Patent Application
20120267110
1. Field of the Invention
The present invention relates to the field of hydrocarbon recovery from subsurface formations. More specifically, the present invention relates to in situ recovery of hydrocarbon fluids from organic-rich rock formations, including, for example, oil shale formations, coal formations and tar sands formations.
2. Background of the Invention
Certain geological formations are known to contain an organic matter known as “kerogen.” Kerogen is a solid, carbonaceous material. When kerogen is imbedded in rock formations, the mixture is referred to as oil shale. This is true whether or not the mineral is, in fact, technically shale, that is, a rock formed from compacted clay.
Kerogen is subject to decomposing upon exposure to heat over a period of time. Upon heating, kerogen molecularly decomposes to produce oil, gas, and carbonaceous coke. Small amounts of water may also be generated. The oil, gas and water fluids are mobile within the rock matrix, while the carbonaceous coke remains essentially immobile.
Oil shale formations are found in various areas world-wide, including the United States. Oil shale formations tend to reside at relatively shallow depths. In the United States, oil shale is most notably found in Wyoming, Colorado, and Utah. These formations are often characterized by limited permeability. Some consider oil shale formations to be hydrocarbon deposits which have not yet experienced the years of heat and pressure thought to be required to create conventional oil and gas reserves.
The decomposition rate of kerogen to produce mobile hydrocarbons is temperature dependent. Temperatures generally in excess of 270° C. (518° F.) over the course of many months may be required for substantial conversion. At higher temperatures substantial conversion may occur within shorter times. When kerogen is heated, chemical reactions break the larger molecules forming the solid kerogen into smaller molecules of oil and gas. The thermal conversion process is referred to as pyrolysis or retorting.
Attempts have been made for many years to extract oil from oil shale formations. Near-surface oil shales have been mined and retorted at the surface for over a century. In 1862, James Young began processing Scottish oil shales. The industry lasted for about 100 years. Commercial oil shale retorting through surface mining has been conducted in other countries as well such as Australia, Brazil, China, Estonia, France, Russia, South Africa, Spain, and Sweden. However, the practice has been mostly discontinued in recent years because it proved to be uneconomical or because of environmental constraints on spent shale disposal. (See T. F. Yen, and G. V. Chilingarian, “Oil Shale,” Amsterdam, Elsevier, p. 292, the entire disclosure of which is incorporated herein by reference.) Further, surface retorting requires mining of the oil shale, which limits application to very shallow formations.
In the United States, the existence of oil shale deposits in northwestern Colorado has been known since the early 1900's. While research projects have been conducted in this area from time to time, no serious commercial development has been undertaken. Most research on oil shale production has been carried out in the latter half of the 1900's. The majority of this research was on shale oil geology, geochemistry, and retorting in surface facilities.
In 1947, U.S. Pat. No. 2,732,195 issued to Ljungstrom. That patent, entitled “Method of Treating Oil Shale and Recovery of Oil and Other Mineral Products Therefrom,” proposed the application of heat at high temperatures to the oil shale formation in situ to distill and produce hydrocarbons. The '195 Ljungstrom patent is incorporated herein by reference.
Ljungstrom coined the phrase “heat supply channels” to describe bore holes drilled into the formation. The bore holes received an electrical heat conductor which transferred heat to the surrounding oil shale. Thus, the heat supply channels served as heat injection wells. The electrical heating elements in the heat injection wells were placed within sand or cement or other heat-conductive material to permit the heat injection well to transmit heat into the surrounding oil shale while preventing the inflow of fluid. According to Ljungstrom, the “aggregate” was heated to between 500° and 1,000° C. in some applications.
Along with the heat injection wells, fluid producing wells were also completed in near proximity to the heat injection wells. As kerogen was pyrolyzed upon heat conduction into the rock matrix, the resulting oil and gas would be recovered through the adjacent production wells.
Ljungstrom applied his approach of thermal conduction from heated wellbores through the Swedish Shale Oil Company. A full scale plant was developed that operated from 1944 into the 1950's. (See G. Salamonsson, “The Ljungstrom In Situ Method for Shale-Oil Recovery,” 2nd Oil Shale and Cannel Coal Conference, v. 2, Glasgow, Scotland, Institute of Petroleum, London, p. 260-280 (1951), the entire disclosure of which is incorporated herein by reference.)
Additional in situ methods have been proposed. These methods generally involve the injection of heat and/or solvent into a subsurface oil shale. Heat may be in the form of heated methane (see U.S. Pat. No. 3,241,611 to J. L. Dougan), flue gas, or superheated steam (see U.S. Pat. No. 3,400,762 to D. W. Peacock). Heat may also be in the form of electric resistive heating, dielectric heating, radio frequency (RF) heating (U.S. Pat. No. 4,140,180, assigned to the ITT Research Institute in Chicago, Ill.) or oxidant injection to support in situ combustion. In some instances, artificial permeability has been created in the matrix to aid the movement of pyrolyzed fluids. Permeability generation methods include mining, rubblization, hydraulic fracturing (see U.S. Pat. No. 3,468,376 to M. L. Slusser and U.S. Pat. No. 3,513,914 to J. V. Vogel), explosive fracturing (see U.S. Pat. No. 1,422,204 to W. W. Hoover, et al.), heat fracturing (see U.S. Pat. No. 3,284,281 to R. W. Thomas), and steam fracturing (see U.S. Pat. No. 2,952,450 to H. Purre).
In 1989, U.S. Pat. No. 4,886,118 issued to Shell Oil Company, the entire disclosure of which is incorporated herein by reference. That patent, entitled “Conductively Heating a Subterranean Oil Shale to Create Permeability and Subsequently Produce Oil,” declared that “[c]ontrary to the implications of . . . prior teachings and beliefs . . . the presently described conductive heating process is economically feasible for use even in a substantially impermeable subterranean oil shale.” (col. 6, ln. 50-54). Despite this declaration, it is noted that few, if any, commercial in situ shale oil operations have occurred other than Ljungstrom's application. The '118 patent proposed controlling the rate of heat conduction within the rock surrounding each heat injection well to provide a uniform heat front.
Additional history behind oil shale retorting and shale oil recovery can be found in co-owned patent U.S. Pat. No. 7,331,385 entitled “Methods of Treating a Subterranean Formation to Convert Organic Matter into Producible Hydrocarbons,” and in patent U.S. Patent No. 7,441,603 entitled “Hydrocarbon Recovery from Impermeable Oil Shales.” The Background and technical disclosures of these two patent publications are incorporated herein by reference.
A need exists for improved processes for the production of shale oil. In addition, a need exists for improved methods of producing shale oil with improved properties.
In one embodiment, the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C6 to benzene weight ratio less than 35.0, a n-C7 to toluene weight ratio less than 7.0, a n-C8 to ethylbenzene weight ratio less than 16.0, a n-C8 to ortho-xylene weight ratio less than 7.0, a n-C8 to meta-xylene weight ratio less than 1.9, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 8.2, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.4, a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.7, a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, a n-C10 to tetralin weight ratio less than 25.0, a n-C12 to 2-methylnaphthalene weight ratio less than 4.9, and a n-C12 to 1-methylnaphthalene weight ratio less than 6.9.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C6 to benzene weight ratio less than 24.0, a n-C7 to toluene weight ratio less than 6.6, a n-C8 to ethylbenzene weight ratio less than 15.0, a n-C8 to ortho-xylene weight ratio less than 6.6, a n-C8 to meta-xylene weight ratio less than 1.8, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 7.9, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.3, a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.6, a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 13.1, a n-C10 to tetralin weight ratio less than 23.7, a n-C12 to 2-methylnaphthalene weight ratio less than 5.0, and a n-C12 to 1-methylnaphthalene weight ratio less than 6.8.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C6 to benzene weight ratio less than 13.4, a n-C7 to toluene weight ratio less than 5.1, a n-C8 to ethylbenzene weight ratio less than 12.3, a n-C8 to ortho-xylene weight ratio less than 5.3, a n-C8 to meta-xylene weight ratio less than 1.5, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 5.9, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 3.8, a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.2, a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 12.2, a n-C10 to tetralin weight ratio less than 23.4, a n-C12 to 2-methylnaphthalene weight ratio less than 4.0, and a n-C12 to 1-methylnaphthalene weight ratio less than 6.1.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluids from an organic-rich rock formation. The method may include heating in situ a section of an organic-rich rock formation containing formation hydrocarbons, where the section of an organic-rich rock formation has a lithostatic stress greater than 200 psi, pyrolyzing at least a portion of the formation hydrocarbons thereby forming a hydrocarbon fluid, and producing the hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid may include a condensable hydrocarbon portion, where the condensable hydrocarbon portion has one or more of a n-C6 to benzene weight ratio less than 35.0, a n-C7 to toluene weight ratio less than 7.0, a n-C8 to ethylbenzene weight ratio less than 16.0, a n-C8 to ortho-xylene weight ratio less than 7.0, a n-C8 to meta-xylene weight ratio less than 1.9, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 8.2, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.4, a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.7, a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, a n-C10 to tetralin weight ratio less than 25.0, a n-C12 to 2-methylnaphthalene weight ratio less than 4.9, and a n-C12 to 1-methylnaphthalene weight ratio less than 6.9.
In one embodiment, the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C9 to IP-9 weight ratio greater than 2.4, a n-C10 to IP-10 weight ratio greater than 1.4, a n-C11 to IP-11 weight ratio greater than 1.0, a n-C13 to IP-13 weight ratio greater than 1.1, a n-C14 to IP-14 weight ratio greater than 1.1, a n-C15 to IP-15 weight ratio greater than 1.0, a n-C16 to IP-16 weight ratio greater than 0.8, a n-C18 to IP-18 weight ratio greater than 1.0, and a n-C19 to pristane weight ratio greater than 1.6.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C9 to IP-9 weight ratio greater than 2.5, a n-C10 to IP-10 weight ratio greater than 1.5, a n-C11 to IP-11 weight ratio greater than 1.1, a n-C13 to IP-13 weight ratio greater than 1.2, a n-C14 to IP-14 weight ratio greater than 1.2, a n-C15 to IP-15 weight ratio greater than 1.1, a n-C16 to IP-16 weight ratio greater than 0.9, a n-C18 to IP-18 weight ratio greater than 1.1, and a n-C19 to pristane weight ratio greater than 1.8.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C9 to IP-9 weight ratio greater than 2.6, a n-C10 to IP-10 weight ratio greater than 1.6, a n-C11 to IP-11 weight ratio greater than 1.2, a n-C13 to IP-13 weight ratio greater than 1.3, a n-C14 to IP-14 weight ratio greater than 1.4, a n-C15 to IP-15 weight ratio greater than 1.4, a n-C16 to IP-16 weight ratio greater than 1.2, a n-C18 to IP-18 weight ratio greater than 1.5, and a n-C19 to pristane weight ratio greater than 2.4.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluids from an organic-rich rock formation. The method may include heating in situ a section of an organic-rich rock formation containing formation hydrocarbons, where the section of an organic-rich rock formation has a lithostatic stress greater than 200 psi, pyrolyzing at least a portion of the formation hydrocarbons thereby forming a hydrocarbon fluid, and producing the hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid may include a condensable hydrocarbon portion, where the condensable hydrocarbon portion has one or more of a n-C9 to IP-9 weight ratio greater than 2.4, a n-C10 to IP-10 weight ratio greater than 1.4, a n-C11 to IP-11 weight ratio greater than 1.0, a n-C13 to IP-13 weight ratio greater than 1.1, a n-C14 to IP-14 weight ratio greater than 1.1, a n-C15 to IP-15 weight ratio greater than 1.0, a n-C16 to IP-16 weight ratio greater than 0.8, a n-C18 to IP-18 weight ratio greater than 1.0, and a n-C19 to pristane weight ratio greater than 1.6.
In one embodiment, the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 13.1, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 14.9, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 7.0, a n-C7 to methyl cyclohexane weight ratio less than 5.2, a n-C7 to ethyl cyclopentane weight ratio less than 11.3, a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 16.0, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 17.5, and a n-C8 to ethyl cyclohexane weight ratio less than 12.3.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 12.7, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 14.7, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 6.6, a n-C7 to methyl cyclohexane weight ratio less than 5.0, a n-C7 to ethyl cyclopentane weight ratio less than 10.9, a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 15.4, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 16.5, and a n-C8 to ethyl cyclohexane weight ratio less than 12.0.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation where the hydrocarbon fluid comprises a condensable hydrocarbon portion and the condensable hydrocarbon portion has one or more of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 10.3, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 11.6, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 5.9, a n-C7 to methyl cyclohexane weight ratio less than 4.1, a n-C7 to ethyl cyclopentane weight ratio less than 9.5, a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 13.9, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 12.3, and a n-C8 to ethyl cyclohexane weight ratio less than 10.3.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluids from an organic-rich rock formation. The method may include heating in situ a section of an organic-rich rock formation containing formation hydrocarbons, where the section of an organic-rich rock formation has a lithostatic stress greater than 200 psi, pyrolyzing at least a portion of the formation hydrocarbons thereby forming a hydrocarbon fluid, and producing the hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid may include a condensable hydrocarbon portion, where the condensable hydrocarbon portion has one or more of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 13.1, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 14.9, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 7.0, a n-C7 to methyl cyclohexane weight ratio less than 5.2, a n-C7 to ethyl cyclopentane weight ratio less than 11.3, a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 16.0, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 17.5, and a n-C8 to ethyl cyclohexane weight ratio less than 12.3.
In one embodiment, the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation. The hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a total C9 to total C20 weight ratio between 2.5 and 6.0, a total C10 to total C20 weight ratio between 2.8 and 7.3, a total C11 to total C20 weight ratio between 2.6 and 6.5, a total C12 to total C20 weight ratio between 2.6 and 6.4 and a total C13 to total C20 weight ratio between 3.2 and 8.0.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation. The hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a total C10 to total C25 weight ratio between 7.1 and 24.5, a total C11 to total C25 weight ratio between 6.5 and 22.0, a total C12 to total C25 weight ratio between 6.5 and 22.0, and a total C13 to total C25 weight ratio between 8.0 and 27.0.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation. The hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a total C10 to total C29 weight ratio between 15.0 and 60.0, a total C11 to total C29 weight ratio between 13.0 and 54.0, a total C12 to total C29 weight ratio between 12.5 and 53.0, and a total C13 to total C29 weight ratio between 16.0 and 65.0.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluid from an organic-rich rock formation. The method includes heating in situ a section of an organic-rich rock formation having a lithostatic stress greater than 200 psi. The method further includes producing a hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a total C7 to total C20 weight ratio greater than 0.8, a total C8 to total C20 weight ratio greater than 1.7, a total C9 to total C20 weight ratio greater than 2.5, a total C10 to total C20 weight ratio greater than 2.8, a total C11 to total C20 weight ratio greater than 2.3, a total C12 to total C20 weight ratio greater than 2.3, a total C13 to total C20 weight ratio greater than 2.9, a total C14 to total C20 weight ratio greater than 2.2, a total C15 to total C20 weight ratio greater than 2.2, and a total C16 to total C20 weight ratio greater than 1.6.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluid from an organic-rich rock formation. The method includes heating in situ a section of an organic-rich rock formation having a lithostatic stress greater than 200 psi. The method further includes producing a hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a total C7 to total C25 weight ratio greater than 2.0, a total C8 to total C25 weight ratio greater than 4.5, a total C9 to total C25 weight ratio greater than 6.5, a total C10 to total C25 weight ratio greater than 7.5, a total C11 to total C25 weight ratio greater than 6.5, a total C12 to total C25 weight ratio greater than 6.5, a total C13 to total C25 weight ratio greater than 8.0, a total C14 to total C25 weight ratio greater than 6.0, a total C15 to total C25 weight ratio greater than 6.0, a total C16 to total C25 weight ratio greater than 4.5, a total C17 to total C25 weight ratio greater than 4.8, and a total C18 to total C25 weight ratio greater than 4.5.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluid from an organic-rich rock formation. The method includes heating in situ a section of an organic-rich rock formation having a lithostatic stress greater than 200 psi. The method further includes producing a hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a total C7 to total C29 weight ratio greater than 3.5, a total C8 to total C29 weight ratio greater than 9.0, a total C9 to total C29 weight ratio greater than 12.0, a total C10 to total C29 weight ratio greater than 15.0, a total C11 to total C29 weight ratio greater than 13.0, a total C12 to total C29 weight ratio greater than 12.5, a total C13 to total C29 weight ratio greater than 16.0, a total C14 to total C29 weight ratio greater than 12.0, a total C15 to total C29 weight ratio greater than 12.0, a total C16 to total C29 weight ratio greater than 9.0, a total C17 to total C29 weight ratio greater than 10.0, a total C18 to total C29 weight ratio greater than 8.8, a total C19 to total C29 weight ratio greater than 7.0, a total C20 to total C29 weight ratio greater than 6.0, a total C21 to total C29 weight ratio greater than 5.5, and a total C22 to total C29 weight ratio greater than 4.2.
In one embodiment, the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation. The hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C7 to normal-C20 weight ratio greater than 0.9, a normal-C8 to normal-C20 weight ratio greater than 2.0, a normal-C9 to normal-C20 weight ratio greater than 1.9, a normal-C10 to normal-C20 weight ratio greater than 2.2, a normal-C11 to normal-C20 weight ratio greater than 1.9, a normal-C12 to normal-C20 weight ratio greater than 1.9, a normal-C13 to normal-C20 weight ratio greater than 2.3, a normal-C14 to normal-C20 weight ratio greater than 1.8, a normal-C15 to normal-C20 weight ratio greater than 1.8, and normal-C16 to normal-C20 weight ratio greater than 1.3.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation. The hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C7 to normal-C25 weight ratio greater than 1.9, a normal-C8 to normal-C25 weight ratio greater than 3.9, a normal-C9 to normal-C25 weight ratio greater than 3.7, a normal-C10 to normal-C25 weight ratio greater than 4.4, a normal-C11 to normal-C25 weight ratio greater than 3.8, a normal-C12 to normal-C25 weight ratio greater than 3.7, a normal-C13 to normal-C25 weight ratio greater than 4.7, a normal-C14 to normal-C25 weight ratio greater than 3.7, a normal-C15 to normal-C25 weight ratio greater than 3.7, a normal-C16 to normal-C25 weight ratio greater than 2.5, a normal-C17 to normal-C25 weight ratio greater than 3.0, and a normal-C18 to normal-C25 weight ratio greater than 3.4.
Another embodiment of the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation. The hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C7 to normal-C29 weight ratio greater than 18.0, a normal-C8 to normal-C29 weight ratio greater than 16.0, a normal-C9 to normal-C29 weight ratio greater than 14.0, a normal-C10 to normal-C29 weight ratio greater than 14.0, a normal-C11 to normal-C29 weight ratio greater than 13.0, a normal-C12 to normal-C29 weight ratio greater than 11.0, a normal-C13 to normal-C29 weight ratio greater than 10.0, a normal-C14 to normal-C29 weight ratio greater than 9.0, a normal-C15 to normal-C29 weight ratio greater than 8.0, a normal-C16 to normal-C29 weight ratio greater than 8.0, a normal-C17 to normal-C29 weight ratio greater than 6.0, a normal-C18 to normal-C29 weight ratio greater than 6.0, a normal-C19 to normal-C29 weight ratio greater than 5.0, a normal-C20 to normal-C29 weight ratio greater than 4.0, a normal-C21 to normal-C29 weight ratio greater than 3.6, and a normal-C22 to normal-C29 weight ratio greater than 2.8.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluid from an organic-rich rock formation. The method includes heating in situ a section of an organic-rich rock formation having a lithostatic stress greater than 200 psi. The method further includes producing a hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C10 to normal-C20 weight ratio greater than 2.2, a normal-C11 to normal-C20 weight ratio greater than 1.9, a normal-C12 to normal-C20 weight ratio greater than 1.9, a normal-C13 to normal-C20 weight ratio greater than 2.3, a normal-C14 to normal-C20 weight ratio greater than 1.8, a normal-C15 to normal-C20 weight ratio greater than 1.8, and normal-C16 to normal-C20 weight ratio greater than 1.3.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluid from an organic-rich rock formation. The method includes heating in situ a section of an organic-rich rock formation having a lithostatic stress greater than 200 psi. The method further includes producing a hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C10 to normal-C25 weight ratio greater than 4.4, a normal-C11 to normal-C25 weight ratio greater than 3.8, a normal-C12 to normal-C25 weight ratio greater than 3.7, a normal-C13 to normal-C25 weight ratio greater than 4.7, a normal-C14 to normal-C25 weight ratio greater than 3.7, a normal-C15 to normal-C25 weight ratio greater than 3.7, a normal-C16 to normal-C25 weight ratio greater than 2.5, a normal-C17 to normal-C25 weight ratio greater than 3.0, and a normal-C18 to normal-C25 weight ratio greater than 3.4.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluid from an organic-rich rock formation. The method includes heating in situ a section of an organic-rich rock formation having a lithostatic stress greater than 200 psi. The method further includes producing a hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C7 to normal-C29 weight ratio greater than 18.0, a normal-C8 to normal-C29 weight ratio greater than 16.0, a normal-C9 to normal-C29 weight ratio greater than 14.0, a normal-C10 to normal-C29 weight ratio greater than 14.0, a normal-C11 to normal-C29 weight ratio greater than 13.0, a normal-C12 to normal-C29 weight ratio greater than 11.0, a normal-C13 to normal-C29 weight ratio greater than 10.0, a normal-C14 to normal-C29 weight ratio greater than 9.0, a normal-C15 to normal-C29 weight ratio greater than 8.0, a normal-C16 to normal-C29 weight ratio greater than 8.0, a normal-C17 to normal-C29 weight ratio greater than 6.0, a normal-C18 to normal-C29 weight ratio greater than 6.0, a normal-C19 to normal-C29 weight ratio greater than 5.0, a normal-C20 to normal-C29 weight ratio greater than 4.0, a normal-C21 to normal-C29 weight ratio greater than 3.6, and a normal-C22 to normal-C29 weight ratio greater than 2.8.
In one embodiment, the invention includes a hydrocarbon fluid produced through in situ pyrolysis of oil shale within an oil shale formation. The hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C10 to total C10 weight ratio less than 0.31, a normal-C11 to total C11 weight ratio less than 0.32, a normal-C12 to total C12 weight ratio less than 0.29, a normal-C13 to total C13 weight ratio less than 0.28, a normal-C14 to total C14 weight ratio less than 0.31, a normal-C15 to total C15 weight ratio less than 0.27, a normal-C16 to total C16 weight ratio less than 0.31, a normal-C17 to total C17 weight ratio less than 0.31, a normal-C18 to total C18 weight ratio less than 0.37, normal-C19 to total C19 weight ratio less than 0.37, a normal-C20 to total C20 weight ratio less than 0.37, a normal-C21 to total C21 weight ratio less than 0.37, a normal-C22 to total C22 weight ratio less than 0.38, normal-C23 to total C23 weight ratio less than 0.43, a normal-C24 to total C24 weight ratio less than 0.48, and a normal-C25 to total C25 weight ratio less than 0.53.
In one embodiment, the invention includes an in situ method of producing hydrocarbon fluid from an organic-rich rock formation. The method includes heating in situ a section of an organic-rich rock formation having a lithostatic stress greater than 200 psi. The method further includes producing a hydrocarbon fluid from the organic-rich rock formation. The produced hydrocarbon fluid including a condensable hydrocarbon portion. The condensable hydrocarbon portion having one or more of a normal-C10 to total C10 weight ratio less than 0.31, a normal-C11 to total C11 weight ratio less than 0.32, a normal-C12 to total C12 weight ratio less than 0.29, a normal-C13 to total C13 weight ratio less than 0.28, a normal-C14 to total C14 weight ratio less than 0.31, a normal-C15 to total C15 weight ratio less than 0.27, a normal-C16 to total C16 weight ratio less than 0.31, a normal-C17 to total C17 weight ratio less than 0.31, a normal-C18 to total C18 weight ratio less than 0.37, normal-C19 to total C19 weight ratio less than 0.37, a normal-C20 to total C20 weight ratio less than 0.37, a normal-C21 to total C21 weight ratio less than 0.37, a normal-C22 to total C22 weight ratio less than 0.38, normal-C23 to total C23 weight ratio less than 0.43, a normal-C24 to total C24 weight ratio less than 0.48, and a normal-C25 to total C25 weight ratio less than 0.53.
So that the manner in which the features of the present invention can be better understood, certain drawings, graphs and flow charts are appended hereto. It is to be noted, however, that the drawings illustrate only selected embodiments of the inventions and are therefore not to be considered limiting of scope, for the inventions may admit to other equally effective embodiments and applications.
As used herein, the term “hydrocarbon(s)” refers to organic material with molecular structures containing carbon bonded to hydrogen. Hydrocarbons may also include other elements, such as, but not limited to, halogens, metallic elements, nitrogen, oxygen, and/or sulfur.
As used herein, the term “hydrocarbon fluids” refers to a hydrocarbon or mixtures of hydrocarbons that are gases or liquids. For example, hydrocarbon fluids may include a hydrocarbon or mixtures of hydrocarbons that are gases or liquids at formation conditions, at processing conditions or at ambient conditions (15° C. and 1 atm pressure). Hydrocarbon fluids may include, for example, oil, natural gas, coal bed methane, shale oil, pyrolysis oil, pyrolysis gas, a pyrolysis product of coal, and other hydrocarbons that are in a gaseous or liquid state.
As used herein, the terms “produced fluids” and “production fluids” refer to liquids and/or gases removed from a subsurface formation, including, for example, an organic-rich rock formation. Produced fluids may include both hydrocarbon fluids and non-hydrocarbon fluids. Production fluids may include, but are not limited to, pyrolyzed shale oil, synthesis gas, a pyrolysis product of coal, carbon dioxide, hydrogen sulfide and water (including steam). Produced fluids may include both hydrocarbon fluids and non-hydrocarbon fluids.
As used herein, the term “condensable hydrocarbons” means those hydrocarbons that condense at 25° C. and one atmosphere absolute pressure. Condensable hydrocarbons may include a mixture of hydrocarbons having carbon numbers greater than 4.
As used herein, the term “non-condensable hydrocarbons” means those hydrocarbons that do not condense at 25° C. and one atmosphere absolute pressure. Non-condensable hydrocarbons may include hydrocarbons having carbon numbers less than 5.
As used herein, the term “heavy hydrocarbons” refers to hydrocarbon fluids that are highly viscous at ambient conditions (15° C. and 1 atm pressure). Heavy hydrocarbons may include highly viscous hydrocarbon fluids such as heavy oil, tar, and/or asphalt. Heavy hydrocarbons may include carbon and hydrogen, as well as smaller concentrations of sulfur, oxygen, and nitrogen. Additional elements may also be present in heavy hydrocarbons in trace amounts. Heavy hydrocarbons may be classified by API gravity. Heavy hydrocarbons generally have an API gravity below about 20 degrees. Heavy oil, for example, generally has an API gravity of about 10-20 degrees, whereas tar generally has an API gravity below about 10 degrees. The viscosity of heavy hydrocarbons is generally greater than about 100 centipoise at 15° C.
As used herein, the term “solid hydrocarbons” refers to any hydrocarbon material that is found naturally in substantially solid form at formation conditions. Non-limiting examples include kerogen, coal, shungites, asphaltites, and natural mineral waxes.
As used herein, the term “formation hydrocarbons” refers to both heavy hydrocarbons and solid hydrocarbons that are contained in an organic-rich rock formation. Formation hydrocarbons may be, but are not limited to, kerogen, oil shale, coal, bitumen, tar, natural mineral waxes, and asphaltites.
As used herein, the term “tar” refers to a viscous hydrocarbon that generally has a viscosity greater than about 10,000 centipoise at 15° C. The specific gravity of tar generally is greater than 1.000. Tar may have an API gravity less than 10 degrees.
As used herein, the term “kerogen” refers to a solid, insoluble hydrocarbon that principally contains carbon, hydrogen, nitrogen, oxygen, and sulfur. Oil shale contains kerogen.
