1. Field of the Invention
This invention relates generally to extraction of hydrocarbon fuels from a body of fixed fossil fuels in subsurface formations such as oil shale, heavy oil in aging wells, coal, lignite, peat and tar sands, and in particular to a method and apparatus for extraction of kerogen oil and hydrocarbon gas from oil shale in situ utilizing electrical energy and critical fluids (CF), and extraction of contaminants or residue from a body of fixed earth or from a vessel in situ utilizing electrical energy and critical fluids (CF).
2. Description of Related Art
Oil shale, also known as organic rich marlstone, contains organic matter comprised mainly of an insoluble solid material called kerogen. Kerogen decomposes during pyrolysis into kerogen oil and hydrocarbon gasses, which can be used as fuels or further refined into other transportation fuels or products. Shale oil and hydrocarbon gas can be generated from kerogen by a pyrolysis process, i.e. a treatment that consists of heating oil shale to elevated temperatures, typically 300 to 500° C. Prior to pyrolysis, kerogen products at room temperature have substantial portions of high viscosity non-transformed material such that they cannot be accessed within the rock/sand matrix. The shale oil is then refined into usable marketable products. Early attempts to process bodies of oil shale in situ by heating the kerogen in the oil shale, for example, injecting super-heated steam, hot liquids or other materials into the oil shale formation, have not been economically viable even if fundamentally feasible (which some were not). Early and current attempts to process bodies of oil shale above ground to obtain the kerogen oil and gas in the oil shale, for example, by mining, crushing and heating the shale in a retort type oven, have not been environmentally feasible nor economically viable.
It is well known to use critical fluids for enhanced oil and gas recovery by injecting naturally occurring carbon dioxide into existing reservoirs in order to maximize the output of oil and gas. By pumping carbon dioxide or air into the reservoirs, the existing oil or gas is displaced, and pushed up to levels where it is more easily extracted.
An article by M. Koel et al. entitled “Using Neoteric Solvents in Oil Shale Studies”, Pure Applied Chemistry, Vol. 73, No. 1, PP 153-159, 2001 discloses that supercritical fluid extraction (SFE) at elevated temperatures with carbon dioxide modified with methanol or water can be used to extract kerogen oil and gas from ground shale. This study was targeted at replacing analytical techniques using conventional solvents. Most of these solvents are not environmentally desirable and are impractical for use on a large scale.
In a paper by Treday, J. and Smith, J, JAIChE, Vol. 34, No. 4, pp 658-668, supercritical toluene is shown to be effective for the extraction of kerogen oil and gas from shale. This study used oil shale which was mined, carried to above ground levels, and ground to ¼″ diameter particles in preparation for the extraction. This labor intensive preparation process was to increase diffusivity, as the in-situ diffusivity reported would not support toluene's critical point of 320 degrees Celsius. “In-Situ” diffusivity of 5×10−9 M2/s was estimated, resulting in a penetration of a few centimeters per day which was insufficient. Furthermore the cost of toluene and the potential environmental impact of using toluene in-situ were prohibitive. Finally, maintaining the temperature of 320 degrees Celsius would be expensive in a toluene system.
In a paper by Willey et. al, “Reactivity Investigation of Mixtures of Propane on Nitrous Oxide”, scheduled for publication in December, 2005 in Process Safety Progress, the use of CO2 to inhibit an oxidation reaction from becoming a hazardous runaway reaction is demonstrated. However in this article it is not contemplated to use such a reactant for in-situ fossil fuel processing, shale heating, etc.
Critical fluids are compounds at temperatures and pressures approaching or exceeding the thermodynamic critical point of the compounds. These fluids are characterized by properties between those of gasses and liquids, e.g. diffusivities are much greater than liquids, but not as great as gasses and viscosity is lower than typical liquid viscosities. Density of critical fluids is a strong function of pressure. Density can range from gas to liquid, while the corresponding solvent properties of a critical fluid also vary with temperature and pressure which can be used to advantage in certain circumstances and with certain methods. Critical fluids were first discovered as a laboratory curiosity in the 1870's and have found many commercial uses. Supercritical and critical CO2 have been used for coffee decaffeination, wastewater cleanup and many other applications.
