JP5858449B2 - Hydrocarbon extraction from hydrocarbon-containing materials - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is based on U.S. Patent Application Serial No. 12 / 174,139 filed on July 16, 2008 and U.S. Patent Application Serial No. 12 / filed on March 21, 2008. No. 053,126, which is a continuation-in-part application, claiming priority of US Provisional Application No. 60 / 973,964, filed on September 20, 2007, each of which is incorporated herein in its entirety. Is incorporated by reference.

The present invention relates to the field of hydrocarbon extraction from hydrocarbon-containing materials.

BACKGROUND OF THE INVENTION Liquefaction, solubilization and / or extraction of fossil fuels (also referred to individually and collectively as fossil fuels) that are solid, semi-solid, very viscous, or viscous forms, also referred to as hydrocarbon-containing organics Has proved to be extremely difficult and difficult. As used herein, such fossil fuels include coal, oil shale, tar sand, and oil sand (hereinafter collectively referred to as tar sand), as well as crude, heavy crude, bitumen, natural bitumen, kerogen, This includes, but is not limited to, natural asphalt and / or hydrocarbon-containing organics in asphaltenes. This difficulty is attributed in part to the fact that these fossil fuels contain complex organic polymers linked by oxygen and sulfur bonds, which are often embedded in inorganic compound substrates. It is done. As demand and consumption of hydrocarbon-based materials increases, additional liquefied hydrocarbon feedstocks for the production of liquid and gas fuels and the production of various chemicals, pharmaceuticals, and engineered materials Need to produce.

  Various techniques or processes have been developed to liquefy, solubilize and / or extract fossil fuels. However, none of the prior art liquefaction, solubilization and extraction techniques or processes have proven to be commercially viable on a large scale for all types of fossil fuels. This is due to the high cost of deploying and operating all the prior art techniques and processes for hydrocarbon liquefaction, solubilization or extraction developed to date. In addition, prior art processes and techniques for hydrocarbon liquefaction, solubilization, and / or extraction can be difficult to scale, operate, and / or control for one or more of the following reasons: There are: (1) operation at excessively high pressure, (2) operation at very high temperatures, (3) need for expensive processing vessels and equipment that require external supply of hydrogen under extreme conditions, (4) Exposure to two or more reagents, catalysts and / or promoter mixtures or compositions that are often highly toxic and are neither renewable nor recyclable, (5) special, such as microwave radiation (6) Long processing time for partial liquefaction, solubilization or extraction, (7) About 200 mesh (0.074 mm) that is very difficult and expensive to manufacture and handle Size of The need for fine particles exceptionally, (8) the necessary reagents, can not be recovered and recycled catalyst and / or promoter. Thus, there is a need to provide additional techniques and processes for increasing the recovery of hydrocarbon materials.

  For primary drilling operations, an existing pressure gradient will be used to remove this hydrocarbon-containing organic matter, employing a process that will enhance the liquefaction of additional or stored hydrocarbon-containing organic matter that can then be recovered and facilitate migration. It would be advantageous to be able to push through the borehole. In particular, it would be useful to solubilize heavier hydrocarbons that normally remain in the reservoir through primary drilling operations.

US Pat. No. 5,328,518

  For oil secondary and tertiary or enhanced recovery operations, a process that would enhance oil solubilization and recover hydrocarbon-containing organics in the reservoir in a cost-effective manner without damaging the reservoir. It would be advantageous to adopt Although effective methods and compositions exist for tertiary operation, current methods are disadvantageous due to operating costs compared to the value of the hydrocarbon-containing organics produced.