As used herein, the term “bitumen” refers to a non-crystalline solid or viscous hydrocarbon material that is substantially soluble in carbon disulfide.
As used herein, the term “oil” refers to a hydrocarbon fluid containing a mixture of condensable hydrocarbons.
As used herein, the term “subsurface” refers to geologic strata occurring below the earth's surface.
As used herein, the term “hydrocarbon-rich formation” refers to any formation that contains more than trace amounts of hydrocarbons. For example, a hydrocarbon-rich formation may include portions that contain hydrocarbons at a level of greater than 5 volume percent. The hydrocarbons located in a hydrocarbon-rich formation may include, for example, oil, natural gas, heavy hydrocarbons, and solid hydrocarbons.
As used herein, the term “organic-rich rock” refers to any rock matrix holding solid hydrocarbons and/or heavy hydrocarbons. Rock matrices may include, but are not limited to, sedimentary rocks, shales, siltstones, sands, silicilytes, carbonates, and diatomites.
As used herein, the term “formation” refers to any finite subsurface region. The formation may contain one or more hydrocarbon-containing layers, one or more non-hydrocarbon containing layers, an overburden, and/or an underburden of any subsurface geologic formation. An “overburden” and/or an “underburden” is geological material above or below the formation of interest. An overburden or underburden may include one or more different types of substantially impermeable materials. For example, overburden and/or underburden may include rock, shale, mudstone, or wet/tight carbonate (i.e., an impermeable carbonate without hydrocarbons). An overburden and/or an underburden may include a hydrocarbon-containing layer that is relatively impermeable. In some cases, the overburden and/or underburden may be permeable.
As used herein, the term “organic-rich rock formation” refers to any formation containing organic-rich rock. Organic-rich rock formations include, for example, oil shale formations, coal formations, and tar sands formations.
As used herein, the term “pyrolysis” refers to the breaking of chemical bonds through the application of heat. For example, pyrolysis may include transforming a compound into one or more other substances by heat alone or by heat in combination with an oxidant. Pyrolysis may include modifying the nature of the compound by addition of hydrogen atoms which may be obtained from molecular hydrogen, water, carbon dioxide, or carbon monoxide. Heat may be transferred to a section of the formation to cause pyrolysis.
As used herein, the term “water-soluble minerals” refers to minerals that are soluble in water. Water-soluble minerals include, for example, nahcolite (sodium bicarbonate), soda ash (sodium carbonate), dawsonite (NaAl(CO3)(OH)2), or combinations thereof. Substantial solubility may require heated water and/or a non-neutral pH solution.
As used herein, the term “formation water-soluble minerals” refers to water-soluble minerals that are found naturally in a formation.
As used herein, the term “migratory contaminant species” refers to species that are both soluble or moveable in water or an aqueous fluid, and are considered to be potentially harmful or of concern to human health or the environment. Migratory contaminant species may include inorganic and organic contaminants. Organic contaminants may include saturated hydrocarbons, aromatic hydrocarbons, and oxygenated hydrocarbons. Inorganic contaminants may include metal contaminants, and ionic contaminants of various types that may significantly alter pH or the formation fluid chemistry. Aromatic hydrocarbons may include, for example, benzene, toluene, xylene, ethylbenzene, and tri-methylbenzene, and various types of polyaromatic hydrocarbons such as anthracenes, naphthalenes, chrysenes and pyrenes. Oxygenated hydrocarbons may include, for example, alcohols, ketones, phenols, and organic acids such as carboxylic acid. Metal contaminants may include, for example, arsenic, boron, chromium, cobalt, molybdenum, mercury, selenium, lead, vanadium, nickel or zinc. Ionic contaminants include, for example, sulfides, sulfates, chlorides, fluorides, ammonia, nitrates, calcium, iron, magnesium, potassium, lithium, boron, and strontium.
As used herein, the term “cracking” refers to a process involving decomposition and molecular recombination of organic compounds to produce a greater number of molecules than were initially present. In cracking, a series of reactions take place accompanied by a transfer of hydrogen atoms between molecules. For example, naphtha may undergo a thermal cracking reaction to form ethene and H2 among other molecules.
As used herein, the term “sequestration” refers to the storing of a fluid that is a by-product of a process rather than discharging the fluid to the atmosphere or open environment.
As used herein, the term “subsidence” refers to a downward movement of a surface relative to an initial elevation of the surface.
As used herein, the term “thickness” of a layer refers to the distance between the upper and lower boundaries of a cross section of a layer, wherein the distance is measured normal to the average tilt of the cross section.
As used herein, the term “thermal fracture” refers to fractures created in a formation caused directly or indirectly by expansion or contraction of a portion of the formation and/or fluids within the formation, which in turn is caused by increasing/decreasing the temperature of the formation and/or fluids within the formation, and/or by increasing/decreasing a pressure of fluids within the formation due to heating. Thermal fractures may propagate into or form in neighboring regions significantly cooler than the heated zone.
As used herein, the term “hydraulic fracture” refers to a fracture at least partially propagated into a formation, wherein the fracture is created through injection of pressurized fluids into the formation. The fracture may be artificially held open by injection of a proppant material. Hydraulic fractures may be substantially horizontal in orientation, substantially vertical in orientation, or oriented along any other plane.
As used herein, the term “wellbore” refers to a hole in the subsurface made by drilling or insertion of a conduit into the subsurface. A wellbore may have a substantially circular cross section, or other cross-sectional shapes (e.g., circles, ovals, squares, rectangles, triangles, slits, or other regular or irregular shapes). As used herein, the term “well”, when referring to an opening in the formation, may be used interchangeably with the term “wellbore.”
The inventions are described herein in connection with certain specific embodiments. However, to the extent that the following detailed description is specific to a particular embodiment or a particular use, such is intended to be illustrative only and is not to be construed as limiting the scope of the invention.
As discussed herein, some embodiments of the invention include or have application related to an in situ method of recovering natural resources. The natural resources may be recovered from an organic-rich rock formation, including, for example, an oil shale formation. The organic-rich rock formation may include formation hydrocarbons, including, for example, kerogen, coal, and heavy hydrocarbons. In some embodiments of the invention the natural resources may include hydrocarbon fluids, including, for example, products of the pyrolysis of formation hydrocarbons such as shale oil. In some embodiments of the invention the natural resources may also include water-soluble minerals, including, for example, nahcolite (sodium bicarbonate, or 2NaHCO3), soda ash (sodium carbonate, or Na2CO3) and dawsonite (NaAl(CO3)(OH)2).
In order to access formation 16 and recover natural resources therefrom, a plurality of wellbores is formed. Wellbores are shown at 14 in
In the view of
The wellbores 14 will be selected for certain functions and may be designated as heat injection wells, water injection wells, oil production wells and/or water-soluble mineral solution production wells. In one aspect, the wellbores 14 are dimensioned to serve two, three, or all four of these purposes. Suitable tools and equipment may be sequentially run into and removed from the wellbores 14 to serve the various purposes.
A fluid processing facility 17 is also shown schematically. The fluid processing facility 17 is equipped to receive fluids produced from the organic-rich rock formation 16 through one or more pipelines or flow lines 18. The fluid processing facility 17 may include equipment suitable for receiving and separating oil, gas, and water produced from the heated formation. The fluid processing facility 17 may further include equipment for separating out dissolved water-soluble minerals and/or migratory contaminant species, including, for example, dissolved organic contaminants, metal contaminants, or ionic contaminants in the produced water recovered from the organic-rich rock formation 16. The contaminants may include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and tri-methylbenzene. The contaminants may also include polyaromatic hydrocarbons such as anthracene, naphthalene, chrysene and pyrene. Metal contaminants may include species containing arsenic, boron, chromium, mercury, selenium, lead, vanadium, nickel, cobalt, molybdenum, or zinc. Ionic contaminant species may include, for example, sulfates, chlorides, fluorides, lithium, potassium, aluminum, ammonia, and nitrates.
In order to recover oil, gas, and sodium (or other) water-soluble minerals, a series of steps may be undertaken.
First, the oil shale (or other organic-rich rock) formation 16 is identified within the development area 10. This step is shown in box 110. Optionally, the oil shale formation may contain nahcolite or other sodium minerals. The targeted development area within the oil shale formation may be identified by measuring or modeling the depth, thickness and organic richness of the oil shale as well as evaluating the position of the organic-rich rock formation relative to other rock types, structural features (e.g. faults, anticlines or synclines), or hydrogeological units (i.e. aquifers). This is accomplished by creating and interpreting maps and/or models of depth, thickness, organic richness and other data from available tests and sources. This may involve performing geological surface surveys, studying outcrops, performing seismic surveys, and/or drilling boreholes to obtain core samples from subsurface rock. Rock samples may be analyzed to assess kerogen content and hydrocarbon fluid generating capability.
The kerogen content of the organic-rich rock formation may be ascertained from outcrop or core samples using a variety of data. Such data may include organic carbon content, hydrogen index, and modified Fischer assay analyses. Subsurface permeability may also be assessed via rock samples, outcrops, or studies of ground water flow. Furthermore the connectivity of the development area to ground water sources may be assessed.
Next, a plurality of wellbores 14 is formed across the targeted development area 10. This step is shown schematically in box 115. The purposes of the wellbores 14 are set forth above and need not be repeated. However, it is noted that for purposes of the wellbore formation step of box 115, only a portion of the wells need be completed initially. For instance, at the beginning of the project heat injection wells are needed, while a majority of the hydrocarbon production wells are not yet needed. Production wells may be brought in once conversion begins, such as after 4 to 12 months of heating.
It is understood that petroleum engineers will develop a strategy for the best depth and arrangement for the wellbores 14, depending upon anticipated reservoir characteristics, economic constraints, and work scheduling constraints. In addition, engineering staff will determine what wellbores 14 shall be used for initial formation 16 heating. This selection step is represented by box 120.
Concerning heat injection wells, there are various methods for applying heat to the organic-rich rock formation 16. The present methods are not limited to the heating technique employed unless specifically so stated in the claims. The heating step is represented generally by box 130. Preferably, for in situ processes the heating of a production zone takes place over a period of months, or even four or more years.
The formation 16 is heated to a temperature sufficient to pyrolyze at least a portion of the oil shale in order to convert the kerogen to hydrocarbon fluids. The bulk of the target zone of the formation may be heated to between 270° C. to 800° C. Alternatively, the targeted volume of the organic-rich formation is heated to at least 350° C. to create production fluids. The conversion step is represented in
Conversion of the oil shale will create permeability in the oil shale section in rocks that were originally impermeable. Preferably, the heating and conversion processes of boxes 130 and 135, occur over a lengthy period of time. In one aspect, the heating period is from three months to four or more years. Also as an optional part of box 135, the formation 16 may be heated to a temperature sufficient to convert at least a portion of nahcolite, if present, to soda ash. Heat applied to mature the oil shale and recover oil and gas will also convert nahcolite to sodium carbonate (soda ash), a related sodium mineral. The process of converting nahcolite (sodium bicarbonate) to soda ash (sodium carbonate) is described herein.
In connection with the heating step 130, the rock formation 16 may optionally be fractured to aid heat transfer or later hydrocarbon fluid production. The optional fracturing step is shown in box 125. Fracturing may be accomplished by creating thermal fractures within the formation through application of heat. By heating the organic-rich rock and transforming the kerogen to oil and gas, the permeability of portions of the formation are increased via thermal fracture formation and subsequent production of a portion of the hydrocarbon fluids generated from the kerogen. Alternatively, a process known as hydraulic fracturing may be used. Hydraulic fracturing is a process known in the art of oil and gas recovery where a fracture fluid is pressurized within the wellbore above the fracture pressure of the formation, thus developing fracture planes within the formation to relieve the pressure generated within the wellbore. Hydraulic fractures may be used to create additional permeability in portions of the formation and/or be used to provide a planar source for heating.
As part of the hydrocarbon fluid production process 100, certain wells 14 may be designated as oil and gas production wells. This step is depicted by box 140. Oil and gas production might not be initiated until it is determined that the kerogen has been sufficiently retorted to allow maximum recovery of oil and gas from the formation 16. In some instances, dedicated production wells are not drilled until after heat injection wells (box 130) have been in operation for a period of several weeks or months. Thus, box 140 may include the formation of additional wellbores 14. In other instances, selected heater wells are converted to production wells.
After certain wellbores 14 have been designated as oil and gas production wells, oil and/or gas is produced from the wellbores 14. The oil and/or gas production process is shown at box 145. At this stage (box 145), any water-soluble minerals, such as nahcolite and converted soda ash may remain substantially trapped in the rock formation 16 as finely disseminated crystals or nodules within the oil shale beds, and are not produced. However, some nahcolite and/or soda ash may be dissolved in the water created during heat conversion (box 135) within the formation.
Box 150 presents an optional next step in the oil and gas recovery method 100. Here, certain wellbores 14 are designated as water or aqueous fluid injection wells. Aqueous fluids are solutions of water with other species. The water may constitute “brine,” and may include dissolved inorganic salts of chloride, sulfates and carbonates of Group I and II elements of The Periodic Table of Elements. Organic salts can also be present in the aqueous fluid. The water may alternatively be fresh water containing other species. The other species may be present to alter the pH. Alternatively, the other species may reflect the availability of brackish water not saturated in the species wished to be leached from the subsurface. Preferably, the water injection wells are selected from some or all of the wellbores used for heat injection or for oil and/or gas production. However, the scope of the step of box 150 may include the drilling of yet additional wellbores 14 for use as dedicated water injection wells. In this respect, it may be desirable to complete water injection wells along a periphery of the development area 10 in order to create a boundary of high pressure.
Next, optionally water or an aqueous fluid is injected through the water injection wells and into the oil shale formation 16. This step is shown at box 155. The water may be in the form of steam or pressurized hot water. Alternatively the injected water may be cool and becomes heated as it contacts the previously heated formation. The injection process may further induce fracturing. This process may create fingered caverns and brecciated zones in the nahcolite-bearing intervals some distance, for example up to 200 feet out, from the water injection wellbores. In one aspect, a gas cap, such as nitrogen, may be maintained at the top of each “cavern” to prevent vertical growth.
Along with the designation of certain wellbores 14 as water injection wells, the design engineers may also designate certain wellbores 14 as water or water-soluble mineral solution production wells. This step is shown in box 160. These wells may be the same as wells used to previously produce hydrocarbons or inject heat. These recovery wells may be used to produce an aqueous solution of dissolved water-soluble minerals and other species, including, for example, migratory contaminant species. For example, the solution may be one primarily of dissolved soda ash. This step is shown in box 165. Alternatively, single wellbores may be used to both inject water and then to recover a sodium mineral solution. Thus, box 165 includes the option of using the same wellbores 14 for both water injection and solution production (Box 165).
Temporary control of the migration of the migratory contaminant species, especially during the pyrolysis process, can be obtained via placement of the injection and production wells 14 such that fluid flow out of the heated zone is minimized. Typically, this involves placing injection wells at the periphery of the heated zone so as to cause pressure gradients which prevent flow inside the heated zone from leaving the zone.
In order to expand upon various features and methods for shale oil development, certain sections are specifically entitled below.
In some fields, formation hydrocarbons, such as oil shale, may exist in more than one subsurface formation. In some instances, the organic-rich rock formations may be separated by rock layers that are hydrocarbon-free or that otherwise have little or no commercial value. Therefore, it may be desirable for the operator of a field under hydrocarbon development to undertake an analysis as to which of the subsurface, organic-rich rock formations to target or in which order they should be developed.
The organic-rich rock formation may be selected for development based on various factors. One such factor is the thickness of the hydrocarbon containing layer within the formation. Greater pay zone thickness may indicate a greater potential volumetric production of hydrocarbon fluids. Each of the hydrocarbon containing layers may have a thickness that varies depending on, for example, conditions under which the formation hydrocarbon containing layer was formed. Therefore, an organic-rich rock formation will typically be selected for treatment if that formation includes at least one formation hydrocarbon-containing layer having a thickness sufficient for economical production of produced fluids.
An organic-rich rock formation may also be chosen if the thickness of several layers that are closely spaced together is sufficient for economical production of produced fluids. For example, an in situ conversion process for formation hydrocarbons may include selecting and treating a layer within an organic-rich rock formation having a thickness of greater than about 5 meters, 10 meters, 50 m, or even 100 meters. In this manner, heat losses (as a fraction of total injected heat) to layers formed above and below an organic-rich rock formation may be less than such heat losses from a thin layer of formation hydrocarbons. A process as described herein, however, may also include selecting and treating layers that may include layers substantially free of formation hydrocarbons or thin layers of formation hydrocarbons.
The richness of one or more organic-rich rock formations may also be considered. Richness may depend on many factors including the conditions under which the formation hydrocarbon containing layer was formed, an amount of formation hydrocarbons in the layer, and/or a composition of formation hydrocarbons in the layer. A thin and rich formation hydrocarbon layer may be able to produce significantly more valuable hydrocarbons than a much thicker, less rich formation hydrocarbon layer. Of course, producing hydrocarbons from a formation that is both thick and rich is desirable.
The kerogen content of an organic-rich rock formation may be ascertained from outcrop or core samples using a variety of data. Such data may include organic carbon content, hydrogen index, and modified Fischer assay analyses. The Fischer Assay is a standard method which involves heating a sample of a formation hydrocarbon containing layer to approximately 500° C. in one hour, collecting fluids produced from the heated sample, and quantifying the amount of fluids produced.
Subsurface formation permeability may also be assessed via rock samples, outcrops, or studies of ground water flow. Furthermore the connectivity of the development area to ground water sources may be assessed. Thus, an organic-rich rock formation may be chosen for development based on the permeability or porosity of the formation matrix even if the thickness of the formation is relatively thin.
Other factors known to petroleum engineers may be taken into consideration when selecting a formation for development. Such factors include depth of the perceived pay zone, stratigraphic proximity of fresh ground water to kerogen-containing zones, continuity of thickness, and other factors. For instance, the assessed fluid production content within a formation will also effect eventual volumetric production.
In producing hydrocarbon fluids from an oil shale field, it may be desirable to control the migration of pyrolyzed fluids. In some instances, this includes the use of injection wells, particularly around the periphery of the field. Such wells may inject water, steam, CO2, heated methane, or other fluids to drive cracked kerogen fluids inwardly towards production wells. In some embodiments, physical barriers may be placed around the area of the organic-rich rock formation under development. One example of a physical barrier involves the creation of freeze walls. Freeze walls are formed by circulating refrigerant through peripheral wells to substantially reduce the temperature of the rock formation. This, in turn, prevents the pyrolyzation of kerogen present at the periphery of the field and the outward migration of oil and gas. Freeze walls will also cause native water in the formation along the periphery to freeze.
The use of subsurface freezing to stabilize poorly consolidated soils or to provide a barrier to fluid flow is known in the art. Shell Exploration and Production Company has discussed the use of freeze walls for oil shale production in several patents, including U.S. Pat. No. 6,880,633 and U.S. Pat. No. 7,032,660. Shell's '660 patent uses subsurface freezing to protect against groundwater flow and groundwater contamination during in situ shale oil production. Additional patents that disclose the use of so-called freeze walls are U.S. Pat. No. 3,528,252, U.S. Pat. No. 3,943,722, U.S. Pat. No. 3,729,965, U.S. Pat. No. 4,358,222, U.S. Pat. No. 4,607,488.
Another example of a physical barrier that may be used to limit fluid flow into or out of an oil shale field is the creation of grout walls. Grout walls are formed by injecting cement into the formation to fill permeable pathways. In the context of an oil shale field, cement would be injected along the periphery of the field. This prevents the movement of pyrolyzed fluids out of the field under development, and the movement of water from adjacent aquifers into the field.
As noted above, several different types of wells may be used in the development of an organic-rich rock formation, including, for example, an oil shale field. For example, the heating of the organic-rich rock formation may be accomplished through the use of heater wells. The heater wells may include, for example, electrical resistance heating elements. The production of hydrocarbon fluids from the formation may be accomplished through the use of wells completed for the production of fluids. The injection of an aqueous fluid may be accomplished through the use of injection wells. Finally, the production of an aqueous solution may be accomplished through use of solution production wells.
The different wells listed above may be used for more than one purpose. Stated another way, wells initially completed for one purpose may later be used for another purpose, thereby lowering project costs and/or decreasing the time required to perform certain tasks. For example, one or more of the production wells may also be used as injection wells for later injecting water into the organic-rich rock formation. Alternatively, one or more of the production wells may also be used as solution production wells for later producing an aqueous solution from the organic-rich rock formation.
In other aspects, production wells (and in some circumstances heater wells) may initially be used as dewatering wells (e.g., before heating is begun and/or when heating is initially started). In addition, in some circumstances dewatering wells can later be used as production wells (and in some circumstances heater wells). As such, the dewatering wells may be placed and/or designed so that such wells can be later used as production wells and/or heater wells. The heater wells may be placed and/or designed so that such wells can be later used as production wells and/or dewatering wells. The production wells may be placed and/or designed so that such wells can be later used as dewatering wells and/or heater wells. Similarly, injection wells may be wells that initially were used for other purposes (e.g., heating, production, dewatering, monitoring, etc.), and injection wells may later be used for other purposes. Similarly, monitoring wells may be wells that initially were used for other purposes (e.g., heating, production, dewatering, injection, etc.). Finally, monitoring wells may later be used for other purposes such as water production.
The wellbores for the various wells may be located in relatively close proximity, being from 10 feet to up to 300 feet in separation. Alternatively, the wellbores may be spaced from 30 to 200 feet or 50 to 100 feet. Typically, the wellbores are also completed at shallow depths, being from 200 to 5,000 feet at total depth. Alternatively, the wellbores may be completed at depths from 1,000 to 4,000 feet, or 1,500 to 3,500 feet. In some embodiments, the oil shale formation targeted for in situ retorting is at a depth greater than 200 feet below the surface. In alternative embodiments, the oil shale formation targeted for in situ retorting is at a depth greater than 500, 1,000, or 1,500 feet below the surface. In alternative embodiments, the oil shale formation targeted for in situ retorting is at a depth between 200 and 5,000 feet, alternatively between 1,000 and 4,000 ft, 1,200 and 3,700 feet, or 1,500 and 3,500 feet below the surface.
It is desirable to arrange the various wells for an oil shale field in a pre-planned pattern. For instance, heater wells may be arranged in a variety of patterns including, but not limited to triangles, squares, hexagons, and other polygons. The pattern may include a regular polygon to promote uniform heating through at least the portion of the formation in which the heater wells are placed. The pattern may also be a line drive pattern. A line drive pattern generally includes a first linear array of heater wells, a second linear array of heater wells, and a production well or a linear array of production wells between the first and second linear array of heater wells. Interspersed among the heater wells are typically one or more production wells. The injection wells may likewise be disposed within a repetitive pattern of units, which may be similar to or different from that used for the heater wells.
One method to reduce the number of wells is to use a single well as both a heater well and a production well. Reduction of the number of wells by using single wells for sequential purposes can reduce project costs. One or more monitoring wells may be disposed at selected points in the field. The monitoring wells may be configured with one or more devices that measure a temperature, a pressure, and/or a property of a fluid in the wellbore. In some instances, a heater well may also serve as a monitoring well, or otherwise be instrumented.
Another method for reducing the number of heater wells is to use well patterns. Regular patterns of heater wells equidistantly spaced from a production well may be used. The patterns may form equilateral triangular arrays, hexagonal arrays, or other array patterns. The arrays of heater wells may be disposed such that a distance between each heater well is less than about 70 feet (21 m). A portion of the formation may be heated with heater wells disposed substantially parallel to a boundary of the hydrocarbon formation.
In alternative embodiments, the array of heater wells may be disposed such that a distance between each heater well may be less than about 100 feet, or 50 feet, or 30 feet. Regardless of the arrangement of or distance between the heater wells, in certain embodiments, a ratio of heater wells to production wells disposed within a organic-rich rock formation may be greater than about 5, 8, 10, 20, or more.
In one embodiment, individual production wells are surrounded by at most one layer of heater wells. This may include arrangements such as 5-spot, 7-spot, or 9-spot arrays, with alternating rows of production and heater wells. In another embodiment, two layers of heater wells may surround a production well, but with the heater wells staggered so that a clear pathway exists for the majority of flow away from the further heater wells. Flow and reservoir simulations may be employed to assess the pathways and temperature history of hydrocarbon fluids generated in situ as they migrate from their points of origin to production wells.
A production well 440 is shown central to the well layers 410 and 420. It is noted that the heater wells 432 in the second layer 420 of wells are offset from the heater wells 431 in the first layer 410 of wells, relative to the production well 440. The purpose is to provide a flowpath for converted hydrocarbons that minimizes travel near a heater well in the first layer 410 of heater wells. This, in turn, minimizes secondary cracking of hydrocarbons converted from kerogen as hydrocarbons flow from the second layer of wells 420 to the production wells 440.
In the illustrative arrangement of
The heater wells in the two layers also may be arranged such that the majority of hydrocarbons generated by heat from each heater well 432 in the second layer 420 are able to migrate to a production well 440 without passing substantially near a heater well 431 in the first layer 410. The heater wells 431, 432 in the two layers 410, 420 further may be arranged such that the majority of hydrocarbons generated by heat from each heater well 432 in the second layer 420 are able to migrate to the production well 440 without passing through a zone of substantially increasing formation temperature.
One method to reduce the number of heater wells is to use well patterns that are elongated in a particular direction, particularly in the direction of most efficient thermal conductivity. Heat convection may be affected by various factors such as bedding planes and stresses within the formation. For instance, heat convection may be more efficient in the direction perpendicular to the least horizontal principal stress on the formation. In some instanced, heat convection may be more efficient in the direction parallel to the least horizontal principal stress.
In connection with the development of an oil shale field, it may be desirable that the progression of heat through the subsurface in accordance with steps 130 and 135 be uniform. However, for various reasons the heating and maturation of formation hydrocarbons in a subsurface formation may not proceed uniformly despite a regular arrangement of heater and production wells. Heterogeneities in the oil shale properties and formation structure may cause certain local areas to be more or less productive. Moreover, formation fracturing which occurs due to the heating and maturation of the oil shale can lead to an uneven distribution of preferred pathways and, thus, increase flow to certain production wells and reduce flow to others. Uneven fluid maturation may be an undesirable condition since certain subsurface regions may receive more heat energy than necessary where other regions receive less than desired. This, in turn, leads to the uneven flow and recovery of production fluids. Produced oil quality, overall production rate, and/or ultimate recoveries may be reduced.
To detect uneven flow conditions, production and heater wells may be instrumented with sensors. Sensors may include equipment to measure temperature, pressure, flow rates, and/or compositional information. Data from these sensors can be processed via simple rules or input to detailed simulations to reach decisions on how to adjust heater and production wells to improve subsurface performance. Production well performance may be adjusted by controlling backpressure or throttling on the well. Heater well performance may also be adjusted by controlling energy input. Sensor readings may also sometimes imply mechanical problems with a well or downhole equipment which requires repair, replacement, or abandonment.
In one embodiment, flow rate, compositional, temperature and/or pressure data are utilized from two or more wells as inputs to a computer algorithm to control heating rate and/or production rates. Unmeasured conditions at or in the neighborhood of the well are then estimated and used to control the well. For example, in situ fracturing behavior and kerogen maturation are estimated based on thermal, flow, and compositional data from a set of wells. In another example, well integrity is evaluated based on pressure data, well temperature data, and estimated in situ stresses. In a related embodiment the number of sensors is reduced by equipping only a subset of the wells with instruments, and using the results to interpolate, calculate, or estimate conditions at uninstrumented wells. Certain wells may have only a limited set of sensors (e.g., wellhead temperature and pressure only) where others have a much larger set of sensors (e.g., wellhead temperature and pressure, bottomhole temperature and pressure, production composition, flow rate, electrical signature, casing strain, etc.).