Many efforts have been attempted or proposed to heat large volumes of subsurface formations in situ using electric resistance, gas burner heating, steam injection and electromagnetic energy such as to obtain kerogen oil and gas from oil shale. Resistance type electrical elements have been positioned down a borehole via a power cable to heat the shale via conduction. Electromagnetic energy has been delivered via an antenna or microwave applicator. The antenna is positioned down a borehole via a coaxial cable or waveguide connecting it to a high-frequency power source on the surface. Shale heating is accomplished by radiation and dielectric absorption of the energy contained in the electromagnetic (EM) wave radiated by the antenna or applicator. This is superior to more common resistance heating which relies solely on conduction to transfer the heat. It is superior to steam heating which requires large amounts of water and energy present at the site.
U.S. Pat. No. 3,881,550 issued May 6, 1975 to Charles B. Barry and assigned to Ralph M. Parson Company, discloses a process for in situ recovery of hydrocarbons or heavy oil from tar sand formations by continuously injecting a hot solvent containing relatively large amounts of aromatics into the formations, and alternatively steam and solvents are cyclically and continuously injected into the formation to recover values by gravity drainage. The solvents are injected at a high temperature and consequently lie on top of the oil shale or tar sand and accordingly no complete mixing and dissolving of the heavy oil takes place.
U.S. Pat. No. 4,140,179 issued Feb. 20, 1979 to Raymond Kasevich, et al. and assigned to Raytheon Company discloses a system and method for producing subsurface heating of a formation comprising a plurality of groups of spaced RF energy radiators (dipole antennas) extending down boreholes to oil shale. The antenna elements must be matched to the electrical conditions of the surrounding formations. However, as the formation is heated, the electrical conditions can change whereby the dipole antenna elements may have to be removed and changed due to changes in temperature and content of organic material.
U.S. Pat. No. 4,508,168, issued Apr. 2, 1985 to Vernon L. Heeren and assigned to Raytheon Company, is incorporated herein by reference and describes an RF applicator positioned down a borehole supplied with electromagnetic energy through a coaxial transmission line whose outer conductor terminates in a choking structure comprising an enlarged coaxial stub extending back along the outer conductor. It is desirable that the frequency of an RF transmitter be variable to adjust for different impedances or different formations, and/or the output impedance of an impedance matching circuit be variable so that by means of a standing wave, the proper impedance is reflected through a relatively short transmission line stub and transmission line to the radiating RF applicator down in the formation. However, this approach by itself requires longer application of RF power and more variation in the power level with time. The injection of critical fluids (CF) will reduce the heating dependence, due solely on RF energy, simplifying the RF generation and monitoring equipment and reducing electrical energy consumed. The same is true if simpler electrical resistance heaters are used in place of the RF. Also, the injection of critical fluids (CF) as in the present invention increases the total output of the system, regardless of heat temperature or application method, due to its dilutent and carrier properties.
The process described in U.S. Pat. No. 4,140,179 and U.S. Pat. No. 4,508,168 and other methods using resistance heaters, require a significant amount of electric power to be generated at the surface to power the process and does not provide an active transport method for removing the products as they are formed and transporting them to the surface facilities. CO2, or another critical fluid, which also acts as an active transport mechanism, can potentially be capped in the shale after the extraction is complete thereby reducing greenhouse gases released to the atmosphere.
U.S. Pat. No. 5,065,819 issued Nov. 19, 1991 to Raymond S. Kasevich and assigned to KAI Technologies discloses an electromagnetic apparatus for in situ heating and recovery of organic and inorganic materials of subsurface formations such as oil shale, tar sands, heavy oil or sulfur. A high power RF generator which operates at either continuous wave or in a pulsed mode, supplies electromagnetic energy over a coaxial transmission line to a downhole collinear array antenna. A coaxial liquid-dielectric impedance transformer located in the wellhead couples the antenna to the RF generator.
However, this requires continuous application and monitoring of the RF power source and the in-ground radiating hardware, to provide the necessary heating required for reclamation.
Accordingly, it is therefore an object of this invention to provide a method and apparatus for extraction of hydrocarbon fuel from a body of fixed fossil fuels using electrical energy and critical fluids (CF).