SUMMARY OF THE INVENTION According to one embodiment of the present invention, a method for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material includes providing a first liquid comprising a terpentine liquid, and forming an extraction mixture and a residue. Contacting the hydrocarbon-containing material with a terpentine solution. The extraction mixture contains at least a part of the hydrocarbon-containing organic substance and a terpentine solution. The residue includes insoluble material from hydrocarbon-containing materials. The residue may also include a reducing portion of hydrocarbon-containing organics, in situations where such hydrocarbon-containing materials are all solubilized by the turpentine liquid and not transferred into the extraction mixture. The residue is then separated from the extraction mixture. The extraction mixture is further separated into a first part and a second part. The first portion of the extraction mixture includes a hydrocarbon product stream that includes at least a portion of the hydrocarbon-containing organics extracted from the hydrocarbon-containing material. The second portion of the extraction mixture includes at least a portion of the terpentine liquid. In one embodiment, substantially all turpentine liquid is recovered in the recycle stream.
In another embodiment, substantially all of the hydrocarbon-containing organic matter is extracted into the extraction mixture. In such embodiments, the residue does not contain essential oils and can be used further or discarded without affecting the environment.

1 is a schematic diagram of one embodiment of an apparatus for the recovery of hydrocarbons from tar sands. FIG. 1 is a schematic diagram of one embodiment of an apparatus for hydrocarbon recovery from an oil shale. FIG. 1 is a schematic diagram of one embodiment of an apparatus for the recovery of hydrocarbons from coal. FIG. FIG. 3 is a schematic view of enhanced recovery of hydrocarbons from an underground reservoir.

DETAILED DESCRIPTION OF THE INVENTION In one aspect, the invention relates to an easily deployed composition for extraction, liquefaction and / or solubilization of fossil fuels from coal, oil shale, tar sands, etc. and from reservoirs. .

  According to one embodiment, hydrocarbon-containing materials such as coal, oil shale, tar sand, or heavy crude oil, crude oil, natural gas (often co-existing with crude oil and other fossil fuels), or combinations thereof A method is provided that includes liquefying, solubilizing, and / or extracting a hydrocarbon-containing organic material, such as from a containing reservoir. The hydrocarbon-containing organic matter includes, but is not limited to, heavy crude oil, crude oil, natural gas, and the like. The hydrocarbon-containing organic material can be solid, semi-solid, liquid, sludge, viscous liquid, liquid or gaseous. Other materials that are hydrocarbon-containing materials suitable for processing using the method of the present invention include liquids and solids containing hydrocarbon-containing materials and residues. Exemplary hydrocarbon-containing materials may also include oil tank bottom residue, oil pit or oil pound sludge and slurry mixtures, waste food, compost, sewage, or municipal waste. The step of liquefying, solubilizing and / or extracting the hydrocarbon-containing organic material includes providing a terpentine solution, and extracting at least a part of the hydrocarbon-containing organic material from the hydrocarbon-containing material into the turpentine solution. Contacting the hydrocarbon-containing material with the terpentine solution to produce an extraction mixture comprising the hydrocarbon-containing organic matter extracted from the hydrocarbon-containing material and the terpentine solution, and the extracted in the turpentine solution. Separating the organic matter from any unextracted residue. The terpentine solution can contain an amount of terpineol. Naturally occurring terpentine solutions contain a certain amount of terpene. In one embodiment, the terpentine solution includes α-terpineol.

  In certain embodiments, the ratio of terpentine liquid to hydrocarbon-containing material is about 1: 2 and 4: 1 or higher, and in some embodiments, about 1: 1 or higher, In form, this ratio can be greater than 2: 1. In embodiments relating to reservoir recovery, this ratio can be about 3: 1 or higher, and in other embodiments relating to reservoir recovery, this ratio can be about 4: 1 or higher. For application in a reservoir, the pore volume is used to determine an estimated measurement of the hydrocarbon-containing material. In other aspects of the invention, such as in the use of tar sands and coal and oil shale, the volume of the hydrocarbon-containing material can be measured more directly.

  In certain embodiments, the minimum organics contained in the hydrocarbon-containing material is about 1% by weight or more of the hydrocarbon-containing material, in other embodiments about 10% by weight or more, yet other embodiments. Is about 14% by weight or more.

