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HK1146732B - Extraction of hydrocarbons from hydrocarbon-containing materials - Google Patents

Extraction of hydrocarbons from hydrocarbon-containing materials Download PDF

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Publication number
HK1146732B
HK1146732B HK11100817.8A HK11100817A HK1146732B HK 1146732 B HK1146732 B HK 1146732B HK 11100817 A HK11100817 A HK 11100817A HK 1146732 B HK1146732 B HK 1146732B
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HK
Hong Kong
Prior art keywords
hydrocarbon
turpentine liquid
terpineol
organic matter
turpentine
Prior art date
Application number
HK11100817.8A
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Chinese (zh)
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HK1146732A1 (en
Inventor
范良正
莫汉麦德‧雷萨‧沙菲
朱立尔斯‧麦可‧陶拉斯
威廉‧亚瑟‧菲兹胡格‧李
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绿色能源有限公司
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Publication date
Priority claimed from US12/053,126 external-priority patent/US8101812B2/en
Priority claimed from US12/174,139 external-priority patent/US8272442B2/en
Application filed by 绿色能源有限公司 filed Critical 绿色能源有限公司
Priority claimed from PCT/US2008/010831 external-priority patent/WO2009038728A1/en
Publication of HK1146732A1 publication Critical patent/HK1146732A1/en
Publication of HK1146732B publication Critical patent/HK1146732B/en

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Description

Extraction of hydrocarbons from hydrocarbonaceous feedstocks
Cross Reference to Related Applications
This application is a continuation-in-part application having U.S. application serial No. 12/174,139 filed on 16/7/2008 and 12/053,126 filed on 21/3/2008, and claiming priority to U.S. provisional patent application No. 60/973,964 filed on 20/9/2007, the entire contents of each of which are incorporated herein by reference.
Technical Field
The present invention relates to the field of extracting hydrocarbons from a hydrocarbon-containing feedstock.
Background
The liquefaction, dissolution and/or extraction of fossil fuels in solid, semi-solid, highly viscous or viscous form (hereinafter individually and collectively referred to as fossil fuels), also known as hydrocarbon-containing organic matter, has proven extremely challenging and difficult. As used herein, these fossil fuels include, but are not limited to, hydrocarbon-containing organic matter within coal, oil shale, tar sands and oil sands (hereinafter collectively referred to as tar sands), as well as crude oil, heavy crude oil, crude bitumen, kerogen, natural bitumen, and/or asphaltenes. The difficulty is due in part to the fact that these fossil fuels comprise complex organic polymers linked by oxygen and sulfur bonds, which are often embedded in a matrix of inorganic compounds. As the demand and consumption of hydrocarbon-based materials continues to increase, there is a need to produce additional liquid hydrocarbon feedstocks for the manufacture of liquid and gaseous fuels, as well as for the production of various chemical, pharmaceutical, and engineering materials.
A number of techniques or processes have been developed to liquefy, dissolve and/or extract fossil fuels. However, none of the liquefaction, solubilization and extraction techniques in the prior art has proven commercially viable for large scale production of all types of fossil fuels. This is because all the prior art and processes developed so far for the liquefaction, dissolution or extraction of hydrocarbons are expensive to implement and operate. Additionally, prior art processes and techniques for liquefaction, solubilization, and/or extraction of hydrocarbons are difficult to scale up, operate, and/or control for one or more of the following reasons: (1) operating at very high pressures; (2) operating at very high temperatures; (3) require expensive process vessels and require means for external hydrogen supply under extreme conditions; (4) contacting a mixture, or composition, of two or more reagents, catalysts and/or adjuvants, which are often highly toxic and not renewable or recyclable; (5) the need to supply a particular form of energy, for example, microwave irradiation; (6) long processing times for partial liquefaction, dissolution or extraction; (7) extra fine particles of about 200 mesh (0.074mm) size are required, which is extremely difficult and costly to manufacture and dispose of; and (8) the inability to recover and recycle the necessary reagents, catalysts and/or auxiliaries. Accordingly, there is a need to provide additional techniques and processes for enhanced recovery of hydrocarbon materials.
For initial drilling operations, it would be beneficial to employ a process that increases the dissolution and promotes the movement of additional or trapped hydrocarbon-containing organic matter, and then allows the existing pressure gradient to force the hydrocarbon-containing organic matter through the borehole for recovery. In particular, it would be useful to dissolve the heavier hydrocarbons that are normally retained in the reservoir (reservoir) by the initial drilling operation.
For secondary and tertiary oil recovery or enhanced oil recovery operations, it would be beneficial to employ a process that increases the dissolution of oil to recover hydrocarbon-containing organic matter in a reservoir in a manner that reduces costs and does not damage the reservoir. While effective methods and compositions exist for enhanced oil recovery operations, existing methods are not cost effective due to the cost of the operations compared to the value of the hydrocarbon-containing organic material produced.
Disclosure of Invention
According to one embodiment of the present invention, a method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material comprises the steps of: providing a first liquid comprising a turpentine liquid and contacting the hydrocarbon-containing material with the turpentine liquid such that an extraction mixture is formed along with a residual material. The extraction mixture comprises at least a portion of the hydrocarbon-containing organic matter and the turpentine liquid. The residual feedstock comprises insoluble material from the hydrocarbon-containing feedstock. The residual feedstock may also include a minor portion of hydrocarbon-containing organic matter in the event that the hydrocarbon-containing feedstock is not fully dissolved by the turpentine liquid and moved into the extraction mixture. The residual material is then separated from the extraction mixture. The extraction mixture is further separated into a first portion and a second portion. The first portion of the extraction mixture comprises a hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter extracted from the hydrocarbon-containing feedstock. The second portion of the extraction mixture includes at least a portion of the turpentine liquid. In one embodiment, substantially all of the turpentine liquid is recovered in the recycle stream.
In another embodiment, substantially all of the hydrocarbonaceous material is extracted into the extraction mixture. In this embodiment, the residual feedstock is substantially free of oil and can be further used or disposed of without environmental impact.
Drawings
FIG. 1 is a schematic diagram of one embodiment of an apparatus for recovering hydrocarbons from tar sands.
Fig. 2 is a schematic diagram of an embodiment of an apparatus for recovering hydrocarbons from oil shale.
FIG. 3 is a schematic diagram of an embodiment of an apparatus for recovering hydrocarbons from coal.
FIG. 4 is a schematic illustration of enhanced hydrocarbon recovery from a subterranean reservoir.
Detailed Description
In one aspect, the present invention relates to a readily available composition for extracting, liquefying and/or solubilizing fossil fuels from coal, oil shale, tar sands, and the like, as well as from oil reservoirs.
According to one embodiment, the method provides the step of liquefying, dissolving and/or extracting hydrocarbon-containing organic matter from a hydrocarbon-containing feedstock, such as, for example, coal, oil shale, tar sands, or a reservoir containing heavy crude oil, natural gas (often in coexistence with crude oil and other described fossil fuels), or combinations thereof. The hydrocarbon-containing organic matter includes, but is not limited to, heavy crude oil, natural gas, and the like. The hydrocarbon-containing organic matter may be in solid, semi-solid, liquid, sludge, viscous liquid, or gaseous form. Other materials that are suitable hydrocarbon-containing materials for treatment using the methods of the present invention include liquids and solids including hydrocarbon-containing materials as well as residual materials. Exemplary hydrocarbon-containing feedstocks may also include tank bottoms (oil tank bottoms), oil pits (oil pits), or pond sludge (pond sludge), and slurry mixtures, food waste, fertilizers, sludge, or municipal waste. Liquefying, dissolving and/or extracting hydrocarbon-containing organic matter comprises the steps of: providing a turpentine liquid, contacting a hydrocarbon-containing material with the turpentine liquid so as to extract at least a portion of the hydrocarbon-containing organic matter from the hydrocarbon-containing material into the turpentine liquid to generate an extraction mixture comprising hydrocarbon-containing organic matter that has been removed from the hydrocarbon-containing material and the turpentine liquid, and separating the extracted organic matter from any residual material in the turpentine liquid that has not been extracted. The turpentine liquid can include an amount of terpineol. Natural turpentine liquids include a certain amount of terpenes. In one embodiment, the turpentine liquid comprises alpha-terpineol.
In certain embodiments, the ratio of turpentine liquid to hydrocarbon-containing feedstock is greater than or equal to about 1: 2 and 4: 1, in some embodiments, greater than or equal to about 1: 1, and in some embodiments, the ratio may be greater than or equal to 2: 1. In embodiments involving recovery of the reservoir, the ratio may be greater than or equal to about 3:1, and in other embodiments involving recovery of the reservoir, the ratio may be greater than or equal to about 4: 1. For use in an oil reservoir, the pore volume is used to determine an estimated measurement of the hydrocarbon-containing material. In other aspects of the invention, such as when tar sands, coal, and oil shale are used, the volume of the hydrocarbon-containing feedstock can be more directly measured.
In certain embodiments, the minimum organic matter content contained in the hydrocarbon-containing material is greater than or equal to about 1%, in other embodiments greater than or equal to about 10%, and in further embodiments greater than or equal to about 14% by weight of the hydrocarbon-containing material.
In one embodiment of the invention, the liquefying, solubilizing or extracting agent selected for the hydrocarbonaceous material is a natural, synthetic or mineral turpentine, which may include or be itself alpha-terpineol.
In certain embodiments, the liquefaction, dissolution and/or extraction of the fossil fuel or hydrocarbon-containing organic matter may be conducted at a temperature in the range of from about 2 ℃ to about 300 ℃. In certain embodiments, the organic matter or feedstock is contacted with the turpentine liquid at a temperature of less than about 300 ℃, or less than about 60 ℃. In other embodiments, the liquefaction, dissolution, and/or extraction temperatures may be in the range of about 20 ℃ to about 200 ℃. The pressure at which liquefaction, dissolution and/or extraction of the fossil fuel is carried out may generally be about 1.0X 104Pascal (0.1atm) to about 5.0X 106Pascal (50.0 atm). In certain embodiments, the process may be at about 5.0X 104Pascal (0.5atm) to about 8.0X 105Pascal (8.0atm) pressure. In certain other embodiments, the fossil fuel or hydrocarbon-containing organic matter that is liquefied, dissolved and/or extracted by immersion in or contact with one or more turpentine liquids may be in the form of particulate, lamellar, lump or agglomerate layers of fossil fuel having a size in the range of from about 0.74mm to about 10mm in a liquefaction, dissolution or extraction vessel (hereinafter referred to as a reactor) containing one or more of the liquefying, dissolving or extracting agents. In certain embodiments, the size of the particles, pieces, chunks, or agglomerates of the fossil fuel is in the range of from about 0.149mm (100 mesh) to about 20 mm. In certain embodiments, the particle, slice, block, or agglomerate layer of fossil fuel is agitated by passing the liquefying, dissolving, and/or extracting agent(s) in liquid form through the particle, slice, block, or agglomerate layer by boiling the agent(s). In certain embodiments, the duration of liquefaction, dissolution, and/or extraction is from about 1 minute to about 90 minutes. The fossil fuel may be partially or fully liquefied, dissolved and/or extractedTaking; the extent of liquefaction, dissolution and/or extraction may be influenced by controlling the operating conditions, such as temperature, pressure, intensity and duration of agitation and/or adjusting the type, relative amounts and concentrations of the liquefying agent(s), the solubilizing agent(s) and/or the extracting agent(s) in the reactor.