It is another object of this invention to provide a method and apparatus for in situ extraction of kerogen oil and gas from oil shale using a combination of RF energy and critical fluids.
It is a further object of this invention to provide a method and apparatus for effectively heating oil shale in situ using a combination of RF energy and a critical fluid.
It is a further object of this invention to provide a method and apparatus for effectively converting kerogen to useful production in-situ using RF energy and a critical fluid.
It is a further object of this invention to provide a method and apparatus for effectively obtaining gaseous and liquefied fuels from deep, otherwise uneconomic deposits of fixed fossil fuels using RF energy and critical fluids.
It is a further object of this invention to provide a method and apparatus for extraction of heavy oils from aging oil wells using electrical energy and critical fluids.
It is another object of this invention to provide a method and apparatus for extraction of hydrocarbon fuels, liquid and gaseous fuels, from coal, lignite, tar sands and peat using electrical energy or critical fluids.
It is a further object of this invention to provide a method and apparatus for remediation of oil and other hydrocarbon fuels from a spill site, land fill or other environmentally sensitive situation by using a combination of electrical energy and critical fluids and to recover liquid and gaseous fuels from same.
It is yet another object of this invention to provide a method and apparatus to remove material from any container with-out danger to an in-situ human, such as cleaning a large industrial tank of paint or oil sludge.
These and other subjects are further accomplished by a method of producing hydrocarbon fuel products from a body of fixed fossil fuels beneath an overburden comprising the steps of (a) transmitting electrical energy down a borehole to heat the body of fixed fossil fuels to a first predetermined temperature, (b) providing critical fluids with reactants or catalysts down the borehole for diffusion into the body of fixed fossil fuels at a predetermined pressure, (c) transmitting electrical energy down the borehole to heat the body of fixed fossil fuels and critical fluids to a second predetermined temperature, and (d) heating the critical fluids and the fixed fossil fuels with the electrical energy to the second predetermined temperature to initiate reaction of the reactants in the critical fluids with a fraction of the hydrocarbon fuel products in the body of fixed fossil fuels causing a portion of the remainder of the hydrocarbon fuel products to be released for extraction as a vapor, liquid or dissolved in the critical fluids. The method comprises the step of removing the hydrocarbon fuel products to a ground surface above the overburden. The method comprises the steps of pressure cycling in the borehole between 500 psi and 5000 psi and performing steps (b), (c) and (d) during each pressure cycling. The method comprises the step of separating the hydrocarbon fuel, critical fluids, gases and contaminants received from the product return line. The step of transmitting electrical energy down a borehole to heat the body of fixed fossil fuels includes the step of heating any one of the body of oil shale, tar sands, heavy petroleum from a spent well, coal, lignite or peat formation. The method comprises the step of monitoring the temperatures in an immediate region of the body of fixed fossil fuels to optimize producing the hydrocarbon fuel products, the temperature being sufficient to initiate oxidation reactions, such reactions providing additional heat required to efficiently release the hydrocarbon fuel products. The step of providing critical fluids with reactants or catalysts comprises the step of providing a mixture of carbon dioxide critical fluids such as carbon dioxide and an oxidant such as nitrous oxide or oxygen or a combination thereof. The step of providing critical fluids with reactants or catalysts down the borehole comprises the step of controlling the flow rate, pressure, and ratio of the critical fluids and reactants or catalysts into the borehole. The step of providing critical fluids down a borehole for diffusion into the body of fixed fossil fuels comprises the step of adding a modifier to the critical fluids, the modifier including one of alcohol, methanol, water or a hydrogen donor solvent. The step of heating the critical fluids and the fixed fossil fuels with the electrical energy initiating reaction of the critical fluids with the body of fixed fossil fuels comprises the step of raising the predetermined temperature to approximately 200 degrees Celsius. The method comprises the steps of providing a wellhead at the surface of the borehole for safely transferring the electrical energy and the critical fluids to the borehole and for receiving and connecting a product return line to means for separating gases, critical fluids, oil and contaminants. The step of transmitting electrical energy down a borehole to heat the body of fixed fossil fuels comprises the steps of generating electromagnetic energy with an RF generator, and providing a radiating structure in the borehole coupled to the RF generator to heat the body of fixed fossil fuels. The method further comprises the steps of performing steps (b), (c) and (d) for N cycles.