As noted above, there are various methods for applying heat to an organic-rich rock formation. For example, one method may include electrical resistance heaters disposed in a wellbore or outside of a wellbore. One such method involves the use of electrical resistive heating elements in a cased or uncased wellbore. Electrical resistance heating involves directly passing electricity through a conductive material such that resistive losses cause it to heat the conductive material. Other heating methods include the use of downhole combustors, in situ combustion, radio-frequency (RF) electrical energy, or microwave energy. Still others include injecting a hot fluid into the oil shale formation to directly heat it. The hot fluid may or may not be circulated. One method may include generating heat by burning a fuel external to or within a subsurface formation. For example, heat may be supplied by surface burners or downhole burners or by circulating hot fluids (such as methane gas or naphtha) into the formation through, for example, wellbores via, for example, natural or artificial fractures. Some burners may be configured to perform flameless combustion. Alternatively, some methods may include combusting fuel within the formation such as via a natural distributed combustor, which generally refers to a heater that uses an oxidant to oxidize at least a portion of the carbon in the formation to generate heat, and wherein the oxidation takes place in a vicinity proximate to a wellbore. The present methods are not limited to the heating technique employed unless so stated in the claims.
One method for formation heating involves the use of electrical resistors in which an electrical current is passed through a resistive material which dissipates the electrical energy as heat. This method is distinguished from dielectric heating in which a high-frequency oscillating electric current induces electrical currents in nearby materials and causes them to heat. The electric heater may include an insulated conductor, an elongated member disposed in the opening, and/or a conductor disposed in a conduit. An early patent disclosing the use of electrical resistance heaters to produce oil shale in situ is U.S. Pat. No. 1,666,488. The '488 patent issued to Crawshaw in 1928. Since 1928, various designs for downhole electrical heaters have been proposed. Illustrative designs are presented in U.S. Pat. No. 1,701,884, U.S. Pat. No. 3,376,403, U.S. Pat. No. 4,626,665, U.S. Pat. No. 4,704,514, and U.S. Pat. No. 6,023,554).
A review of application of electrical heating methods for heavy oil reservoirs is given by R. Sierra and S. M. Farouq Ali, “Promising Progress in Field Application of Reservoir Electrical Heating Methods”, Society of Petroleum Engineers Paper 69709, 2001. The entire disclosure of this reference is hereby incorporated by reference.
Certain previous designs for in situ electrical resistance heaters utilized solid, continuous heating elements (e.g., metal wires or strips). However, such elements may lack the necessary robustness for long-term, high temperature applications such as oil shale maturation. As the formation heats and the oil shale matures, significant expansion of the rock occurs. This leads to high stresses on wells intersecting the formation. These stresses can lead to bending and stretching of the wellbore pipe and internal components. Cementing (e.g., U.S. Pat. No. 4,886,118) or packing (e.g., U.S. Pat. No. 2,732,195) a heating element in place may provide some protection against stresses, but some stresses may still be transmitted to the heating element.
As an alternative, U.S. Pat. No. 7,331,385 teaches the use of electrically conductive fractures to heat the oil shale. A heating element is constructed by forming wellbores and then hydraulically fracturing the oil shale formation around the wellbores. The fractures are filled with an electrically conductive material which forms the heating element. Calcined petroleum coke is an exemplary suitable conductant material. Preferably, the fractures are created in a vertical orientation along longitudinal, horizontal planes formed by horizontal wellbores. Electricity may be conducted through the conductive fractures from the heel to the toe of each well. The electrical circuit may be completed by an additional horizontal well that intersects one or more of the vertical fractures near the toe to supply the opposite electrical polarity. The U.S. Pat. No. 7,331,385 process creates an “in situ toaster” that artificially matures oil shale through the application of electric heat. Thermal conduction heats the oil shale to conversion temperatures in excess of 300° C. causing artificial maturation.
U.S. Pat. No. 7,441,603 teaches an alternative heating means that employs the circulation of a heated fluid within an oil shale formation. In the process of U.S. Pat. No. 7,441,603 supercritical heated naphtha may be circulated through fractures in the formation. This means that the oil shale is heated by circulating a dense, hot hydrocarbon vapor through sets of closely-spaced hydraulic fractures. In one aspect, the fractures are horizontally formed and conventionally propped. Fracture temperatures of 320°-400° C. are maintained for up to five to ten years. Vaporized naptha may be the preferred heating medium due to its high volumetric heat capacity, ready availability and relatively low degradation rate at the heating temperature. In the U.S. Pat. No. 7,441,603 process, as the kerogen matures, fluid pressure will drive the generated oil to the heated fractures, where it will be produced with the cycling hydrocarbon vapor.
The purpose for heating the organic-rich rock formation is to pyrolyze at least a portion of the solid formation hydrocarbons to create hydrocarbon fluids. The solid formation hydrocarbons may be pyrolyzed in situ by raising the organic-rich rock formation, (or zones within the formation), to a pyrolyzation temperature. In certain embodiments, the temperature of the formation may be slowly raised through the pyrolysis temperature range. For example, an in situ conversion process may include heating at least a portion of the organic-rich rock formation to raise the average temperature of the zone above about 270° C. at a rate less than a selected amount (e.g., about 10° C., 5° C.; 3° C., 1° C., 0.5° C., or 0.1° C.) per day. In a further embodiment, the portion may be heated such that an average temperature of the selected zone may be less than about 375° C. or, in some embodiments, less than about 400° C. The formation may be heated such that a temperature within the formation reaches (at least) an initial pyrolyzation temperature (e.g., a temperature at the lower end of the temperature range where pyrolyzation begins to occur.
The pyrolysis temperature range may vary depending on the types of formation hydrocarbons within the formation, the heating methodology, and the distribution of heating sources. For example, a pyrolysis temperature range may include temperatures between about 270° C. and about 900° C. Alternatively, the bulk of the target zone of the formation may be heated to between 300° to 600° C. In an alternative embodiment, a pyrolysis temperature range may include temperatures between about 270° C. to about 500° C.
Preferably, for in situ processes the heating of a production zone takes place over a period of months, or even four or more years. Alternatively, the formation may be heated for one to fifteen years, alternatively, 3 to 10 years, 1.5 to 7 years, or 2 to 5 years. The bulk of the target zone of the formation may be heated to between 270° to 800° C. Preferably, the bulk of the target zone of the formation is heated to between 300° to 600° C. Alternatively, the bulk of the target zone is ultimately heated to a temperature below 400° C. (752° F.).
In certain embodiments of the methods of the present invention, downhole burners may be used to heat a targeted oil shale zone. Downhole burners of various design have been discussed in the patent literature for use in oil shale and other largely solid hydrocarbon deposits. Examples include U.S. Pat. No. 2,887,160; U.S. Pat. No. 2,847,071; U.S. Pat. No. 2,895,555; U.S. Pat. No. 3,109,482; U.S. Pat. No. 3,225,829; U.S. Pat. No. 3,241,615; U.S. Pat. No. 3,254,721; U.S. Pat. No. 3,127,936; U.S. Pat. No. 3,095,031; U.S. Pat. No. 5,255,742; and U.S. Pat. No. 5,899,269. Downhole burners operate through the transport of a combustible fuel (typically natural gas) and an oxidizer (typically air) to a subsurface position in a wellbore. The fuel and oxidizer react downhole to generate heat. The combustion gases are removed (typically by transport to the surface, but possibly via injection into the formation). Oftentimes, downhole burners utilize pipe-in-pipe arrangements to transport fuel and oxidizer downhole, and then to remove the flue gas back up to the surface. Some downhole burners generate a flame, while others may not.
The use of downhole burners is an alternative to another form of downhole heat generation called steam generation. In downhole steam generation, a combustor in the well is used to boil water placed in the wellbore for injection into the formation. Applications of the downhole heat technology have been described in F. M. Smith, “A Down-hole burner—Versatile tool for well heating,” 25th Technical Conference on Petroleum Production, Pennsylvania State University, pp 275-285 (Oct. 19-21, 1966); H. Brandt, W. G. Poynter, and J. D. Hummell, “Stimulating Heavy Oil Reservoirs with Downhole Air-Gas Burners,” World Oil, pp. 91-95 (September 1965); and C.I. DePriester and A. J. Pantaleo, “Well Stimulation by Downhole Gas-Air Burner,” Journal of Petroleum Technology, pp. 1297-1302 (December 1963).
Downhole burners have advantages over electrical heating methods due to the reduced infrastructure cost. In this respect, there is no need for an expensive electrical power plant and distribution system. Moreover, there is increased thermal efficiency because the energy losses inherently experienced during electrical power generation are avoided.
Few applications of downhole burners exist. Downhole burner design issues include temperature control and metallurgy limitations. In this respect, the flame temperature can overheat the tubular and burner hardware and cause them to fail via melting, thermal stresses, severe loss of tensile strength, or creep. Certain stainless steels, typically with high chromium content, can tolerate temperatures up to ˜700° C. for extended periods. (See for example H. E. Boyer and T. L. Gall (eds.), Metals Handbook, “Chapter 16: Heat-Resistant Materials”, American Society for Metals, (1985.) The existence of flames can cause hot spots within the burner and in the formation surrounding the burner. This is due to radiant heat transfer from the luminous portion of the flame. However, a typical gas flame can produce temperatures up to about 1,650° C. Materials of construction for the burners must be sufficient to withstand the temperatures of these hot spots. The heaters are therefore more expensive than a comparable heater without flames.
For downhole burner applications, heat transfer can occur in one of several ways. These include conduction, convection, and radiative methods. Radiative heat transfer can be particularly strong for an open flame. Additionally, the flue gases can be corrosive due to the CO2 and water content. Use of refractory metals or ceramics can help solve these problems, but typically at a higher cost. Ceramic materials with acceptable strength at temperatures in excess of 900° C. are generally high alumina content ceramics. Other ceramics that may be useful include chrome oxide, zirconia oxide, and magnesium oxide based ceramics. Additionally, depending on the nature of the downhole combustion NOx generation may be significant.
Heat transfer in a pipe-in-pipe arrangement for a downhole burner can also lead to difficulties. The down going fuel and air will heat exchange with the up going hot flue gases. In a well there is minimal room for a high degree of insulation and hence significant heat transfer is typically expected. This cross heat exchange can lead to higher flame temperatures as the fuel and air become preheated. Additionally, the cross heat exchange can limit the transport of heat downstream of the burner since the hot flue gases may rapidly lose heat energy to the rising cooler flue gases.
In the production of oil and gas resources, it may be desirable to use the produced hydrocarbons as a source of power for ongoing operations. This may be applied to the development of oil and gas resources from oil shale. In this respect, when electrically resistive heaters are used in connection with in situ shale oil recovery, large amounts of power are required.
Electrical power may be obtained from turbines that turn generators. It may be economically advantageous to power the gas turbines by utilizing produced gas from the field. However, such produced gas must be carefully controlled so not to damage the turbine, cause the turbine to misfire, or generate excessive pollutants (e.g., NOx).
One source of problems for gas turbines is the presence of contaminants within the fuel. Contaminants include solids, water, heavy components present as liquids, and hydrogen sulfide. Additionally, the combustion behavior of the fuel is important. Combustion parameters to consider include heating value, specific gravity, adiabatic flame temperature, flammability limits, autoignition temperature, autoignition delay time, and flame velocity. Wobbe Index (WI) is often used as a key measure of fuel quality. WI is equal to the ratio of the lower heating value to the square root of the gas specific gravity. Control of the fuel's Wobbe Index to a target value and range of, for example, ±10% or ±20% can allow simplified turbine design and increased optimization of performance.
Fuel quality control may be useful for shale oil developments where the produced gas composition may change over the life of the field and where the gas typically has significant amounts of CO2, CO, and H2 in addition to light hydrocarbons. Commercial scale oil shale retorting is expected to produce a gas composition that changes with time.
Inert gases in the turbine fuel can increase power generation by increasing mass flow while maintaining a flame temperature in a desirable range. Moreover inert gases can lower flame temperature and thus reduce NOx pollutant generation. Gas generated from oil shale maturation may have significant CO2 content. Therefore, in certain embodiments of the production processes, the CO2 content of the fuel gas is adjusted via separation or addition in the surface facilities to optimize turbine performance.
Achieving a certain hydrogen content for low-BTU fuels may also be desirable to achieve appropriate burn properties. In certain embodiments of the processes herein, the H2 content of the fuel gas is adjusted via separation or addition in the surface facilities to optimize turbine performance. Adjustment of H2 content in non-shale oil surface facilities utilizing low BTU fuels has been discussed in the patent literature (e.g., U.S. Pat. No. 6,684,644 and U.S. Pat. No. 6,858,049, the entire disclosures of which are hereby incorporated by reference).
The process of heating formation hydrocarbons within an organic-rich rock formation, for example, by pyrolysis, may generate fluids. The heat-generated fluids may include water which is vaporized within the formation. In addition, the action of heating kerogen produces pyrolysis fluids which tend to expand upon heating. The produced pyrolysis fluids may include not only water, but also, for example, hydrocarbons, oxides of carbon, ammonia, molecular nitrogen, and molecular hydrogen. Therefore, as temperatures within a heated portion of the formation increase, a pressure within the heated portion may also increase as a result of increased fluid generation, molecular expansion, and vaporization of water. Thus, some corollary exists between subsurface pressure in an oil shale formation and the fluid pressure generated during pyrolysis. This, in turn, indicates that formation pressure may be monitored to detect the progress of a kerogen conversion process.
The pressure within a heated portion of an organic-rich rock formation depends on other reservoir characteristics. These may include, for example, formation depth, distance from a heater well, a richness of the formation hydrocarbons within the organic-rich rock formation, the degree of heating, and/or a distance from a producer well.
It may be desirable for the developer of an oil shale field to monitor formation pressure during development. Pressure within a formation may be determined at a number of different locations. Such locations may include, but may not be limited to, at a wellhead and at varying depths within a wellbore. In some embodiments, pressure may be measured at a producer well. In an alternate embodiment, pressure may be measured at a heater well. In still another embodiment, pressure may be measured downhole of a dedicated monitoring well.
The process of heating an organic-rich rock formation to a pyrolysis temperature range not only will increase formation pressure, but will also increase formation permeability. The pyrolysis temperature range should be reached before substantial permeability has been generated within the organic-rich rock formation. An initial lack of permeability may prevent the transport of generated fluids from a pyrolysis zone within the formation. In this manner, as heat is initially transferred from a heater well to an organic-rich rock formation, a fluid pressure within the organic-rich rock formation may increase proximate to that heater well. Such an increase in fluid pressure may be caused by, for example, the generation of fluids during pyrolysis of at least some formation hydrocarbons in the formation.
Alternatively, pressure generated by expansion of pyrolysis fluids or other fluids generated in the formation may be allowed to increase. This assumes that an open path to a production well or other pressure sink does not yet exist in the formation. In one aspect, a fluid pressure may be allowed to increase to or above a lithostatic stress. In this instance, fractures in the hydrocarbon containing formation may form when the fluid pressure equals or exceeds the lithostatic stress. For example, fractures may form from a heater well to a production well. The generation of fractures within the heated portion may reduce pressure within the portion due to the production of produced fluids through a production well.
Once pyrolysis has begun within an organic-rich rock formation, fluid pressure may vary depending upon various factors. These include, for example, thermal expansion of hydrocarbons, generation of pyrolysis fluids, rate of conversion, and withdrawal of generated fluids from the formation. For example, as fluids are generated within the formation, fluid pressure within the pores may increase. Removal of generated fluids from the formation may then decrease the fluid pressure within the near wellbore region of the formation.
In certain embodiments, a mass of at least a portion of an organic-rich rock formation may be reduced due, for example, to pyrolysis of formation hydrocarbons and the production of hydrocarbon fluids from the formation. As such, the permeability and porosity of at least a portion of the formation may increase. Any in situ method that effectively produces oil and gas from oil shale will create permeability in what was originally a very low permeability rock. The extent to which this will occur is illustrated by the large amount of expansion that must be accommodated if fluids generated from kerogen are unable to flow. The concept is illustrated in
In an embodiment, heating a portion of an organic-rich rock formation in situ to a pyrolysis temperature may increase permeability of the heated portion. For example, permeability may increase due to formation of thermal fractures within the heated portion caused by application of heat. As the temperature of the heated portion increases, water may be removed due to vaporization. The vaporized water may escape and/or be removed from the formation. In addition, permeability of the heated portion may also increase as a result of production of hydrocarbon fluids from pyrolysis of at least some of the formation hydrocarbons within the heated portion on a macroscopic scale.
Certain systems and methods described herein may be used to treat formation hydrocarbons in at least a portion of a relatively low permeability formation (e.g., in “tight” formations that contain formation hydrocarbons). Such formation hydrocarbons may be heated to pyrolyze at least some of the formation hydrocarbons in a selected zone of the formation. Heating may also increase the permeability of at least a portion of the selected zone.
Hydrocarbon fluids generated from pyrolysis may be produced from the formation, thereby further increasing the formation permeability.
Permeability of a selected zone within the heated portion of the organic-rich rock formation may also rapidly increase while the selected zone is heated by conduction. For example, permeability of an impermeable organic-rich rock formation may be less than about 0.1 millidarcy before heating. In some embodiments, pyrolyzing at least a portion of organic-rich rock formation may increase permeability within a selected zone of the portion to greater than about 10 millidarcies, 100 millidarcies, 1 Darcy, 10 Darcies, 20 Darcies, or 50 Darcies. Therefore, a permeability of a selected zone of the portion may increase by a factor of more than about 10, 100, 1,000, 10,000, or 100,000. In one embodiment, the organic-rich rock formation has an initial total permeability less than 1 millidarcy, alternatively less than 0.1 or 0.01 millidarcies, before heating the organic-rich rock formation. In one embodiment, the organic-rich rock formation has a post heating total permeability of greater than 1 millidarcy, alternatively, greater than 10, 50 or 100 millidarcies, after heating the organic-rich rock formation.
In connection with heating the organic-rich rock formation, the organic-rich rock formation may optionally be fractured to aid heat transfer or hydrocarbon fluid production. In one instance, fracturing may be accomplished naturally by creating thermal fractures within the formation through application of heat. Thermal fracture formation is caused by thermal expansion of the rock and fluids and by chemical expansion of kerogen transforming into oil and gas. Thermal fracturing can occur both in the immediate region undergoing heating, and in cooler neighboring regions. The thermal fracturing in the neighboring regions is due to propagation of fractures and tension stresses developed due to the expansion in the hotter zones. Thus, by both heating the organic-rich rock and transforming the kerogen to oil and gas, the permeability is increased not only from fluid formation and vaporization, but also via thermal fracture formation. The increased permeability aids fluid flow within the formation and production of the hydrocarbon fluids generated from the kerogen.
In addition, a process known as hydraulic fracturing may be used. Hydraulic fracturing is a process known in the art of oil and gas recovery where a fracture fluid is pressurized within the wellbore above the fracture pressure of the formation, thus developing fracture planes within the formation to relieve the pressure generated within the wellbore. Hydraulic fractures may be used to create additional permeability and/or be used to provide an extended geometry for a heater well. The U.S. Pat. No. 7,331,385 patent publication incorporated above describes one such method.
In connection with the production of hydrocarbons from a rock matrix, particularly those of shallow depth, a concern may exist with respect to earth subsidence. This is particularly true in the in situ heating of organic-rich rock where a portion of the matrix itself is thermally converted and removed. Initially, the formation may contain formation hydrocarbons in solid form, such as, for example, kerogen. The formation may also initially contain water-soluble minerals. Initially, the formation may also be substantially impermeable to fluid flow.
The in situ heating of the matrix pyrolyzes at least a portion of the formation hydrocarbons to create hydrocarbon fluids. This, in turn, creates permeability within a matured (pyrolyzed) organic-rich rock zone in the organic-rich rock formation. The combination of pyrolyzation and increased permeability permits hydrocarbon fluids to be produced from the formation. At the same time, the loss of supporting matrix material also creates the potential for subsidence relative to the earth surface.
In some instances, subsidence is sought to be minimized in order to avoid environmental or hydrogeological impact. In this respect, changing the contour and relief of the earth surface, even by a few inches, can change runoff patterns, affect vegetation patterns, and impact watersheds. In addition, subsidence has the potential of damaging production or heater wells formed in a production area. Such subsidence can create damaging hoop and compressional stresses on wellbore casings, cement jobs, and equipment downhole.
In order to avoid or minimize subsidence, it is proposed to leave selected portions of the formation hydrocarbons substantially unpyrolyzed. This serves to preserve one or more unmatured, organic-rich rock zones. In some embodiments, the unmatured organic-rich rock zones may be shaped as substantially vertical pillars extending through a substantial portion of the thickness of the organic-rich rock formation.
The heating rate and distribution of heat within the formation may be designed and implemented to leave sufficient unmatured pillars to prevent subsidence. In one aspect, heat injection wellbores are formed in a pattern such that untreated pillars of oil shale are left therebetween to support the overburden and prevent subsidence.
It is preferred that thermal recovery of oil and gas be conducted before any solution mining of nahcolite or other water-soluble minerals present in the formation. Solution mining can generate large voids in a rock formation and collapse breccias in an oil shale development area. These voids and brecciated zones may pose problems for in situ and mining recovery of oil shale, further increasing the utility of supporting pillars.
In some embodiments, compositions and properties of the hydrocarbon fluids produced by an in situ conversion process may vary depending on, for example, conditions within an organic-rich rock formation. Controlling heat and/or heating rates of a selected section in an organic-rich rock formation may increase or decrease production of selected produced fluids.
In one embodiment, operating conditions may be determined by measuring at least one property of the organic-rich rock formation. The measured properties may be input into a computer executable program. At least one property of the produced fluids selected to be produced from the formation may also be input into the computer executable program. The program may be operable to determine a set of operating conditions from at least the one or more measured properties. The program may also be configured to determine the set of operating conditions from at least one property of the selected produced fluids. In this manner, the determined set of operating conditions may be configured to increase production of selected produced fluids from the formation.
Certain heater well embodiments may include an operating system that is coupled to any of the heater wells such as by insulated conductors or other types of wiring. The operating system may be configured to interface with the heater well. The operating system may receive a signal (e.g., an electromagnetic signal) from a heater that is representative of a temperature distribution of the heater well. Additionally, the operating system may be further configured to control the heater well, either locally or remotely. For example, the operating system may alter a temperature of the heater well by altering a parameter of equipment coupled to the heater well. Therefore, the operating system may monitor, alter, and/or control the heating of at least a portion of the formation.
In some embodiments, a heater well may be turned down and/or off after an average temperature in a formation may have reached a selected temperature. Turning down and/or off the heater well may reduce input energy costs, substantially inhibit overheating of the formation, and allow heat to substantially transfer into colder regions of the formation.
Temperature (and average temperatures) within a heated organic-rich rock formation may vary, depending on, for example, proximity to a heater well, thermal conductivity and thermal diffusivity of the formation, type of reaction occurring, type of formation hydrocarbon, and the presence of water within the organic-rich rock formation. At points in the field where monitoring wells are established, temperature measurements may be taken directly in the wellbore. Further, at heater wells the temperature of the immediately surrounding formation is fairly well understood. However, it is desirable to interpolate temperatures to points in the formation intermediate temperature sensors and heater wells.
In accordance with one aspect of the production processes of the present inventions, a temperature distribution within the organic-rich rock formation may be computed using a numerical simulation model. The numerical simulation model may calculate a subsurface temperature distribution through interpolation of known data points and assumptions of formation conductivity. In addition, the numerical simulation model may be used to determine other properties of the formation under the assessed temperature distribution. For example, the various properties of the formation may include, but are not limited to, permeability of the formation.
The numerical simulation model may also include assessing various properties of a fluid formed within an organic-rich rock formation under the assessed temperature distribution. For example, the various properties of a formed fluid may include, but are not limited to, a cumulative volume of a fluid formed in the formation, fluid viscosity, fluid density, and a composition of the fluid formed in the formation. Such a simulation may be used to assess the performance of a commercial-scale operation or small-scale field experiment. For example, a performance of a commercial-scale development may be assessed based on, but not limited to, a total volume of product that may be produced from a research-scale operation.
Some embodiments include producing at least a portion of the hydrocarbon fluids from the organic-rich rock formation. The hydrocarbon fluids may be produced through production wells. Production wells may be cased or uncased wells and drilled and completed through methods known in the art.
Some embodiments further include producing a production fluid from the organic-rich rock formation where the production fluid contains the hydrocarbon fluids and an aqueous fluid. The aqueous fluid may contain water-soluble minerals and/or migratory contaminant species. In such case, the production fluid may be separated into a hydrocarbon stream and an aqueous stream at a surface facility. Thereafter the water-soluble minerals and/or migratory contaminant species may be recovered from the aqueous stream. This embodiment may be combined with any of the other aspects of the invention discussed herein.
The produced hydrocarbon fluids may include a pyrolysis oil component (or condensable component) and a pyrolysis gas component (or non-condensable component). Condensable hydrocarbons produced from the formation will typically include paraffins, cycloalkanes, mono-aromatics, and di-aromatics as components. Such condensable hydrocarbons may also include other components such as tri-aromatics and other hydrocarbon species.
In certain embodiments, a majority of the hydrocarbons in the produced fluid may have a carbon number of less than approximately 25. Alternatively, less than about 15 weight % of the hydrocarbons in the fluid may have a carbon number greater than approximately 25. The non-condensable hydrocarbons may include, but are not limited to, hydrocarbons having carbon numbers less than 5.
In certain embodiments, the API gravity of the condensable hydrocarbons in the produced fluid may be approximately 20 or above (e.g., 25, 30, 40, 50, etc.). In certain embodiments, the hydrogen to carbon atomic ratio in produced fluid may be at least approximately 1.7 (e.g., 1.8, 1.9, etc.).
One embodiment of the invention includes an in situ method of producing hydrocarbon fluids with improved properties from an organic-rich rock formation. Applicants have surprisingly discovered that the quality of the hydrocarbon fluids produced from in situ heating and pyrolysis of an organic-rich rock formation may be improved by selecting sections of the organic-rich rock formation with higher lithostatic stress for in situ heating and pyrolysis.
The method may include in situ heating of a section of the organic-rich rock formation that has a high lithostatic stress to form hydrocarbon fluids with improved properties. The method may include creating the hydrocarbon fluid by pyrolysis of a solid hydrocarbon and/or a heavy hydrocarbon present in the organic-rich rock formation. Embodiments may include the hydrocarbon fluid being partially, predominantly or substantially completely created by pyrolysis of the solid hydrocarbon and/or heavy hydrocarbon present in the organic-rich rock formation. The method may include heating the section of the organic-rich rock formation by any method, including any of the methods described herein. For example, the method may include heating the section of the organic-rich rock formation by electrical resistance heating. Further, the method may include heating the section of the organic-rich rock formation through use of a heated heat transfer fluid. The method may include heating the section of the organic-rich rock formation to above 270° C. Alternatively, the method may include heating the section of the organic-rich rock formation between 270° C. and 500° C.
The method may include heating in situ a section of the organic-rich rock formation having a lithostatic stress greater than 200 psi and producing a hydrocarbon fluid from the heated section of the organic-rich rock formation. In alternative embodiments, the heated section of the organic-rich rock formation may have a lithostatic stress greater than 400 psi. In alternative embodiments, the heated section of the organic-rich rock formation may have a lithostatic stress greater than 800 psi, greater than 1,000 psi, greater than 1,200 psi, greater than 1,500 psi or greater than 2,000 psi. Applicants have found that in situ heating and pyrolysis of organic-rich rock formations with increasing amounts of stress lead to the production of hydrocarbon fluids with improved properties.
The lithostatic stress of a section of an organic-rich formation can normally be estimated by recognizing that it will generally be equal to the weight of the rocks overlying the formation. The density of the overlying rocks can be expressed in units of psi/ft. Generally, this value will fall between 0.8 and 1.1 psi/ft and can often be approximated as 0.9 psi/ft. As a result the lithostatic stress of a section of an organic-rich formation can be estimated by multiplying the depth of the organic-rich rock formation interval by 0.9 psi/ft. Thus the lithostatic stress of a section of an organic-rich formation occurring at about 1,000 ft can be estimated to be about (0.9 psi/ft) multiplied by (1,000 ft) or about 900 psi. If a more precise estimate of lithostatic stress is desired the density of overlying rocks can be measured using wireline logging techniques or by making laboratory measurements on samples recovered from coreholes. The method may include heating a section of the organic-rich rock formation that is located at a depth greater than 200 ft below the earth's surface. Alternatively, the method may include heating a section of the organic-rich rock formation that is located at a depth greater than 500 ft below the earth's surface, greater than 1,000 ft below the earth's surface, greater than 1,200 ft below the earth's surface, greater than 1,500 ft below the earth's surface, or greater than 2,000 ft below the earth's surface.