The basis of one aspect of the present invention is the unexpected discovery that when about 500 grams of the reagent alpha-terpineol is added to about 250 grams of a 60 mesh coal sample from pittsburgh coal seam in washington county, pennsylvania in a dish, the color of the reagent immediately becomes almost jet black and remains so after a few hours. This indicates that the color change is not due to suspension of the coal particles, but rather is indicative of the extraction of hydrocarbon-containing organic matter from the coal. Subsequently, the 2:1 mixture of alpha-terpineol and coal sample was transferred from the tray to a closed and tightly sealed jar at about 20 ℃ and slightly less than about 1.01X 105Pascal (1atm) ambient conditions were maintained for about 25 days. The conversion (i.e., degree of liquefaction) of the coal sample was determined to be about 71 wt.% after filtration, washing with ethanol, drying, and weighing. This 71 wt.% conversion corresponds to almost all soluble bitumen (organic matter) present in the coal sample, which was analyzed approximately as 2.00 wt.% as-received moisture, 9.25 wt.% dry ash, 38.63 wt.% dry volatiles, and 50.12 wt.% dry fixed carbon. A series of subsequent experiments using coal, as well as oil shale and tar sands under a variety of operating conditions, have shown that the family of agents that include natural and/or synthetic turpentine containing pinene as well as alcohols of pinene, i.e., terpineol, is exceptionally effective in liquefying, solubilizing and/or extracting kerogen (organic species) and/or asphaltene (organic species) in fossil fuels, including coal, oil shale, tar sands, heavy crude oil and/or crude oil, without the aid of any catalyst or alkali metal. These agents, with the exception of mineral turpentine derived from petroleum, are renewable and "green", i.e. are of low toxicity and relatively inexpensive, compared to all other known liquefaction, solubilization and/or extraction agents for fossil fuels, such as tetralin, xylene, anthracene, and various solutions or mixtures of these agents with other compounds. Even the mineral turpentine oil from petroleumThe tubes are non-renewable, relatively low-toxicity and inexpensive. It has been found that even under conditions that are much more moderate than those required by the recent inventions regarding the liquefaction, solubilization and/or extraction of fossil fuels such as coal, oil shale, tar sands, crude oil and heavy crude oil, for example, ambient temperature and pressure, any of the liquefaction, solubilization and/or extraction agents permeates or diffuses through the pores of the fossil fuel at an appreciable rate into the particles, flakes, agglomerates or chunks of the fossil fuel, thereby causing these particles, flakes, agglomerates or chunks to subsequently release, often almost entirely, a liquefiable, dissolvable or extractable fraction in the liquefaction, solubilization and/or extraction agent.
One aspect of the present invention provides a method for liquefying, solubilizing and/or extracting fossil fuels or hydrocarbon-containing organic matter from hydrocarbon-containing feedstocks such as coal, oil shale and tar sands in which a portion of the solid or semi-solid fossil fuel is contacted with a turpentine liquid in an extraction mixture that may be devoid of alkali metals, catalysts, hydrogen (H)2) And/or carbon monoxide (CO). Although hydrogen and CO may be used as a blending agent, one embodiment of the present invention provides processes and compositions that lack both hydrogen and CO.
In certain embodiments, the turpentine liquid is selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, polymers thereof, and mixtures thereof. In certain other embodiments, the turpentine liquid is selected from the group consisting of geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinane, 2-pinane hydroperoxide, hydroterpineol, 2-pinanol, dihydromyrcenol, isoborneol, p-menthan-8-ol (p-methan-8-ol), terpinyl alpha-acetate, citronellol, p-menthan-8-ol acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In other embodiments, the turpentine liquid is selected from anethole, camphene; p-cymene, anisaldehyde, 3, 7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimenol, 2-methoxy-2, 6-dimethyl-7, 8-epoxyoctane, camphor, citral, 7-methoxy dihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, and mixtures thereof.
According to one aspect, solid or semi-solid fossil fuels or other hydrocarbon-containing feedstocks, such as coal, oil shale, tar sands, and heavy crude oil, or, for example, tank bottoms, oil pit or pond sludge, food waste, fertilizers, sludge, or municipal waste, may be provided in any size that facilitates contact with the turpentine liquid. Fossil fuels or hydrocarbonaceous feedstocks can be provided as particles, flakes, chunks, or agglomerates, such as large fragments or flakes of coal or oil shale. According to a certain aspect of the invention, the fossil fuel or hydrocarbon-containing feedstock is provided as pellets. According to a certain aspect of the invention, the average particle size of the particles of the fossil fuel or hydrocarbonaceous feedstock is from about 0.074mm to about 100 mm. In certain other embodiments, the particles of the fossil fuel have an average particle size of from about 0.074mm to about 25 mm.
According to one aspect of the invention, a second liquid may be added to the turpentine liquid. According to a certain aspect of the invention, the second liquid is selected from the group consisting of lower aliphatic alcohols, paraffins, aromatic hydrocarbons, aliphatic amines, aromatic amines, carbon disulphide and mixtures thereof. Exemplary mixtures include solvents made in petroleum refining such as decant oil (decanot oil), light cycle oil, and naphtha, or solvents made in retorted coal and fractionated liquefied coal.
As used herein, lower aliphatic alcohols refer to primary, secondary and tertiary monohydric and polyhydric alcohols of 2 to 12 carbon atoms. As used herein, paraffins refer to straight and branched chain paraffins of 5 to 22 carbon atoms. As used herein, aromatic refers to monocyclic, heterocyclic and polycyclic compounds. As used herein, fatty amines refer to primary, secondary and tertiary amines having alkyl substituents of 1 to 15 carbon atoms. In certain embodiments, benzene, naphthalene, toluene, or combinations thereof are used. In another embodiment, the lower aliphatic alcohols described above may be used. In one embodiment, the solvent is selected from the group consisting of ethanol, propanol, isopropanol, butanol, pentane, hexane, benzene, toluene, xylene, naphthalene, anthracene, tetralin, triethylamine, aniline, carbon disulfide, and mixtures thereof, at a temperature and pressure operable to maintain the solvent in a liquid state.
In certain embodiments, the ratio of turpentine liquid to any other turpentine-miscible solvent contained in the fluid is greater than or equal to 1: 1, and in certain embodiments greater than or equal to about 9: 4. In certain embodiments, the ratio is greater than or equal to about 3: 1. In other embodiments, the ratio is greater than or equal to 4: 1.
According to one aspect of the invention, the fossil fuel and the turpentine liquid are contacted at a temperature of about 2 ℃ to about 300 ℃. In certain embodiments, the fossil fuel is contacted with the turpentine liquid at a temperature of less than about 200 ℃.
According to a further aspect of the invention, the fossil fuel and turpentine liquid are at about 1.0X 104Pascal (0.1atm) to about 5.0X 106The contact is carried out under a pressure of Pascal (50 atm). According to one aspect, the process is carried out at a pressure of from about 0.5atm to about 8 atm.
According to one aspect of the invention, the method further comprises providing an extraction vessel in which the solid or semi-solid fossil fuel is contacted with the turpentine liquid. According to one aspect, a stirring device may be provided whereby the fossil fuel and the turpentine liquid contained within the reactor or extractor are mixed and stirred.
According to one aspect of the invention, the fossil fuel and turpentine liquid can be incubated in a storage tank to extend their contact time. According to further aspects, the extent of liquefaction, dissolution and/or extraction is controlled by the length of time the solid or semi-solid fossil fuel is contacted with the turpentine liquid and/or the temperature of the mixture of fossil fuel and turpentine liquid.
According to one aspect of the invention, the fossil fuel is contacted with a heterogeneous liquid comprising a turpentine liquid and water as an agitating agent (agitant).
In certain embodiments, the turpentine liquid to water ratio is greater than or equal to about 1: 1 by volume to avoid slurry formation that can make separation of extracted organic matter in a fluid containing turpentine liquid difficult.
According to one aspect of the invention, the fossil fuel is contacted with the turpentine liquid in the presence of an energy input selected from the group consisting of: pressures in excess of about 300 ℃, in excess of 50atm, microwave energy, ultrasonic energy, ionizing radiation energy, mechanical shear, and mixtures thereof.
According to one aspect of the invention, a liquefaction or dissolution catalyst is provided to a mixture of fossil fuel and turpentine liquid.
According to one aspect of the invention, the reaction or dissolution mixture is supplemented by the addition of a compound selected from the group consisting of hydrogen, carbon monoxide, water, metal oxides, metals, and mixtures thereof.
According to one aspect of the invention, the microorganism is included in the reaction or dissolution mixture. Selective chemical bonds, e.g., sulfur crosslinks and oxygen crosslinks, in hydrocarbons of fossil fuels and other hydrocarbonaceous feedstocks are disrupted by biological treatment with a thermophilic microorganism of the bacillus type selected from natural isolates derived from sulphur spas and chemolithotrophic microorganisms. The destruction of these selective chemical bonds promotes the dissolution of hydrocarbons in fossil fuels and other hydrocarbonaceous feedstocks.
Still other aspects and advantages of the present invention will become apparent to those skilled in the art from the present specification, wherein it is shown and described only certain embodiments of this invention by way of illustration of the best mode contemplated for carrying out the invention. As will be realized, the invention is capable of other and different embodiments and its several details are capable of modifications in various obvious respects, all without departing from the spirit of the present invention. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
According to one embodiment of the present invention, a method is provided for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material, including viscous liquid, liquid or gaseous fossil fuel materials. The method provides a first liquid comprising a turpentine liquid. The turpentine liquid is contacted with a hydrocarbon-containing material in situ in a subterranean formation containing the fossil fuel material to form an extraction mixture for extracting hydrocarbon-containing organic matter into the turpentine liquid and forming an extraction liquid. Removing an extraction liquid from the formation, wherein the extraction liquid comprises a turpentine liquid containing extracted hydrocarbon-containing organic matter. The extracted hydrocarbon-containing organic matter is separated from the residual material that is not extracted. The method may further comprise separating said extracted hydrocarbon material from the turpentine liquid. The viscous liquid, liquid or gaseous fossil fuel feedstock can be heavy crude oil, natural gas, or combinations thereof. For example, the subterranean formation may be a crude oil reservoir or a natural gas reservoir.
The present invention can be readily used to liquefy and/or dissolve fossil fuels directly in situ in subterranean formations and extract the resulting liquid products from these formations.
The extractant of the present invention is a liquid that has a very strong physicochemical affinity for bitumen, kerogen and/or tar in bituminous organic matter, including solid coal, oil shale and tar sands. When the extractant of the present invention and the bituminous organic substance comprising mainly hydrocarbons are brought into contact with each other, the organic substance is dissolved in the extractant of the present invention, thereby liquefying the organic substance. Upon contact, the hydrocarbons and the extractant of the present invention rapidly form a homogeneous solution, i.e., a one-phase liquid.
It is possible to exploit the physicochemical affinity between the extractant of the invention and the bituminous material for enhanced oil recovery from the reservoir under in situ conditions. Prior art in situ recovery techniques applied to date in reservoirs rely mostly on the so-called front displacement method. The process is strictly controlled by the characteristics of the multiphase fluid flow in the porous medium. This process often leaves most, often more than about 40%, virgin oil (original oil) unrecoverable, even for "good" low viscosity reservoirs. The extractant of the present invention improves oil recovery by overcoming the complex behavior of multiphase fluids that prevail under in situ conditions.
The present invention utilizes the very strong physicochemical affinity of turpentine liquids.
One method of the invention injects the extraction agent of the invention into an oil or natural gas reservoir through an injection well.
When oil and the extractant of the present invention are contacted in the reservoir, the oil dissolves in the extractant, thereby producing a homogeneous solution, i.e., a one-phase liquid. The extractant of the present invention is not simply flooding because it moves from an injection well to a production well; the previously trapped (trapped) oil is dissolved in the extractant of the present invention until the extractant is completely saturated with oil. The extractant is then inactive in other oil recovery processes and simply flows as a one-phase liquid through the pores of the reservoir, eventually reaching the production well.
Three specific embodiments of the in situ oil recovery process of the present invention are described below.
In a first in situ embodiment, about 3(3.0) to 7(7.0) pore volumes of an extraction agent of the present invention are injected into a reservoir that has been waterflooded to residual oil saturation while producing about 51% of the original oil in the reservoir. Injection of the extraction agent unexpectedly produces about another 41% of the original oil in the reservoir. This embodiment of the method was confirmed in the experiment as described in example 22 below.
In a second in situ embodiment, about two (2.0) to five (5.0) pore volumes of the extraction agent of the present invention are injected into the reservoir. At the beginning, injection before injection of about one-third (0.3) to three-quarters (0.75) of the pore volume of the extractant produced only oil; thereafter, the extractant of the present invention in which the oil is dissolved is produced. Most of the oil deposit is recovered when about one and one-half (1.5) to three and one-half (3.75) pore volumes of extractant are injected. This process unexpectedly recovers about 90% of the original oil in the reservoir. This embodiment of the method was also confirmed in the experiment as described in example 22 below.