  In one embodiment of this invention, the liquefaction, solubilization, or extraction reagent selected for the hydrocarbon content can be natural, synthetic or mineral terpentine, which can include α-terpineol, or α-terpineol itself. .

In certain embodiments, liquefaction, solubilization, and / or extraction of fossil fuels or hydrocarbon-containing organics can be performed at a temperature that is in the range of about 2 ° C to about 300 ° C. In certain embodiments, the organic or material is contacted with the terpentine solution at a temperature of less than about 300 ° C or less than about 60 ° C. In other embodiments, the liquefaction, solubilization and / or extraction temperature can be in the range of about 20 ° C to about 200 ° C. The pressure at which the fossil fuel is liquefied, solubilized and / or extracted typically ranges from about 1.0 × 10 ⁴ Pascal (0.1 atm) to about 5.0 × 10 ⁶ Pascal (50.0 atm). It may be within. In certain embodiments, the process may be performed at a pressure of about 5.0 × 10 ⁴ Pascal (0.5 atm) to about 8.0 × 10 ⁵ Pascal (8.0 atm). In certain other embodiments, the fossil fuel or hydrocarbon-containing organic matter to be liquefied, solubilized and / or extracted by immersion in or in contact with one or more terpentaine liquids is A fossil fuel having a size in the range of about 0.74 mm to about 10 mm in a liquefaction, solubilization or extraction vessel (hereinafter reactor) containing one or more of the above liquefaction, solubilization and / or extraction reagents May be in the form of a layer of particles, fragments, lumps, or blocks. In certain embodiments, the size of the fossil fuel particles, fragments, lumps or blocks is in the range of about 0.149 mm (100 mesh) to about 20 mm. In certain embodiments, a layer of fossil fuel particles, fragments, lumps or blocks may be obtained by boiling the one or more liquid liquefaction, solubilization and / or extraction reagents into particles, fragments, lumps or blocks. Stir by passing through a layer of blocks. In certain embodiments, the duration of liquefaction, solubilization and / or extraction is from about 1 minute to about 90 minutes. The fossil fuel can be partially or completely liquefied, solubilized and / or extracted. The degree of liquefaction, solubilization and / or extraction is controlled by controlling operating conditions such as temperature, pressure, intensity of stirring and duration of operation and / or liquefaction, solubilization or It can be influenced by adjusting the type, relative amount and concentration of the extraction reagent.

One aspect of the invention is based on an unexpected discovery. This finding shows that when about 500 grams of reagent, α-terpineol, is added to a tray of about 60 grams of a 60 mesh sample of Pittsburgh vein coal in Washington County, Pennsylvania, the reagent color is almost immediately black. It was changed to a few hours later. This indicated that the discoloration was not due to the suspension of coal particles but to indicate the extraction of hydrocarbon-containing organics from the coal. The 2: 1 mixture of this α-terpineol and coal sample is then transferred from the tray to a tightly sealed bottle with a lid, and the ambient is slightly below about 20 ° C. and about 1.01 × 10 ⁵ Pascals (1 atm). The conditions were maintained for about 25 days. The conversion (ie, degree of liquefaction) of the coal sample was determined to be about 71% by weight after filtration, coal preparation with ethanol, drying, and weighing. This 71 wt.% Conversion corresponds to almost all the soluble bitumen (organic matter) present in the coal sample, and an industrial analysis of this coal sample shows that 2.00 wt.% As-received. ) Moisture, 9.25 wt% dry ash, 38.63 wt% dry volatiles, and 50.12 wt% dry fixed carbon. Through a series of subsequent experiments under different operating conditions of coal and oil shale and tar sands, a family of reagents comprising natural and / or synthetic terpentine containing pinene and pinene alcohols such as terpineol, Kerogen (organic), bitumen (organic) and / or asphaltenes in fossil fuels, including coal, oil shale, tar sand, heavy crude oil and / or crude oil, without the aid of any catalyst or alkali metal It has been shown to be exceptionally effective in liquefying, solubilizing and / or extracting (organic). These reagents, except for mineral terpentine derived from petroleum, are renewable, “green” or low toxic, and all other known liquefactions for fossil fuels such as tetralin, xylene, anthracene, etc. Compared to various solutions or mixtures with solubilizing and / or extraction reagents and other compounds of these reagents, they are relatively inexpensive. Although not renewable, even mineral terpentine derived from petroleum is relatively low in toxicity and inexpensive. Any of the above liquefaction, solubilization and / or extraction reagents can penetrate or diffuse through the pores of the fossil fuel at a significant rate through the fossil fuel particles, fragments, blocks or lumps, coal, oil Under conditions much milder than those required by recent inventions related to liquefaction, solubilization and / or extraction of fossil fuels such as shale, tar sand, crude oil and heavy crude oil, such as under ambient temperature and pressure Even then, it has also been found that these particles, fragments, lumps or blocks release almost nearly completely the liquefiable solubilizable or extractable parts therein.