The organic-rich rock formation may be, for example, a heavy hydrocarbon formation or a solid hydrocarbon formation. Particular examples of such formations may include an oil shale formation, a tar sands formation or a coal formation. Particular formation hydrocarbons present in such formations may include oil shale, kerogen, coal, and/or bitumen.
The hydrocarbon fluid produced from the organic-rich rock formation may include both a condensable hydrocarbon portion (e.g. liquid) and a non-condensable hydrocarbon portion (e.g. gas). The hydrocarbon fluid may additionally be produced together with non-hydrocarbon fluids. Exemplary non-hydrocarbon fluids include, for example, water, carbon dioxide, hydrogen sulfide, hydrogen, ammonia, and/or carbon monoxide.
The condensable hydrocarbon portion of the hydrocarbon fluid may be a fluid present within different locations associated with an organic-rich rock development project. For example, the condensable hydrocarbon portion of the hydrocarbon fluid may be a fluid present within a production well that is in fluid communication with the organic-rich rock formation. The production well may serve as a device for withdrawing the produced hydrocarbon fluids from the organic-rich rock formation. Alternatively, the condensable hydrocarbon portion may be a fluid present within processing equipment adapted to process hydrocarbon fluids produced from the organic-rich rock formation. Exemplary processing equipment is described herein. Alternatively, the condensable hydrocarbon portion may be a fluid present within a fluid storage vessel. Fluid storage vessels may include, for example, fluid storage tanks with fixed or floating roofs, knock-out vessels, and other intermediate, temporary or product storage vessels. Alternatively, the condensable hydrocarbon portion may be a fluid present within a fluid transportation pipeline. A fluid transportation pipeline may include, for example, piping from production wells to processing equipment or fluid storage vessels, piping from processing equipment to fluid storage vessels, or pipelines associated with collection or transportation of fluids to or from intermediate or centralized storage locations.
The following discussion of
The following discussion of
From
From the above-described data, it can be seen that heating and pyrolysis of oil shale under increasing levels of stress results in a condensable hydrocarbon fluid product that is lighter (i.e., greater proportion of lower carbon number compounds or components relative to higher carbon number compounds or components) and contains a lower concentration of normal alkane hydrocarbon compounds. Such a product may be suitable for refining into gasoline and distillate products. Further, such a product, either before or after further fractionation, may have utility as a feed stock for certain chemical processes.
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have one or more of a total C7 to total C20 weight ratio greater than 0.8, a total C8 to total C20 weight ratio greater than 1.7, a total C9 to total C20 weight ratio greater than 2.5, a total C10 to total C20 weight ratio greater than 2.8, a total C11 to total C20 weight ratio greater than 2.3, a total C12 to total C20 weight ratio greater than 2.3, a total C13 to total C20 weight ratio greater than 2.9, a total C14 to total C20 weight ratio greater than 2.2, a total C15 to total C20 weight ratio greater than 2.2, and a total C16 to total C20 weight ratio greater than 1.6. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C7 to total C20 weight ratio greater than 2.5, a total C8 to total C20 weight ratio greater than 3.0, a total C9 to total C20 weight ratio greater than 3.5, a total C10 to total C20 weight ratio greater than 3.5, a total C11 to total C20 weight ratio greater than 3.0, and a total C12 to total C20 weight ratio greater than 3.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C7 to total C20 weight ratio greater than 3.5, a total C8 to total C20 weight ratio greater than 4.3, a total C9 to total C20 weight ratio greater than 4.5, a total C10 to total C20 weight ratio greater than 4.2, a total C11 to total C20 weight ratio greater than 3.7, and a total C12 to total C20 weight ratio greater than 3.5. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a total C7 to total C20 weight ratio greater than 0.8. Alternatively, the condensable hydrocarbon portion may have a total C7 to total C20 weight ratio greater than 1.0, greater than 1.5, greater than 2.0, greater than 2.5, greater than 3.5 or greater than 3.7. In alternative embodiments, the condensable hydrocarbon portion may have a total C7 to total C20 weight ratio less than 10.0, less than 7.0, less than 5.0 or less than 4.0. In some embodiments the condensable hydrocarbon portion has a total C8 to total C20 weight ratio greater than 1.7. Alternatively, the condensable hydrocarbon portion may have a total C8 to total C20 weight ratio greater than 2.0, greater than 2.5, greater than 3.0, greater than 4.0, greater than 4.4, or greater than 4.6. In alternative embodiments, the condensable hydrocarbon portion may have a total C8 to total C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a total C9 to total C20 weight ratio greater than 2.5. Alternatively, the condensable hydrocarbon portion may have a total C9 to total C20 weight ratio greater than 3.0, greater than 4.0, greater than 4.5, or greater than 4.7. In alternative embodiments, the condensable hydrocarbon portion may have a total C9 to total C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a total C10 to total C20 weight ratio greater than 2.8. Alternatively, the condensable hydrocarbon portion may have a total C10 to total C20 weight ratio greater than 3.0, greater than 3.5, greater than 4.0, or greater than 4.3. In alternative embodiments, the condensable hydrocarbon portion may have a total C10 to total C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a total C11 to total C20 weight ratio greater than 2.3. Alternatively, the condensable hydrocarbon portion may have a total C11 to total C20 weight ratio greater than 2.5, greater than 3.5, greater than 3.7, greater than 4.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C11 to total C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a total C12 to total C20 weight ratio greater than 2.3. Alternatively, the condensable hydrocarbon portion may have a total C12 to total C20 weight ratio greater than 2.5, greater than 3.0, greater than 3.5, or greater than 3.7. In alternative embodiments, the condensable hydrocarbon portion may have a total C12 to total C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a total C13 to total C20 weight ratio greater than 2.9. Alternatively, the condensable hydrocarbon portion may have a total C13 to total C20 weight ratio greater than 3.0, greater than 3.1, or greater than 3.2. In alternative embodiments, the condensable hydrocarbon portion may have a total C13 to total C20 weight ratio less than 6.0 or less than 5.0. In some embodiments the condensable hydrocarbon portion has a total C14 to total C20 weight ratio greater than 2.2. Alternatively, the condensable hydrocarbon portion may have a total C14 to total C20 weight ratio greater than 2.5, greater than 2.6, or greater than 2.7. In alternative embodiments, the condensable hydrocarbon portion may have a total C14 to total C20 weight ratio less than 6.0 or less than 4.0. In some embodiments the condensable hydrocarbon portion has a total C15 to total C20 weight ratio greater than 2.2. Alternatively, the condensable hydrocarbon portion may have a total C15 to total C20 weight ratio greater than 2.3, greater than 2.4, or greater than 2.6. In alternative embodiments, the condensable hydrocarbon portion may have a total C15 to total C20 weight ratio less than 6.0 or less than 4.0. In some embodiments the condensable hydrocarbon portion has a total C16 to total C20 weight ratio greater than 1.6. Alternatively, the condensable hydrocarbon portion may have a total C16 to total C20 weight ratio greater than 1.8, greater than 2.3, or greater than 2.5. In alternative embodiments, the condensable hydrocarbon portion may have a total C16 to total C20 weight ratio less than 5.0 or less than 4.0. Certain features of the present invention are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have the one or more of a total C7 to total C25 weight ratio greater than 2.0, a total C8 to total C25 weight ratio greater than 4.5, a total C9 to total C25 weight ratio greater than 6.5, a total C10 to total C25 weight ratio greater than 7.5, a total C11 to total C25 weight ratio greater than 6.5, a total C12 to total C25 weight ratio greater than 6.5, a total C13 to total C25 weight ratio greater than 8.0, a total C14 to total C25 weight ratio greater than 6.0, a total C15 to total C25 weight ratio greater than 6.0, a total C16 to total C25 weight ratio greater than 4.5, a total C17 to total C25 weight ratio greater than 4.8, and a total C18 to total C25 weight ratio greater than 4.5. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C7 to total C25 weight ratio greater than 7.0, a total C8 to total C25 weight ratio greater than 10.0, a total C9 to total C25 weight ratio greater than 10.0, a total C10 to total C25 weight ratio greater than 10.0, a total C11 to total C25 weight ratio greater than 8.0, and a total C12 to total C25 weight ratio greater than 8.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C7 to total C25 weight ratio greater than 13.0, a total C8 to total C25 weight ratio greater than 17.0, a total C9 to total C25 weight ratio greater than 17.0, a total C10 to total C25 weight ratio greater than 15.0, a total C11 to total C25 weight ratio greater than 14.0, and a total C12 to total C25 weight ratio greater than 13.0. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a total C7 to total C25 weight ratio greater than 2.0. Alternatively, the condensable hydrocarbon portion may have a total C7 to total C25 weight ratio greater than 3.0, greater than 5.0, greater than 10.0, greater than 13.0, or greater than 15.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C7 to total C25 weight ratio less than 30.0 or less than 25.0. In some embodiments the condensable hydrocarbon portion has a total C8 to total C25 weight ratio greater than 4.5. Alternatively, the condensable hydrocarbon portion may have a total C8 to total C25 weight ratio greater than 5.0, greater than 7.0, greater than 10.0, greater than 15.0, or greater than 17.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C8 to total C25 weight ratio less than 35.0, or less than 30.0. In some embodiments the condensable hydrocarbon portion has a total C9 to total C25 weight ratio greater than 6.5. Alternatively, the condensable hydrocarbon portion may have a total C9 to total C25 weight ratio greater than 8.0, greater than 10.0, greater than 15.0, greater than 17.0, or greater than 19.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C9 to total C25 weight ratio less than 40.0 or less than 35.0. In some embodiments the condensable hydrocarbon portion has a total C10 to total C25 weight ratio greater than 7.5. Alternatively, the condensable hydrocarbon portion may have a total C10 to total C25 weight ratio greater than 10.0, greater than 14.0, or greater than 17.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C10 to total C25 weight ratio less than 35.0 or less than 30.0. In some embodiments the condensable hydrocarbon portion has a total C11 to total C25 weight ratio greater than 6.5. Alternatively, the condensable hydrocarbon portion may have a total C11 to total C25 weight ratio greater than 8.5, greater than 10.0, greater than 12.0, or greater than 14.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C11 to total C25 weight ratio less than 35.0 or less than 30.0. In some embodiments the condensable hydrocarbon portion has a total C12 to total C25 weight ratio greater than 6.5. Alternatively, the condensable hydrocarbon portion may have a total C12 to total C25 weight ratio greater than 8.5, a total C12 to total C25 weight ratio greater than 10.0, greater than 12.0, or greater than 14.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C12 to total C25 weight ratio less than 30.0 or less than 25.0. In some embodiments the condensable hydrocarbon portion has a total C13 to total C25 weight ratio greater than 8.0. Alternatively, the condensable hydrocarbon portion may have a total C13 to total C25 weight ratio greater than 10.0, greater than 12.0, or greater than 14.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C13 to total C25 weight ratio less than 25.0 or less than 20.0. In some embodiments the condensable hydrocarbon portion has a total C14 to total C25 weight ratio greater than 6.0. Alternatively, the condensable hydrocarbon portion may have a total C14 to total C25 weight ratio greater than 8.0, greater than 10.0, or greater than 12.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C14 to total C25 weight ratio less than 25.0 or less than 20.0. In some embodiments the condensable hydrocarbon portion has a total C15 to total C25 weight ratio greater than 6.0. Alternatively, the condensable hydrocarbon portion may have a total C15 to total C25 weight ratio greater than 8.0, or greater than 10.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C15 to total C25 weight ratio less than 25.0 or less than 20.0. In some embodiments the condensable hydrocarbon portion has a total C16 to total C25 weight ratio greater than 4.5. Alternatively, the condensable hydrocarbon portion may have a total C16 to total C25 weight ratio greater than 6.0, greater than 8.0, or greater than 10.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C16 to total C25 weight ratio less than 20.0 or less than 15.0. In some embodiments the condensable hydrocarbon portion has a total C17 to total C25 weight ratio greater than 4.8. Alternatively, the condensable hydrocarbon portion may have a total C17 to total C25 weight ratio greater than 5.5 or greater than 7.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C17 to total C25 weight ratio less than 20.0. In some embodiments the condensable hydrocarbon portion has a total C18 to total C25 weight ratio greater than 4.5. Alternatively, the condensable hydrocarbon portion may have a total C18 to total C25 weight ratio greater than 5.0 or greater than 5.5. In alternative embodiments, the condensable hydrocarbon portion may have a total C18 to total C25 weight ratio less than 15.0. Certain features of the present invention are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have the one or more of a total C7 to total C29 weight ratio greater than 3.5, a total C8 to total C29 weight ratio greater than 9.0, a total C9 to total C29 weight ratio greater than 12.0, a total C10 to total C29 weight ratio greater than 15.0, a total C11 to total C29 weight ratio greater than 13.0, a total C12 to total C29 weight ratio greater than 12.5, and a total C13 to total C29 weight ratio greater than 16.0, a total C14 to total C29 weight ratio greater than 12.0, a total C15 to total C29 weight ratio greater than 12.0, a total C16 to total C29 weight ratio greater than 9.0, a total C17 to total C29 weight ratio greater than 10.0, a total C18 to total C29 weight ratio greater than 8.8, a total C19 to total C29 weight ratio greater than 7.0, a total C20 to total C29 weight ratio greater than 6.0, a total C21 to total C29 weight ratio greater than 5.5, and a total C22 to total C29 weight ratio greater than 4.2. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C7 to total C29 weight ratio greater than 16.0, a total C8 to total C29 weight ratio greater than 19.0, a total C9 to total C29 weight ratio greater than 20.0, a total C10 to total C29 weight ratio greater than 18.0, a total C11 to total C29 weight ratio greater than 16.0, a total C12 to total C29 weight ratio greater than 15.0, and a total C13 to total C29 weight ratio greater than 17.0, a total C14 to total C29 weight ratio greater than 13.0, a total C15 to total C29 weight ratio greater than 13.0, a total C16 to total C29 weight ratio greater than 10.0, a total C17 to total C29 weight ratio greater than 11.0, a total C18 to total C29 weight ratio greater than 9.0, a total C19 to total C29 weight ratio greater than 8.0, a total C20 to total C29 weight ratio greater than 6.5, and a total C21 to total C29 weight ratio greater than 6.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C7 to total C29 weight ratio greater than 24.0, a total C8 to total C29 weight ratio greater than 30.0, a total C9 to total C29 weight ratio greater than 32.0, a total C10 to total C29 weight ratio greater than 30.0, a total C11 to total C29 weight ratio greater than 27.0, a total C12 to total C29 weight ratio greater than 25.0, and a total C13 to total C29 weight ratio greater than 22.0, a total C14 to total C29 weight ratio greater than 18.0, a total C15 to total C29 weight ratio greater than 18.0, a total C16 to total C29 weight ratio greater than 16.0, a total C17 to total C29 weight ratio greater than 13.0, a total C18 to total C29 weight ratio greater than 10.0, a total C19 to total C29 weight ratio greater than 9.0, and a total C20 to total C29 weight ratio greater than 7.0. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a total C7 to total C29 weight ratio greater than 3.5. Alternatively, the condensable hydrocarbon portion may have a total C7 to total C29 weight ratio greater than 5.0, greater than 10.0, greater than 18.0, greater than 20.0, or greater than 24.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C7 to total C29 weight ratio less than 60.0 or less than 50.0. In some embodiments the condensable hydrocarbon portion has a total C8 to total C29 weight ratio greater than 9.0. Alternatively, the condensable hydrocarbon portion may have a total C8 to total C29 weight ratio greater than 10.0, greater than 18.0, greater than 20.0, greater than 25.0, or greater than 30.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C8 to total C29 weight ratio less than 85.0 or less than 75.0. In some embodiments the condensable hydrocarbon portion has a total C9 to total C29 weight ratio greater than 12.0. Alternatively, the condensable hydrocarbon portion may have a total C9 to total C29 weight ratio greater than 15.0, greater than 20.0, greater than 23.0, greater than 27.0, or greater than 32.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C9 to total C29 weight ratio less than 85.0 or less than 75.0. In some embodiments the condensable hydrocarbon portion has a total C10 to total C29 weight ratio greater than 15.0. Alternatively, the condensable hydrocarbon portion may have a total C10 to total C29 weight ratio greater than 18.0, greater than 22.0, or greater than 28.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C10 to total C29 weight ratio less than 80.0 or less than 70.0. In some embodiments the condensable hydrocarbon portion has a total C11 to total C29 weight ratio greater than 13.0. Alternatively, the condensable hydrocarbon portion may have a total C11 to total C29 weight ratio greater than 16.0, greater than 18.0, greater than 24.0, or greater than 27.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C11 to total C29 weight ratio less than 75.0 or less than 65.0. In some embodiments the condensable hydrocarbon portion has a total C12 to total C29 weight ratio greater than 12.5. Alternatively, the condensable hydrocarbon portion may have a total C12 to total C29 weight ratio greater than 14.5, greater than 18.0, greater than 22.0, or greater than 25.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C12 to total C29 weight ratio less than 75.0 or less than 65.0. In some embodiments the condensable hydrocarbon portion has a total C13 to total C29 weight ratio greater than 16.0. Alternatively, the condensable hydrocarbon portion may have a total C13 to total C29 weight ratio greater than 18.0, greater than 20.0, or greater than 22.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C13 to total C29 weight ratio less than 70.0 or less than 60.0. In some embodiments the condensable hydrocarbon portion has a total C14 to total C29 weight ratio greater than 12.0. Alternatively, the condensable hydrocarbon portion may have a total C14 to total C29 weight ratio greater than 14.0, greater than 16.0, or greater than 18.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C14 to total C29 weight ratio less than 60.0 or less than 50.0. In some embodiments the condensable hydrocarbon portion has a total C15 to total C29 weight ratio greater than 12.0. Alternatively, the condensable hydrocarbon portion may have a total C15 to total C29 weight ratio greater than 15.0 or greater than 18.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C15 to total C29 weight ratio less than 60.0 or less than 50.0. In some embodiments the condensable hydrocarbon portion has a total C16 to total C29 weight ratio greater than 9.0. Alternatively, the condensable hydrocarbon portion may have a total C16 to total C29 weight ratio greater than 10.0, greater than 13.0, or greater than 16.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C16 to total C29 weight ratio less than 55.0 or less than 45.0. In some embodiments the condensable hydrocarbon portion has a total C17 to total C29 weight ratio greater than 10.0. Alternatively, the condensable hydrocarbon portion may have a total C17 to total C29 weight ratio greater than 11.0 or greater than 12.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C17 to total C29 weight ratio less than 45.0. In some embodiments the condensable hydrocarbon portion has a total C18 to total C29 weight ratio greater than 8.8. Alternatively, the condensable hydrocarbon portion may have a total C18 to total C29 weight ratio greater than 9.0 or greater than 10.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C18 to total C29 weight ratio less than 35.0. In some embodiments the condensable hydrocarbon portion has a total C19 to total C29 weight ratio greater than 7.0. Alternatively, the condensable hydrocarbon portion may have a total C19 to total C29 weight ratio greater than 8.0 or greater than 9.0. In alternative embodiments, the condensable hydrocarbon portion may have a total C19 to total C29 weight ratio less than 30.0. Certain features of the present invention are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have the one or more of a total C9 to total C20 weight ratio between 2.5 and 6.0, a total C10 to total C20 weight ratio between 2.8 and 7.3, a total C11 to total C20 weight ratio between 2.6 and 6.5, a total C12 to total C20 weight ratio between 2.6 and 6.4 and a total C13 to total C20 weight ratio between 3.2 and 8.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C9 to total C20 weight ratio between 3.0 and 5.5, a total C10 to total C20 weight ratio between 3.2 and 7.0, a total C11 to total C20 weight ratio between 3.0 and 6.0, a total C12 to total C20 weight ratio between 3.0 and 6.0, and a total C13 to total C20 weight ratio between 3.3 and 7.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C9 to total C20 weight ratio between 4.6 and 5.5, a total C10 to total C20 weight ratio between 4.2 and 7.0, a total C11 to total C20 weight ratio between 3.7 and 6.0, a total C12 to total C20 weight ratio between 3.6 and 6.0, and a total C13 to total C20 weight ratio between 3.4 and 7.0. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a total C9 to total C20 weight ratio between 2.5 and 6.0. Alternatively, the condensable hydrocarbon portion may have a total C9 to total C20 weight ratio between 3.0 and 5.8, between 3.5 and 5.8, between 4.0 and 5.8, between 4.5 and 5.8, between 4.6 and 5.8, or between 4.7 and 5.8. In some embodiments the condensable hydrocarbon portion has a total C10 to total C20 weight ratio between 2.8 and 7.3. Alternatively, the condensable hydrocarbon portion may have a total C10 to total C20 weight ratio between 3.0 and 7.2, between 3.5 and 7.0, between 4.0 and 7.0, between 4.2 and 7.0, between 4.3 and 7.0, or between 4.4 and 7.0. In some embodiments the condensable hydrocarbon portion has a total C11 to total C20 weight ratio between 2.6 and 6.5. Alternatively, the condensable hydrocarbon portion may have a total C11 to total C20 weight ratio between 2.8 and 6.3, between 3.5 and 6.3, between 3.7 and 6.3, between 3.8 and 6.3, between 3.9 and 6.2, or between 4.0 and 6.2. In some embodiments the condensable hydrocarbon portion has a total C12 to total C20 weight ratio between 2.6 and 6.4. Alternatively, the condensable hydrocarbon portion may have a total C12 to total C20 weight ratio between 2.8 and 6.2, between 3.2 and 6.2, between 3.5 and 6.2, between 3.6 and 6.2, between 3.7 and 6.0, or between 3.8 and 6.0. In some embodiments the condensable hydrocarbon portion has a total C13 to total C20 weight ratio between 3.2 and 8.0. Alternatively, the condensable hydrocarbon portion may have a total C13 to total C20 weight ratio between 3.3 and 7.8, between 3.3 and 7.0, between 3.4 and 7.0, between 3.5 and 6.5, or between 3.6 and 6.0. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have one or more of a total C10 to total C25 weight ratio between 7.1 and 24.5, a total C11 to total C25 weight ratio between 6.5 and 22.0, a total C12 to total C25 weight ratio between 6.5 and 22.0, and a total C13 to total C25 weight ratio between 8.0 and 27.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C10 to total C25 weight ratio between 10.0 and 24.0, a total C11 to total C25 weight ratio between 10.0 and 21.5, a total C12 to total C25 weight ratio between 10.0 and 21.5, and a total C13 to total C25 weight ratio between 9.0 and 25.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C10 to total C25 weight ratio between 14.0 and 24.0, a total C11 to total C25 weight ratio between 12.5 and 21.5, a total C12 to total C25 weight ratio between 12.0 and 21.5, and a total C13 to total C25 weight ratio between 10.5 and 25.0. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a total C10 to total C25 weight ratio between 7.1 and 24.5. Alternatively, the condensable hydrocarbon portion may have a total C10 to total C25 weight ratio between 7.5 and 24.5, between 12.0 and 24.5, between 13.8 and 24.5, between 14.0 and 24.5, or between 15.0 and 24.5. In some embodiments the condensable hydrocarbon portion has a total C11 to total C25 weight ratio between 6.5 and 22.0. Alternatively, the condensable hydrocarbon portion may have a total C11 to total C25 weight ratio between 7.0 and 21.5, between 10.0 and 21.5, between 12.5 and 21.5, between 13.0 and 21.5, between 13.7 and 21.5, or between 14.5 and 21.5. In some embodiments the condensable hydrocarbon portion has a total C12 to total C25 weight ratio between 10.0 and 21.5. Alternatively, the condensable hydrocarbon portion may have a total C12 to total C25 weight ratio between 10.5 and 21.0, between 11.0 and 21.0, between 12.0 and 21.0, between 12.5 and 21.0, between 13.0 and 21.0, or between 13.5 and 21.0. In some embodiments the condensable hydrocarbon portion has a total C13 to total C25 weight ratio between 8.0 and 27.0. Alternatively, the condensable hydrocarbon portion may have a total C13 to total C25 weight ratio between 9.0 and 26.0, between 10.0 and 25.0, between 10.5 and 25.0, between 11.0 and 25.0, or between 11.5 and 25.0. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have one or more of a total C10 to total C29 weight ratio between 15.0 and 60.0, a total C11 to total C29 weight ratio between 13.0 and 54.0, a total C12 to total C29 weight ratio between 12.5 and 53.0, and a total C13 to total C29 weight ratio between 16.0 and 65.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C10 to total C29 weight ratio between 17.0 and 58.0, a total C11 to total C29 weight ratio between 15.0 and 52.0, a total C12 to total C29 weight ratio between 14.0 and 50.0, and a total C13 to total C29 weight ratio between 17.0 and 60.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a total C10 to total C29 weight ratio between 20.0 and 58.0, a total C11 to total C29 weight ratio between 18.0 and 52.0, a total C12 to total C29 weight ratio between 18.0 and 50.0, and a total C13 to total C29 weight ratio between 18.0 and 50.0. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a total C10 to total C29 weight ratio between 15.0 and 60.0. Alternatively, the condensable hydrocarbon portion may have a total C10 to total C29 weight ratio between 18.0 and 58.0, between 20.0 and 58.0, between 24.0 and 58.0, between 27.0 and 58.0, or between 30.0 and 58.0. In some embodiments the condensable hydrocarbon portion has a total C11 to total C29 weight ratio between 13.0 and 54.0. Alternatively, the condensable hydrocarbon portion may have a total C11 to total C29 weight ratio between 15.0 and 53.0, between 18.0 and 53.0, between 20.0 and 53.0, between 22.0 and 53.0, between 25.0 and 53.0, or between 27.0 and 53.0. In some embodiments the condensable hydrocarbon portion has a total C12 to total C29 weight ratio between 12.5 and 53.0. Alternatively, the condensable hydrocarbon portion may have a total C12 to total C29 weight ratio between 14.5 and 51.0, between 16.0 and 51.0, between 18.0 and 51.0, between 20.0 and 51.0, between 23.0 and 51.0, or between 25.0 and 51.0. In some embodiments the condensable hydrocarbon portion has a total C13 to total C29 weight ratio between 16.0 and 65.0. Alternatively, the condensable hydrocarbon portion may have a total C13 to total C29 weight ratio between 17.0 and 60.0, between 18.0 and 60.0, between 20.0 and 60.0, between 22.0 and 60.0, or between 25.0 and 60.0. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have one or more of a normal-C7 to normal-C20 weight ratio greater than 0.9, a normal-C8 to normal-C20 weight ratio greater than 2.0, a normal-C9 to normal-C20 weight ratio greater than 1.9, a normal-C10 to normal-C20 weight ratio greater than 2.2, a normal-C11 to normal-C20 weight ratio greater than 1.9, a normal-C12 to normal-C20 weight ratio greater than 1.9, a normal-C13 to normal-C20 weight ratio greater than 2.3, a normal-C14 to normal-C20 weight ratio greater than 1.8, a normal-C15 to normal-C20 weight ratio greater than 1.8, and normal-C16 to normal-C20 weight ratio greater than 1.3. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C7 to normal-C20 weight ratio greater than 4.4, a normal-C8 to normal-C20 weight ratio greater than 3.7, a normal-C9 to normal-C20 weight ratio greater than 3.5, a normal-C10 to normal-C20 weight ratio greater than 3.4, a normal-C11 to normal-C20 weight ratio greater than 3.0, and a normal-C12 to normal-C20 weight ratio greater than 2.7. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C7 to normal-C20 weight ratio greater than 4.9, a normal-C8 to normal-C20 weight ratio greater than 4.5, a normal-C9 to normal-C20 weight ratio greater than 4.4, a normal-C10 to normal-C20 weight ratio greater than 4.1, a normal-C11 to normal-C20 weight ratio greater than 3.7, and a normal-C12 to normal-C20 weight ratio greater than 3.0. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a normal-C7 to normal-C20 weight ratio greater than 0.9. Alternatively, the condensable hydrocarbon portion may have a normal-C7 to normal-C20 weight ratio greater than 1.0, than 2.0, greater than 3.0, greater than 4.0, greater than 4.5, or greater than 5.