In a third in situ embodiment, the extraction agent of the present invention is injected to improve Oil recovery from a reservoir containing very viscous Oil, for example, the reservoir of the "Orinoco Oil Belt (Orinoco Oil Belt)" of venezuela. The recovery ratio of the oil recovery method adopting the prior art is very low, and 10 to 15 percent of original oil is in the oil reservoir. The unexpected increase in recovery of these reservoirs by injection of the turpentine liquid extractants of the present invention can be further enhanced by employing horizontal wells for both the production and injection wells, and periodic steam stimulation of these wells.
Injecting the extractant into a large gas reservoir can increase the ultimate recovery ratio of the natural gas in the gas reservoir. Gas production from these reservoirs often produces dangerously large scale subsidences on the surface of the field, for example, the "Groeningen" field in the netherlands. Therefore, reservoir pressure needs to be maintained by injecting water (reservoir pressure). Water injected into the reservoir traps about 30% of the gas at high pressure due to two-phase flow of water and gas through the reservoir having a low permeability. By injecting the extractant of the present invention, the trapped gas in the gas reservoir is dissolved in the extractant and flows to the production well. By separating the extractant and gas at the surface, the gas is recovered and the extractant is recycled for reuse.
The extraction process of the invention may be carried out in one or more of the known processes for promoting oil production, e.g. CO injection2Or natural gas and adding a surfactant.
Detailed Description
Coal (coal)
In certain embodiments, anthracite or bituminous coal may be pulverized to a size of about 0.841mm (20 mesh) to about 0.149mm (100 mesh), and then passed through a screen at about 1.0X 105Pascal (1atm) to about 2.0X 105Is dissolved and/or extracted by immersion in a turpentine liquid at a pressure in the range of pascal (2.0atm),i.e. liquefied. In certain other embodiments, the turpentine liquid can be a natural, synthetic, or mineral turpentine that includes up to about 50-70% by volume α -terpineol, about 20-40% by volume β -terpineol, and about 10% by volume of other components. In certain embodiments, the layer of crushed anthracite or bituminous coal may be agitated by the turpentine liquid at a temperature of 80 ℃ to about 130 ℃, or possibly up to the boiling point of the turpentine liquid. In certain embodiments, the duration of dissolution and/or extraction, i.e., liquefaction, may be from about 10 minutes to about 40 minutes. In certain embodiments, the contact time for extracting hydrocarbon-containing organic matter from coal is less than 5 minutes.
In some embodiments, lignite, brown coal or any other low rank coal may be pulverized to a size of about 0.419mm (40 mesh) to about 0.074mm (200 mesh), and then passed through at about 1.0 x 105Pascal (1atm) to about 2.0X 105Is dissolved and/or extracted, i.e. liquefied, by immersion in the turpentine liquid at a pressure in the range of pascals (2.0 atm). In certain other embodiments, the turpentine liquid can be a natural, synthetic, or mineral turpentine that includes about 70-90% by volume α -terpineol, about 5-25% by volume β -terpineol, and about 5% by volume of other components. In other embodiments, the crushed lignite, lignite bed or any other low grade coal may be agitated by the turpentine liquid at a temperature of about 80 ℃ to about 130 ℃, or possibly up to the boiling point of the turpentine liquid. In certain embodiments, the dissolving and/or extracting, i.e., liquefying, may last from about 20 minutes to about 60 minutes. In certain embodiments, the contact time for extracting hydrocarbon-containing organic matter from coal is less than 5 minutes.
Oil shale
In certain embodiments, the oil shale may be comminuted to a size of about 0.419mm (40 mesh) to about 0.074mm (200 mesh), and then passed through a mill at about 1.0 x 105Pascal (1atm) to about 2.0X 105Pressure in the range of Pascal (2.0atm)Immersed in the turpentine liquid to be dissolved and/or extracted, i.e., liquefied. In other embodiments, the turpentine liquid can be a natural, synthetic, or mineral turpentine that includes about 70-90% by volume α -terpineol, about 5-25% by volume β -terpineol, and about 5% by volume of other components. In certain other embodiments, the crushed oil shale layer may be agitated by the turpentine liquid at a temperature of about 80 ℃ to about 130 ℃, or possibly up to the boiling point of the turpentine liquid. In other embodiments, the dissolving and/or extracting, i.e., liquefying, may last from about 30 minutes to about 60 minutes. In certain embodiments, the contact time for extracting hydrocarbon-containing organic matter from oil shale is less than 5 minutes.
Tar sand
In certain embodiments, tar sands may be comminuted to a size of about 25.4mm (1 mesh) to about 4.76mm (4 mesh), and then passed through a filter at about 1.0 x 105Pascal (1atm) to about 2.0X 105Is dissolved and/or extracted, i.e. liquefied, by immersion in the turpentine liquid at a pressure in the range of pascals (2.0 atm). In other embodiments, the turpentine liquid can be a natural, synthetic, or mineral turpentine that includes a mixture containing about 40-60% by volume α -terpineol, about 30-50% by volume β -terpineol, and about 5% by volume of other components. In another embodiment, the layer of crushed tar sand may be agitated by the turpentine liquid at a temperature of about 60 ℃ to about 90 ℃, or possibly up to the boiling point of the turpentine liquid. In other embodiments, the dissolving and/or extracting, i.e., liquefying, may last from about 10 minutes to about 30 minutes. In certain embodiments, the contact time for extracting hydrocarbon-containing organic matter from tar sands is less than 5 minutes.
Crude oil
In certain embodiments, light and medium crude oils may be produced in situ, i.e., may be removed from a subterranean reservoir for primary, secondary, or tertiary recovery by injection of about one (1.0) to about five (5.0) pore volumes of turpentine liquid. In other embodiments, about two (2.0) to about four (4.0) pore volumes of turpentine liquid can be injected. In certain embodiments, the turpentine liquid can be a natural, synthetic, or mineral turpentine that includes about 40-70% by volume α -terpineol, about 30-40% by volume β -terpineol, about 10% by volume α and/or β -pinene, and about 10% by volume of other components. In certain embodiments, the injection of the turpentine liquid can be followed by water injection with about one (1.0) to about three (3.0) pore volumes of water.
In certain embodiments, heavy and extra heavy crude oils may be produced in situ, i.e., removed from a subterranean reservoir for primary, secondary, or tertiary recovery, by injection of about one (1.0) to about five (5.0) pore volumes of turpentine liquid. In other embodiments, about two (2.0) to about four (4.0) pore volumes of turpentine liquid can be injected. In certain embodiments, the turpentine liquid can be a natural, synthetic, or mineral turpentine that includes about 50-70% by volume α -terpineol, about 20-35% by volume β -terpineol, 10% by volume α and/or β -pinene, and about 5% by volume other components, which can be used in conjunction with steam injection.
Referring to fig. 1, an apparatus for recovering hydrocarbon-containing organic matter from tar sands is provided. The apparatus 100 includes a turpentine liquid supply 102, the supply 102 optionally being connected to a pump 104 to supply turpentine liquid to a contacting vessel or extraction vessel 110. In certain embodiments, the turpentine liquid supply can include a device for heating the turpentine liquid. In certain embodiments, the contacting vessel may be an inclined rotary filter or a trommel. The tar sands sample 106 is provided to a conveyor 108 or similar feeding device for supplying tar sands to an inlet of a contacting vessel 110. Optionally, the conveyor 108 may include a screen or similar sorting device to prevent large particles from being introduced into the process. The contacting vessel 110 includes at least one inlet for the introduction of turpentine liquid and contact with tar sands. The contacting vessel 110 may include a plurality of trays or fins 114 designed to retain the tar sands in the contacting vessel for a specific period of time and to increase or control contact between the tar sand particles and the turpentine liquid. In certain embodiments, the contacting vessel can be an inclined rotary filter. An extraction mixture comprising extraction liquid and hydrocarbon-containing organic matter extracted from the tar sands is removed from the contacting vessel 110 via outlet 116, and outlet 116 can include a filter 118 to prevent solids from being removed with the extraction mixture comprising extracted hydrocarbon-containing organic matter. A pump 120 may be connected to the outlet 116 to assist in supplying the extraction mixture to a tank 122. Line 124 may be connected to storage tank 112 for supplying the extraction mixture for further processing. After extraction of the hydrocarbon-containing organic matter, inorganic solids and other matter that are insoluble in the turpentine liquid can be removed from the contacting vessel via second conveyor 126. Some turpentine liquids include, but are not limited to, liquids comprising alpha-terpineol and beta-terpineol.
Referring now to fig. 2, an apparatus 200 is provided for recovering hydrocarbon-containing organic matter from oil shale and other sedimentary formations that include recoverable hydrocarbon material. The oil shale sample 202 is supplied to a grinder or crusher 204 to reduce the size of the oil shale. Preferably, the grinder or crusher 204 reduces the oil shale to about 0.074 to 0.42mm in diameter. The crushed oil shale may optionally be supplied to a filter to ensure uniform and/or consistent particle size. A first conveyor 206 provides particles from the grinder or crusher 204 to a contact vessel 208. The contacting vessel 208 is connected to a turpentine liquid supply 210, the turpentine liquid supply 210 optionally being connected to a pump, and supplying turpentine liquid to at least one inlet 212 connected to the contacting vessel 208. In certain embodiments, the turpentine liquid supply can include a device for heating the turpentine liquid. Contacting vessel 208 may include a plurality of trays or fins 214 designed to retain the oil shale in the contacting vessel for a specific period of time and to increase or control contact between the oil shale particles and the turpentine liquid. In certain embodiments, the contacting vessel may be an inclined rotary filter or a trommel. An extraction mixture stream comprising turpentine liquid and recovered hydrocarbon-containing organic matter from the oil shale is collected via outlet 216 and supplied to storage tank 220. A pump 218 may optionally be connected to outlet 216 to assist in supplying the extraction mixture stream to a holding tank 220. The extraction mixture stream can be connected to line 222 for supplying the extraction mixture stream for further processing. The second conveyor 224 assists in removing inorganic or insoluble materials from the contacting vessel 208. Turpentine liquids can include, but are not limited to, alpha-terpineol and beta-terpineol.
Referring now to fig. 3, an apparatus 300 is provided for recovering hydrocarbon-containing organic matter from coal. The coal sample 302 is supplied to a grinder or crusher 304 to reduce the size of the coal. Preferably, the grinder or crusher 304 reduces the coal to about 0.074-0.84 mm in diameter, depending on the quality of the coal sample. In certain embodiments, the grinder or crusher 304 may be a wet grinder. The crushed coal may optionally be supplied to a filter to ensure uniform and/or consistent particle size. Crushed coal is supplied to the first contact vessel 306. The first contacting vessel 306 is also connected to a turpentine liquid supply 308, the turpentine liquid supply 308 optionally being connected to a pump 310, the pump 310 supplying the turpentine liquid to the first contacting vessel 306. In certain embodiments, the turpentine liquid supply can include a device for heating the turpentine liquid. The first contacting vessel 306 includes a mixing device designed to agitate and improve or control contact between the solid coal particles and the turpentine liquid. An extraction mixture stream comprising turpentine liquid and hydrocarbon-containing organic matter recovered from the coal is collected via first contacting vessel outlet 313 and supplied to second contacting vessel 316. A pump 314 is optionally connected to outlet 313 to assist in supplying the extraction mixture stream to the second contacting vessel 316. The second contacting vessel 316 can include a series of trays or fins 318 designed to increase or control the separation of solids and turpentine liquid. Optionally, the second contacting vessel 316 can be an inclined rotary filter or a trommel. A flow of the extraction mixture may be collected from the second contacting vessel outlet 320, and the outlet 320 may optionally be connected to a pump 322 to assist in supplying the flow of the extraction mixture to a storage tank 324. The liquid coal and any turpentine liquid present in storage tank 324 can be supplied via line 326 to a liquid coal refinery or other processing step. A conveyor 328 may be connected to the second contacting vessel 316 for removing and recovering solids as a by-product of the process. Turpentine liquids can include, but are not limited to, alpha-terpineol and beta-terpineol. The apparatus 300 may also be used to process premium and low grade oil shale.