The objects are further accomplished by a method of producing hydrocarbon fuel products from a body of fixed fossil fuels beneath an overburden comprising the steps of (a) providing critical fluids with reactants or catalysts down the borehole for diffusion into the body of fixed fossil fuels at a predetermined pressure, (b) transmitting electrical energy down a borehole to heat the body of fixed fossil fuels and critical fluids to a predetermined temperature, and (c) heating the critical fluids and the fixed fossil fuels with the electrical energy to the predetermined temperature to initiate reaction of the reactants in the critical fluids with a fraction of the hydrocarbon fuel products in the body of fixed fossil fuels causing a portion of the remainder of the hydrocarbon fuel products to be released for extraction as a vapor, liquid or dissolved in the critical fluids. The method comprises the step of removing the hydrocarbon fuel products to a ground surface above the overburden. The method comprises the steps of pressure cycling in the borehole between 500 psi and 5000 psi and performing steps (a), (b) and (c) during each pressure cycle. The method comprises the step of separating the hydrocarbon fuel, critical fluids, gases and contaminants received from the product return line. The step of transmitting electrical energy down a borehole to heat the body of fixed fossil fuels includes the step of heating any one of the body of oil shale, tar sands, heavy petroleum from a spent well, coal, lignite or peat formation. The method comprises the step of monitoring the temperature in an immediate region of the body of fixed fossil fuels to optimize producing the hydrocarbon fuel products, the temperature being sufficient to initiate oxidation reactions, such reactions providing additional heat required to efficiently release the hydrocarbon fuel products. The step of providing critical fluids with reactants or catalysts comprises the step of providing a mixture of carbon dioxide critical fluids such as carbon dioxide and an oxidant such as nitrous oxide or oxygen or combinations thereof. The step of providing critical fluids with reactants or catalysts down the borehole comprises the step of controlling the flow rate, pressure, and ratio of the critical fluids and reactants or catalysts into the borehole. The step of providing critical fluids down a borehole for diffusion into the body of fixed fossil fuels comprises the step of adding a modifier to the critical fluids, the modifier including one of alcohol, methanol, water or a hydrogen donor solvent. The step of heating the critical fluids and the fixed fossil fuels with the electrical energy initiating reaction of the critical fluids with the body of fixed fossil fuels comprises the step of raising the predetermined temperature to approximately 200 degrees Celsius. The method comprises the steps of providing a wellhead at the surface of the borehole for safely transferring the electrical energy and the critical fluids to the borehole, and for receiving and connecting a product return line to means for separating gases, critical fluids, oil and contaminants. The step of transmitting electrical energy down a borehole to heat the body of fixed fossil fuels comprises the steps of generating electromagnetic energy with an RF generator, and providing a radiating structure in the borehole coupled to the RF generator to heat the body of fixed fossil fuels.
The objects are further accomplished by a method of producing hydrocarbon fuel products from a body of fixed fossil fuels beneath an overburden comprising the steps of (a) providing a carbon dioxide critical fluid down a borehole for diffusion into the body of fixed fossil fuels at a predetermined pressure, (b) transmitting electrical energy down the borehole to heat the body of fixed fossil fuels and the carbon dioxide critical fluid to a predetermined temperature, (c) pressure cycling in the borehole between 500 psi and 5000 psi, and (d) removing the hydrocarbon fuel products in the critical fluid with a product return line extending to a ground surface above the overburden. The method comprises the step of performing steps (a), (b), (c), and (d) during each predetermined pressure of the pressure cycling. The method comprises the step of separating the hydrocarbon fuel, critical fluids, gases and contaminants received from the product return line. The step of transmitting electrical energy down a borehole to heat the body of fixed fossil fuels and the critical fluids to a predetermined temperature comprises the step of setting the temperature to approximately 300 degrees Celsius. The step of transmitting electrical energy down a borehole to heat the body of fixed fossil fuels comprises the steps of generating electromagnetic energy with an RF generator, and providing a radiating structure in the borehole coupled to the RF generator to heat the body of fixed fossil fuels.