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C7 to normal-C20 weight ratio less than 8.0 or less than 7.0. In some embodiments the condensable hydrocarbon portion has a normal-C8 to normal-C20 weight ratio greater than 1.7. Alternatively, the condensable hydrocarbon portion may have a normal-C8 to normal-C20 weight ratio greater than 2.0, greater than 2.5, greater than 3.0, greater than 3.5, greater than 4.0, or greater than 4.4. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C8 to normal-C20 weight ratio less than 8.0 or less than 7.0. In some embodiments the condensable hydrocarbon portion has a normal-C9 to normal-C20 weight ratio greater than 1.9. Alternatively, the condensable hydrocarbon portion may have a normal-C9 to normal-C20 weight ratio greater than 2.0, greater than 3.0, greater than 4.0, or greater than 4.5. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C9 to normal-C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a normal-C10 to normal-C20 weight ratio greater than 2.2. Alternatively, the condensable hydrocarbon portion may have a normal-C10 to normal-C20 weight ratio greater than 2.8, greater than 3.3, greater than 3.5, or greater than 4.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C10 to normal-C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a normal-C11 to normal-C20 weight ratio greater than 1.9. Alternatively, the condensable hydrocarbon portion may have a normal-C11 to normal-C20 weight ratio greater than 2.5, greater than 3.0, greater than 3.5, or greater than 3.7. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C11 to normal-C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a normal-C12 to normal-C20 weight ratio greater than 1.9. Alternatively, the condensable hydrocarbon portion may have a normal-C12 to normal-C20 weight ratio greater than 2.0, greater than 2.2, greater than 2.6, or greater than 3.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C12 to normal-C20 weight ratio less than 7.0 or less than 6.0. In some embodiments the condensable hydrocarbon portion has a normal-C13 to normal-C20 weight ratio greater than 2.3. Alternatively, the condensable hydrocarbon portion may have a normal-C13 to normal-C20 weight ratio greater than 2.5, greater than 2.7, or greater than 3.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C13 to normal-C20 weight ratio less than 6.0 or less than 5.0. In some embodiments the condensable hydrocarbon portion has a normal-C14 to normal-C20 weight ratio greater than 1.8. Alternatively, the condensable hydrocarbon portion may have a normal-C14 to normal-C20 weight ratio greater than 2.0, greater than 2.2, or greater than 2.5. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C14 to normal-C20 weight ratio less than 6.0 or less than 4.0. In some embodiments the condensable hydrocarbon portion has a normal-C15 to normal-C20 weight ratio greater than 1.8. Alternatively, the condensable hydrocarbon portion may have a normal-C15 to normal-C20 weight ratio greater than 2.0, greater than 2.2, or greater than 2.4. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C15 to normal-C20 weight ratio less than 6.0 or less than 4.0. In some embodiments the condensable hydrocarbon portion has a normal-C16 to normal-C20 weight ratio greater than 1.3. Alternatively, the condensable hydrocarbon portion may have a normal-C16 to normal-C20 weight ratio greater than 1.5, greater than 1.7, or greater than 2.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C16 to normal-C20 weight ratio less than 5.0 or less than 4.0. Certain features of the present invention are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have one or more of a normal-C7 to normal-C25 weight ratio greater than 1.9, a normal-C8 to normal-C25 weight ratio greater than 3.9, a normal-C9 to normal-C25 weight ratio greater than 3.7, a normal-C10 to normal-C25 weight ratio greater than 4.4, a normal-C11 to normal-C25 weight ratio greater than 3.8, a normal-C12 to normal-C25 weight ratio greater than 3.7, a normal-C13 to normal-C25 weight ratio greater than 4.7, a normal-C14 to normal-C25 weight ratio greater than 3.7, a normal-C15 to normal-C25 weight ratio greater than 3.7, a normal-C16 to normal-C25 weight ratio greater than 2.5, a normal-C17 to normal-C25 weight ratio greater than 3.0, and a normal-C18 to normal-C25 weight ratio greater than 3.4. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C7 to normal-C25 weight ratio greater than 10, a normal-C8 to normal-C25 weight ratio greater than 8.0, a normal-C9 to normal-C25 weight ratio greater than 7.0, a normal-C10 to normal-C25 weight ratio greater than 7.0, a normal-C11 to normal-C25 weight ratio greater than 7.0, and a normal-C12 to normal-C25 weight ratio greater than 6.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C7 to normal-C25 weight ratio greater than 10.0, a normal-C8 to normal-C25 weight ratio greater than 12.0, a normal-C9 to normal-C25 weight ratio greater than 11.0, a normal-C10 to normal-C25 weight ratio greater than 11.0, a normal-C11 to normal-C25 weight ratio greater than 9.0, and a normal-C12 to normal-C25 weight ratio greater than 8.0. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a normal-C7 to normal-C25 weight ratio greater than 1.9. Alternatively, the condensable hydrocarbon portion may have a normal-C7 to normal-C25 weight ratio greater than 3.0, greater than 5.0, greater than 8.0, greater than 10.0, or greater than 13.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C7 to normal-C25 weight ratio less than 35.0 or less than 25.0. In some embodiments the condensable hydrocarbon portion has a normal-C8 to normal-C25 weight ratio greater than 3.9. Alternatively, the condensable hydrocarbon portion may have a normal-C8 to normal-C25 weight ratio greater than 4.5, greater than 6.0, greater than 8.0, greater than 10.0, or greater than 13.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C8 to normal-C25 weight ratio less than 35.0 or less than 25.0. In some embodiments the condensable hydrocarbon portion has a normal-C9 to normal-C25 weight ratio greater than 3.7. Alternatively, the condensable hydrocarbon portion may have a normal-C9 to normal-C25 weight ratio greater than 4.5, greater than 7.0, greater than 10.0, greater than 12.0, or greater than 13.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C9 to normal-C25 weight ratio less than 35.0 or less than 25.0. In some embodiments the condensable hydrocarbon portion has a normal-C10 to normal-C25 weight ratio greater than 4.4. Alternatively, the condensable hydrocarbon portion may have a normal-C10 to normal-C25 weight ratio greater than 6.0, greater than 8.0, or greater than 11.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C10 to normal-C25 weight ratio less than 35.0 or less than 25.0. In some embodiments the condensable hydrocarbon portion has a normal-C11 to normal-C25 weight ratio greater than 3.8. Alternatively, the condensable hydrocarbon portion may have a normal-C11 to normal-C25 weight ratio greater than 4.5, greater than 7.0, greater than 8.0, or greater than 10.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C11 to normal-C25 weight ratio less than 35.0 or less than 25.0. In some embodiments the condensable hydrocarbon portion has a normal-C12 to normal-C25 weight ratio greater than 3.7. Alternatively, the condensable hydrocarbon portion may have a normal-C12 to normal-C25 weight ratio greater than 4.5, greater than 6.0, greater than 7.0, or greater than 8.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C12 to normal-C25 weight ratio less than 30.0 or less than 20.0. In some embodiments the condensable hydrocarbon portion has a normal-C13 to normal-C25 weight ratio greater than 4.7. Alternatively, the condensable hydrocarbon portion may have a normal-C13 to normal-C25 weight ratio greater than 5.0, greater than 6.0, or greater than 7.5. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C13 to normal-C25 weight ratio less than 25.0 or less than 20.0. In some embodiments the condensable hydrocarbon portion has a normal-C14 to normal-C25 weight ratio greater than 3.7. Alternatively, the condensable hydrocarbon portion may have a normal-C14 to normal-C25 weight ratio greater than 4.5, greater than 5.5, or greater than 7.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C14 to normal-C25 weight ratio less than 25.0 or less than 20.0. In some embodiments the condensable hydrocarbon portion has a normal-C15 to normal-C25 weight ratio greater than 3.7. Alternatively, the condensable hydrocarbon portion may have a normal-C15 to normal-C25 weight ratio greater than 4.2 or greater than 5.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C15 to normal-C25 weight ratio less than 25.0 or less than 20.0. In some embodiments the condensable hydrocarbon portion has a normal-C16 to normal-C25 weight ratio greater than 2.5. Alternatively, the condensable hydrocarbon portion may have a normal-C16 to normal-C25 weight ratio greater than 3.0, greater than 4.0, or greater than 5.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C16 to normal-C25 weight ratio less than 20.0 or less than 15.0. In some embodiments the condensable hydrocarbon portion has a normal-C17 to normal-C25 weight ratio greater than 3.0. Alternatively, the condensable hydrocarbon portion may have a normal-C17 to normal-C25 weight ratio greater than 3.5 or greater than 4.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C17 to normal-C25 weight ratio less than 20.0. In some embodiments the condensable hydrocarbon portion has a normal-C18 to normal-C25 weight ratio greater than 3.4. Alternatively, the condensable hydrocarbon portion may have a normal-C18 to normal-C25 weight ratio greater than 3.6 or greater than 4.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C18 to normal-C25 weight ratio less than 15.0. Certain features of the present invention are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have one or more of a normal-C7 to normal-C29 weight ratio greater than 18.0, a normal-C8 to normal-C29 weight ratio greater than 16.0, a normal-C9 to normal-C29 weight ratio greater than 14.0, a normal-C10 to normal-C29 weight ratio greater than 14.0, a normal-C11 to normal-C29 weight ratio greater than 13.0, a normal-C12 to normal-C29 weight ratio greater than 11.0, a normal-C13 to normal-C29 weight ratio greater than 10.0, a normal-C14 to normal-C29 weight ratio greater than 9.0, a normal-C15 to normal-C29 weight ratio greater than 8.0, a normal-C16 to normal-C29 weight ratio greater than 8.0, a normal-C17 to normal-C29 weight ratio greater than 6.0, a normal-C18 to normal-C29 weight ratio greater than 6.0, a normal-C19 to normal-C29 weight ratio greater than 5.0, a normal-C20 to normal-C29 weight ratio greater than 4.0, a normal-C21 to normal-C29 weight ratio greater than 3.6, and a normal-C22 to normal-C29 weight ratio greater than 2.8. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C7 to normal-C29 weight ratio greater than 20.0, a normal-C8 to normal-C29 weight ratio greater than 18.0, a normal-C9 to normal-C29 weight ratio greater than 17.0, a normal-C10 to normal-C29 weight ratio greater than 16.0, a normal-C11 to normal-C29 weight ratio greater than 15.0, a normal-C12 to normal-C29 weight ratio greater than 12.5, a normal-C13 to normal-C29 weight ratio greater than 11.0, a normal-C14 to normal-C29 weight ratio greater than 10.0, a normal-C15 to normal-C29 weight ratio greater than 8.0, a normal-C16 to normal-C29 weight ratio greater than 8.0, a normal-C17 to normal-C29 weight ratio greater than 7.0, a normal-C18 to normal-C29 weight ratio greater than 6.5, a normal-C19 to normal-C29 weight ratio greater than 5.5, a normal-C20 to normal-C29 weight ratio greater than 4.5, and a normal-C21 to normal-C29 weight ratio greater than 4.0. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C7 to normal-C29 weight ratio greater than 23.0, a normal-C8 to normal-C29 weight ratio greater than 21.0, a normal-C9 to normal-C29 weight ratio greater than 20.0, a normal-C10 to normal-C29 weight ratio greater than 19.0, a normal-C11 to normal-C29 weight ratio greater than 17.0, a normal-C12 to normal-C29 weight ratio greater than 14.0, a normal-C13 to normal-C29 weight ratio greater than 12.0, a normal-C14 to normal-C29 weight ratio greater than 11.0, a normal-C15 to normal-C29 weight ratio greater than 9.0, a normal-C16 to normal-C29 weight ratio greater than 9.0, a normal-C17 to normal-C29 weight ratio greater than 7.5, a normal-C18 to normal-C29 weight ratio greater than 7.0, a normal-C19 to normal-C29 weight ratio greater than 6.5, a normal-C20 to normal-C29 weight ratio greater than 4.8, and a normal-C21 to normal-C29 weight ratio greater than 4.5. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a normal-C7 to normal-C29 weight ratio greater than 18.0. Alternatively, the condensable hydrocarbon portion may have a normal-C7 to normal-C29 weight ratio greater than 20.0, greater than 22.0, greater than 25.0, greater than 30.0, or greater than 35.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C7 to normal-C29 weight ratio less than 70.0 or less than 60.0. In some embodiments the condensable hydrocarbon portion has a normal-C8 to normal-C29 weight ratio greater than 16.0. Alternatively, the condensable hydrocarbon portion may have a normal-C8 to normal-C29 weight ratio greater than 18.0, greater than 22.0, greater than 25.0, greater than 27.0, or greater than 30.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C8 to normal-C29 weight ratio less than 85.0 or less than 75.0. In some embodiments the condensable hydrocarbon portion has a normal-C9 to normal-C29 weight ratio greater than 14.0. Alternatively, the condensable hydrocarbon portion may have a normal-C9 to normal-C29 weight ratio greater than 18.0, greater than 20.0, greater than 23.0, greater than 27.0, or greater than 30.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C9 to normal-C29 weight ratio less than 85.0 or less than 75.0. In some embodiments the condensable hydrocarbon portion has a normal-C10 to normal-C29 weight ratio greater than 14.0. Alternatively, the condensable hydrocarbon portion may have a normal-C10 to normal-C29 weight ratio greater than 20.0, greater than 25.0, or greater than 30.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C10 to normal-C29 weight ratio less than 80.0 or less than 70.0. In some embodiments the condensable hydrocarbon portion has a normal-C11 to normal-C29 weight ratio greater than 13.0. Alternatively, the condensable hydrocarbon portion may have a normal-C11 to normal-C29 weight ratio greater than 16.0, greater than 18.0, greater than 24.0, or greater than 27.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C11 to normal-C29 weight ratio less than 75.0 or less than 65.0. In some embodiments the condensable hydrocarbon portion has a normal-C12 to normal-C29 weight ratio greater than 11.0. Alternatively, the condensable hydrocarbon portion may have a normal-C12 to normal-C29 weight ratio greater than 14.5, greater than 18.0, greater than 22.0, or greater than 25.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C12 to normal-C29 weight ratio less than 75.0 or less than 65.0. In some embodiments the condensable hydrocarbon portion has a normal-C13 to normal-C29 weight ratio greater than 10.0. Alternatively, the condensable hydrocarbon portion may have a normal-C13 to normal-C29 weight ratio greater than 18.0, greater than 20.0, or greater than 22.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C13 to normal-C29 weight ratio less than 70.0 or less than 60.0. In some embodiments the condensable hydrocarbon portion has a normal-C14 to normal-C29 weight ratio greater than 9.0. Alternatively, the condensable hydrocarbon portion may have a normal-C14 to normal-C29 weight ratio greater than 14.0, greater than 16.0, or greater than 18.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C14 to normal-C29 weight ratio less than 60.0 or less than 50.0. In some embodiments the condensable hydrocarbon portion has a normal-C15 to normal-C29 weight ratio greater than 8.0. Alternatively, the condensable hydrocarbon portion may have a normal-C15 to normal-C29 weight ratio greater than 12.0 or greater than 16.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C15 to normal-C29 weight ratio less than 60.0 or less than 50.0. In some embodiments the condensable hydrocarbon portion has a normal-C16 to normal-C29 weight ratio greater than 8.0. Alternatively, the condensable hydrocarbon portion may have a normal-C16 to normal-C29 weight ratio greater than 10.0, greater than 13.0, or greater than 15.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C16 to normal-C29 weight ratio less than 55.0 or less than 45.0. In some embodiments the condensable hydrocarbon portion has a normal-C17 to normal-C29 weight ratio greater than 6.0. Alternatively, the condensable hydrocarbon portion may have a normal-C17 to normal-C29 weight ratio greater than 8.0 or greater than 12.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C17 to normal-C29 weight ratio less than 45.0. In some embodiments the condensable hydrocarbon portion has a normal-C18 to normal-C29 weight ratio greater than 6.0. Alternatively, the condensable hydrocarbon portion may have a normal-C18 to normal-C29 weight ratio greater than 8.0 or greater than 10.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C18 to normal-C29 weight ratio less than 35.0. In some embodiments the condensable hydrocarbon portion has a normal-C19 to normal-C29 weight ratio greater than 5.0. Alternatively, the condensable hydrocarbon portion may have a normal-C19 to normal-C29 weight ratio greater than 7.0 or greater than 9.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C19 to normal-C29 weight ratio less than 30.0. In some embodiments the condensable hydrocarbon portion has a normal-C20 to normal-C29 weight ratio greater than 4.0. Alternatively, the condensable hydrocarbon portion may have a normal-C20 to normal-C29 weight ratio greater than 6.0 or greater than 8.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C20 to normal-C29 weight ratio less than 30.0. In some embodiments the condensable hydrocarbon portion has a normal-C21 to normal-C29 weight ratio greater than 3.6. Alternatively, the condensable hydrocarbon portion may have a normal-C21 to normal-C29 weight ratio greater than 4.0 or greater than 6.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C21 to normal-C29 weight ratio less than 30.0. In some embodiments the condensable hydrocarbon portion has a normal-C22 to normal-C29 weight ratio greater than 2.8. Alternatively, the condensable hydrocarbon portion may have a normal-C22 to normal-C29 weight ratio greater than 3.0. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C22 to normal-C29 weight ratio less than 30.0. Certain features of the present invention are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion may have one or more of a normal-C10 to total C10 weight ratio less than 0.31, a normal-CuI to total C11 weight ratio less than 0.32, a normal-C12 to total C12 weight ratio less than 0.29, a normal-C13 to total C13 weight ratio less than 0.28, a normal-C14 to total C14 weight ratio less than 0.31, a normal-C15 to total C15 weight ratio less than 0.27, a normal-C16 to total C16 weight ratio less than 0.31, a normal-C17 to total C17 weight ratio less than 0.31, a normal-C18 to total C18 weight ratio less than 0.37, normal-C19 to total C19 weight ratio less than 0.37, a normal-C20 to total C20 weight ratio less than 0.37, a normal-C21 to total C21 weight ratio less than 0.37, a normal-C22 to total C22 weight ratio less than 0.38, normal-C23 to total C23 weight ratio less than 0.43, a normal-C24 to total C24 weight ratio less than 0.48, and a normal-C25 to total C25 weight ratio less than 0.53. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C11 to total C11 weight ratio less than 0.30, a normal-C12 to total C12 weight ratio less than 0.27, a normal-C13 to total C13 weight ratio less than 0.26, a normal-C14 to total C14 weight ratio less than 0.29, a normal-C15 to total C15 weight ratio less than 0.24, a normal-C16 to total C16 weight ratio less than 0.25, a normal-C17 to total C17 weight ratio less than 0.29, a normal-C18 to total C18 weight ratio less than 0.31, normal-C19 to total C19 weight ratio less than 0.35, a normal-C20 to total C20 weight ratio less than 0.33, a normal-C21 to total C21 weight ratio less than 0.33, a normal-C22 to total C22 weight ratio less than 0.35, normal-C23 to total C23 weight ratio less than 0.40, a normal-C24 to total C24 weight ratio less than 0.45, and a normal-C25 to total C25 weight ratio less than 0.49. In alternative embodiments the condensable hydrocarbon portion has one or more of a normal-C11 to total C11 weight ratio less than 0.28, a normal-C12 to total C12 weight ratio less than 0.25, a normal-C13 to total C13 weight ratio less than 0.24, a normal-C14 to total C14 weight ratio less than 0.27, a normal-C15 to total C15 weight ratio less than 0.22, a normal-C16 to total C16 weight ratio less than 0.23, a normal-C17 to total C17 weight ratio less than 0.25, a normal-C18 to total C18 weight ratio less than 0.28, normal-C19 to total C19 weight ratio less than 0.31, a normal-C20 to total C20 weight ratio less than 0.29, a normal-C21 to total C21 weight ratio less than 0.30, a normal-C22 to total C22 weight ratio less than 0.28, normal-C23 to total C23 weight ratio less than 0.33, a normal-C24 to total C24 weight ratio less than 0.40, and a normal-C25 to total C25 weight ratio less than 0.45. As used in this paragraph and in the claims, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
In some embodiments the condensable hydrocarbon portion has a normal-C10 to total C10 weight ratio less than 0.31. Alternatively, the condensable hydrocarbon portion may have a normal-C10 to total C10 weight ratio less than 0.30 or less than 0.29. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C10 to total C10 weight ratio greater than 0.15 or greater than 0.20. In some embodiments the condensable hydrocarbon portion has a normal-C11 to total C11 weight ratio less than 0.32. Alternatively, the condensable hydrocarbon portion may have a normal-C11 to total C11 weight ratio less than 0.31, less than 0.30, or less than 0.29. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C11 to total C11 weight ratio greater than 0.15 or greater than 0.20. In some embodiments the condensable hydrocarbon portion has a normal-C12 to total C12 weight ratio less than 0.29. Alternatively, the condensable hydrocarbon portion may have a normal-C12 to total C12 weight ratio less than 0.26, or less than 0.24. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C12 to total C12 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C13 to total C13 weight ratio less than 0.28. Alternatively, the condensable hydrocarbon portion may have a normal-C13 to total C13 weight ratio less than 0.27, less than 0.25, or less than 0.23. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C13 to total C13 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C14 to total C14 weight ratio less than 0.31. Alternatively, the condensable hydrocarbon portion may have a normal-C14 to total C14 weight ratio less than 0.30, less than 0.28, or less than 0.26. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C14 to total C14 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C15 to total C15 weight ratio less than 0.27. Alternatively, the condensable hydrocarbon portion may have a normal-C15 to total C15 weight ratio less than 0.26, less than 0.24, or less than 0.22. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C15 to total C15 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C16 to total C16 weight ratio less than 0.31. Alternatively, the condensable hydrocarbon portion may have a normal-C16 to total C16 weight ratio less than 0.29, less than 0.26, or less than 0.24. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C16 to total C16 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C17 to total C17 weight ratio less than 0.31. Alternatively, the condensable hydrocarbon portion may have a normal-C17 to total C17 weight ratio less than 0.29, less than 0.27, or less than 0.25. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C17 to total C17 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C18 to total C18 weight ratio less than 0.37. Alternatively, the condensable hydrocarbon portion may have a normal-C18 to total C18 weight ratio less than 0.35, less than 0.31, or less than 0.28. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C18 to total C18 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C19 to total C19 weight ratio less than 0.37. Alternatively, the condensable hydrocarbon portion may have a normal-C19 to total C19 weight ratio less than 0.36, less than 0.34, or less than 0.31. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C19 to total C19 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C20 to total C20 weight ratio less than 0.37. Alternatively, the condensable hydrocarbon portion may have a normal-C20 to total C20 weight ratio less than 0.35, less than 0.32, or less than 0.29. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C20 to total C20 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C21 to total C21 weight ratio less than 0.37. Alternatively, the condensable hydrocarbon portion may have a normal-C21 to total C21 weight ratio less than 0.35, less than 0.32, or less than 0.30. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C21 to total C21 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C22 to total C22 weight ratio less than 0.38. Alternatively, the condensable hydrocarbon portion may have a normal-C22 to total C22 weight ratio less than 0.36, less than 0.34, or less than 0.30. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C22 to total C22 weight ratio greater than 0.10 or greater than 0.15. In some embodiments the condensable hydrocarbon portion has a normal-C23 to total C23 weight ratio less than 0.43. Alternatively, the condensable hydrocarbon portion may have a normal-C23 to total C23 weight ratio less than 0.40, less than 0.35, or less than 0.29. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C23 to total C23 weight ratio greater than 0.15 or greater than 0.20. In some embodiments the condensable hydrocarbon portion has a normal-C24 to total C24 weight ratio less than 0.48. Alternatively, the condensable hydrocarbon portion may have a normal-C24 to total C24 weight ratio less than 0.46, less than 0.42, or less than 0.40. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C24 to total C24 weight ratio greater than 0.15 or greater than 0.20. In some embodiments the condensable hydrocarbon portion has a normal-C25 to total C25 weight ratio less than 0.48. Alternatively, the condensable hydrocarbon portion may have a normal-C25 to total C25 weight ratio less than 0.46, less than 0.42, or less than 0.40. In alternative embodiments, the condensable hydrocarbon portion may have a normal-C25 to total C25 weight ratio greater than 0.20 or greater than 0.25. Certain features of the present invention are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in this paragraph may be combined with any of the other aspects of the invention discussed herein.
The use of “total C_” (e.g., total C10) herein and in the claims is meant to refer to the amount of a particular pseudo component found in a condensable hydrocarbon fluid determined as described herein, particularly as described in the section labeled “Experiments” herein. That is “total C_” is determined using the whole oil gas chromatography (WOGC) analysis methodology according to the procedure described in the Experiments section of this application. Further, “total C_” is determined from the whole oil gas chromatography (WOGC) peak integration methodology and peak identification methodology used for identifying and quantifying each pseudo-component as described in the Experiments section herein. Further, “total C_” weight percent and mole percent values for the pseudo components were obtained using the pseudo component analysis methodology involving correlations developed by Katz and Firoozabadi (Katz, D. L., and A. Firoozabadi, 1978. Predicting phase behavior of condensate/crude-oil systems using methane interaction coefficients, J. Petroleum Technology (November 1978), 1649-1655) as described in the Experiments section, including the exemplary molar and weight percentage determinations.
The use of “normal-C_” (e.g., normal-C10) herein and in the claims is meant to refer to the amount of a particular normal alkane hydrocarbon compound found in a condensable hydrocarbon fluid determined as described herein, particularly in the section labeled “Experiments” herein. That is “normal-C_” is determined from the GC peak areas determined using the whole oil gas chromatography (WOGC) analysis methodology according to the procedure described in the Experiments section of this application. Further, “total C_” is determined from the whole oil gas chromatography (WOGC) peak identification and integration methodology used for identifying and quantifying individual compound peaks as described in the Experiments section herein. Further, “normal-C_” weight percent and mole percent values for the normal alkane compounds were obtained using methodology analogous to the pseudo component exemplary molar and weight percentage determinations explained in the Experiments section, except that the densities and molecular weights for the particular normal alkane compound of interest were used and then compared to the totals obtained in the pseudo component methodology to obtain weight and molar percentages.
The following discussion of
The hydrocarbon fluid produced from the organic-rich rock formation may include both a condensable hydrocarbon portion (e.g. liquid) and a non-condensable hydrocarbon portion (e.g. gas). In some embodiments the non-condensable hydrocarbon portion includes methane and propane. In some embodiments the molar ratio of propane to methane in the non-condensable hydrocarbon portion is greater than 0.32. In alternative embodiments, the molar ratio of propane to methane in the non-condensable hydrocarbon portion is greater than 0.34, 0.36 or 0.38. As used herein “molar ratio of propane to methane” is the molar ratio that may be determined as described herein, particularly as described in the section labeled “Experiments” herein. That is “molar ratio of propane to methane” is determined using the hydrocarbon gas sample gas chromatography (GC) analysis methodology, gas sample GC peak identification and integration methodology and molar concentration determination procedures described in the Experiments section of this application.
In some embodiments the condensable hydrocarbon portion of the hydrocarbon fluid includes benzene. In some embodiments the condensable hydrocarbon portion has a benzene content between 0.1 and 0.8 weight percent. Alternatively, the condensable hydrocarbon portion may have a benzene content between 0.15 and 0.6 weight percent, a benzene content between 0.15 and 0.5, or a benzene content between 0.15 and 0.5.
In some embodiments the condensable hydrocarbon portion of the hydrocarbon fluid includes cyclohexane. In some embodiments the condensable hydrocarbon portion has a cyclohexane content less than 0.8 weight percent. Alternatively, the condensable hydrocarbon portion may have a cyclohexane content less than 0.6 weight percent or less than 0.43 weight percent. Alternatively, the condensable hydrocarbon portion may have a cyclohexane content greater than 0.1 weight percent or greater than 0.2 weight percent.