One aspect of the present invention provides a method for liquefying, solubilizing and / or extracting fossil fuels or hydrocarbon-containing organics from hydrocarbon-containing materials such as coal, oil shale and tar sands. A portion is contacted with the terpentine solution in the extraction mixture, which may be free of alkali metals, catalysts, hydrogen (H ₂ ) and / or carbon monoxide (CO). While hydrogen and CO may be useful as admixtures, one embodiment of this invention includes processes and compositions that are free of hydrogen and CO.

  In certain embodiments, the turpentine solution is natural turpentine, synthetic terpentine, mineral terpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, polymers thereof, And mixtures thereof. In certain other embodiments, the terpentine solution is geraniol, 3-carene, dipentene (ρ-menta-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpine hydrate, 2-pinanol, Selected from dihydromycenol, isoborneol, ρ-menthan-8-ol, α-terpinyl acetate, citronellol, ρ-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof The In other embodiments, the terpentine solution is anethole, camphene, ρ-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, osmene, alloocimene, allocymene alcohol, 2- Methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, and mixtures thereof.

  According to certain aspects, solids or semi-solids such as coal, oil shale, tar sands and heavy crude, or such as oil tank bottom sediment, oil pit or oil pound sludge, waste food, compost, sewage sludge or municipal waste The solid fossil fuel or other hydrocarbon-containing material may be provided in any size that facilitates contact with the terpentine liquid. The fossil fuel or hydrocarbon-containing material can be provided as particles, fragments, lumps or blocks, such as large pieces or fragments of coal or oil shale, for example. In accordance with certain aspects of the invention, the fossil fuel or hydrocarbon-containing material is provided as particles. In accordance with certain aspects of the present invention, the average particle size of the fossil fuel or hydrocarbon-containing material particles is from about 0.074 mm to about 100 mm. In certain other embodiments, the average particle size of the fossil fuel particles is from about 0.074 mm to about 25 mm.

  In accordance with certain aspects of the present invention, a second liquid can be added to the terpentine liquid. According to this particular aspect of the invention, the second liquid may be selected from lower aliphatic alcohols, alkanes, aromatic compounds, aliphatic amines, aromatic amines, carbon disulfide, and mixtures thereof. Exemplary mixtures include solvents produced in petroleum refining, such as decant oil, light cycle oil and naphtha, or solvents produced in coal dry distillation and liquefied coal fractional distillation.

  As used herein, lower aliphatic alcohol refers to primary, secondary and tertiary monohydric and polyhydric alcohols having 2 to 12 carbon atoms. As used herein, alkane refers to straight and branched chain alkanes of 5 to 22 carbon atoms. As used herein, aromatic compounds refer to monocyclic, heterocyclic, and polycyclic compounds. As used herein, aliphatic amines refer to primary, secondary and tertiary amines having an alkyl substituent 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 can be used. In one embodiment, the solvent is ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, naphthalene, anthracene, tetralin, triethylamine, at a temperature and pressure that serves to maintain the solvent in a liquid state. Selected from aniline, carbon disulfide, and mixtures thereof.