Referring now to fig. 4, a process 400 is provided for enhancing the recovery of hydrocarbon-containing organic matter from a hydrocarbon-containing subterranean formation. Hydrocarbon-bearing reservoir 404 is shown below surface 402. Production well 406 is already in operation. Injection well 408 is provided for injecting turpentine liquid via line 410. The turpentine liquid facilitates liquefaction, dissolution, and/or extraction of hydrocarbon-containing organic matter present in the reservoir, as well as providing a driving force to push hydrocarbon-containing organic matter in the formation towards the production wells. The hydrocarbon product stream, including the injected turpentine liquid, is collected via line 412. Turpentine liquids can include, but are not limited to, alpha-terpineol and beta-terpineol.
In certain embodiments, the turpentine liquid provided for increasing production from an oil well comprises at least 30% by volume of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, terpene resins, alpha-terpene, beta-terpene, gamma-terpene, or mixtures thereof. In other embodiments, the turpentine liquid comprises at least 30% by volume of geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinane, 2-pinane hydroperoxide, hydroterpineol, 2-pinanol, dihydromyrcenol, isoborneol, p-menthan-8-ol, terpinyl a-acetate, citronellol, p-menth-8-ol acetate, 7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In still other embodiments, the turpentine liquid comprises at least 30% by volume anethole, camphene; p-cymene, anisaldehyde, 3, 7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimenol, 2-methoxy-2, 6-dimethyl-7, 8-epoxyoctane, camphor, citral, 7-methoxy dihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, or mixtures thereof.
In certain embodiments, the turpentine liquid comprises at least about 40% by volume α -terpineol. In other embodiments, the turpentine liquid comprises at least about 25% by volume of β -terpineol. In still other embodiments, the turpentine liquid includes at least about 40% by volume α -terpineol and at least about 25% by volume β -terpineol. In other embodiments, the turpentine liquid includes at least about 50% by volume α -terpineol, and in certain embodiments also includes β -terpineol. In certain embodiments, the turpentine liquid comprises at least 20% by volume of β -terpineol. In certain embodiments, the turpentine liquid comprises about 50-70% by volume α -terpineol and about 10-40% by volume β -terpineol.
In another aspect, a process for increasing production from an enhanced oil recovery operated subterranean hydrocarbon-containing reservoir is provided, the process comprising injecting a turpentine liquid into the reservoir through an injection well to promote production of hydrocarbon-containing material. The turpentine liquid can include at least one compound selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, terpene resins, alpha-terpene, beta-terpene, gamma-terpene, or mixtures thereof. In other embodiments, the turpentine liquid can include at least one compound selected from the group consisting of geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinane, 2-pinane hydroperoxide, hydroterpineol, 2-pinanol, dihydromyrcenol, isoborneol, p-menthan-8-ol, terpinyl a-acetate, citronellol, p-menthan-8-ol acetate, 7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In still other embodiments, the turpentine liquid can include a liquid selected from anethole, camphene; at least one compound selected from p-cymene, anisaldehyde, 3, 7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimenol, 2-methoxy-2, 6-dimethyl-7, 8-epoxyoctane, camphor, citral, 7-methoxy dihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, or a mixture thereof. A hydrocarbon-containing organic matter product stream comprising turpentine liquid and recovered hydrocarbons is recovered from a production well coupled to the hydrocarbon-containing reservoir. The hydrocarbon-containing organic matter product stream can be separated into a recovery hydrocarbon stream and a turpentine liquid recycle stream. In certain embodiments, the further method may further comprise the step of injecting the turpentine liquid recycle stream into the injection well.
In another aspect, a method for increasing production of a hydrocarbon-bearing subterranean hydrocarbon formation subjected to an enhanced oil recovery operation is provided. The method includes the step of injecting a turpentine liquid into the formation through an injection well. In certain embodiments, the turpentine liquid comprises at least 40% by volume α -terpineol and at least 10% by volume β -terpineol. The turpentine liquid dissolves, extracts, and/or displaces hydrocarbon-containing materials from the formation, and the hydrocarbon-containing materials are subsequently recovered from the formation through the turpentine liquid for production wells. In certain embodiments, the method further comprises separating hydrocarbons from the turpentine liquid. In still other embodiments, the method further comprises recycling the turpentine liquid to the production well. In certain embodiments, α -terpineol is present in an amount of about 40-70% by volume. In certain other embodiments, α -terpineol is present in an amount of at least 70% by volume. In still other embodiments, the beta-terpineol is present in an amount of about 10-40% by volume. In other embodiments, the turpentine liquid further comprises up to about 10% by volume of gamma-terpineol. In other embodiments, the turpentine liquid can include up to about 25% by volume of an organic solvent selected from the group consisting of methanol, ethanol, propanol, toluene, and xylene. The method is useful for the recovery of hydrocarbon-containing organic matter during primary, secondary, and tertiary recovery operations, including after secondary recovery operations, including water flooding.
In another aspect, a turpentine liquid for recovering hydrocarbon-containing organic matter from tar sands is provided. In one embodiment, the turpentine liquid includes at least about 30% by volume α -terpineol and at least about 25% by volume β -terpineol. In another embodiment, the turpentine liquid includes about 30-70% by volume α -terpineol, about 25-55% by volume β -terpineol, up to about 10% by volume α -terpene and up to about 10% by volume β -terpene.
In another aspect, a turpentine liquid for recovering hydrocarbon-containing organic matter from a high-quality coal resource, such as, for example, anthracite or bituminous coal, is provided. In one embodiment, the turpentine liquid includes at least about 45% by volume α -terpineol and at least about 15% by volume β -terpineol. In another embodiment, the turpentine liquid comprises about 45-80% by volume α -terpineol, about 15-45% by volume β -terpineol, up to about 10% by volume α -terpene and up to about 10% by volume β -terpene.
In another aspect, a turpentine liquid for recovering hydrocarbon-containing organic matter from low-grade coal resources is provided. In one embodiment, the turpentine liquid includes at least about 60% by volume α -terpineol and up to about 30% by volume β -terpineol. In another embodiment, the turpentine liquid includes from about 60 to about 95% by volume α -terpineol, up to about 30% by volume β -terpineol, up to about 5% by volume α -terpene, and up to about 5% by volume β -terpene.
In another aspect, a turpentine liquid for recovering hydrocarbon-containing organic matter from oil shale is provided. As used herein, oil shale generally refers to any sedimentary rock containing bituminous material. In one embodiment, the turpentine liquid includes at least about 60% by volume α -terpineol and up to about 30% by volume β -terpineol. In another embodiment, the turpentine liquid includes from about 60 to about 95% by volume α -terpineol, up to about 30% by volume β -terpineol, up to about 5% by volume α -terpene, and up to about 5% by volume β -terpene.
In another aspect, a turpentine liquid for recovering hydrocarbon-containing organic matter from light and medium crude oil is provided. In one embodiment, the turpentine liquid includes at least about 40-70% by volume alpha-terpineol and at least about 30-40% by volume beta-terpineol. In another embodiment, the turpentine liquid includes about 40-70% by volume α -terpineol, about 30-40% by volume β -terpineol, up to about 10% by volume α -terpene and up to about 10% by volume β -terpene.
In another aspect, a turpentine liquid for recovering hydrocarbon-containing organic matter from heavy and extra heavy crude oil is provided. In one embodiment, the turpentine liquid includes at least about 50-70% by volume alpha-terpineol and at least about 30-40% by volume beta-terpineol. In another embodiment, the turpentine liquid includes about 50-70% by volume α -terpineol, about 30-40% by volume β -terpineol, up to about 10% by volume α -terpene and up to about 10% by volume β -terpene.
In another aspect, a method for recovering hydrocarbon-containing organic matter from tar sands is provided. The method includes mining a tar sands rich formation to provide a tar sand sample, wherein the tar sand sample includes recoverable hydrocarbon-containing organic matter and residual inorganic or insoluble matter. Tar sand sample supply refers to a contacting vessel, wherein the contacting vessel comprises at least one inlet for supplying turpentine liquid for recovering hydrocarbons from tar sands. The tar sands sample is contacted with a turpentine liquid to extract hydrocarbon-containing organic matter from the tar sands to produce a residual matter and an extraction mixture. The extraction mixture includes a turpentine liquid and recovered hydrocarbon-containing organic matter, and residual matter is separated from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recycle stream. In certain embodiments, the method further comprises the step of recycling the turpentine liquid recycle stream to the contacting vessel. In other embodiments, the extraction mixture may be separated by distillation to produce a hydrocarbon product stream and a turpentine liquid recycle stream.
In certain embodiments, the turpentine liquid can include alpha-terpineol. In other embodiments, the turpentine liquid can include at least about 40% by volume α -terpineol and 10-40% by weight β -terpineol. In certain embodiments, 0.5 to 4 equivalents of turpentine liquid is used to contact tar sand and recover hydrocarbons. In certain embodiments, 0.5 to 2.0 equivalents of turpentine liquid is used to contact tar sand and recover hydrocarbons.
In another aspect, a method for recovering hydrocarbon-containing organic matter from hydrocarbon-rich oil shale is provided. The method includes mining a formation including hydrocarbon-containing organic matter to produce hydrocarbon-containing oil shale including recoverable hydrocarbon material and inorganic or insoluble material. The oil shale is comminuted to produce a comminuted hydrocarbon-containing oil shale. The crushed hydrocarbon-containing oil shale is then filtered with a screen to prevent or control oversized particles from being fed into the extraction process. Charging the crushed hydrocarbon-containing oil shale to a contacting vessel, wherein the contacting vessel comprises at least one inlet for supplying a turpentine liquid for recovering hydrocarbons from the crushed hydrocarbon-containing oil shale. The crushed hydrocarbon-containing oil shale is contacted with a turpentine liquid to extract hydrocarbon-containing organic matter from the crushed hydrocarbon-containing oil shale to produce inorganic solids and an extraction mixture comprising the turpentine liquid and recovered hydrocarbons. Inorganic or insoluble materials are removed from the extraction mixture and the recovered hydrocarbons are separated from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recycle stream. In certain embodiments, the turpentine liquid recycle stream is recycled to the contacting vessel. In other embodiments, the crushed hydrocarbon-containing oil shale has an average particle size of less than about 0.42mm in diameter. In other embodiments of the method of recovering hydrocarbon-containing organic matter from oil shale, the turpentine liquid comprises at least one compound selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, terpene resins, alpha-terpene, beta-terpene, gamma-terpene, or mixtures thereof. In other embodiments, the turpentine liquid can include at least one compound selected from the group consisting of geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinane, 2-pinane hydroperoxide, hydroterpineol, 2-pinanol, dihydromyrcenol, isoborneol, p-menthan-8-ol, terpinyl a-acetate, citronellol, p-menthan-8-ol acetate, 7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In other embodiments, the turpentine liquid can include a liquid selected from anethole, camphene; at least one compound selected from p-cymene, anisaldehyde, 3, 7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimenol, 2-methoxy-2, 6-dimethyl-7, 8-epoxyoctane, camphor, citral, 7-methoxy dihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, or a mixture thereof. In certain embodiments, the turpentine liquid can include alpha-terpineol. In other embodiments, the turpentine liquid can include at least about 40% by volume α -terpineol and 10-40% by weight β -terpineol. In certain embodiments, 0.5 to 4 equivalents of turpentine liquid are used to contact oil shale and recover the hydrocarbon-containing organic matter. In certain embodiments, 0.5 to 2.0 equivalents of turpentine liquid are used to contact the oil shale and recover hydrocarbons.
In another aspect, a method for recovering hydrocarbon-containing organic matter from a coal-rich subterranean formation is provided. The method includes mining a subterranean formation to produce coal, wherein the coal includes recoverable hydrocarbon-containing organic matter and inorganic or insoluble matter. The coal is pulverized to produce crushed coal and filtered to provide a sample of uniform or desired size. Crushed coal is fed to a contacting vessel, wherein the contacting vessel includes at least one inlet for supplying a turpentine liquid for recovering hydrocarbons from the crushed coal, and the crushed coal is contacted with the turpentine liquid to extract hydrocarbons from the crushed coal to produce an inorganic solid and an extraction mixture. The extraction mixture includes turpentine liquid and recovered hydrocarbons. Inorganic or insoluble materials are separated from the extraction mixture and recovered hydrocarbons are separated from the turpentine liquid to produce a liquid coal product stream and a turpentine liquid recycle stream. In certain embodiments, the method further comprises recycling the turpentine liquid recycle stream to the contacting vessel. In still other embodiments, the liquid coal product stream is supplied to a liquid coal refinery. In certain embodiments, the coal sample comprises low grade coal having an average particle size of less than about 0.42 mm. In certain embodiments, the coal sample comprises high quality coal having an average particle size of less than about 0.84 mm.