In some embodiments the condensable hydrocarbon portion of the hydrocarbon fluid includes methyl-cyclohexane. In some embodiments the condensable hydrocarbon portion has a methyl-cyclohexane content greater than 0.5 weight percent. Alternatively, the condensable hydrocarbon portion may have a methyl-cyclohexane content greater than 0.7 weight percent or greater than 0.75 weight percent. Alternatively, the condensable hydrocarbon portion may have a methyl-cyclohexane content less than 1.2 or 1.0 weight percent.
The use of weight percentage contents of benzene, cyclohexane, and methyl-cyclohexane herein and in the claims is meant to refer to the amount of benzene, cyclohexane, and methyl-cyclohexane found in a condensable hydrocarbon fluid determined as described herein, particularly as described in the section labeled “Experiments” herein. That is, respective compound weight percentages are determined from the whole oil gas chromatography (WOGC) analysis methodology and whole oil gas chromatography (WOGC) peak identification and integration methodology discussed in the Experiments section herein. Further, the respective compound weight percentages were obtained as described for
In some embodiments the condensable hydrocarbon portion of the hydrocarbon fluid has an API gravity greater than 30. Alternatively, the condensable hydrocarbon portion may have an API gravity greater than 30, 32, 34, 36, 40, 42 or 44. As used herein and in the claims, API gravity may be determined by any generally accepted method for determining API gravity.
In some embodiments the condensable hydrocarbon portion of the hydrocarbon fluid has a basic nitrogen to total nitrogen ratio between 0.1 and 0.50. Alternatively, the condensable hydrocarbon portion may have a basic nitrogen to total nitrogen ratio between 0.15 and 0.40. As used herein and in the claims, basic nitrogen and total nitrogen may be determined by any generally accepted method for determining basic nitrogen and total nitrogen. Where results conflict, the generally accepted more accurate methodology shall control.
One embodiment of the invention includes an in situ method of producing hydrocarbon fluids with improved properties from an organic-rich rock formation. Applicants have surprisingly discovered that the quality of the hydrocarbon fluids produced from in situ heating and pyrolysis of an organic-rich rock formation may be improved by selecting sections of the organic-rich rock formation with a certain lithostatic stress for in situ heating and pyrolysis. Further, applicants have discovered that the temperature at which the in situ pyrolysis is accomplished has an effect on the composition of the produced fluid, that the effect of increasing temperature generally affects the composition of the produced fluid in the same direction as increasing lithostatic stress, and that the effect of decreasing temperature generally affects the composition of the produced fluid in the same direction as decreasing lithostatic stress. Further, applicants have discovered that the pressure at which the in situ pyrolysis is conducted affects the composition of the produced fluid, that the compositional effect of increasing pressure is generally in a direction opposite to the effects of lithostatic stress and temperature and that the compositional effect of pressure is generally of a much lower magnitude than the effects of temperature and lithostatic stress.
The method may include creating the hydrocarbon fluid by pyrolysis of a solid hydrocarbon and/or a heavy hydrocarbon present in the organic-rich rock formation. Embodiments may include the hydrocarbon fluid being partially, predominantly or substantially completely created by pyrolysis of the solid hydrocarbon and/or heavy hydrocarbon present in the organic-rich rock formation.
Applicants have found that in situ heating and pyrolysis of organic-rich rock formations with differing amounts of stress lead to the production of hydrocarbon fluids with changed properties. The method may include in situ heating of a section of the organic-rich rock formation that has a selected lithostatic stress to form hydrocarbon fluids with desired properties. Selecting or maintaining a higher lithostatic stress will increase the production of aromatic and cyclic hydrocarbon compounds, while decreasing the production of normal and isoprenoid (or branched) hydrocarbon compounds. Alternatively, maintaining a lower lithostatic stress will decrease the production of aromatic and cyclic hydrocarbon compounds, while increasing the production of normal and isoprenoid (or branched) hydrocarbon compounds. The method may include heating in situ a section of the organic-rich rock formation having a lithostatic stress greater than 200 psi and producing a hydrocarbon fluid from the heated section of the organic-rich rock formation. In alternative embodiments, the heated section of the organic-rich rock formation may have a lithostatic stress greater than 400 psi. In alternative embodiments, the heated section of the organic-rich rock formation may have a lithostatic stress greater than 800 psi, greater than 1,000 psi, greater than 1,200 psi, greater than 1,500 psi or greater than 2,000 psi depending on the composition desired. In alternative embodiments, the heated section of the organic-rich rock formation may have a lithostatic stress less than 800 psi, less than 1,000 psi, less than 1,500 psi, less than 2,500 psi or less than 3,000 psi depending on the composition desired. In alternative embodiments, the heated section of the organic-rich rock formation may have a lithostatic stress between 200 psi and 1,000 psi, between 200 psi and 900 psi, between 200 psi and 800 psi, between 200 psi and 700 psi or between 200 psi and 600 psi depending on the composition desired. In alternative embodiments, the heated section of the organic-rich rock formation may have a lithostatic stress between 800 psi and 3,000 psi, between 900 psi and 3,000 psi, between 1,000 psi and 3,000 psi, between 1,200 psi and 3,000 psi or between 1,500 psi and 3,000 psi depending on the composition desired.
Further, the method may include controlling the temperature or range of temperatures the section of the organic-rich rock formation experiences in order to effect the composition of the produced hydrocarbon fluids. For example, the heating rate of sources of in situ heat may be set or adjusted to affect the temperature profile of the section of the organic-rich rock formation. Further, the density or configuration of the sources of in situ heat may be implemented or adjusted to effect the composition of the produced hydrocarbon fluid. Higher temperatures will favor the production of aromatics and cyclic hydrocarbon compounds, while lower temperatures will favor the production of normal and isoprenoid (or branched) hydrocarbon compounds. Alternatively, lower temperatures will tend to decrease aromatic and cyclic hydrocarbon compound production while higher temperatures will tend to decrease production of normal and isoprenoid (or branched) hydrocarbon compounds. Thus, the method may include heating a section of the organic-rich rock formation to a maximum temperature above 270° C. Alternatively, the method may include heating the section of the organic-rich rock formation to a maximum temperature between 270° C. and 600° C., between 270° C. to 550° C., between 270° C. to 500° C., between 270° C. to 450° C., between 270° C. to 400° C. or between 270° C. to 350° C. depending on the composition desired. Alternatively, the method may include heating the section of the organic-rich rock formation to a maximum temperature between 350° C. and 500° C., between 350° C. to 550° C., between 350° C. to 600° C., between 350° C. to 650° C., between 350° C. to 700° C. or between 350° C. to 750° C. depending on the composition desired. The method may include heating the section of the organic-rich rock formation by any method, including any of the methods described herein. For example, the method may include heating the section of the organic-rich rock formation by electrical resistance heating. Further, the method may include heating the section of the organic-rich rock formation through use of a heated heat transfer fluid.
Further, the method may include maintaining a range of pressures in the section of the organic-rich rock formation in order to effect the composition of the produced hydrocarbon fluid. One method of maintaining a range of pressures in the section of the organic-rich rock formation includes selecting the section by estimating the section's lithostatic stress in order to limit the maximum pressure that such a section is likely to experience by relying on the creation of fractures to relieve the pressure force due to in situ heating. The effect of pressure when combined with lithostatic stress will tend to alter the effect of lithostatic stress on the composition of the produced fluid. Lower pressures when combined with lithostatic stress will tend to enhance production of aromatic and cyclic hydrocarbon compounds and decrease production of normal and isoprenoid (or branched) hydrocarbon compounds. Alternatively, higher pressures when combined with lithostatic stress will tend to incrementally reduce production of aromatic and cyclic hydrocarbon compounds and increase production of normal and isoprenoid (or branched) hydrocarbon compounds. Thus, the method may include maintaining the pressure of a heated section of an organic-rich rock formation above 200 psig and producing a hydrocarbon fluid from the heated section of the organic-rich rock formation. In alternative embodiments, the method may include maintaining the pressure of a heated section of the organic-rich rock formation below 3,000 psig. In alternative embodiments, the method may include maintaining the pressure of a heated section of the organic-rich rock formation below 2,500 psig, below 2,000 psig, below 2,500 psig, below 2,000 psig or below 1,500 psig depending on the composition desired. In alternative embodiments, the method may include allowing the pressure of a heated section of the organic-rich rock formation to reach a maximum pressure above 400 psig, above 500 psig, above 800 psig, above 1,000 psig, above 1,500 psig or above 2,000 psig depending on the composition desired. In alternative embodiments, the method may include allowing the pressure of a heated section of the organic-rich rock formation to reach a maximum pressure between 200 psig and 1,000 psig, between 200 psig and 900 psig, between 200 psig and 800 psig, between 200 psig and 700 psig or between 200 psig and 600 psig depending on the composition desired. In alternative embodiments, the method may include allowing the pressure of a heated section of the organic-rich rock formation to reach a maximum pressure between 800 psig and 3,000 psig, between 900 psig and 3,000 psig, between 1,000 psig and 3,000 psig, between 1,200 psig and 3,000 psig or between 1,500 psig and 3,000 psig depending on the composition desired.
The organic-rich rock formation may be, for example, a heavy hydrocarbon formation or a solid hydrocarbon formation. Particular examples of such formations may include an oil shale formation, a tar sands formation or a coal formation. Particular formation hydrocarbons present in such formations may include oil shale, kerogen, coal, and/or bitumen.
The hydrocarbon fluid produced from the organic-rich rock formation may include both a condensable hydrocarbon portion (e.g. liquid) and a non-condensable hydrocarbon portion (e.g. gas). The hydrocarbon fluid may additionally be produced together with non-hydrocarbon fluids. Exemplary non-hydrocarbon fluids include, for example, water, carbon dioxide, hydrogen sulfide, hydrogen, ammonia, and/or carbon monoxide.
The condensable hydrocarbon portion of the hydrocarbon fluid may be a fluid present within different locations associated with an organic-rich rock development project. For example, the condensable hydrocarbon portion of the hydrocarbon fluid may be a fluid present within a production well that is in fluid communication with the organic-rich rock formation. The production well may serve as a device for withdrawing the produced hydrocarbon fluids from the organic-rich rock formation. Alternatively, the condensable hydrocarbon portion may be a fluid present within processing equipment adapted to process hydrocarbon fluids produced from the organic-rich rock formation. Exemplary processing equipment is described herein. Alternatively, the condensable hydrocarbon portion may be a fluid present within a fluid storage vessel. Fluid storage vessels may include, for example, fluid storage tanks with fixed or floating roofs, knock-out vessels, and other intermediate, temporary or product storage vessels. Alternatively, the condensable hydrocarbon portion may be a fluid present within a fluid transportation pipeline. A fluid transportation pipeline may include, for example, piping from production wells to processing equipment or fluid storage vessels, piping from processing equipment to fluid storage vessels, or pipelines associated with collection or transportation of fluids to or from intermediate or centralized storage locations.
The following discussion of
From
From
From
From
Isoprenoid hydrocarbon compounds are hydrocarbon compounds based on the isoprene structure. They are constructed by linking 2 or more 5 carbon isoprene units together building molecules with up to 40 or more carbon atoms. Isoprene is a diolefin but the double bonds are typically saturated during diagenesis so compounds built up from isoprene units are referred to as isoprenoids. Although the 5 carbon isoprene unit implies that isoprenoids should contain carbons in multiples of 5 this is not the case as carbons can be cleaved off during diagenesis. The use of “IP-_” (e.g., IP-10) herein and in the claims is meant to refer to a hydrocarbon structure based on isoprene with the number following the hyphen denoting the carbon number of a particular isoprenoid. For example, IP-10 means a hydrocarbon structure based on isoprene having 10 carbon atoms.
From
From
From
From
From
From
From
From
From
From the above-described data discussed in
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have one or more of a n-C6 to benzene weight ratio less than 35.0, a n-C7 to toluene weight ratio less than 7.0, a n-C8 to ethylbenzene weight ratio less than 16.0, a n-C8 to ortho-xylene weight ratio less than 7.0, a n-C8 to meta-xylene weight ratio less than 1.9, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 8.2, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.4, a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.7, a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, a n-C10 to tetralin weight ratio less than 25.0, a n-C12 to 2-methylnaphthalene weight ratio less than 4.9, and a n-C12 to 1-methylnaphthalene weight ratio less than 6.9. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion has a n-C6 to benzene weight ratio less than 35.0, less than 25, 15, 10 or 7. In some embodiments the condensable hydrocarbon portion has a n-C7 to toluene weight ratio less than 7.0, less than 6, 5, 4 or 3. In some embodiments the condensable hydrocarbon portion has a n-C8 to ethylbenzene weight ratio less than 16.0, less than 13, 10, 5 or 2. In some embodiments the condensable hydrocarbon portion has a n-C8 to ortho-xylene weight ratio less than 7.0, less than 6, 5, 4 or 2. In some embodiments the condensable hydrocarbon portion has a n-C8 to meta-xylene weight ratio less than 1.9, less than 1.8, 1.7, 1.6 or 1.5. In some embodiments the condensable hydrocarbon portion has a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 8.2, less than 7, 6, 4 or 2. In some embodiments the condensable hydrocarbon portion has a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.4, less than 4.0, 3.5, 3.0 or 2.0. In some embodiments the condensable hydrocarbon portion has a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.7, less than 2.5, 2.0, 1.5 or 1.0. In some embodiments the condensable hydrocarbon portion has a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 13.5, less than 12, 10, 7 or 5. In some embodiments the condensable hydrocarbon portion has a n-C10 to tetralin weight ratio less than 25.0, less than 20, 15, or 10. In some embodiments the condensable hydrocarbon portion has a n-C12 to 2-methylnaphthalene weight ratio less than 4.9, less than 4.5, 4.0, 3.5 or 3. In some embodiments the condensable hydrocarbon portion has a n-C12 to 1-methylnaphthalene weight ratio less than 6.9, 6.0, 4.0, 3.0, or 2.5.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C6 to benzene weight ratio less than 24.0, a n-C7 to toluene weight ratio less than 6.6, a n-C8 to ethylbenzene weight ratio less than 15.0, a n-C8 to ortho-xylene weight ratio less than 6.6, a n-C8 to meta-xylene weight ratio less than 1.8, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 7.9, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 4.3, a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.6, a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 13.1, a n-C10 to tetralin weight ratio less than 23.7, a n-C12 to 2-methylnaphthalene weight ratio less than 5.0, and a n-C12 to 1-methylnaphthalene weight ratio less than 6.8. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C6 to benzene weight ratio less than 13.4, a n-C7 to toluene weight ratio less than 5.1, a n-C8 to ethylbenzene weight ratio less than 12.3, a n-C8 to ortho-xylene weight ratio less than 5.3, a n-C8 to meta-xylene weight ratio less than 1.5, a n-C9 to 1-ethyl-3-methylbenzene weight ratio less than 5.9, a n-C9 to 1-ethyl-4-methylbenzene weight ratio less than 3.8, a n-C9 to 1,2,4-trimethylbenzene weight ratio less than 2.2, a n-C10 to 1-ethyl-2,3-dimethylbenzene weight ratio less than 12.2, a n-C10 to tetralin weight ratio less than 23.4, a n-C12 to 2-methylnaphthalene weight ratio less than 4.0, and a n-C12 to 1-methylnaphthalene weight ratio less than 6.1. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 13.1, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 14.9, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 7.0, a n-C7 to methyl cyclohexane weight ratio less than 5.2, a n-C7 to ethyl cyclopentane weight ratio less than 11.3, a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 16.0, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 17.5, and a n-C8 to ethyl cyclohexane weight ratio less than 12.3. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 12.7, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 14.7, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 6.6, a n-C7 to methyl cyclohexane weight ratio less than 5.0, a n-C7 to ethyl cyclopentane weight ratio less than 10.9, a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 15.4, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 16.5, and a n-C8 to ethyl cyclohexane weight ratio less than 12.0. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 10.3, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 11.6, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 5.9, a n-C7 to methyl cyclohexane weight ratio less than 4.1, a n-C7 to ethyl cyclopentane weight ratio less than 9.5, a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 13.9, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 12.3, and a n-C8 to ethyl cyclohexane weight ratio less than 10.3. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion has a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio less than 13.1, 12, 10, 7, or 5. In some embodiments the condensable hydrocarbon portion has a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio less than 14.9, 13, 10, 7 or 5. In some embodiments the condensable hydrocarbon portion has a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio less than 7.0, 6.0, 5.0 or 4.0. In some embodiments the condensable hydrocarbon portion has a n-C7 to methyl cyclohexane weight ratio less than 5.2, 4.7, 4.2, 3.5 or 2.0. In some embodiments the condensable hydrocarbon portion has a n-C7 to ethyl cyclopentane weight ratio less than 11.3, 10.0, 8.0, 6.5 or 5.0. In some embodiments the condensable hydrocarbon portion has a n-C8 to 1,1-dimethyl cyclohexane weight ratio less than 15.4, 14.0, 12.0, 10.0 or 9.0. In some embodiments the condensable hydrocarbon portion has a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio less than 16.5, 15.0, 12.0, 9.0 or 6.0. In some embodiments the condensable hydrocarbon portion has a n-C8 to ethyl cyclohexane weight ratio less than 12.0, 10.0, 8.0, 6.0 or 5.0.
In some embodiments the condensable hydrocarbon portion has a n-C7 to cis 1,3-dimethyl cyclopentane weight ratio greater than 0.5 or 1.0, a n-C7 to trans 1,3-dimethyl cyclopentane weight ratio greater than 0.5 or 1.0, a n-C7 to trans 1,2-dimethyl cyclopentane weight ratio greater than 0.5 or 1.0, a n-C7 to methyl cyclohexane weight ratio greater than 0.2 or 0.5, a n-C7 to ethyl cyclopentane weight ratio greater than 0.5 or 1.0, a n-C8 to 1,1-dimethyl cyclohexane weight ratio greater than 0.5 or 1.0, a n-C8 to trans 1,2-dimethyl cyclohexane weight ratio greater than 0.5 or 1.0, and/or a n-C8 to ethyl cyclohexane weight ratio greater than 0.5 or 1.0.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C9 to IP-9 weight ratio greater than 2.4, a n-C10 to IP-10 weight ratio greater than 1.4, a n-C11 to IP-11 weight ratio greater than 1.0, a n-C13 to IP-13 weight ratio greater than 1.1, a n-C14 to IP-14 weight ratio greater than 1.1, a n-C15 to IP-15 weight ratio greater than 1.0, a n-C16 to IP-16 weight ratio greater than 0.8, a n-C18 to IP-18 weight ratio greater than 1.0, and a n-C19 to pristane weight ratio greater than 1.6. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C9 to IP-9 weight ratio greater than 2.5, a n-C10 to IP-10 weight ratio greater than 1.5, a n-C11 to IP-11 weight ratio greater than 1.1, a n-C13 to IP-13 weight ratio greater than 1.2, a n-C14 to IP-14 weight ratio greater than 1.2, a n-C15 to IP-15 weight ratio greater than 1.1, a n-C16 to IP-16 weight ratio greater than 0.9, a n-C18 to IP-18 weight ratio greater than 1.1, and a n-C19 to pristane weight ratio greater than 1.8. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a n-C9 to IP-9 weight ratio greater than 2.6, a n-C10 to IP-10 weight ratio greater than 1.6, a n-C11 to IP-11 weight ratio greater than 1.2, a n-C13 to IP-13 weight ratio greater than 1.3, a n-C14 to IP-14 weight ratio greater than 1.4, a n-C15 to IP-15 weight ratio greater than 1.4, a n-C16 to IP-16 weight ratio greater than 1.2, a n-C18 to IP-18 weight ratio greater than 1.5, and a n-C19 to pristane weight ratio greater than 2.4. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion has a n-C9 to IP-9 weight ratio greater than 2.4, 3.0, 4.0, 5.0 or 6.0. In some embodiments the condensable hydrocarbon portion has a n-C10 to IP-10 weight ratio greater than 1.4, 2.0, 2.5, 3.0 or 4.0. In some embodiments the condensable hydrocarbon portion has a n-C11 to IP-11 weight ratio greater than 1.0, 1.5, 2.0, 2.5 or 3.5. In some embodiments the condensable hydrocarbon portion has a n-C13 to IP-13 weight ratio greater than 1.1, 1.5, 2.0, 2.5 or 3.0. In some embodiments the condensable hydrocarbon portion has a n-C14 to IP-14 weight ratio greater than 1.1, 2.0, 3.0, 4.0 or 5.0. In some embodiments the condensable hydrocarbon portion has a n-C15 to IP-15 weight ratio greater than 1.0, 1.5, 2.0, 3.0 or 4.0. In some embodiments the condensable hydrocarbon portion has a n-C16 to IP-16 weight ratio greater than 0.8, 1.0, 1.5, 2.0, 3.0 or 7.0. In some embodiments the condensable hydrocarbon portion has a n-C18 to IP-18 weight ratio greater than 1.0, 1.5, 2.0, 2.5 or 5.0. In some embodiments the condensable hydrocarbon portion has a n-C19 to pristane weight ratio greater than 2.4, 3.0, 3.5, 4.0 or 6.0.
In some embodiments the condensable hydrocarbon portion has a n-C9 to IP-9 weight ratio less than 15.0 or 10.0, a n-C10 to IP-10 weight ratio less than 15.0 or 10.0, a n-C11 to IP-11 weight ratio less than 15.0 or 10.0, a n-C13 to IP-13 weight ratio less than 15.0 or 10.0, a n-C14 to IP-14 weight ratio less than 15.0 or 10.0, a n-C15 to IP-15 weight ratio less than 15.0 or 10.0, a n-C16 to IP-16 weight ratio less than 15.0 or 10.0, a n-C18 to IP-18 weight ratio less than 15.0 or 10.0, and/or a n-C19 to pristane weight ratio less than 15.0 or 10.0.
In some embodiments the condensable hydrocarbon portion may have one or more of a ethyl-3,5-dimethylbenzene to IP-10 weight ratio greater than 0.3, a 1 ethyl-3,5-dimethylbenzene to IP-11 weight ratio greater than 0.2, a 3-methyldodecane to IP-13 weight ratio greater than 0.2, a 3-methyldodecane to IP-14 weight ratio greater than 0.2, a 3-methyldodecane to IP-15 weight ratio greater than 0.2, a 3-methyldodecane to IP-16 weight ratio greater than 0.2, a 3-methyldodecane to IP-18 weight ratio greater than 0.2, and a 3-methyldodecane to pristane weight ratio greater than 0.2. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
As used in the preceding paragraphs and in the claims with respect to aromatic, cyclic, isoprenoid and normal hydrocarbon compounds, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in the preceding paragraphs may be combined with any of the other aspects of the invention discussed herein. Certain features of the present invention discussed in the preceding paragraphs are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g. “greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in the preceding paragraphs may be combined with any of the other aspects of the invention discussed in such paragraphs or otherwise herein.
The use of “n-C_” (e.g., n-C10) herein and in the claims is meant to refer to the amount of a particular normal alkane hydrocarbon compound found in a condensable hydrocarbon fluid determined by C4-C19 liquid sample gas chromatography (C4-C19 GC) as described herein, particularly in the section labeled “Experiments” herein. That is “n-C_” is determined from the respective C4-C19 peak area determined using the C4-C19 analysis methodology according to the procedure described in the Experiments section of this application. Further, when a particular “n-C_” normal alkane hydrocarbon compound is compared to another hydrocarbon compound in a weight ratio herein and in the claims, such a weight ratio is obtained by the ratio of the particular “n-C_” normal alkane hydrocarbon compound's C4-C19 peak area to the other particular hydrocarbon compound's C4-C19 peak area. For example, an n-C8 to ethylbenzene weigh ratio is obtained by dividing the n-C8 C4-C19 GC peak area for a respective condensable hydrocarbon fluid by the C4-C19 GC peak area for ethylbenzene, where both of such respective C4-C19 GC peak areas are determined by the C4-C19 GC analysis procedures, C4-C19 GC peak identification methodologies, and C4-C19 GC peak integration methodologies discussed in the Experiments section herein.
As used herein and in the claims, weight ratios of aromatic hydrocarbon compounds (e.g., toluene, ortho-xylene, or 1,2,4-trimethylbenzene), cyclic hydrocarbon compounds (e.g., 1,3-dimethyl cyclopentane, ethyl cyclopentane, or ethyl cyclohexane) and isoprenoid compounds (e.g., IP-9, IP-11, or pristane) is meant to refer to the amount of a particular hydrocarbon compound found in a condensable hydrocarbon fluid as determined by C4-C19 liquid sample gas chromatography (C4-C19 GC) as described herein, particularly in the section labeled “Experiments” herein. That is the amount of a respective compound is determined from the respective C4-C19 peak area determined using the C4-C19 analysis methodology according to the procedure described in the Experiments section of this application. Further, when a first hydrocarbon compound is compared to a second hydrocarbon compound in a weight ratio herein and in the claims, such a weight ratio is obtained by the ratio of the first hydrocarbon compound's C4-C19 peak area to the second hydrocarbon compound's C4-C19 peak area. For example, an n-C9 to IP-9 weigh ratio is obtained by dividing the n-C9 C4-C19 GC peak area for a respective condensable hydrocarbon fluid by the C4-C19 GC peak area for IP-9, where both of such respective C4-C19 GC peak areas are determined by the C4-C19 GC analysis procedures, C4-C19 GC peak identification methodologies, and C4-C19 GC peak integration methodologies discussed in the Experiments section herein.
Certain hydrocarbon compounds, particularly certain stereoisomers of certain hydrocarbon compounds, can be used for a variety of purposes including, for example: determine the relative age of naturally occurring petroleum deposits, characterizing the source kerogen of naturally occurring oils, and estimating the level of thermal maturation of a naturally occurring oil or kerogen. Examples of such techniques can be found in Peters, K. E., Walters, C. C., and Moldowan, J. M., The Biomarker Guide, Vol. 1 & 2, Cambridge University Press (2005). Applicants have investigated certain biomarkers for the hydrocarbon fluids produced in Examples 6-19 and the liquid chromatographic extraction described in Example 20, and some of the biomarker data generated in such experiments is presented in
Hopanes, steranes and phenanthrenes are hydrocarbon molecules that show systematic isomerization reactions governed by thermal maturation in natural hydrocarbon systems. Hopanes, and steranes like many molecules of biologic origin, are generally found in certain stereoisomer forms in biological matter. The biological stereoisomers may be a less thermodynamically stable form of the compound, but are generated enzymatically for a specific biological function in a living organism. As the biological matter is altered by diagenesis, catagenesis, and metagenesis additional stereoisomeric compounds may be formed as the biological stereoisomeric form is transformed into more thermodynamically stable isomers. Moreover, the amount of a particular biological compound or derivative thereof present in a source rock or petroleum deposit may be reduced or eliminated by diagenesis, catagenesis, and metagenesis. Generally the proportion of a geologic, more thermodynamically stable stereoisomer relative to the proportion of the biological, less thermodynamically stable stereoisomer in a source rock or naturally occurring petroleum deposit can be used to gauge the amount of maturation of such source rock or petroleum deposit. Methylated phenanthrenes behave in a similar fashion during progressive maturation with certain attachment sites for the methyl group favored within certain maturation ranges.
From the above-described data discussed in
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have a (trisnorhopane maturable (Tm)) to (trisnorhopane maturable (Tm)+trisnorhopane stable (Ts)) or alternatively (Tm/Tm+Ts) weight ratio greater than 0.7. In alternate embodiments the condensable hydrocarbon portion may have a (trisnorhopane maturable) to (trisnorhopane maturable+trisnorhopane stable) weight ratio greater than 0.8, 0.9 or 0.95. In alternate embodiments the condensable hydrocarbon portion may have a (trisnorhopane maturable) to (trisnorhopane maturable+trisnorhopane stable) weight ratio between 0.7 and 0.995, between 0.8 and 0.990, or between 0.7 and 0.995.