  In certain embodiments, the ratio of terpentine solution to any other terpentine miscible solvent contained in the fluid is 1: 1 or greater, and in certain embodiments is about 9: 4 or greater. In certain embodiments, this ratio is about 3: 1 or greater. In yet other embodiments, the ratio is 4: 1 or greater.

  In accordance with one aspect of the invention, the fossil fuel and turpentine liquid are contacted at a temperature of about 2 ° C to about 300 ° C. In certain embodiments, the fossil fuel is contacted with a turpentine liquid at a temperature of less than about 200 ° C.

According to another aspect of the invention, the fossil fuel and turpentine liquid are contacted at a pressure from about 1.0 × 10 ⁴ pascal (0.1 atm) to about 5.0 × 10 ⁶ pascal (50 atm). According to one aspect, the method is performed at a pressure from about 0.5 atm to about 8 atm.

  According to one aspect of the invention, the method further includes providing an extraction vessel in which a solid or semi-solid fossil fuel is contacted with the turpentine liquid. According to an aspect, a stirring means can be provided, whereby the fossil fuel and the turpentine liquid contained in the reactor or extraction vessel are mixed and stirred.

  According to one aspect of the invention, fossil fuel and turpentine liquid may be incubated in a storage tank to increase contact time. According to another aspect, the degree of liquefaction, solubilization and / or extraction is determined by the length of time that the solid or semi-solid fossil fuel is in contact with the turpentine liquid and / or the mixture of fossil fuel and turpentine liquid. Controlled by temperature.

  In accordance with one aspect of the invention, the fossil fuel is contacted with a heterogeneous liquid that includes a turpentine liquid and water as agitated.

  In certain embodiments, the volume ratio of terpentine liquid to water is about 1: 1 or greater, and no slurry is formed that may make it difficult to separate the extracted organics in the terpentine liquid-containing fluid. Like that.

  According to one aspect of the invention, the fossil fuel is selected from thermal energy above about 300 ° C., pressure above 50 atm, microwave energy, ultrasonic energy, ionizing radiation energy, mechanical shear force, and mixtures thereof. Contacted by the terpentine liquid in the presence of the energy input.

  According to one aspect of the present invention, a liquefaction or solubilization catalyst is provided for a mixture of fossil fuel and turpentine liquid.

  According to one aspect of the invention, the reaction or solubilization mixture is supplemented by the addition of a compound selected from hydrogen, carbon monoxide, water, metal oxides, metals, and mixtures thereof.

  According to one aspect of the invention, microorganisms are included in the reaction or solubilization mixture. Neisseria gonorrhoeae-type thermophilic and chemically synthesized inorganic vegetative microorganisms selected from naturally occurring isolates from sulfur hot springs for selective chemical bonds in fossil fuels and other hydrocarbon-containing hydrocarbons, such as sulfur and oxygen bridges Break by biological treatment in. Breaking these selective chemical bonds facilitates solubilization of hydrocarbons in fossil fuels and other hydrocarbon-containing materials.

  Still other aspects and advantages of the present invention will become readily apparent to those skilled in the art from this description, and specific embodiments of the invention will be described in the best mode contemplated for carrying out the invention. It is shown and described by way of example only. 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 invention. is there. The description is thus to be regarded as illustrative in nature and not as restrictive.