In still other embodiments of the method for recovering hydrocarbon-containing organic matter from coal, the turpentine liquid comprises at least one compound selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, terpene resins, alpha-terpene, beta-terpene, gamma-terpene, or mixtures thereof. In other embodiments, the turpentine liquid can include at least one compound selected from the group consisting of geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinane, 2-pinane hydroperoxide, hydroterpineol, 2-pinanol, dihydromyrcenol, isoborneol, p-menthan-8-ol, terpinyl a-acetate, citronellol, p-menthan-8-ol acetate, 7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In other embodiments, the turpentine liquid can include a liquid selected from anethole, camphene; at least one compound selected from p-cymene, anisaldehyde, 3, 7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimenol, 2-methoxy-2, 6-dimethyl-7, 8-epoxyoctane, camphor, citral, 7-methoxy dihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, or a mixture thereof. In certain embodiments, the turpentine liquid comprises at least 60% by volume α -terpineol. In certain embodiments, the turpentine liquid comprises at least 45% by volume α -terpineol and at least about 15% by volume β -terpineol. In certain other embodiments, the turpentine liquid comprises at least 60% by volume α -terpineol and up to about 30% by volume β -terpineol. In certain embodiments, 0.5 to 4 equivalents of turpentine liquid are used to contact oil shale and recover the hydrocarbon-containing organic matter. In certain embodiments, 0.5 to 2.0 equivalents of turpentine liquid are used to contact oil shale and recover hydrocarbonaceous organic material.
In another aspect, a system for recovering hydrocarbon-containing organic matter from tar sands is provided. The tar sand recovery system includes a storage tank for supplying a turpentine liquid and a contacting vessel, wherein the contacting vessel includes at least one inlet for introducing the turpentine liquid and at least one outlet for recovering an extraction mixture from the contacting vessel. The system also includes a first conveyor for supplying the tar sands to the contacting vessel. A tank is provided that includes a line connecting the tank and the contacting vessel, wherein the line connecting the contacting vessel and the tank includes a filter to prevent solids from entering the tank. The system also includes a second conveyor for recovering and conveying the solids.
In one embodiment, the contacting vessel is a rotary inclined filter comprising a series of fins or trays for separating and/or controlling tar sands. In another embodiment, fins or trays are provided to increase or control the contact time between the tar sands and the turpentine liquid. In certain embodiments, the turpentine liquid can include alpha-terpineol. In other embodiments, the turpentine liquid can include about 30-70% by volume α -terpineol and about 25-55% by weight β -terpineol.
In another aspect, a system for recovering hydrocarbon-containing organic matter from oil shale is provided. The system includes a storage tank for supplying a turpentine liquid and a mill for pulverizing oil shale into smaller particle sizes. A contacting vessel is provided that includes at least one inlet for introducing a turpentine liquid, at least one inlet for receiving crushed oil shale, at least one outlet for recovering solids from the contacting vessel, and at least one outlet for recovering an extraction mixture from the contacting vessel. A first conveyor is provided for supplying crushed oil shale to the contacting vessel. The system further comprises a holding tank, wherein the holding tank comprises a line connecting the holding tank and the contacting vessel, wherein the line comprises a filter to prevent the entry of solids into the holding tank; a second conveyor for recovering solids. In certain embodiments, the system further comprises a line for supplying the reaction mixture comprising recovered hydrocarbons and turpentine liquid to a refinery for further separation and/or processing. In certain embodiments, the turpentine liquid can include alpha-terpineol. In certain embodiments, the turpentine liquid can include at least about 60-95% by volume alpha-terpineol and up to about 30% by weight beta-terpineol. In other embodiments, the turpentine liquid can include about 70-90% by volume α -terpineol and about 5-25% by weight β -terpineol.
In another aspect, a system for recovering hydrocarbon-containing organic matter from coal is provided. The system includes a tank for supplying a turpentine liquid and a grinder for pulverizing coal to produce smaller sized particulate matter. A contacting vessel is provided that includes at least one inlet for introducing a turpentine liquid and at least one outlet for recovering solids and liquid from the contacting vessel. The contacting vessel further comprises an agitation device for thoroughly mixing the turpentine liquid and the crushed coal. A separator is provided for separating solids and liquids, wherein the separator comprises an inlet, an outlet, and a line connecting the inlet of the separator to the outlet of the contacting vessel. The system also includes a holding tank, wherein the holding tank includes a line connecting the holding tank to the separator, wherein the line may include a filter to prevent solids from entering the holding tank.
In certain embodiments, the system further comprises a filter for selectively preventing particles having an average diameter greater than about 0.85mm from being introduced into the contacting vessel. In certain other embodiments, the system further comprises a line for supplying the liquid coal product to a refinery for further processing. In certain embodiments, the system further comprises a first conveyor for supplying crushed coal to the contacting vessel. In other embodiments, the system further comprises a second conveyor for removing solids from the separator. In certain embodiments, the turpentine liquid can include alpha-terpineol. In embodiments directed to the recovery of hydrocarbons from high quality coal, the turpentine liquid can include about 45-80% by volume alpha-terpineol and about 15-45% by weight beta-terpineol. In embodiments directed to recovering hydrocarbons from low-grade coal, the turpentine liquid can include about 60-95% by volume alpha-terpineol and about 0-30% by weight beta-terpineol.
In another aspect, a method for optimizing the extraction of hydrocarbon-containing organic matter from hydrocarbon-containing matter by a turpentine liquid is provided. Generally, the method includes providing a sample of a hydrocarbon-containing material and analyzing the hydrocarbon-containing material to determine the type of hydrocarbons extracted. A scheme is provided for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material, wherein the scheme is a function of the type of formation and the size of the particulate hydrocarbon material. Generally, the formulation includes at least about 40% by volume α -terpineol and at least about 10% by volume β -terpineol. The amounts of alpha-terpineol and beta-terpineol in the formulation were then adjusted based on the parameters described above. Generally, while the above-described method provides a good starting point for determining the desired formulation for extraction of various hydrocarbon-containing materials, for other hydrocarbon-containing materials and specific operating conditions, a series of statistically designed tests or a series of tests according to an optimization method can be performed to determine the optimum composition of the liquid turpentine.
As shown in table 1, the specific formulations used to extract, liquefy and/or dissolve the hydrocarbon-containing organic matter from tar sands vary according to particle size. In certain embodiments, a method for preparing a turpentine liquid for extracting hydrocarbon-containing organic matter from tar sands includes adjusting the amount of alpha-terpineol and beta-terpineol in a formulation as a function of the size of the hydrocarbon-rich solid particulates being extracted. In other embodiments, if the hydrocarbon-containing organic particulate matter comprises low grade coal or oil shale, the amount of alpha-terpineol in the turpentine liquid is increased and the amount of beta-terpineol in the turpentine liquid is decreased. In other embodiments, if the hydrocarbon-containing organic particulate matter comprises tar sands, the amount of alpha-terpineol in the turpentine liquid is reduced and the amount of beta-terpineol in the turpentine liquid is increased. In other embodiments, if the hydrocarbon-containing organic particulate matter comprises tar sands and the average diameter of the particulate matter is less than about 4.76mm, the amount of alpha-terpineol in the turpentine liquid is reduced and the amount of beta-terpineol in the turpentine liquid is increased. In other embodiments, if the hydrocarbon-containing organic particulate matter comprises tar sands and the average diameter of the particulate matter is greater than about 1 inch (1 mesh), the amount of alpha-terpineol in the turpentine liquid is increased and the amount of beta-terpineol in the turpentine liquid is decreased.
TABLE 1 formulation for tar sands extraction based on particle size
Similar to the formulations shown above with respect to the extraction of tar sands, as shown in tables 2 and 3, the formulations used for extraction, liquefaction and/or solubilization of coal depend on the particle size and the quality of the coal being extracted. In one embodiment of a method for preparing a turpentine liquid from which hydrocarbon-containing organic matter is extracted, if the hydrocarbon-containing matter comprises anthracite, bituminous, or other high-quality coal and the particulate matter has an average diameter of less than about 0.15mm, the amount of alpha-terpineol in the turpentine liquid is reduced and the amount of beta-terpineol in the turpentine liquid is increased. In other embodiments, if the hydrocarbon-rich particulate matter comprises anthracite, bituminous, or other high-quality coal and the average diameter of the particulate matter is greater than about 0.84mm, the amount of alpha-terpineol in the turpentine liquid is increased and the amount of beta-terpineol in the turpentine liquid is decreased. In another embodiment, if the hydrocarbon-rich particulate matter comprises low grade coal and the average diameter of the particulate matter is less than about 0.074mm, the amount of alpha-terpineol in the turpentine liquid is reduced and the amount of beta-terpineol in the turpentine liquid is increased. In another embodiment, if the hydrocarbon-rich particulate matter comprises low grade coal and the average diameter of the particulate matter is greater than about 0.42mm, the amount of alpha-terpineol in the turpentine liquid is increased and the amount of beta-terpineol in the turpentine liquid is decreased.
TABLE 2 formulation for extracting high quality coal based on particle size
TABLE 3 formulation for extracting low-grade coal based on particle size
Similar to the formulations shown above with respect to the extraction of tar sands, as shown in table 4, the formulations used for the extraction, liquefaction and/or solubilization of oil shale depend on particle size. In one embodiment of the method of making a composition for extracting hydrocarbon-containing organic matter, if the hydrocarbon-rich particulate matter comprises oil shale and the average diameter of the particulate matter is less than about 0.074mm, the amount of alpha-terpineol in the turpentine liquid is reduced and the amount of beta-terpineol in the turpentine liquid is increased. In another embodiment, if the hydrocarbon-rich particulate matter comprises oil shale and the average diameter of the particulate matter is greater than about 0.42mm, the amount of alpha-terpineol in the turpentine liquid is increased and the amount of beta-terpineol in the turpentine liquid is decreased.
TABLE 4 formulation for oil shale extraction based on particle size
< 200 mesh (0.074mm) 60-80％vol 10-30％vol 5％vol 0％vol
40 mesh (0.420mm) -200 mesh (0.074mm) 70-90％vol 5-25％vol 5％vol 0％vol
> 40 mesh (0.420mm) 75-95％vol 0-20％vol 5％vol 0％vol
The extraction of crude oil similarly depends on the type of crude oil being extracted, liquefied, and/or dissolved. As shown in table 5, the formulation used to extract, liquefy and/or solubilize the crude oil is a function of both the particle size and the quality of the density of the extracted crude oil. The method comprises providing a turpentine liquid formulation comprising at least 50% by volume α -terpineol and at least 20% by volume β -terpineol; the amount of alpha-terpineol and beta-terpineol in the turpentine liquid formulation is adjusted based on the density of the liquid hydrocarbon being extracted. In one embodiment, if the extracted liquid hydrocarbons have an API gravity greater than about 22 °, the amount of alpha-terpineol in the turpentine liquid is reduced and the amount of beta-terpineol in the turpentine liquid is increased. In another embodiment, if the extracted liquid hydrocarbons have an API gravity of less than about 22 °, the amount of alpha-terpineol in the turpentine liquid is increased and the amount of beta-terpineol in the turpentine liquid is decreased. As used herein, the API for light oils is at least about 31 °, the API for medium crude oils is from about 22 ° to about 31 °, the API for heavy oils is from about 10 ° to about 22 °, and the API for extra heavy oils is less than about 10 °.
TABLE 5 formulation for crude oil extraction based on API density
In another aspect, a method of preparing a turpentine liquid for enhanced recovery of liquid hydrocarbon-containing organic matter from a subterranean formation is provided. The method includes providing a formulation including at least 50% by volume α -terpineol and at least 20% by volume β -terpineol; and adjusting the amounts of alpha-terpineol and beta-terpineol in the formulation based on the geological characteristics of the subterranean formation.