The objects are further accomplished by a method of producing hydrocarbon fuel products from an aging oil well having heavy oil comprising the steps of (a) transmitting electrical energy down a borehole to heat the heavy oil to a first predetermined temperature, (b) providing critical fluids with reactants or catalysts down the borehole for diffusion into the heavy oil at a predetermined pressure, (c) transmitting electrical energy down the borehole to heat the heavy oil and critical fluids to a second predetermined temperature, and (d) heating the critical fluids and the heavy oil with the electrical energy to the second predetermined temperature to initiate reaction of the reactants in the critical fluids with a portion of the hydrocarbon fuel products in the body of fixed fossil fuels causing the hydrocarbon fuel products to be released for extraction as a vapor, liquid or dissolved in the critical fluids. The method comprises the step of removing the hydrocarbon fuel products to a ground surface above the overburden. The method comprises the steps of pressure cycling the critical fluids in the oil well between 500 psi and 5000 psi and performing steps (b), (c) and (d) during each pressure cycle. The method comprises the step of separating the hydrocarbon fuel, critical fluids, gases and contaminants received from the product return line. The step of transmitting electrical energy down a borehole comprises the step of providing a radio frequency (RF) generator coupled to a transmission line for transferring electrical energy to an RF applicator positioned in the borehole.
The objects are further accomplished by a method of cleaning an industrial tank comprising the steps of (a) transmitting electrical energy into the tank to heat a contents of the tank to a first predetermined temperature, (b) providing critical fluids with reactants or catalysts into the tank for diffusion into the contents of the tank at a predetermined pressure, (c) transmitting electrical energy into the tank to heat the contents and critical fluids to a second predetermined temperature, and (d) heating the critical fluids and the contents of the tank with the electrical energy to the second predetermined temperature to initiate reaction of the reactants in the critical fluids with a portion of the contents of the tank causing hydrocarbons and contaminants to be released for extraction as a vapor, liquid or dissolved in the critical fluids. The method comprises the step of removing the hydrocarbons and contaminants from the tank. The method comprises the steps of pressure cycling in the tank between 500 psi and 5000 psi, and performing steps (b), (c) and (d) during each pressure cycling. The method comprises the step of separating the hydrocarbons, critical fluids, gases and contaminants removed from the tank.
Additional objects, features and advantages of the invention will become apparent to those skilled in the art upon consideration of the following detailed description of the preferred embodiments exemplifying the best mode of carrying out the invention as presently perceived.
The appended claims particularly point out and distinctly claim the subject matter of this invention. The various objects, advantages and novel features of this invention will be more fully apparent from a reading of the following detailed description in conjunction with the accompanying drawings in which like reference numerals refer to like parts, and in which:
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The method 19 comprises a step 21 of transmitting electrical energy to heat a body of fixed fossil fuels, such as oil shale 14, to a first predetermined temperature such as 150 degrees Celsius to begin the kerogen 98 pyrolysis process, fracturing and modifying of the shale sufficiently to allow the critical fluids to easily penetrate deep into the formation and to reduce the total energy input required in some instances.
Step 21 is a preheating step to increase the speed of the critical fluid diffusion and depth of the critical fluids penetration into the body of fixed fossil fuels. The electrical energy down a borehole is provided by an RF generator 44 which generates electromagnetic energy and known to one skilled in the art.
The next step 23 provides critical fluids (CF), such as carbon dioxide (CO2), with reactants, such as nitrous oxide (N2O) or oxygen (O2), and catalysts may be added such as nano-sized iron oxide (Fe2O3), silica aerogel, and nano-sized Alumina (Al2O3) aerogel, down the borehole 16 for diffusion into the body of fixed fossil fuel or oil shale 14. However, in addition to the oxidants and catalysts, other modifiers can be added to the critical fluids to enhance the extraction of kerogen oil and gas. Materials such as water or alcohols (e.g. methanol), can be added to modify the polarity and solvent characteristics of the critical fluid. Modifiers can also participate in reactions improving the product quality and quantity by the addition of hydrogen to kerogen (known as hydrogen donor solvents). Tetralin and methanol are examples of hydrogen donor solvents.