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29H αβ/29H αβ+29H ββ) weight ratio less than 0.9. In alternate embodiments the condensable hydrocarbon portion may have a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] weight ratio less than 0.8, 0.7 or 0.6. In alternate embodiments the condensable hydrocarbon portion may have a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] weight ratio between 0.2 and 0.9, between 0.25 and 0.6, or between 0.3 and 0.5.
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have a [C-30 17α(H), 21β(H) hopane] to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30H αβ/30H αβ+30H ββ) weight ratio less than 0.9. In alternate embodiments the condensable hydrocarbon portion may have a [C-30 17α(H), 21β(H) hopane] to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] weight ratio less than 0.8, 0.7 or 0.6. In alternate embodiments the condensable hydrocarbon portion may have a [C-30 17α(H), 21β(H) hopane] to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] weight ratio between 0.3 and 0.62, between 0.35 and 0.60, or between 0.4 and 0.58.
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have a [C-31 17α(H), 21β(H), 22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22R homohopane] or alternatively (31H-S/31H-S+31H-R) weight ratio less than 0.6. In alternate embodiments the condensable hydrocarbon portion may have a [C-31 17α(H), 21β(H), 22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22R homohopane] weight ratio less than 0.58, 0.55 or 0.50. In alternate embodiments the condensable hydrocarbon portion may have a [C-31 17α(H), 21β(H), 22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22R homohopane] weight ratio between 0.25 and 0.6, between 0.3 and 0.58, or between 0.4 and 0.55.
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14 α, 17α(H) 20S steranes] or alternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio less than 0.7. In alternate embodiments the condensable hydrocarbon portion may have a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14 α, 17α(H) 20S steranes] weight ratio less than 0.6, 0.5 or 0.4. In alternate embodiments the condensable hydrocarbon portion may have a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] weight ratio between 0.2 and 0.7, between 0.25 and 0.5, or between 0.25 and 0.3.
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] or alternatively (C-29αββ S&R/C-29αββ S&R+C-29ααα S&R) weight ratio less than 0.7. In alternate embodiments the condensable hydrocarbon portion may have a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] weight ratio less than 0.6, 0.4, 0.25 or 0.24. In alternate embodiments the condensable hydrocarbon portion may have a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] weight ratio between 0.15 and 0.7, between 0.17 and 0.5, or between 0.17 and 0.25.
In some embodiments, the produced hydrocarbon fluid includes a condensable hydrocarbon portion. In some embodiments the condensable hydrocarbon portion may have a [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)]/[1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratio greater than 0.5. In alternate embodiments the condensable hydrocarbon portion may have a [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)]/[1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratio greater than 0.75, 1.0 or 1.25. In alternate embodiments the condensable hydrocarbon portion may have a [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)]/[1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratio between 0.5 and 3.0, between 1.0 and 2.5, or between 1.25 and 2.5.
In some embodiments the condensable hydrocarbon portion may have one or more of a (trisnorhopane maturable (Tm)) to (trisnorhopane maturable (Tm)+trisnorhopane stable (Ts)) or alternatively (Tm/Tm+Ts) weight ratio greater than 0.7, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29H αβ/29H αβ+29H ββ3) weight ratio less than 0.9, a [C-30 17α(H), 21β(H) hopane] to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30H αβ/30H αβ+30H ββ) weight ratio less than 0.9, a [C-31 17α(H), 21β(H), 22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22R homohopane] or alternatively (31H-S/31H-S+31H-R) weight ratio less than 0.6, a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] or alternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio less than 0.7, a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] or alternatively (C-29αββ S&R/C-29αββ S&R+C-29 ααα S&R) weight ratio less than 0.7, and a [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)] to [1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratio greater than 0.5. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a (trisnorhopane maturable (Tm)) to (trisnorhopane maturable (Tm)+trisnorhopane stable (Ts)) or alternatively (Tm/Tm+Ts) weight ratio greater than 0.8, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29H αβ/29H αβ+29H ββ) weight ratio less than 0.8, a [C-30 17α(H), 21β(H) hopane] to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30H αβ/30H αβ+30H β(3) weight ratio less than 0.8, a [C-31 17α(H), 21β(H), 22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22R homohopane] or alternatively (31H-S/31H-S+31H-R) weight ratio less than 0.58, a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] or alternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio less than 0.6, a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to [C-29 5α, 14β, 17β (H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] or alternatively (C-29 αββ S&R/C-29αββ S&R+C-29 ααα S&R) weight ratio less than 0.6, and a [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)] to [1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratio greater than 0.75. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
In some embodiments the condensable hydrocarbon portion may have one or more of a (trisnorhopane maturable (Tm)) to (trisnorhopane maturable (Tm)+trisnorhopane stable (Ts)) or alternatively (Tm/Tm+Ts) weight ratio greater than 0.7, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21β(H) hopane] or alternatively (29H αβ/29H αβ+29H ββ) weight ratio less than 0.7, a [C-30 17α(H), 21β(H) hopane] to [C-30 17α(H), 21β(H) hopane+C-30 17β(H), 21β(H) hopane] or alternatively (30H αβ/30H αβ+30H ββ) weight ratio less than 0.7, a [C-31 17α(H), 21β(H), 22S homohopane] to [C-31 17α(H), 21β(H), 22S homohopane+C-31 17α(H), 21β(H), 22R homohopane] or alternatively (31H-S/31H-S+31H-R) weight ratio less than 0.55, a [C-29 5α, 14α, 17α(H) 20R steranes] to [C-29 5α, 14α, 17α(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S steranes] or alternatively (C-29 ααα S/C-29 ααα S+C-29 ααα R) weight ratio less than 0.5, a [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes] to [C-29 5α, 14β, 17β(H) 20S+C-29 5α, 14β, 17β(H) 20R steranes+C-29 5α, 14α, 17α(H) 20S+C-29 5α, 14α, 17α(H) 20R steranes] or alternatively (C-29αββ S&R/C-29 αββ S&R+C-29 ααα S&R) weight ratio less than 0.55, and a [3-methyl phenanthrene (3-MP)+2-methyl phenanthrene (2-MP)] to [1-methyl phenanthrene (1-MP)+9-methyl phenanthrene (9-MP)] weight ratio greater than 0.1.0. In some embodiments the condensable hydrocarbon portion may have two or more, three or more or four or more of the weight ratios described above in the paragraph.
As used in the preceding paragraphs and in the claims with respect to hopanes, steranes and phenanthrenes, the phrase “one or more” followed by a listing of different compound or component ratios with the last ratio introduced by the conjunction “and” is meant to include a condensable hydrocarbon portion that has at least one of the listed ratios or that has two or more, or three or more, or four or more, etc., or all of the listed ratios. Further, a particular condensable hydrocarbon portion may also have additional ratios of different compounds or components that are not included in a particular sentence or claim and still fall within the scope of such a sentence or claim. The embodiments described in the preceding paragraphs may be combined with any of the other aspects of the invention discussed herein. Certain features of the present invention discussed in the preceding paragraphs are described in terms of a set of numerical upper limits (e.g. “less than”) and a set of numerical lower limits (e.g.
“greater than”) in the preceding paragraph. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. The embodiments described in the preceding paragraphs may be combined with any of the other aspects of the invention discussed in such paragraphs or otherwise herein.
As used herein and in the claims, weight ratios of hopanes (e.g., C-29 17α(H), 21β(H) hopane), steranes (e.g., C-29 5α, 14α, 17α(H) 20R steranes) and phenanthrenes (e.g., 3-methyl phenanthrene) is meant to refer to the amount of a particular hydrocarbon compound found in a condensable hydrocarbon fluid as determined by liquid chromatography (LC) followed by gas chromatography/mass spectrometry (GC/MS) as described herein, particularly in the section labeled “Experiments” herein. That is, the amount of a respective compound is determined from the respective GC/MS peak height determined using the LC and GC/MS analysis methodology according to the procedure described in the Experiments section of this application. Further, when a first compound is compared to a second compound in a weight ratio herein and in the claims, such a weight ratio is obtained by the ratio of the first compound's GC/MS peak height to the second compound's GC/MS peak height. For example, a [C-29 17α(H), 21β(H) hopane] to [C-29 17α(H), 21β(H) hopane+C-29 17β(H), 21[3(H) hopane] weigh ratio is obtained by dividing the [C-29 17α(H), 21β(H) hopane] GC/MS peak height for a respective condensable hydrocarbon fluid by the total GC/MS peak height for [C-29 17α(H), 21β(H) hopane] and [C-29 17β(H), 21β(H) hopane], where both of such respective GC/MS peak heights are determined by the by liquid chromatography (LC) and gas chromatography/mass spectrometry (GC/MS) analysis procedures, GC/MS peak identification methodologies, and GC/MS peak measurement methodologies discussed in the Experiments section herein.
The discovery that lithostatic stress can affect the composition of produced fluids generated within an organic-rich rock via heating and pyrolysis implies that the composition of the produced hydrocarbon fluid can also be influenced by altering the lithostatic stress of the organic-rich rock formation. For example, the lithostatic stress of the organic-rich rock formation may be altered by choice of pillar geometries and/or locations and/or by choice of heating and pyrolysis formation region thickness and/or heating sequencing.
Pillars are regions within the organic-rich rock formation left unpyrolized at a given time to lessen or mitigate surface subsidence. Pillars may be regions within a formation surrounded by pyrolysis regions within the same formation. Alternatively, pillars may be part of or connected to the unheated regions outside the general development area. Certain regions that act as pillars early in the life of a producing field may be converted to producing regions later in the life of the field.
Typically in its natural state, the weight of a formation's overburden is fairly uniformly distributed over the formation. In this state the lithostatic stress existing at particular point within a formation is largely controlled by the thickness and density of the overburden. A desired lithostatic stress may be selected by analyzing overburden geology and choosing a position with an appropriate depth and position.
Although lithostatic stresses are commonly assumed to be set by nature and not changeable short of removing all or part of the overburden, lithostatic stress at a specific location within a formation can be adjusted by redistributing the overburden weight so it is not uniformly supported by the formation. For example, this redistribution of overburden weight may be accomplished by two exemplary methods. One or both of these methods may be used within a single formation. In certain cases, one method may be primarily used earlier in time whereas the other may be primarily used at a later time. Favorably altering the lithostatic stress experienced by a formation region may be performed prior to instigating significant pyrolysis within the formation region and also before generating significant hydrocarbon fluids. Alternately, favorably altering the lithostatic stress may be performed simultaneously with the pyrolysis.
A first method of altering lithostatic stress involves making a region of a subsurface formation less stiff than its neighboring regions. Neighboring regions thus increasingly act as pillars supporting the overburden as a particular region becomes less stiff. These pillar regions experience increased lithostatic stress whereas the less stiff region experiences reduced lithostatic stress. The amount of change in lithostatic stress depends upon a number of factors including, for example, the change in stiffness of the treated region, the size of the treated region, the pillar size, the pillar spacing, the rock compressibility, and the rock strength. In an organic-rich rock formation, a region within a formation may be made to experience mechanical weakening by pyrolyzing the region and creating void space within the region by removing produced fluids. In this way a region within a formation may be made less stiff than neighboring regions that have not experienced pyrolysis or have experienced a lesser degree of pyrolysis or production.
A second method of altering lithostatic stress involves causing a region of a subsurface formation to expand and push against the overburden with greater force than neighboring regions. This expansion may remove a portion of the overburden weight from the neighboring regions thus increasing the lithostatic stress experienced by the heated region and reducing the lithostatic stress experienced by neighboring regions. If the expansion is sufficient, horizontal fractures will form in the neighboring regions and the contribution of these regions to supporting the overburden will decrease. The amount of change in lithostatic stress depends upon a number of factors including, for example, the amount of expansion in the treated region, the size of the treated region, the pillar size, the pillar spacing, the rock compressibility, and the rock strength. A region within a formation may be made to expand by heating it so to cause thermal expansion of the rock. Fluid expansion or fluid generation can also contribute to expansion if the fluids are largely trapped within the region. The total expansion amount may be proportional to the thickness of the heated region. It is noted that if pyrolysis occurs in the heated region and sufficient fluids are removed, the heated region may mechanically weaken and thus may alter the lithostatic stresses experienced by the neighboring regions as described in the first exemplary method.
Embodiments of the method may include controlling the composition of produced hydrocarbon fluids generated by heating and pyrolysis from a first region within an organic-rich rock formation by increasing the lithostatic stresses within the first region by first heating and pyrolyzing formation hydrocarbons present in the organic-rich rock formation and producing fluids from a second neighboring region within the organic-rich rock formation such that the Young's modulus (i.e., stiffness) of the second region is reduced.
Embodiments of the method may include controlling the composition of produced hydrocarbon fluids generated by heating and pyrolysis from a first region within an organic-rich rock formation by increasing the lithostatic stresses within the first region by heating the first region prior to or to a greater degree than neighboring regions within the organic-rich rock formation such that the thermal expansion within the first region is greater than that within the neighboring regions of the organic-rich rock formation.
Embodiments of the method may include controlling the composition of produced hydrocarbon fluids generated by heating and pyrolysis from a first region within an organic-rich rock formation by decreasing the lithostatic stresses within the first region by heating one or more neighboring regions of the organic-rich rock formation prior to or to a greater degree than the first region such that the thermal expansion within the neighboring regions is greater than that within the first region.
Embodiments of the method may include locating, sizing, and/or timing the heating of heated regions within an organic-rich rock formation so as to alter the in situ lithostatic stresses of current or future heating and pyrolysis regions within the organic-rich rock formation so as to control the composition of produced hydrocarbon fluids.
Some production procedures include in situ heating of an organic-rich rock formation that contains both formation hydrocarbons and formation water-soluble minerals prior to substantial removal of the formation water-soluble minerals from the organic-rich rock formation. In some embodiments of the invention there is no need to partially, substantially or completely remove the water-soluble minerals prior to in situ heating. For example, in an oil shale formation that contains naturally occurring nahcolite, the oil shale may be heated prior to substantial removal of the nahcolite by solution mining. Substantial removal of a water-soluble mineral may represent the degree of removal of a water-soluble mineral that occurs from any commercial solution mining operation as known in the art. Substantial removal of a water-soluble mineral may be approximated as removal of greater than 5 weight percent of the total amount of a particular water-soluble mineral present in the zone targeted for hydrocarbon fluid production in the organic-rich rock formation. In alternative embodiments, in situ heating of the organic-rich rock formation to pyrolyze formation hydrocarbons may be commenced prior to removal of greater than 3 weight percent, alternatively 7 weight percent, 10 weight percent or 13 weight percent of the formation water-soluble minerals from the organic-rich rock formation.
The impact of heating oil shale to produce oil and gas prior to producing nahcolite is to convert the nahcolite to a more recoverable form (soda ash), and provide permeability facilitating its subsequent recovery. Water-soluble mineral recovery may take place as soon as the retorted oil is produced, or it may be left for a period of years for later recovery. If desired, the soda ash can be readily converted back to nahcolite on the surface. The ease with which this conversion can be accomplished makes the two minerals effectively interchangeable.
In some production processes, heating the organic-rich rock formation includes generating soda ash by decomposition of nahcolite. The method may include processing an aqueous solution containing water-soluble minerals in a surface facility to remove a portion of the water-soluble minerals. The processing step may include removing the water-soluble minerals by precipitation caused by altering the temperature of the aqueous solution.
The water-soluble minerals may include sodium. The water-soluble minerals may also include nahcolite (sodium bicarbonate), soda ash (sodium carbonate), dawsonite (NaAl(CO3)(OH)2), or combinations thereof. The surface processing may further include converting the soda ash back to sodium bicarbonate (nahcolite) in the surface facility by reaction with CO2. After partial or complete removal of the water-soluble minerals, the aqueous solution may be reinjected into a subsurface formation where it may be sequestered. The subsurface formation may be the same as or different from the original organic-rich rock formation.
In some production processes, heating of the organic-rich rock formation both pyrolyzes at least a portion of the formation hydrocarbons to create hydrocarbon fluids and makes available migratory contaminant species previously bound in the organic-rich rock formation. The migratory contaminant species may be formed through pyrolysis of the formation hydrocarbons, may be liberated from the formation itself upon heating, or may be made accessible through the creation of increased permeability upon heating of the formation. The migratory contaminant species may be soluble in water or other aqueous fluids present in or injected into the organic-rich rock formation.
Producing hydrocarbons from pyrolyzed oil shale will generally leave behind some migratory contaminant species which are at least partially water-soluble. Depending on the hydrological connectivity of the pyrolyzed shale oil to shallower zones, these components may eventually migrate into ground water in concentrations which are environmentally unacceptable. The types of potential migratory contaminant species depend on the nature of the oil shale pyrolysis and the composition of the oil shale being converted. If the pyrolysis is performed in the absence of oxygen or air, the contaminant species may include aromatic hydrocarbons (e.g. benzene, toluene, ethylbenzene, xylenes), polyaromatic hydrocarbons (e.g. anthracene, pyrene, naphthalene, chrysene), metal contaminants (e.g. As, Co, Pb, Mo, Ni, and Zn), and other species such as sulfates, ammonia, Al, K, Mg, chlorides, flourides and phenols. If oxygen or air is employed, contaminant species may also include ketones, alcohols, and cyanides. Further, the specific migratory contaminant species present may include any subset or combination of the above-described species.
It may be desirable for a field developer to assess the connectivity of the organic-rich rock formation to aquifers. This may be done to determine if, or to what extent, in situ pyrolysis of formation hydrocarbons in the organic-rich rock formation may create migratory species with the propensity to migrate into an aquifer. If the organic-rich rock formation is hydrologically connected to an aquifer, precautions may be taken to reduce or prevent species generated or liberated during pyrolysis from entering the aquifer. Alternatively, the organic-rich rock formation may be flushed with water or an aqueous fluid after pyrolysis as described herein to remove water-soluble minerals and/or migratory contaminant species. In other embodiments, the organic-rich rock formation may be substantially hydrologically unconnected to any source of ground water. In such a case, flushing the organic-rich rock formation may not be desirable for removal of migratory contaminant species but may nevertheless be desirable for recovery of water-soluble minerals.
Following production of hydrocarbons from an organic-rich formation, some migratory contaminant species may remain in the rock formation. In such case, it may be desirable to inject an aqueous fluid into the organic-rich rock formation and have the injected aqueous fluid dissolve at least a portion of the water-soluble minerals and/or the migratory contaminant species to form an aqueous solution. The aqueous solution may then be produced from the organic-rich rock formation through, for example, solution production wells. The aqueous fluid may be adjusted to increase the solubility of the migratory contaminant species and/or the water-soluble minerals. The adjustment may include the addition of an acid or base to adjust the pH of the solution. The resulting aqueous solution may then be produced from the organic-rich rock formation to the surface for processing.
After initial aqueous fluid production, it may further be desirable to flush the matured organic-rich rock zone and the unmatured organic-rich rock zone with an aqueous fluid. The aqueous fluid may be used to further dissolve water-soluble minerals and migratory contaminant species. The flushing may optionally be completed after a substantial portion of the hydrocarbon fluids have been produced from the matured organic-rich rock zone. In some embodiments, the flushing step may be delayed after the hydrocarbon fluid production step. The flushing may be delayed to allow heat generated from the heating step to migrate deeper into surrounding unmatured organic-rich rock zones to convert nahcolite within the surrounding unmatured organic-rich rock zones to soda ash. Alternatively, the flushing may be delayed to allow heat generated from the heating step to generate permeability within the surrounding unmatured organic-rich rock zones. Further, the flushing may be delayed based on current and/or forecast market prices of sodium bicarbonate, soda ash, or both as further discussed herein. This method may be combined with any of the other aspects of the invention as discussed herein
Upon flushing of an aqueous solution, it may be desirable to process the aqueous solution in a surface facility to remove at least some of the migratory contaminant species. The migratory contaminant species may be removed through use of, for example, an adsorbent material, reverse osmosis, chemical oxidation, bio-oxidation, and/or ion exchange. Examples of these processes are individually known in the art. Exemplary adsorbent materials may include activated carbon, clay, or fuller's earth.
In certain areas with oil shale resources, additional oil shale resources or other hydrocarbon resources may exist at lower depths. Other hydrocarbon resources may include natural gas in low permeability formations (so-called “tight gas”) or natural gas trapped in and adsorbed on coal (so called “coal bed methane”). In some embodiments with multiple shale oil resources it may be advantageous to develop deeper zones first and then sequentially shallower zones. In this way, wells will need not cross hot zones or zones of weakened rock. In other embodiments in may be advantageous to develop deeper zones by drilling wells through regions being utilized as pillars for shale oil development at a shallower depth.
Simultaneous development of shale oil resources and natural gas resources in the same area can synergistically utilize certain facility and logistic operations. For example, gas treating may be performed at a single plant. Likewise personnel may be shared among the developments.
Produced fluids from in situ oil shale production contain a number of components which may be separated in surface facilities. The produced fluids typically contain water, noncondensable hydrocarbon alkane species (e.g., methane, ethane, propane, n-butane, isobutane), noncondensable hydrocarbon alkene species (e.g., ethene, propene), condensable hydrocarbon species composed of (alkanes, olefins, aromatics, and polyaromatics among others), CO2, CO, H2, H2S, and NH3.
In a surface facility, condensable components may be separated from non-condensable components by reducing temperature and/or increasing pressure. Temperature reduction may be accomplished using heat exchangers cooled by ambient air or available water. Alternatively, the hot produced fluids may be cooled via heat exchange with produced hydrocarbon fluids previously cooled. The pressure may be increased via centrifugal or reciprocating compressors. Alternatively, or in conjunction, a diffuser-expander apparatus may be used to condense out liquids from gaseous flows. Separations may involve several stages of cooling and/or pressure changes.
Water in addition to condensable hydrocarbons may be dropped out of the gas when reducing temperature or increasing pressure. Liquid water may be separated from condensable hydrocarbons via gravity settling vessels or centrifugal separators. Demulsifiers may be used to aid in water separation.
Methods to remove CO2, as well as other so-called acid gases (such as H2S), from produced hydrocarbon gas include the use of chemical reaction processes and of physical solvent processes. Chemical reaction processes typically involve contacting the gas stream with an aqueous amine solution at high pressure and/or low temperature. This causes the acid gas species to chemically react with the amines and go into solution. By raising the temperature and/or lowering the pressure, the chemical reaction can be reversed and a concentrated stream of acid gases can be recovered. An alternative chemical reaction process involves hot carbonate solutions, typically potassium carbonate. The hot carbonate solution is regenerated and the concentrated stream of acid gases is recovered by contacting the solution with steam. Physical solvent processes typically involve contacting the gas stream with a glycol at high pressure and/or low temperature. Like the amine processes, reducing the pressure or raising the temperature allows regeneration of the solvent and recovery of the acid gases. Certain amines or glycols may be more or less selective in the types of acid gas species removed. Sizing of any of these processes requires determining the amount of chemical to circulate, the rate of circulation, the energy input for regeneration, and the size and type of gas-chemical contacting equipment. Contacting equipment may include packed or multi-tray countercurrent towers. Optimal sizing for each of these aspects is highly dependent on the rate at which gas is being produced from the formation and the concentration of the acid gases in the gas stream.
Acid gas removal may also be effectuated through the use of distillation towers. Such towers may include an intermediate freezing section wherein frozen CO2 and H25 particles are allowed to form. A mixture of frozen particles and liquids fall downward into a stripping section, where the lighter hydrocarbon gasses break out and rise within the tower. A rectification section may be provided at an upper end of the tower to further facilitate the cleaning of the overhead gas stream.
The hydrogen content of a gas stream may be adjusted by either removing all or a portion of the hydrogen or by removing all or a portion of the non-hydrogen species (e.g., CO2, CH4, etc.) Separations may be accomplished using cryogenic condensation, pressure-swing or temperature-swing adsorption, or selective diffusion membranes. If additional hydrogen is needed, hydrogen may be made by reforming methane via the classic water-shift reaction.
Heating experiments were conducted on several different oil shale specimens and the liquids and gases released from the heated oil shale examined in detail. An oil shale sample from the Mahogany formation in the Piceance Basin in Colorado was collected. A solid, continuous block of the oil shale formation, approximately 1 cubic foot in size, was collected from the pilot mine at the Colony mine site on the eastern side of Parachute Creek. The oil shale block was designated CM-1B. The core specimens taken from this block, as described in the following examples, were all taken from the same stratigraphic interval. The heating tests were conducted using a Parr vessel, model number 243HC5, which is shown in
Oil shale block CM-1B was cored across the bedding planes to produce a cylinder 1.391 inches in diameter and approximately 2 inches long. A gold tube 7002 approximately 2 inches in diameter and 5 inches long was crimped and a screen 7000 inserted to serve as a support for the core specimen 7001 (
The room temperature Parr vessel was sampled to obtain a representative portion of the gas remaining in the vessel following the heating experiment. A small gas sampling cylinder 150 milliliters in volume was evacuated, attached to the Parr vessel and the pressure allowed to equilibrate. Gas chromatography (GC) analysis testing and non-hydrocarbon gas sample gas chromatography (GC) (GC not shown) of this gas sample yielded the results shown in
The Parr vessel was then vented to achieve atmospheric pressure, the vessel opened, and liquids collected from both inside the gold tube and in the bottom of the Parr vessel. Water was separated from the hydrocarbon layer and weighed. The amount collected is noted in Table 1. The collected hydrocarbon liquids were placed in a small vial, sealed and stored in the absence of light. No solids were observed on the walls of the gold tube or the walls of the Parr vessel. The solid core specimen was weighed and determined to have lost 19.21 grams as a result of heating. Whole oil gas chromatography (WOGC) testing of the liquid yielded the results shown in
Oil shale block CM-1B was cored in a manner similar to that of Example 1 except that a 1 inch diameter core was created. With reference to
As described in Example 1, the room temperature Parr vessel was then sampled to obtain a representative portion of the gas remaining in the vessel following the heating experiment. Gas sampling, hydrocarbon gas sample gas chromatography (GC) testing, and non-hydrocarbon gas sample gas chromatography (GC) was conducted as in Example 1. Results are shown in
At this point, the Parr vessel was vented to achieve atmospheric pressure, the vessel opened, and liquids collected from inside the Parr vessel. Water was separated from the hydrocarbon layer and weighed. The amount collected is noted in Table 1. The collected hydrocarbon liquids were placed in a small vial, sealed and stored in the absence of light. Any additional liquid coating the surface of the apparatus or sides of the Parr vessel was collected with a paper towel and the weight of this collected liquid added to the total liquid collected. Any liquid remaining in the Berea sandstone was extracted with methylene chloride and the weight accounted for in the liquid total reported in Table 1. The Berea sandstone cylinder and end caps were clearly blackened with organic material as a result of the heating. The organic material in the Berea was not extractable with either toluene or methylene chloride, and was therefore determined to be coke formed from the cracking of hydrocarbon liquids. After the heating experiment, the Berea was crushed and its total organic carbon (TOC) was measured. This measurement was used to estimate the amount of coke in the Berea and subsequently how much liquid must have cracked in the Berea. A constant factor of 2.283 was used to convert the TOC measured to an estimate of the amount of liquid, which must have been present to produce the carbon found in the Berea. This liquid estimated is the “inferred oil” value shown in Table 1. The solid core specimen was weighed and determined to have lost 10.29 grams as a result of heating.