In another aspect, a composition for cleaning and/or recovering hydrocarbons from a liquid hydrocarbon-containing container is provided, wherein the composition comprises at least one compound selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, terpene resins, alpha-terpene, beta-terpene, gamma-terpene, or mixtures thereof. In other embodiments, the composition for cleaning and/or recovering hydrocarbons may comprise at least one compound selected from geraniol, 3-carene, dipentene (p-menthane-1, 8-diene), nopol, pinane, 2-pinane hydroperoxide, hydroterpineol, 2-pinanol, dihydromyrcenol, isoborneol, p-menthan-8-ol, terpinyl a-acetate, citronellol, p-menth-8-ol acetate, 7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In still other embodiments, the composition for cleaning and/or recovering hydrocarbons may include a solvent selected from the group consisting of anethole, camphene; at least one compound selected from p-cymene, anisaldehyde, 3, 7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimenol, 2-methoxy-2, 6-dimethyl-7, 8-epoxyoctane, camphor, citral, 7-methoxy dihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, or a mixture thereof. In one embodiment, the composition comprises at least one compound selected from the group consisting of: alpha-pinene, beta-pinene, alpha-terpineol and beta-terpineol. In another embodiment, the composition comprises at least 25% by volume α -terpineol or β -terpineol.
In another aspect, a method for cleaning and/or recovering hydrocarbons from a vessel containing liquid hydrocarbons is provided. The method includes contacting the interior of the container with a hydrocarbon cleaning composition to produce a mixture, the composition including at least one compound selected from the group consisting of alpha-pinene, beta-pinene, alpha-terpineol, and beta-terpineol, wherein the mixture includes a liquid hydrocarbon residue and the hydrocarbon cleaning composition. The mixture is recovered from the vessel and removed. In certain embodiments, the cleaning composition comprises at least 25% by volume α -terpineol or β -terpineol. In certain other embodiments, the cleaning composition comprises at least 25% by volume α -terpineol and at least 25% by volume β -terpineol.
Examples
Example 1. in this example, coal from pittsburgh coal seam in washington county, pennsylvania was liquefied with reagent α -terpineol. Coal samples were obtained from the Coal Bank of pennsylvania state university (Coal Bank) for which the university provided approximate analysis as follows: 2.00 wt.% received base moisture, 9.25 wt.% dry ash, 38.63 wt.% dry volatiles, and 50.12 wt.% dry fixed carbon. The particle size of the coal sample was about 60 mesh. About 60 grams of alpha-terpineol was gently added to about 30 grams of the coal sample placed in the extraction vessel, resulting in a 2:1 ratio of reagent samples. The capped, but not tightly sealed extraction vessel containing the resulting mixture of α -terpineol and coal was maintained at a constant temperature of about 96 ℃ with constant stirring. The pressure in the extraction vessel is maintained at a level slightly below about 1.01X 105Pascal (1atm) and does not boil alpha-terpineol. After about 30 minutes, the mixture was filtered and the coal particles remaining on the filter were washed with ethanol and dried to constant weight. The conversion, i.e., the degree of liquefaction, of the coal sample was determined to be about 68 wt.% based on weight loss.
Example 2 this example is almost the same as example 1, except for two points. After maintaining the temperature at about 96 ℃ for about 30 minutes, the extraction vessel containing the coal sample and alpha-terpineol was maintained at a temperature of about 135 ℃ for an additional period of about 30 minutes, as in example 1. The pressure in the extraction vessel is maintained at a level slightly below about 1.01X 105Ambient pressure of pascal (1 atm). The conversion, i.e. the degree of liquefaction, of the coal sample was determined to be about 70 wt.%.
Example 3. the coal samples used were the same source and had the same approximate analysis as the coal samples used in the first two examples. About 31 grams of alpha-terpineol was added to about 31 grams of the coal sample in the extraction vessel. The mixture is at about 96 ℃ and slightly below about 1.01X 105Maintained at ambient pressure of about 1atmFor 30 minutes. The conversion, i.e. the degree of liquefaction, of the obtained coal sample was determined by weighing the sample after filtration, washing and drying as in the previous two examples to about 71 wt.%.
Example 4 this example is the same as example 3 except that hexane was substituted for about 30 wt.% of alpha-terpineol to give a reagent comprising 70 wt.% of alpha-terpineol and 30 wt.% hexane. This reduces the conversion, i.e. the degree of liquefaction, to about 1.3 wt.%.
Example 5. for this example, the source and approximate analysis of the coal sample, and the experimental conditions for temperature, pressure and reagent sample ratio were the same as in example 3. However, the duration of extraction was reduced from about 30 minutes to about 20 minutes. Additionally, 1-butanol was substituted for about 30 wt.% of α -terpineol, resulting in a reagent comprising 70 wt.% of α -terpineol and 30 wt.% of 1-butanol. The amount of coal liquefied was only about 0.30 grams, corresponding to a conversion of about 1.0 wt.%.
Example 6 this example is the same as example 3 in terms of source and approximate analysis of the coal sample, and temperature, pressure and duration of extraction. However, the amount of coal sample used was about 25 grams, and the reagent included about 24 grams (80 wt.%) alpha-terpineol and about 6 grams (20 wt.%) xylene. A reagent comprising 70 wt.% alpha-terpineol and 30 wt.% xylene was obtained. The liquefied coal was about 10.0 grams, corresponding to a conversion of about 40 wt.%.
Example 7. in this example, coal from wyoming coal seam (Wyodakseam) in campbell county, wyoming was liquefied with the reagent α -terpineol. Coal samples were obtained from the coal bank of pennsylvania state university (CoalBank), for which the university provided approximate analysis as follows: 26.30 wt.% received base moisture, 7.57 wt.% dry ash, 44.86 wt.% dry volatiles, and 47.57 wt.% dry fixed carbon. The particle size of the coal sample was about 20 mesh. About 60 grams of alpha-terpineol was gently added to about 30 grams of the coal sample placed in the extraction vessel at a reagent sample ratio of about 2: 1. The covered but not tightly sealed extraction vessel containing the resulting mixture of alpha-terpineol and coal is maintained at a constant temperature of about 96 ℃ with constant stirring. The pressure in the extraction vessel is maintained at a level slightly below about 1.01X 105Pascal (1atm) and does not boil alpha-terpineol. After about 30 minutes, the mixture in the extraction vessel was filtered, and the coal particles remaining on the filter were washed with ethanol and dried to constant weight. The conversion, i.e., the degree of liquefaction, of the coal sample was determined to be 75 wt.% based on weight loss.
Example 8 the experiment in this example was carried out under the same conditions as in the previous example, except for one aspect. About 15 grams of alpha-terpineol, instead of about 60 grams as in the previous example, was added to a sample of about 30 grams of coal, thus obtaining a reagent coal ratio of 0.5: 1. The conversion, i.e. degree of liquefaction, of the obtained coal sample was reduced from about 75 wt.% obtained in the previous example to about 69 wt.%.
Example 9. in this example, about 3 grams of oil shale from the Green-river region of colorado (Green-river region) was dissolved with about 9 grams of alpha-terpineol, resulting in a 3:1 sample ratio of reagents from which to extract kerogen (organic material) and/or bitumen (organic material). The organic carbon content, including volatiles and fixed carbon, was determined to be about 22.66 wt.% by certified analytical company. Using oil shale samples with a particle size of 60 mesh at ambient temperature of about 25 ℃ and slightly below about 1.01 x 105Two tests were performed at a pressure of pascals (1 atm). The weight loss of the sample was determined by weighing after filtration, washing with ethanol and drying. The weight loss was about 9 wt.% after about 30 minutes and about 17 wt.% after about 45 minutes. From these weight losses, the conversion, i.e. degree of extraction, of organic material, i.e. kerogen and/or bitumen, the former is estimated to be about 40 wt.%, and the latter about 75 wt.%.
Example 10. this example repeats the previous example except that a single test is run at a temperature of about 96 c, rather than at a temperature of about 25 c, for about 15 minutes. The weight loss of oil shale is about 12 wt.%, corresponding to a conversion of kerogen (organic matter), i.e. a degree of extraction, of about 53 wt.%.
Example 11. In this example, commercial grade synthetic turpentine was used to dissolve and extract bitumen (organic matter) from tar sands from alberta canada. Tar sand samples were obtained from the Alberta Research Council (Alberta Research Council) and provided an approximate analysis for the samples as follows: 84.4 wt.% dry solids, 11.6 wt.% dry asphalt and 4.0 wt.% received base moisture. Approximately 30 grams of synthetic turpentine was gently added to a sample of approximately 15 grams of tar sand in a capped, but not tightly sealed, extraction container using a reagent sample ratio of approximately 2:1 by weight. This extraction vessel containing the resulting mixture of synthetic turpentine and tar sands was maintained at a constant temperature of about 96 ℃ with constant agitation. The pressure in the extraction vessel is maintained at a level slightly below about 1.01X 105Pascal (1atm) and does not boil the synthetic turpentine. After about 20 minutes, the mixture in the extraction vessel was filtered, and the solids remaining on the filter (tar sands) were washed with ethanol and dried to constant weight. The conversion of bitumen, i.e., the degree of extraction, from the tar sand sample was determined to be about 100 wt.% based on weight loss.
Example 12 in this example, a tar sands sample from the same source as in the previous example and having the same approximate analysis was extracted with about 60 grams of alpha-terpineol instead of commercial grade synthetic turpentine oil that includes alpha-terpineol. The resulting ratio of reagent samples was 1: 1 instead of 2:1 as in the previous example. The test is carried out at a temperature of about 96 ℃ and at a temperature slightly below about 1.01X 105At ambient pressure of pascal (1atm) for about 30 minutes. The conversion, i.e. the degree of extraction, of bitumen (organic matter) in the tar sand sample was determined to be about 100 wt.%.
Example 13 in this example, a tar sand sample from the same source as in the previous two examples and having the same approximate analysis was extracted by a commercial grade synthetic turpentine of about 60 grams. Thus, the resulting reagent sample ratio was about 1: 1. The test is carried out at a temperature of about 96 ℃ and at a temperature slightly below about 1.01X 105At ambient pressure of pascal (1atm) for about 30 minutes. Conversion of bitumen (organic matter) in tar sand samples, i.e. extractionThe degree was determined to be about 70 wt.%.
Example 14. the experiment in this example repeats the procedure in example 8, except that the reagent sample ratio is reduced from about 2:1 to about 0.5: 1. A sample of about 60 grams tar sands was extracted with about 30 grams of commercial grade synthetic turpentine. The conversion of bitumen (organic matter), i.e. the degree of extraction, was reduced from about 100 wt.% to about 70 wt.% obtained in example 9.
Example 15. experiments in this example the procedure of the previous example was repeated using alpha-terpineol instead of commercial grade synthetic turpentine. The conversion, i.e. degree of extraction, of bitumen (organic matter) in the tar sand sample was about 70 wt.%, as in the previous example.
Example 16. the experiment in this example used a tar sand sample from the same source and with the same approximate analysis as the previous example using tar sand at slightly below about 1.01 x 105At ambient pressure of pascal (1 atm). About 60 grams of commercial grade synthetic turpentine was added to about 60 grams of tar sand sample, resulting in a reagent sample ratio of about 1: 1. The temperature of the sample and commercial grade synthetic turpentine was maintained at about 65 ℃ for about 30 minutes and then cooled to about 15 ℃ over about 5 minutes. Subsequently, the tar sand sample was filtered, washed, dried and weighed. The conversion of bitumen (organic matter) in the tar sand sample, i.e. the degree of extraction, was determined to be about 70 wt.% based on weight loss.
Example 17. experiments in this example the procedure of the previous example was repeated using alpha-terpineol instead of commercial grade synthetic turpentine. The conversion, i.e., degree of extraction, of bitumen (organic matter) increases from about 70 wt.% to about 90 wt.%.