  In accordance with one embodiment of the present invention, there is provided a method for extracting hydrocarbon-containing organics from hydrocarbon-containing materials including viscous liquid, liquid or gaseous fossil fuel materials. This method provides a first liquid comprising a terpentine liquid. By contacting the turpentine liquid with the hydrocarbon-containing material in-situ (in situ) in the underground formation containing the fossil fuel material, the hydrocarbon-containing organic matter is extracted into the turpentine liquid and extracted. An extraction mixture is formed so that a liquid is formed. The extract is taken out from the formation, and the extract contains a terpentine solution containing the extracted hydrocarbon-containing organic matter. The extracted hydrocarbon-containing organics are separated from the residue that has not been extracted. The method can further include separating the extracted hydrocarbon material from the terpentine liquid. The viscous liquid, liquid or gaseous fossil fuel material can be heavy crude oil, crude oil, natural gas, or a combination thereof. The underground formation may be, for example, a crude oil reservoir or a natural gas reservoir.

  The invention can be easily deployed in-situ to directly liquefy and / or solubilize fossil fuels in underground formations and extract the resulting liquid products from such formations.

  The extraction reagent of this invention is a liquid, which has a very strong physiochemical affinity with bitumen organics including bitumen, kerogen and / or tar in solid coal, oil shale and tar sands. . When the extraction reagent of the present invention and the bituminous organic substance containing mainly hydrocarbon are in direct contact with each other, the organic substance is dissolved in the extraction reagent of the present invention to liquefy the organic substance. Upon contact, the hydrocarbon and the extraction reagent of the present invention rapidly form a homogeneous solution, i.e. a single phase liquid.

  The physiochemical affinity between the extraction reagent of this invention and the bituminous material can be utilized to enhance oil recovery from oil reservoirs under in-situ conditions. Prior art in-situ recovery techniques applied to date in oil reservoirs mostly take the so-called frontal displacement method. This process is strictly controlled by the characteristics of the multiphase fluid flow in the porous medium. This tends to leave a large portion of the original oil, often more than about 40%, unrecovered, even for “good” low viscosity oil reservoirs. The extraction reagent of the present invention enhances oil recovery by overcoming the complex behavior of dominant multiphase flow under in-situ conditions.

This invention takes advantage of the very strong physiochemical affinity of terpentine solutions.
One method of the present invention injects the extraction reagent of the present invention into an oil or natural gas reservoir through an injection well.

  Petroleum is dissolved in the extraction reagent of the present invention when it comes into contact with the extraction reagent of the present invention in the petroleum reservoir, thereby producing a homogeneous solution, ie, a single phase liquid. The extraction reagent of this invention does not simply replace petroleum as it travels from the injection well to the production well. Dissolution of previously stored petroleum in the reagents of this invention continues until the extraction reagent is fully saturated with petroleum. The extraction reagent then becomes inactive in the additional oil recovery process and simply flows through the reservoir pores as a single phase liquid and gradually reaches the production well.

  The following describes three specific embodiments of the in-situ oil recovery method of the present invention.

  In a first in-situ embodiment, about 3 (3.0) to 7 (7.0) pore volume of the extraction reagent of the present invention is produced while producing about 51% of the original reserve in the reservoir. Into an oil reservoir that has already undergone water flooding until the residual oil saturation. By injecting the extraction reagent, about 41% of the original reserves in the reservoir can be produced unexpectedly. This embodiment of the method has been confirmed experimentally as described herein below in Example 22.

  In a second in-situ embodiment, about 2 (2.0) to 5 (5.0) pore volume of the extraction reagent of the present invention is pressed into the oil reservoir. Initially, injection will produce only petroleum until it is injected with about one third (0.3) to three quarters (0.75) of the extraction reagent of this invention. Thereafter, the extraction reagent of the present invention in which petroleum is dissolved is produced. The vast majority of petroleum present can be recovered as soon as the reagent is injected, from about 1 and 1/2 (1.5) to 3 and 1/2 (3.5) of the pore volume. This method unexpectedly recovers about 90% of the original reserves in the reservoir. This embodiment of the method has also been confirmed experimentally as described in Example 22 herein below.