Conducted in a manner similar to that of Example 2 on a core specimen from oil shale block CM-1B, where the effective stress applied was 400 psi. Results for the gas sample collected and analyzed by hydrocarbon gas sample gas chromatography (GC) and non-hydrocarbon gas sample gas chromatography (GC) (GC not shown) are shown in
Conducted in a manner similar to that of Example 2 on a core specimen from oil shale block CM-1B; however, in this example the applied effective stress was 1,000 psi. Results for the gas collected and analyzed by hydrocarbon gas sample gas chromatography (GC) and non-hydrocarbon gas sample gas chromatography (GC) (GC not shown) are shown in
Conducted in a manner similar to that of Example 2 on a core specimen from oil shale block CM-1B; however, in this example the applied effective stress was 1,000 psi. Results for the gas collected and analyzed by hydrocarbon gas sample gas chromatography (GC) and non-hydrocarbon gas sample gas chromatography (GC) (GC not shown) are shown in
Heating experiments were conducted on several additional oil shale specimens and the liquids and gases released from the heated oil shale examined in detail. An oil shale sample from the Mahogany formation in the Uinta Basin in Utah was collected. A solid, continuous block of the oil shale formation, approximately 0.5 cubic foot in size, was collected from Hell's Hole Canyon in Utah. The oil shale block was designated HHC-2. The core specimens taken from this block, as described in the following examples, were all taken from the same stratigraphic interval. The heating tests were conducted using a Parr vessel, model number 243HC5, which is shown in
Oil shale block HHC-2 was sampled across the bedding planes to produce samples with an approximately uniform distribution of laminae that were used in four zero effective stress experiments (Examples 6, 7, 13 & 14). This example describes the experimental methodology common to these experiments with individual details for each experiment summarized in Table 15.
For each unstressed experiment, a screen 7000 served as a support for each specimen 7001 (
The room temperature Parr vessel was sampled to obtain a representative portion of the gas remaining in the vessel following the heating experiment. A gas sampling cylinder 150 milliliters in volume was evacuated, attached to the Parr vessel and the pressure allowed to equilibrate. The Parr vessel was then vented, to achieve atmospheric pressure, opened, and liquid collected from the bottom of the Parr vessel. Water was separated from the hydrocarbon layer and weighed. The amount collected is noted in Table 15. The collected hydrocarbon liquids were placed in a small vial, sealed and stored in the absence of light at a constant temperature of 7° C. The solid core specimen was weighed and its new mass recorded (see Table 15). All samples lost mass as a result of heating. C4-C19 liquid sample gas-chromatography (C4-C19 GC) testing of the liquid yielded the results shown in
Oil shale block HHC-2 described in Example 6 was cored perpendicular to bedding to yield a 1 inch diameter cores for use in experiments subjected to effective stress conditions. With reference to
The core specimens 7050 were then placed in Berea sandstone cylinders 7051 with a 1-inch inner diameter and a 1.39 inch outer diameter. Berea plugs 7052 and 7053 were placed at each end of this assembly, so that the core specimens were completely surrounded by Berea. The Berea cylinders and plugs were fired at 500° C. for two hours prior to use with the mini load frame. The Berea cylinder 7051 along with the core specimen 7050 and the Berea end plugs 7052 and 7053 were placed in a slotted stainless steel sleeve and clamped into place. The sample assembly 7060 was placed in a spring-loaded mini-load-frame 7061 as shown in
As described in Example 6, the room temperature Parr vessel was then sampled to obtain a representative portion of the gas remaining in the vessel following the heating experiment. At this point, the Parr vessel was vented to achieve atmospheric pressure, the vessel opened, and liquids collected from inside the Parr vessel. Water was separated from the hydrocarbon layer and weighed. The amount collected is noted in Table 15. The collected hydrocarbon liquids were placed in a small vial, sealed and stored in the absence of light at a constant temperature of 7° C. C4-C19 liquid sample gas-chromatography (C4-C19 GC) testing of the liquid yielded the results shown in
This procedure describes the extraction method used to obtain soluble organic matter (bitumen) from the oil shale sample of Example 20 which was subsequently analyzed by the liquid chromatography (LC) followed by gas chromatography/mass spectrometry (GC/MS) procedures discussed later herein and discussed with reference to
Extraction Method: The Extraction procedure utilized the laboratory equipment and chemicals described in Table 17 as well as other typical laboratory supplies and equipment.
Sample preparation: The Retsch mill and crusher were thoroughly cleaned and the sample was micronized to a particle size of 0.5 micron. About 30 grams of the micronized sample was weighed in the thimble to be used in the extraction.
Extraction procedure: Table 18 describes the extraction method.
Quality Control:
To ensure reproducible results, a known sediment standard was maintained as the QC extraction standard and was tested in conjunction with the sample. The extraction yield for the standard was within the acceptable 2 standard deviation range.
Heating experiments on oil shale at 375 deg. C. under stressed and unstressed conditions confirm that porosity is enhanced by the kerogen conversion process. Exemplary core plugs are provided in
The gas and liquid samples obtained through the experimental procedures and gas and liquid sample collection procedures described for Examples 1-5, were analyzed by the following hydrocarbon gas sample gas chromatography (GC) analysis methodology, non-hydrocarbon gas sample gas chromatography (GC) analysis methodology, gas sample GC peak identification and integration methodology, whole oil gas chromatography (WOGC) analysis methodology, and whole oil gas chromatography (WOGC) peak identification and integration methodology.
Gas samples collected during the heating tests as described in Examples 1-5 were analyzed for both hydrocarbon and non-hydrocarbon gases, using an Agilent Model 6890 Gas Chromatograph coupled to an Agilent Model 5973 quadrapole mass selective detector. The 6890GC was configured with two inlets (front and back) and two detectors (front and back) with two fixed volume sample loops for sample introduction. Peak identifications and integrations were performed using the Chemstation software (Revision A.03.01) supplied with the GC instrument. For hydrocarbon gases, the GC configuration consisted of the following:
For non-hydrocarbon gases (e.g., argon, carbon dioxide and hydrogen sulfide) the GC configuration consisted of the following:
For Examples 1-5, a stainless steel sample cylinder containing gas collected from the Parr vessel (
Calibration curves, correlating integrated peak areas with concentration, were generated for quantification of gas compositions using certified gas standards. For hydrocarbon gases, standards containing a mixture of methane, ethane, propane, butane, pentane and hexane in a helium matrix in varying concentrations (parts per million, mole basis) were injected into the GC through the fixed volume sample loop at atmospheric pressure. For non-hydrocarbon gases, standards containing individual components, i.e., carbon dioxide in helium and hydrogen sulfide in natural gas, were injected into the GC at varying pressures in the sample loop to generate calibration curves.
The hydrocarbon gas sample molar percentages reported in
Liquid samples collected during the heating tests as described in Examples 1, 3 and 4 were analyzed by whole oil gas chromatography (WOGC) according to the following procedure. Samples, QA/QC standards and blanks (carbon disulfide) were analyzed using an Ultra 1 Methyl Siloxane column (25 m length, 0.32 μm diameter, 0.52 μm film thickness) in an Agilent 6890 GC equipped with a split/splitless injector, autosampler and flame ionization detector (FID). Samples were injected onto the capillary column in split mode with a split ratio of 80:1. The GC oven temperature was kept constant at 20° C. for 5 min, programmed from 20° C. to 300° C. at a rate of 5° C. min−1, and then maintained at 300° C. for 30 min (total run time=90 min.). The injector temperature was maintained at 300° C. and the FID temperature set at 310° C. Helium was used as carrier gas at a flow of 2.1 mL min−1. Peak identifications and integrations were performed using Chemstation software Rev.A.10.02 [1757] (Agilent Tech. 1990-2003) supplied with the Agilent instrument.
Standard mixtures of hydrocarbons were analyzed in parallel by the WOGC method described above and by an Agilent 6890 GC equipped with a split/splitless injector, autosampler and mass selective detector (MS) under the same conditions. Identification of the hydrocarbon compounds was conducted by analysis of the mass spectrum of each peak from the GC-MS. Since conditions were identical for both instruments, peak identification conducted on the GC-MS could be transferred to the peaks obtained on the GC-FID. Using these data, a compound table relating retention time and peak identification was set up in the GC-FID Chemstation. This table was used for peak identification.
The gas chromatograms obtained on the liquid samples (
An exemplary pseudo component weight percent calculation is presented below with reference to Table 10 for the C10 pseudo component for Example 1 in order to illustrate the technique. First, the C-10 pseudo-component total area is obtained from integration of the area beginning just past normal-C9 and continued just through normal-C10 as described above. The total integration area for the C10 pseudo component is 10551.700 pico-ampere-seconds (pAs). The total C10 pseudo component integration area (10551.700 pAs) is then multiplied by the C10 pseudo component density (0.7780 g/ml) to yield an “area X density” of 8209.22 pAs g/ml. Similarly, the peak integration areas for each pseudo component and all lighter listed compounds (i.e., nC3, iC4, nC4, iC5 & nC5) are determined and multiplied by their respective densities to yield “area X density” numbers for each respective pseudo component and listed compound. The respective determined “area X density” numbers for each pseudo component and listed compound is then summed to determine a “total area X density” number. The “total area X density” number for Example 1 is 96266.96 pAs g/ml. The C10 pseudo component weight percentage is then obtained by dividing the C10 pseudo component “area X density” number (8209.22 pAs g/ml) by the “total area X density” number (96266.96 pAs g/ml) to obtain the C10 pseudo component weight percentage of 8.53 weight percent.
An exemplary pseudo component molar percent calculation is presented below with reference to Table 10 for the C10 pseudo component for Example 1 in order to further illustrate the pseudo component technique. First, the C-10 pseudo-component total area is obtained from integration of the area beginning just past normal-C9 and continued just through normal-C10 as described above. The total integration area for the C10 pseudo component is 10551.700 pico-ampere-seconds (pAs). The total C10 pseudo component integration area (10551.700 pAs) is then multiplied by the C10 pseudo component density (0.7780 g/ml) to yield an “area X density” of 8209.22 pAs g/ml. Similarly, the integration areas for each pseudo component and all lighter listed compounds (i.e., nC3, iC4, nC4, iC5 & nC5) are determined and multiplied by their respective densities to yield “area X density” numbers for each respective pseudo component and listed compound. The C10 pseudo component “area X density” number (8209.22 pAs g/ml) is then divided by the C10 pseudo component molecular weight (134.00 g/mol) to yield a C10 pseudo component “area X density/molecular weight” number of 61.26 pAs mol/ml. Similarly, the “area X density” number for each pseudo component and listed compound is then divided by such components or compounds respective molecular weight to yield an “area X density/molecular weight” number for each respective pseudo component and listed compound. The respective determined “area X density/molecular weight” numbers for each pseudo component and listed compound is then summed to determine a “total area X density/molecular weight” number. The total “total area X density/molecular weight” number for Example 1 is 665.28 pAs mol/ml. The C10 pseudo component molar percentage is then obtained by dividing the C10 pseudo component “area X density/molecular weight” number (61.26 pAs mol/ml) by the “total area X density/molecular weight” number (665.28 pAs mol/ml) to obtain the C10 pseudo component molar percentage of 9.21 molar percent.
nC3
iC4
nC4
iC5
nC5
nC3
iC4
nC4
iC5
nC5
nC3
iC4
nC4
iC5
nC5
TOC and Rock-eval tests were performed on specimens from oil shale block CM-1B taken at the same stratigraphic interval as the specimens tested by the Parr heating method described in Examples 1-5. These tests resulted in a TOC of 21% and a Rock-eval Hydrogen Index of 872 mg/g-toc.
The TOC and rock-eval procedures described below were performed on the oil shale specimens remaining after the Parr heating tests described in Examples 1-5. Results are shown in Table 13.
The Rock-Eval pyrolysis analyses described above were performed using the following procedures. Rock-Eval pyrolysis analyses were performed on calibration rock standards (IFP standard #55000), blanks, and samples using a Delsi Rock-Eval II instrument. Rock samples were crushed, micronized, and air-dried before loading into Rock-Eval crucibles. Between 25 and 100 mg of powdered-rock samples were loaded into the crucibles depending on the total organic carbon (TOC) content of the sample. Two or three blanks were run at the beginning of each day to purge the system and stabilize the temperature. Two or three samples of IFP calibration standard #55000 with weight of 100+/−1 mg were run to calibrate the system. If the Rock-Eval Tmax parameter was 419° C.+/−2° C. on these standards, analyses proceeded with samples. The standard was also run before and after every 10 samples to monitor the instrument's performance.
The Rock-Eval pyrolysis technique involves the rate-programmed heating of a powdered rock sample to a high temperature in an inert (helium) atmosphere and the characterization of products generated from the thermal breakdown of chemical bonds. After introduction of the sample the pyrolysis oven was held isothermally at 300° C. for three minutes. Hydrocarbons generated during this stage are detected by a flame-ionization detector (FID) yielding the S1 peak. The pyrolysis-oven temperature was then increased at a gradient of 25° C./minute up to 550° C., where the oven was held isothermally for one minute. Hydrocarbons generated during this step were detected by the FID and yielded the S2 peak.
Hydrogen Index (HI) is calculated by normalizing the S2 peak (expressed as mghydrocarbons/grock) to weight % TOC (Total Organic Carbon determined independently) as follows:
HI=(S2/TOC)*100
where HI is expressed as Mghydrocarbons/gTOC
Total Organic Carbon (TOC) was determined by well known methods suitable for geological samples—i.e., any carbonate rock present was removed by acid treatment followed by combustion of the remaining material to produce and measure organic based carbon in the form of CO2.
The API gravity of Examples 1-5 was estimated by estimating the room temperature specific gravity (SG) of the liquids collected and the results are reported in Table 14. The API gravity was estimated from the determined specific gravity by applying the following formula:
API gravity=(141.5/SG)−131.5
The specific gravity of each liquid sample was estimated using the following procedure. An empty 50 μl Hamilton Model 1705 gastight syringe was weighed on a Mettler AE 163 digital balance to determine the empty syringe weight. The syringe was then loaded by filling the syringe with a volume of liquid. The volume of liquid in the syringe was noted. The loaded syringe was then weighed. The liquid sample weight was then estimated by subtracting the loaded syringe measured weight from the measured empty syringe weight. The specific gravity was then estimated by dividing the liquid sample weight by the syringe volume occupied by the liquid sample.
The liquid samples obtained through the experimental procedures and gas and liquid sample collection procedures described for Examples 6-19, were analyzed by the following hydrocarbon liquid sample C4-C19 gas chromatography (C4-C19 GC) analysis methodology, C4-C19 GC peak identification and integration methodology. While the liquid samples from Examples 6-19 were also analyzed using the whole oil gas chromatography (WOGC) analysis methodology, and whole oil gas chromatography (WOGC) peak identification and integration methodology discussed above with reference to Examples 1-5.
Liquid samples collected during the heating tests described in Examples 7-19 were analyzed by a gas chromatographic (GC) procedure designed to produce well separated GC peaks for materials having carbon numbers in the range C4-C19. The following procedure describes that analysis.
The gas chromatographic separation was accomplished in two stages—a first stage to separate the C4-C19 fraction from the sample, discarding those components present with higher carbon numbers. This C4-C19 fraction was then passed to the second stage of GC analysis, where a more complete, analytical separation was accomplished.
The gas chromatography equipment consisted of a Hewlett Packard 5890 (Series II) Gas Chromatograph equipped with an FID detector, an HP 6890 autosampler, a split injector and a computer supplied with Agilent ChemStation software. This GC was augmented with a pre-fractionator as described below.
The first stage of separation, the pre-fractionator, consisted of an injector port and oven, the oven containing one packed stainless steel column (20% OV101 on 80/100 mesh Chromosorb WHP, ⅛ inch I.D and 4 feet long), a second packed stainless steel column (5 A mole sieve, 60/80 mesh, ⅛ inch ID and 2 feet long), and a multi-port valve. Both the oven and the injector port were maintained at 300° C. UHP Helium carrier gas flowing at a rate of 25 ml/min was used. The OV101 column was used to isolate the C4-C19 fraction in the sample and the heavier compounds (C19+) were backflushed into the mole sieve column. The multi-port valve was used in a timed manner to isolate the C4-C19 fraction and provide that fraction as input to the second stage of separation.
The second stage of separation, the analytical separation, consisted of a split injector, an oven equipped with temperature control, an analytical column acquired from Agilent (PONA fused silica column 50 m in length, 0.2 mm ID and 0.5 μm film thickness) and flame ionization detector (FID). The injector and FID detector were maintained at 300° C.
Liquid samples to be analyzed were placed in sealed glass vials suitable for use in the autosampler and weighed. To each sample 1 μl of 1-hexene (GC grade from Sigma Aldrich) was added. The 1-hexene served as an internal standard with known amount and also as a retention time standard. 10 μl of a mixture of additional reference standards was added to each sample. These reference standards consisted of a mixture of equal volumes of the following four compounds: 2,3-dimethyl-2-pentene, cis-2-octene, 1-nonene, and 1,2,3,4-tetramethylbenzene. These reference standards were used as retention time standards.
The autosampler was set to inject 1 μl of sample (containing the standards). The second stage of separation was accomplished using a helium flow rate of 1 ml/min and a GC oven temperature program as follows:
Agilent ChemStation Revision A.10.02 software was used to control the instrument and perform data integration. This software was used to make any necessary retention time adjustments based on the responses of the standard materials contained in each sample. Peak assignments were made based on retention times of known compounds and separate analyses using GC/mass spectrometry for compound identification.
A quality control sample of a previously collected C4-C19 fraction was maintained and run routinely to ensure instrument and data reproducibility.
The C4-C19 GC chromatograms for Examples 6-19 are depicted in
The C4-C19 GC chromatograms for Examples 6-19 were integrated to obtain individual peak areas for each identified compound as previously discussed. Some compounds, routinely identified by C4-C19 GC analysis, were not included in the analysis presented here. Compounds whose concentrations were sufficiently low that they were found to be below the detection limit, as determined by the automated peak integration techniques, for one or more of Examples 6-19 are not included in Table 16, nor were such compounds included in the calculations used to prepare
In Table 16 below certain common abbreviations are used to denote particular compounds or compound elements. For example, “C_” refers to the carbon number of a referenced compound or portion of a compound as in C5 (pentane), “i” refers to “iso” as in iC5 (isopentane), “M” refers to a “methyl” substituent as in MCyC5 (methyl-cyclopentane), a number before a substituent refers to the position of attachment of the substituent as in 2MC6 (2-methyl-cyclohexane), “Cy” refers to “cyclo” as in MCyC6 (methyl-cyclohexane, “n” refers to “normal” as in nC5 (normal-pentane), “Bz” refers to benzene, “c” refers to “cis”, “t” refers to “trans”, “D” refers to “di” as in dimethyl (DM), “T” refers to “tri” as in “1—3—5 TMBz” (1,3,5-trimethylbenzene), “E” refers to “ethyl” as in ECyC5 (ethyl-cyclopentane), “Tol” refers to toluene, mXly and oXly refer to meta-xylene and ortho-xylene respectively, “IP_” refers to an isoprenoid compound with the number denoting the carbon number of the particular isoprenoid compound as in IP9, “naph” refers to naphthalene as in 2MNaph (2-methyl-naphthalene), and “Hexyl” refers to “hexyl” as in HexylCyC6 (hexyl-cyclohexane).
nC3
iC4
nC4
iC5
nC5
nC6
nC7
nC8
nC9
nC10
nC11
nC12
nC13
nC14
nC15
nC16
nC17
nC18
nC19
nC3
iC4
nC4
iC5
nC5
nC6
nC7
nC8
nC9
nC10
nC11
nC12
nC13
nC14
nC15
nC16
nC17
nC18
nC19
Analyses by liquid chromatography (LC) followed by gas chromatography/mass spectrometry (GC/MS) were performed on liquid samples from Examples 6-20 (as indicated in the Examples). The LC procedure separated the saturate and aromatic hydrocarbon fractions from the liquid or sediment sample produced in each Example. The saturate and aromatic fractions were then analyzed separately by GC/MS. The procedures for these analyses are described in the following sections.
The LC procedure utilized silica gel as the separation medium and a selection of solvents in order to produce the saturate and aromatic extracts.
The LC procedure utilized the following laboratory equipment and chemicals:
The internal standards mixture was made in hexane with the compounds and concentrations as shown Table 19:
The amount of the internal standards mixture to be added (as described in the procedure to follow) was determined according to Table 20.
The internal standards were used to enable calculation of concentrations and as known markers to facilitate compound identifications.
This LC method was used because it easily separates the crude oil or sediment extract sample into 4 compound classes including saturates, aromatics, NSO's (nitrogen, sulfur and oxygenate compounds), and asphaltenes.
The first separations in this LC procedure were the removal of asphaltenes and the collection of the pentane soluble fraction as described in Table 21:
Table 22 describes the liquid chromatographic separation procedure.
Quality control for this LC procedure was maintained via the testing of a standard oil sample (North Sea), which was run with the samples of interest. Percentages of the SAT, ARO,
NSO and ASPH fractions (based on the whole sample) were calculated and QC charts maintained.
GC/MS Method: The GC/MS was performed using an HP 6890 gas chromatograph (GC) connected to an HP 5973 MSD mass spectrometer (MS) equipped with a mass selective detector. In addition, an autosampler (equipped with a 10 μl syringe) and Agilent ChemStation software (version G1710DA for Microsoft XP®) were used. The mass spectrometric method used was SIM (selected ion monitoring) for analysis of the saturated and aromatic components, which were collected as described in the previous section.
Materials used:
Sample Preparation: Each liquid sample to be analyzed was transferred to a sample vial suitable for use in the GC/MS equipment, the concentration adjusted to 25 μg/μl by the addition of hexane. The vial was sealed and placed in the autosampler.
GC conditions: The GC employed a J&W DB-5 fused silica capillary column, which was 30 meters in length, 0.25 mm inner diameter and had 0.25 μm film thickness. GC settings for the saturate fractions were those shown in Table 23.
GC settings for the aromatic fractions were as indicated in Table 24.
MS conditions: Methylene chloride was used to clean components of the MS as needed. MS source and quad temperatures were set as shown in Table 25.
MS SIM parameters for the saturate and aromatic fractions were set as shown in Table 26.
Additionally the following list of saturates and aromatics was used to facilitate compound identification.
m/z 123: terpenoids
m/z 125: beta-carotane
m/z 177: C29 terpanes, 25-norhopanes
m/z 183: isoprenoids
m/z 191: terpanes
m/z 205: methyl hopanes
m/z 217: steranes
m/z 218: abb-steranes
m/z 231: steranes
m/z 259: diasteranes
Naphthalenes: m/z 128 (C0), m/z 142 (C1), m/z 156 (C2), m/z 170 (C3), m/z 184 (C4 & dibenzothiophene)
Dibenzothiophenes: m/z 184 (C0 & C4 naphthalenes), m/z 198 (C1), m/z 212 (C2)
Aromatic Steroids: m/z 231 (and C1 benzocarbozoles), m/z 245 (and C2 benzocarbozoles), m/z 253
Benzocarbozoles: m/z 217 (C0), m/z 231 (C1 and triaromatic steroids), m/z 245 (C2 and triaromatic dinosteroids)
MS instrument settings were adjusted to achieve the detection limits listed in Table 27 over a range of mass values:
Analysis and reporting of the data: Peak assignments in the GC/MS chromatograms were made utilizing a known oil reference standard (North Sea, Jurassic sourced oil from the Kimmeridge) and an internal standard (5(3-Cholane for the saturates and o-Terphenyl, C13 Benzene for the aromatics). The geochemical patterns were confirmed by both retention time and diagnostic mass to charge ratios since most of these geochemical compounds are not commercially available. In addition, use was made of spectral patterns of typical compounds found in oil samples and studied extensively in the literature such as those described in the following reference: The Biomarker Guide, by Kenneth E. Peters and J. Michael Moldowan, Prentice Hall Publishing, 1993.
The spectral quality and reproducibility of the GC/MS data were maintained by frequent runs of a previously known crude oil that was separated into fractions by liquid chromatography (as described in this method). Ratios from this standard (i.e., the North Sea oil mentioned above) were used for quality control purposes. A mass calibrant (perfluorotributylamine) was used for the MS prior to instrumental analysis. These data were used to ensure accurate peak positions and to ensure reproducibility of peak area ratios through time.
The concentrations of molecular species found in the chromatograms generated by the GC/MS analysis were determined by manually measuring peak heights for each compound of interest. The baseline for each measurement was taken as the mean baseline for the peak extrapolated from the low background to the high background. When nearby peaks caused the immediately adjacent background to be too high the background was estimated by linear fit to average background for compounds eluting within 2 minutes of the molecule of interest. For each sample, all peak heights were measured in the same chromatogram or scaled to a single chromatogram in instances where very large peak heights introduced graphical error in measuring smaller peaks.
The above-described processes may be of merit in connection with the recovery of hydrocarbons in the Piceance Basin of Colorado. Some have estimated that in some oil shale deposits of the Western United States, up to 1 million barrels of oil may be recoverable per surface acre. One study has estimated the oil shale resource within the nahcolite-bearing portions of the oil shale formations of the Piceance Basin to be 400 billion barrels of shale oil in place. Overall, up to 1 trillion barrels of shale oil may exist in the Piceance Basin alone.
Certain features of the present invention are described in terms of a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated. Although some of the dependent claims have single dependencies in accordance with U.S. practice, each of the features in any of such dependent claims can be combined with each of the features of one or more of the other dependent claims dependent upon the same independent claim or claims.
While it will be apparent that the invention herein described is well calculated to achieve the benefits and advantages set forth above, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the spirit thereof.
This application is a divisional of co-pending U.S. application Ser. No. 11/973,898 filed Oct. 10, 2007 titled, Heating An Organic-Rich Rock Formation in Situ To Produce Products With Improved Properties, hereby incorporated by reference in its entirety, which claims the benefit of U.S. Provisional application 60/997,654, titled “Products with Improved Aromatic Hydrocarbon Properties Produced by In Situ Heating of an Organic-Rich Rock Formation”, docket No. 2007EM267, which was filed on Oct. 4, 2007, U.S. Provisional application 60/997,650, titled “Heating an Organic-Rich Rock Formation In Situ to Produce Products with Improved Aromatic Hydrocarbon Properties”, docket No. 2007EM266, which was filed on Oct. 4, 2007, U.S. Provisional application 60/997,646, titled “Products with Improved Branched Hydrocarbon Properties Produced by In Situ Heating of an Organic-Rich Rock Formation”, docket No. 2007EM269, which was filed on Oct. 4, 2007, U.S. Provisional application 60/997,645, titled “Heating an Organic-Rich Rock Formation In Situ to Produce Products with Improved Branched Hydrocarbon Properties”, docket No. 2007EM268, which was filed on Oct. 4, 2007, U.S. Provisional application 60/997,648, titled “Products with Improved Cyclic Hydrocarbon Properties Produced by In Situ Heating of an Organic-Rich Rock Formation”, docket No. 2007EM271, which was filed on Oct. 4, 2007, U.S. Provisional application 60/997,653, titled “Heating an Organic-Rich Rock Formation In Situ to Produce Products with Improved Cyclic Hydrocarbon Properties”, docket No. 2007EM270, which was filed on Oct. 4, 2007, U.S. Provisional application 60/997,649, titled “Products with Identifying Compound Marker Properties Produced by In Situ Heating of an Organic-Rich Rock Formation”, docket No. 2007EM272, which was filed on Oct. 4, 2007, U.S. Provisional application 60/851,432 which was filed on Oct. 13, 2006, U.S. Provisional application 60/851,534 which was filed on Oct. 13, 2006, U.S. Provisional application 60/851,535 which was filed on Oct. 13, 2006, U.S. Provisional application 60/851,819 which was filed on Oct. 13, 2006, U.S. Provisional application 60/851,786 which was filed on Oct. 13, 2006, and U.S. Provisional application 60/851,820 which was filed on Oct. 13, 2006. The above-referenced provisional applications are incorporated herein in their entirety by reference.
| Number | Date | Country | |
|---|---|---|---|
| 60997654 | Oct 2007 | US | |
| 60997650 | Oct 2007 | US | |
| 60997646 | Oct 2007 | US | |
| 60997645 | Oct 2007 | US | |
| 60997648 | Oct 2007 | US | |
| 60997653 | Oct 2007 | US | |
| 60997649 | Oct 2007 | US | |
| 60851432 | Oct 2006 | US | |
| 60851534 | Oct 2006 | US | |
| 60851535 | Oct 2006 | US | |
| 60851819 | Oct 2006 | US | |
| 60851786 | Oct 2006 | US | |
| 60851820 | Oct 2006 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11973898 | Oct 2007 | US |
| Child | 13072335 | US |