Example 18. in this example, a tar sands sample weighing about 30 grams from the same source as examples 11-17 and having the same approximate analysis was measured with a liquid comprising about 20 grams (80 wt.%) of alpha-terpineol and about 5 grams (20 wt.%) of toluene at a temperature of about 96 c and slightly below about 1.01 x 105Extracting at ambient pressure of Pascal (1atm). The duration of the test (reaction or extraction time) was about 30 minutes. The weight loss of the sample was about 10.2 grams. From this weight loss, the conversion of bitumen (organic matter), i.e. the degree of extraction, was estimated to be about 33 wt.%.
Example 19 three tar sands samples from the same source and with the same approximate analysis as the tar sands used in all the previous examples employing tar sands were tested with reagents comprising different amounts of alpha-terpineol and ethanol at temperatures of about 15 deg.C and at slightly below about 1.01 x 105Extracting under the ambient pressure of Pascal (1 atm). The duration of each test (reaction or extraction time) was about 15 minutes for each tar sand sample. The first sample was extracted with a mixture comprising about 0 grams (0 wt.%) alpha-terpineol and about 15 grams (100 wt.%) ethanol, i.e., pure ethanol. A second sample was extracted with a mixture comprising about 7.5 grams (50 wt.%) alpha-terpineol and about 7.5 grams (50 wt.%) ethanol. A third sample was extracted with a mixture comprising about 12 grams (80 wt.%) alpha-terpineol and about 3 grams (20 wt.%) ethanol. The weight loss and estimated conversion of bitumen (organic matter), i.e. the degree of extraction, in the three samples were about 0.2 g (1.0 wt.%), 0.6 g (3.0 wt.%), and 0.9 g (4.5 wt.%), respectively, for the first, second and third samples.
Example 20 irregular shaped pellets of commercial grade asphalt having an average size of about 15mm at a temperature of about 22 deg.C and slightly below about 1.01X 105Dissolving and extracting with alpha-terpineol under ambient pressure of Pascal (1 atm). A first sample weighing about 20 grams was dissolved and extracted with about 40 grams of alpha-terpineol and a second sample weighing also about 20 grams was dissolved and extracted with about 20 grams of alpha-terpineol. Both samples were completely dissolved after 30 minutes. These tests were conducted to simulate the dissolution and extraction of heavy crude oils, which tend to be rich in asphaltenes similar to bitumen.
Example 21 in this example bitumen (organic matter) in tar sands from the same source and with the same approximate analysis as the tar sands used in all the previous examples employing tar sands was used with two different vegetable oils, largeSoybean oil and corn oil. The vegetable oil is completely miscible with the turpentine liquid. In the first test, a tar sands sample weighing about 15 grams was weighed with about 30 grams of soybean oil at a temperature of about 96 ℃ and slightly below about 1.01X 105Mix and continue stirring at ambient pressure of pascals (1atm) for about 20 minutes. The weight loss was about 0.5 grams, from which the conversion of bitumen in the sample, i.e. the degree of extraction, was estimated to be about 3.3 wt.%. In the second test, a tar sands sample weighing about 30 grams was weighed with about 60 grams of corn oil at a temperature of about 175 deg.C and slightly below about 1.01X 105Mix and continue stirring at ambient pressure of pascals (1atm) for about 30 minutes. The weight loss was about 4.8 grams, from which the conversion of bitumen in the sample, i.e. the degree of extraction, was estimated to be about 12 wt.%.
Example 22. two experiments were performed on Berea sandstone plug core (Berea sandstone plug core) samples to determine the effect of agent injection on core oil recovery. The first experiment was designed to measure the increase in oil recovery from alpha terpineol injection after the field had been waterflood to the limit. The selected core contained 9.01mL of a crude-oil-like test oil. Flooding with an aqueous solution containing 3.0% potassium chloride produced 4.6mL of oil. Injection of five (5) pore volumes of alpha-terpineol produced an additional 3.61mL of oil, leaving the core with less than 8.0% oil remaining from the original volume. The second experiment was designed to represent the higher recovery expected from injecting undeveloped reservoirs with alpha-terpineol. The selected core contained 8.85mL of a test oil similar to crude oil. Oil production started after injection of about 0.5 pore volume of alpha-terpineol and continued until 3.5 pore volume was injected; however, most of the oil was recovered after injecting only 2.5 pore volume of α -terpineol. A total of 7.94mL of experimental oil was recovered, leaving less than 7.5% of the original volume of oil remaining in the core.
In one experiment, various different ratios of turpentine liquid to tar sand samples were tested. For each of the tests provided below, the turpentine liquid had the same formulation, wherein the composition included about 60% by volume α -terpineol, about 20% by volume β -terpineol, and about 20% by volume γ -terpineol. Tar sands are different ore mixes from the alberta canada with a bitumen content of about 12 wt% and a water content of about 4-5 wt%. The tests were all carried out at ambient temperature.
As shown in Table 6 below, good hydrocarbon recovery was obtained from tar sands at all ratios provided below (i.e., 1: 2 to 2:1 ratio of turpentine liquid to tar sands) with little discernable difference. With respect to the temperature at which the extraction is carried out, it is believed that the optimum temperature for extracting, dissolving and/or liquefying hydrocarbons from tar sands is 65 ℃. As shown in the table, at about 130 ℃, the amount of hydrocarbons recovered decreased. It is noted, however, that for certain solids where recovery of hydrocarbons is particularly difficult, increasing the temperature of the extraction solvent may increase the amount of hydrocarbons that are recovered. Finally, it was shown that the influence of the contact time on the amount of extracted substance is very small. This is probably because the shortest extraction time, which is believed to be sufficient to extract hydrocarbons from tar sands, is 20 minutes.
TABLE 6
Weight of tar sand, g Extractable HC weight, g Weight of extraction solvent Ratio of tar sand to solvent Amount of extracted HC, g Percent of extracted HC Temperature, C Contact time, min
15 2.0 30.0 1∶2 3.2 161 96 20
60 7.8 120.0 1∶2 5.4 69 96 30
60 7.8 31.6 2∶1 9.6 123 96 30
60 7.8 60.0 1∶1 7.6 97 65 30
60 7.8 60.0 1∶1 4.0 51 130 30
[0131]
60 7.8 60.0 1∶1 6.3 80 65 30
Additional tests were conducted using alternative solvents, i.e., ethanol and corn oil, compared to a composition comprising about 60% by volume α -terpineol, about 20% by volume β -terpineol, and about 20% by volume γ -terpineol. It is noted in table 7 provided below that the performance of ethanol and corn oil is unexpectedly substantially lower than compositions comprising about 60% by volume α -terpineol, about 20% by volume β -terpineol, and about 20% by volume γ -terpineol. For example, the terpineol composition extracts extractable hydrocarbons completely or almost completely, whereas ethanol only yields 10% recoverable hydrocarbons, and heated corn oil only yields 33% recoverable hydrocarbons.
TABLE 7
Chemical substance Weight of tar sand, g Extractable HC weight, g Weight of extraction solvent Ratio of tar sand to solvent Amount of extracted HC, g Percent of extracted HC Temperature, C Contact time, min
Ethanol 15 2.0 15.0 1∶1 0.2 10 15 15
Corn oil 30 3.9 60.0 2∶1 1.3 33 175 30
60/20/20 terpineol 60 7.8 60.0 1∶1 7.6 97 65 30
60/20/20 terpineol 60 7.8 31.6 2∶1 9.6 123 96 30
As shown in table 8 below, the properties of various turpentine liquid formulations are provided, including turpentine liquid formulations including only alpha-terpineol and combinations of alpha-terpineol with various known organic solvents. The first three compositions given in the table included alpha-terpineol, beta-terpineol and gamma-terpineol. For example, the first composition includes about 60% by volume α -terpineol, about 30% by volume β -terpineol, and about 10% by volume γ -terpineol. The results unexpectedly show that as the concentration of alpha-terpineol increases, the properties of the turpentine liquid increase to the point when the turpentine liquid includes about 70% alpha-terpineol, at which time extraction of all hydrocarbon material from the tar sands sample can be achieved.
A second set of data is given for the extraction of hydrocarbon-containing tar sands with pure alpha-terpineol. As shown in the table, the extraction was over 100% probably due to inconsistent hydrocarbon content of the samples. However, the results generally demonstrate the unexpected result that α -terpineol is able to extract substantially all recoverable hydrocarbons from tar sands samples.
Finally, the last set of data provided in table 8 illustrates the efficacy of the hybrid system of alpha-terpineol and known organic solvents. As shown, substantially complete recovery of recoverable hydrocarbons was achieved using a composition comprising alpha-terpineol and ethanol in a 1: 1 ratio. This result is unexpected because pure ethanol removes only about 10% of the total recoverable hydrocarbons. In addition, the mixing system including alpha-terpineol and toluene in a ratio of 1: 1 or 3:1 still recovered 77% and 92% of the total recoverable hydrocarbons. This result was unexpected.
TABLE 8
Chemical composition Weight of tar sand, g Extractable HC weight, g Weight of solvent Ratio of tar sand to solvent Amount of extracted HC, g Percent of extracted HC Temperature, C Contact time, min
60/30/10 terpineol 60 2.0 60.0 1∶1 7.1 91 96 30
40/30/20 terpineol 60 7.8 60.0 1∶1 4.7 60 96 30
70/20/10 terpineol 60 7.8 60.0 1∶1 7.9 101 96 30
100/0/0 terpineol 60 7.8 60.0 1∶1 10.0 128 96 30
100/0/0 terpineol 60 7.8 120.0 1∶2 8.7 111 96 30
100/0/0 terpineol 60 7.8 31.0 2∶1 9.6 123 96 30
50% alpha-terpineol/50% ethanol 15 2.0 15.0 1∶1 8.1 103 65 30
80% alpha-terpineol/20% ethanol 15 2.0 15.0 1∶1 1.2 62 15 15
75% alpha-terpineol/25% toluene 30 3.9 25.0 1∶0.8 1.8 92 15 15
50% alpha-terpineol/50% toluene 30 3.9 26.0 1∶0.9 3.0 77 96 30
50% alpha-terpineol/50% xylene 30 3.9 26.0 1∶0.9 2.4 61 96 30
The results of extracting hydrocarbon-containing organic matter from hydrocarbon-containing materials described in the specification, and in particular in the examples above, are unexpected.
The terms first, second, third and the like as used herein should be interpreted as uniquely identifying an element and not as referring to or limited to any particular order of elements or steps.
The terms about and approximately as used herein should be understood to include any value within 5% of the stated numerical value. Also, the recitation of the terms about and about in a numerical range should be interpreted to include the upper and lower ends of the range. The terms first, second, third and the like as used herein should be interpreted as uniquely identifying an element and not as referring to or limited to any particular order of elements or steps.
While the invention has been shown or described in only some of its embodiments, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention.

Claims (38)

1. A method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material into a turpentine liquid, comprising the steps of:
providing a turpentine liquid, wherein the turpentine liquid comprises at least about 30% by volume α -terpineol and at least about 15% by volume β -terpineol, wherein the term "about" includes any value within 5% of the stated value and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range;
contacting the hydrocarbon-containing material with the turpentine liquid to form a homogeneous one-phase extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter extracted into the turpentine liquid and a residual material comprising at least a portion of insoluble matter from the hydrocarbon-containing material that is insoluble in the turpentine liquid;
separating the extraction mixture from the residual feedstock; and
separating the extraction mixture into a first portion and a second portion, the first portion of the extraction mixture comprising a hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter, the second portion of the extraction mixture comprising at least a portion of the turpentine liquid.
2. The method of claim 1, wherein the hydrocarbon-containing organic matter is a solid or semi-solid, wherein the hydrocarbon-containing material comprises a plurality of particles, the particles having an average particle size.
3. The method of claim 2, wherein the average particle size is from about 0.74mm to about 25mm, wherein the term "about" includes any value within 5% of the stated value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range.
4. The method of claim 1, further comprising the step of adding a second liquid to said turpentine liquid, said second liquid selected from the group consisting of lower aliphatic alcohols, lower alkanes, lower aromatic hydrocarbons, aliphatic amines, aromatic amines, and mixtures thereof.
5. The method of claim 4, wherein the second liquid is selected from the group consisting of ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, anthracene, tetralin, triethylamine, aniline, and mixtures thereof.
6. The method of claim 5, wherein the step of contacting the hydrocarbon-containing material with the turpentine liquid further comprises the step of adding water at a temperature around the boiling point of water.
