). |
Vitorović, D., et al., “Relationship between kerogens of various structural types and the products of their multistep oxidative degradation”, Org. Geochem. 6:333-342 (1984). |
Vitorović, D., et al., “The feasibilities of the alkaline permanganate degradation method for the characterization and classification of kerogens”, J. Serb. Chem. Soc. 53(4):175-189 (1988). |
Burlingame, A.L. and Simoneit, B.R., “High Resolution Mass Spectrometry of Green River Formation Kerogen Oxidations”, Nature 222:741-747 (1969). |
Simoneit, B.R., et al., “Sterochemical studies of acyclis isoprenoid compounds—V. Oxidation products of Green River Formation oil shale kerogen”, Geochimica et Cosmochimica Acta 39:1143-1145 (1975). |
Burlingame, A.L. and Simoneit, B.R., “Isoprenoid Fatty Acids Isolated from the Kerogen Matrix of the Green River Formation (Eocene)”, Science 160:531-533 (1968). |
Simoneit, B.R. And Burlingame, A.L., “Carboxylic acids derived from Tasmanian tasmanite by extractions and kerogen oxidations”, Geochimica et Cosmochimica Acta 37:595-610 (1973). |
Hayatsu, Ryoichi, et al., “Investigation of aqueous sodium dichromate oxidation for coal structural studies”, Fuel 60:77-82 (1981). |
Hayatsu, Ryoichi, et al., “Is kerogen-like material present in coal: 2. Chromic acid oxidation of coal and kerogen”, Fuel 60:161-203 (1981). |
Barakat, A.O. and Yen, T.F., “Distribution of Acyclic Isoprenoids in Fractions from Stepwise Oxidation of Greene River Kerogen”, Energy Sources 10:253-259 ((1988). |
Barakat, A.O., “Carboxylic Acids Obtained by Alkaline Hydrolysis of Monterey Kerogen”, Energy and Fuels 7:988-993 (1993). |
Barakat, Assem O., Size Distribution of the Straight-Chain Structures in Type I and II Kerogens, Energy and Fuels 2:181-185 (1988). |
Barakat, A.O. and Yen, T.F., “Distribution of pentacyclic triterpenoids in Green River oil shale kerogen”, Org. Geochem. 15(3):299-311 (1990). |
Barakat, A.O. and Yen, T.F., “The Nature of Porphyrins in Kerogen. Evidence of Entrapped Etioporphyrin Species”, Energy & Fuels 3:613-616 (1989). |
Barakat, A.O. and Yen, T.F., “Novel Identification of 17β(H)-Hopanoids in Green River Oil Shale Kerogen”, Energy & Fuels 2:105-108 (1988). |
Barakat, Assem O. and Yen, Teh Fu, “Kerogen structure by stepwise oxidation; Use of sodium dichromate in glacial acetic acid”, Fuel 66:587-753 (1987). |
Khaddor, M, Ziyad, M. and Ambles, A. , “Structural characterization of the kerogen from Youssoufia phosphate formation using mild potassium permanganate oxidation” Organic Geochemistry 39(6):730-740 (2008). |
Number | Date | Country | |
---|---|---|---|
20130161001 A1 | Jun 2013 | US |