  In a third in-situ embodiment, the extraction reagent of the present invention improves oil recovery from oil reservoirs containing highly viscous oil such as the “Olinoko Petroleum” reservoir in Venezuela. Press fit to do. The recovery rates with prior art recovery methods are low, ranging from 10% to 15% of the original reserves in such reservoirs. The unexpected increase in recovery of this invention's turpentine liquid extraction reagent from these reservoirs is due to the adoption of horizontal wells in both production and injection wells and the periodic water vapor in these wells. It can be further enhanced by steam soaking.

  The ultimate recovery of natural gas from a large gas reservoir can be increased by injecting the extraction reagent of this invention into the reservoir. Gas production from such reservoirs often causes dangerous large-scale subsidence on the surface of gas fields, such as the “Groningen” field in the Netherlands. Therefore, it is necessary to maintain the reservoir pressure by water injection. The water injected into the reservoir stores about 30% of the gas at high pressure in-situ by a two-phase flow consisting of water and gas passing through the reservoir with low permeability. By press-fitting the extraction reagent of this invention, the gas stored in the reservoir is dissolved in the reagent and flows to the production well. By separating the reagent and gas at the surface, the gas is recovered and the reagent is recycled for reuse.

The extraction method of the present invention can be realized after one or more known oil production promotion methods have been implemented, such as CO ₂ or natural gas injection and surfactants.

Exemplary Embodiments for Carrying Out the Invention
In certain embodiments of coal, anthracite or bituminous coal is ground to a size in the range of about 0.841 mm (20 mesh) to about 0.149 mm (100 mesh), and then about 1.0 × 10 ⁵ Pascal (1 atm). ) To about 2.0 × 10 ⁵ Pascals (2.0 atm) can be solubilized and / or extracted, ie liquefied, by immersion in a terpentine solution. In certain other embodiments, the terpentine solution is a natural product comprising up to about 50-70% by volume α-terpineol, about 20-40% by volume β-terpineol, and about 10% by volume of other components. It can be synthetic or mineral terpentine. In certain embodiments, a layer of pulverized anthracite or bituminous coal may be agitated by passing the terpentine liquid at a temperature in the range of 80 ° C. to about 130 ° C., or perhaps up to the boiling point of the turpentine liquid. In certain other embodiments, the duration of solubilization and / or extraction, ie, liquefaction, can be within about 10 minutes to about 40 minutes. In certain embodiments, the contact time for extraction of hydrocarbon-containing organics from coal is less than 5 minutes.

In some embodiments, lignite, brown coal or any other lower coal is ground to a size in the range of about 0.419 mm (40 mesh) to about 0.074 mm (200 mesh). And then solubilized and / or soaked in a turpentine solution under a pressure in the range of about 1.0 × 10 ⁵ Pascal (1 atm) to about 2.0 × 10 ⁵ Pascal (2.0 atm). Or it can be extracted, ie liquefied. In certain other embodiments, the terpentine solution is a natural comprising about 70-90% by volume α-terpineol, about 5-25% by volume β-terpineol, and about 5% by volume of other components. It can be synthetic or mineral terpentine. In other embodiments, the pulverized lignite, lignite or any other lower coal layer is applied to the turpentine liquid at a temperature in the range of about 80 ° C to about 130 ° C, or perhaps up to the boiling point of the terpentine liquid. Can be agitated by passing it through. In certain other embodiments, solubilization and / or extraction, or liquefaction, can be within about 20 minutes to about 60 minutes. In certain embodiments, the contact time for extraction of hydrocarbon-containing organics from coal can be less than 5 minutes.