7. The method of claim 1, further comprising the step of heating said turpentine liquid to a temperature above ambient temperature to about 200 ℃ prior to contacting said turpentine liquid with said hydrocarbon-containing material, wherein the term "about" includes any value within 5% of said value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of said range.
8. The method of claim 1, wherein said hydrocarbon-containing material and said turpentine liquid are at about 1.0 x 104Pascal to about 5.0 x 106Contact under pressure of pascals, wherein the term "about" includes any value within 5% of the stated value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range.
9. The method of claim 1, further comprising supplying at least a portion of the second portion of the extraction mixture to the contacting step.
10. The method of claim 1, further comprising the steps of: means are provided for contacting the hydrocarbon-containing organic matter and the turpentine liquid in situ in a subterranean formation containing the hydrocarbon-containing organic matter, and means for extracting the hydrocarbon-containing organic matter from the subterranean formation.
11. The method of claim 1, wherein the hydrocarbon-containing material is contacted with the turpentine liquid at a temperature of less than about 300 ℃, wherein the term "about" includes any value within 5% of the stated value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range.
12. The method of claim 1, wherein the hydrocarbon-containing material is contacted with the turpentine liquid at a temperature of less than about 60 ℃, wherein the term "about" includes any value within 5% of the stated value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range.
13. The method of claim 1, wherein the hydrocarbon-containing material is in a subterranean formation and contacting of the hydrocarbon-containing material with the turpentine liquid occurs in situ in the subterranean formation; and further comprising the steps of:
recovering the extraction mixture through a production well in fluid communication with the subterranean formation, wherein the residual feedstock remains in situ in the subterranean formation.
14. The method of claim 13, further comprising the step of re-injecting a recycle stream into the injection well for further extraction of hydrocarbon material.
15. The method of claim 13, wherein the subterranean formation is undergoing primary recovery of hydrocarbon material.
16. The method of claim 1, wherein the turpentine liquid comprises about 50% by volume α -terpineol and at least about 20% by volume β -terpineol, wherein the term "about" includes any value within 5% of the stated value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range.
17. The method of claim 1, wherein the turpentine further comprises at least one of an alpha-terpene, a beta-terpene, or a gamma-terpene.
18. The method of claim 1, wherein the turpentine liquid comprises alpha-terpineol and beta-terpineol, wherein the ratio of alpha-terpineol to beta-terpineol is at least about 1.3:1, wherein the term "about" includes any value within 5% of the stated value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range.
19. The method of claim 1, wherein the turpentine liquid comprises alpha-terpineol and beta-terpineol, wherein the ratio of alpha-terpineol to beta-terpineol is at least about 2:1, wherein the term "about" includes any value within 5% of the stated value, and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range.
20. The method of claim 1, the hydrocarbon-containing feedstock comprising tar sands,
wherein the contacting of the hydrocarbon-containing material with the turpentine liquid comprises the steps of: supplying the tar sands to an interior portion of an extraction vessel and supplying the turpentine liquid to the interior portion of the extraction vessel for a period of time operable to extract a major portion of the hydrocarbon-containing organic matter from the hydrocarbon-containing material.
21. The method of claim 1, the hydrocarbon-containing feedstock comprising oil shale, the method further comprising the steps of:
grinding the hydrocarbon-containing organic matter to form a plurality of particles, the particles being limited to an average diameter of 4.8mm to 25mm such that the plurality of particles are in contact with the turpentine liquid.
22. The method of claim 1, the hydrocarbon-containing feed comprising coal, the method further comprising the steps of:
grinding the hydrocarbon-containing organic matter to form a plurality of particles, the particles being limited to an average diameter of 0.8mm to 0.07mm such that the plurality of particles are in contact with the turpentine liquid.
23. The method of any one of claims 1-22, wherein the extracting is performed after addition of a surfactant.
24. The method of claim 1, further comprising the steps of: separating the extraction mixture into a hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter and a recycle stream containing at least a portion of the turpentine liquid.
25. The method of claim 24, further comprising the step of recycling the recycle stream to contact the hydrocarbon-containing feedstock.
26. An apparatus for recovering hydrocarbon-containing organic matter from a solid or semi-solid hydrocarbon-containing material according to the method of claim 1, comprising:
a turpentine liquid supply comprising a turpentine liquid containing terpineol for extracting hydrocarbon-containing organic matter from said hydrocarbon-containing material, wherein said turpentine liquid comprises at least about 30% by volume α -terpineol and at least about 15% by volume β -terpineol, wherein the term "about" includes any value within 5% of said value and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range;
a contacting vessel having a first inlet and in fluid communication with the turpentine liquid supply through the first inlet, the contacting vessel operable to receive the hydrocarbon-containing material through a second inlet in an interior portion, the contacting vessel operable to hold the hydrocarbon-containing material and the turpentine liquid in the interior portion of the contacting vessel for a predetermined amount of time to operably form an extraction mixture of a homogeneous one-phase comprising at least a portion of the hydrocarbon-containing organic matter extracted into the turpentine liquid and a residual material comprising at least a portion of insoluble matter from the hydrocarbon-containing material that is insoluble in the turpentine liquid; the contacting vessel comprising a first outlet for recovering the extraction mixture from the contacting vessel and a second outlet for recovering the residual feedstock from the contacting vessel, the contacting vessel operable to allow mechanical agitation;
a holding tank in fluid communication with the contacting vessel via a line, wherein the holding tank is operable to receive the extraction mixture from the contacting vessel, wherein the line comprises a filter to prevent solids from passing into the holding tank; and
a collection device for collecting the residual feedstock from the second outlet of the contacting vessel.
27. The apparatus of claim 26, further comprising a separation vessel for receiving said extraction mixture, said separation vessel operable to substantially separate said hydrocarbon-containing organic matter from said turpentine liquid.
28. The apparatus of claim 27, further comprising a recycle stream for receiving the turpentine liquid from the separation vessel, the recycle stream operable to return the turpentine liquid from the separation vessel to the contacting vessel for reuse.
29. The apparatus of claim 26, further comprising a grinder configured to reduce the size of the hydrocarbon-containing material for contact with the liquid turpentine in the contact vessel.
30. The apparatus of claim 26, wherein the contacting vessel is a rotary inclined filter, further comprising a plurality of ribs or trays configured to control the contact time between the turpentine liquid and the hydrocarbon-containing material.
31. The apparatus of claim 26, wherein the means for introducing a hydrocarbon-containing material into the contacting vessel comprises a conveyor.
32. The apparatus of claim 26, wherein said contacting vessel further comprises means for mixing said hydrocarbon-containing material and said turpentine liquid.
33. The apparatus of claim 26, further comprising a second contacting vessel connected to said first contacting vessel, wherein said second contacting vessel comprises an inlet for receiving turpentine liquid and coal-like material, a first outlet for recovering at least a portion of said extraction mixture, and a second outlet for removing at least a portion of said residual feedstock from said mixing vessel, wherein said second contacting vessel is located between and connects said first contacting vessel and said storage tank.
34. The apparatus of claim 26, further comprising a filter positioned at an inlet of the contacting vessel.
35. A method of recovering hydrocarbon-containing organic matter from tar sands, the method comprising:
obtaining tar sands including recoverable hydrocarbon-containing organic matter;
providing a turpentine liquid, wherein the turpentine liquid comprises at least about 30% by volume α -terpineol and at least about 15% by volume β -terpineol, wherein the term "about" includes any value within 5% of the stated value and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range;
supplying the tar sands sample to a contacting vessel comprising at least one inlet for supplying the turpentine liquid;
contacting the tar sand sample with the turpentine liquid in a contacting vessel and agitating the tar sand sample and the turpentine liquid to form a homogeneous one-phase extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter extracted into the turpentine liquid and a residual feedstock comprising at least a portion of insoluble materials from the tar sand that are insoluble in the turpentine liquid, the contacting vessel comprising at least one inlet for supplying turpentine liquid;
separating the extraction mixture from the residual feedstock;
separating the extraction mixture into a hydrocarbon product stream and a turpentine liquid recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter from the tar sands; and
recycling at least a portion of the turpentine liquid recycle stream to the contacting step.
36. A method for recovering hydrocarbon-containing organic matter from comminuted hydrocarbon-containing oil shale, the method comprising:
providing the comminuted hydrocarbon-containing oil shale;
providing a turpentine liquid, wherein the turpentine liquid comprises at least about 30% by volume α -terpineol and at least about 15% by volume β -terpineol, wherein the term "about" includes any value within 5% of the stated value and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range;
filtering the comminuted hydrocarbon-containing oil shale;
feeding the comminuted hydrocarbon-containing oil shale to a contacting vessel comprising at least one inlet for supplying the turpentine liquid to the contacting vessel;
contacting the comminuted hydrocarbon-containing oil shale with a turpentine liquid to form a homogeneous one-phase extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter extracted into the turpentine liquid and a residual feedstock comprising at least a portion of insoluble matter from the oil shale that is insoluble in the turpentine liquid;
separating the extraction mixture from the residual feedstock; and
separating the hydrocarbon-containing organic matter from the turpentine liquid in the extraction mixture to produce a hydrocarbon product stream and a turpentine liquid recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter from the comminuted hydrocarbon-containing oil shale; and
recycling at least a portion of the turpentine liquid recycle stream to the contacting step.
37. A method of recovering hydrocarbon-containing organic matter from a hydrocarbon-containing fat coal subterranean formation, the method comprising:
obtaining coal, the coal comprising recoverable hydrocarbon-containing organic matter;
grinding the coal to produce crushed coal;
filtering the crushed coal;
feeding the crushed coal to a contacting vessel comprising at least one inlet for supplying a turpentine liquid to the contacting vessel;
contacting the crushed coal with a turpentine liquid to form a homogeneous one-phase extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter extracted into the turpentine liquid and a residual feedstock comprising at least a portion of insoluble matter from the coal that is insoluble in the turpentine liquid, wherein the turpentine liquid comprises at least about 30% by volume α -terpineol and at least about 15% by volume β -terpineol, wherein the term "about" includes any value within 5% of the stated value and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range;
separating the residual feedstock from the extraction mixture; and
separating the hydrocarbon-containing organic matter from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter from the coal; and
recycling at least a portion of the turpentine liquid recycle stream to the contacting step.
38. A method of increasing recovery of hydrocarbon-containing organic matter from a production well coupled to a hydrocarbon-containing subterranean formation, the subterranean formation comprising a hydrocarbon-containing material, the method comprising:
providing an injection well in fluid communication with the subterranean formation;
providing a turpentine liquid, wherein the turpentine liquid comprises at least about 30% by volume α -terpineol and at least about 15% by volume β -terpineol, wherein the term "about" includes any value within 5% of the stated value and recitation of the term "about" with respect to a range of values includes the upper and lower ends of the range;
injecting said turpentine liquid through said injection well and into said formation, wherein said turpentine liquid and hydrocarbon-containing organic matter from said hydrocarbon-containing subterranean formation form a homogeneous one-phase extraction mixture comprising at least a portion of said extraction mixture hydrocarbon-containing organic matter extracted into at least a portion of said turpentine liquid;
recovering the extraction mixture from the formation through the production well; and
separating the extraction mixture to produce a hydrocarbon product stream and a turpentine liquid stream.
HK11100817.8A 2007-09-20 2008-09-17 Extraction of hydrocarbons from hydrocarbon-containing materials HK1146732B (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US97396407P 2007-09-20 2007-09-20
US60/973,964 2007-09-20
US12/053,126 2008-03-21
US12/053,126 US8101812B2 (en) 2007-09-20 2008-03-21 Extraction of hydrocarbons from hydrocarbon-containing materials
US12/174,139 2008-07-16
US12/174,139 US8272442B2 (en) 2007-09-20 2008-07-16 In situ extraction of hydrocarbons from hydrocarbon-containing materials
PCT/US2008/010831 WO2009038728A1 (en) 2007-09-20 2008-09-17 Extraction of hydrocarbons from hydrocarbon-containing materials

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HK1146732A1 HK1146732A1 (en) 2011-07-08
HK1146732B true HK1146732B (en) 2015-07-03

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