The introduction of critical fluids may be at various pressures, from 300 PSI to 5000 PSI. In the preferred embodiment of
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A critical fluid, such as carbon dioxide (CO2), is provided in a CO2 storage tank 70, and CO2 may also be provided from the gas/liquid separator 42 which separates gases and liquids obtained from the external product return line 40 provided by the system 10. A pump or compressor 72 moves the CO2 from the separator 42 to an in-line mixer 78. A nitrous oxide (N2O) storage tank 74 and an oxygen (O2) storage tank 76 are provided and their outputs are connected to the in-line mixer 78. Additional tanks 73 may be provided containing modifiers other reactants and other catalysts, such as nano-sized iron oxide (Fe2O3), silica aerogel or nano-sized Alumina (Al2O3). The mixture of the critical fluid, carbon dioxide (CO2), the nitrous oxide (N2O) and Oxygen (O2) are provided by the in-line mixer 78 into the wellhead 34, down the borehole 16 and into the body of fixed fossil fuels for enhanced extracting, for example, of kerogen oil and gas 98 from oil shale 14.
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The product return line 54 is located within the coax center conductor 52, and it is supported by the landing nipple 30 in the wellhead 34. A ceramic crossover pipe 36 or other non-conductive pressure capable pipe isolates an external product return line 40 from RF voltage in the wellhead 34. A flexible coupling hose 38 is used to make up tolerances in the product return line 40 and to reduce strain on the ceramic crossover pipe 36. A feed port 41 is provided at the top of the wellhead 34 in the external product return line 40 for a gas lift line.
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The coaxial transmission line 53 (
The region from the upper end of the upper stub or tubular member 110 to the lower end of lower stub or tubular member 108 is made an odd number of quarter wavelengths effective in oil shale in the operating frequency band of the device and forms an impedance matching section 104. More specifically, the distance from the adapter coupling 112 to the lower end of tubular member 108 is made approximately a quarter wavelength effective in air at the operating frequency of the system 10. The impedance matching section 104 of RF applicator 100 comprising lower stub 108 together with portions of the inner conductor 50 adjacent thereto act as an impedance matching transformer which improves the impedance match between coaxial transmission line 53 and the RF radiator 102.
The RF radiator 102 is formed by an enlarged section of a pipe or tubular member 88 threadably attached to the lower end of the lowest inner conductor 50 by an enlarging coupling adapter 86 and the lower end of enlarged tubular member 88 has a ceramic spacer 92 attached to the outer surface through to space member 88 from the borehole 16 surface (
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The predetermined pressure is formation dependant, taking into account variables such as depth of the borehole, richness of the shale deposit or concentration of contaminants, local geothermal conditions and the specific processing objectives. The objectives are a combination of technical factors such as the solubility of the shale oil and economic factors such as optimum amount of oil to recover or the amount of hydrocarbon fuels or contaminants to recover from a peat bog, remediation site, etc. They include variables that the operator may choose to optimize the process. An example includes a process optimized to recover a lower percentage of total recoverable fuel in a rapid fashion. Such a quick recovery of a low percentage of fuels would have shorter cycle times and fewer cycles than a process optimized to recover a high percentage of the fuel from a specific borehole area. Each site specific iteration of the process can use a different combination of temperature and pressure of the incoming critical fluid. In some instances, the critical fluid can be pressurized and preheated, for example, if the critical fluids are preheated to 200 degrees Celsius, they would typically be injected into the borehole at about 3000 psi. If the critical fluids are injected with no preheating, and remain at their typical storage temperature of −20 degrees Celsius, they could be injected at the storage pressure of 300 psi if that temperature/pressure combination meets favorably with the other variables at that site. Naturally, the actual temperature and pressure of the critical fluids at the bottom of the borehole 16 vary, being affected by several local conditions including depth, porosity of the site, and geothermal temperatures.
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Further, a plurality of auxiliary production or extraction wells comprising pipes 66 and well apparatus 64 shown in
This invention has been disclosed in terms of certain embodiment. It will be apparent that many modifications can be made to the disclosed methods and apparatus without departing from the invention. Therefore, it is the intent of the appended claims to cover all such variations and modification as come within the true spirit and scope of this invention.
This application is a continuation of application Ser. No. 11/314,857, filed on Dec. 20, 2005 (Attorney Docket No. 33848).
Number | Date | Country | |
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Parent | 11314857 | Dec 2005 | US |
Child | 12261807 | US |