Oil Shale In certain embodiments, the oil shale is ground to a size in the range of about 0.419 mm (40 mesh) to 0.074 mm (200 mesh) and then about 1.0 × 10 ⁵ pascals (1 atm). Can be solubilized and / or extracted, i.e. liquefied, by immersion in a turpentine solution under a pressure in the range of from about 2.0 x 10 < ⁵ > Pascals (2.0 atm). In other embodiments, the terpentine solution is natural, synthetic or comprising about 70-90% by volume α-terpineol, about 5-25% by volume β-terpineol, and about 5% by volume of other components. It can be mineral terpentine. In certain other embodiments, the ground oil shale layer is agitated by passing the terpentine solution at a temperature in the range of about 80 ° C. to about 130 ° C., or perhaps up to the boiling point of the terpentine solution. obtain. In other embodiments, solubilization and / or extraction, or liquefaction, can be within about 30 minutes to about 60 minutes. In certain embodiments, the contact time for extraction of hydrocarbon-containing organics from oil shale is less than 5 minutes.

Tar Sand In certain embodiments, the tar sand is crushed to a size in the range of about 25.4 mm (1 mesh) to 4.76 mm (4 mesh) and then from about 1.0 × 10 ⁵ Pascal (1 atm). It can be solubilized and / or extracted, i.e. liquefied, by immersion in a turpentine solution under a pressure in the range of about 2.0 x 10 < ⁵ > Pascal (2.0 atm). In other embodiments, the terpentine solution is about 40-60% by volume α-terpineol, about 30-50% by volume β-terpineol, 5% by volume α and / or β-pinene, and about 5%. It may be natural, synthetic or mineral containing and containing other components by volume. In other embodiments, the ground tar sand layer may be agitated by passing the terpentine solution at a temperature in the range of about 60 ° C. to about 90 ° C., or perhaps up to the boiling point of the terpentine solution. In other embodiments, solubilization and / or extraction, ie liquefaction, can be within about 10 minutes to about 30 minutes. In certain embodiments, the contact time for extraction of hydrocarbon-containing organics from tar sand is less than 5 minutes.

In certain embodiments, light and medium crude oils are infused with about 1 (1.0) to about 5 (5.0) pore volume turpentine liquid for primary, secondary or tertiary recovery. Thus, it can be generated in situ, i.e. removed from the underground reservoir. In other embodiments, about 2 (2.0) to about 4 (4.0) pore volume of turpentine liquid may be injected. In certain embodiments, the terpentine solution is about 40-70% by volume α-terpineol, about 30-40% by volume β-terpineol, 10% by volume α and / or β-pinene, It may be natural, synthetic or mineral terpentine containing with other components by volume. In certain embodiments, the intrusion of the terpentine solution may be followed by a water flood with about 1 (1.0) to about 3 (3.0) pore volume water.

  In certain embodiments, heavy and superheavy crude oil is injected with about 1 (1.0) to about 5 (5.0) pore volume of turpentine liquid for primary, secondary or tertiary recovery. By doing so, it can be generated in situ, i.e. removed from the underground reservoir. In other embodiments, about 2 (2.0) to about 4 (4.0) pore volume of turpentine liquid may be injected. In certain embodiments, the terpentine solution is about 50-70% by volume α-terpineol, about 20-35% by volume β-terpineol, 10% by volume α and / or β-pinene, It can be natural, synthetic or mineral turpentine containing other components by volume and can be used in connection with steam injection.

  With reference to FIG. 1, an apparatus for the recovery of hydrocarbon-containing organics from tar sands is provided. The apparatus 100 includes a turpentine liquid supply source 102 that can optionally be coupled to a pump 104 to supply the turpentine liquid to a contact or extraction vessel 110. In certain embodiments, the turpentine liquid source may include means for heating the turpentine liquid. In certain embodiments, the contact vessel can be a tilted rotary filter or a trommel. The tar sand sample 106 is provided to a conveyor 108 or similar supply device for supplying the tar sand to the inlet of the contact vessel 110. Optionally, conveyor 108 may include a filtration sieve or similar separation device to prevent large particles from being introduced into the process. The contact vessel 110 includes at least one inlet for the turpentine liquid to be introduced and contacted with the tar sand. Contact vessel 110 may include a plurality of trays or fins 114 designed to hold the tar sand in the contact vessel for a specified time and to increase or control contact between the tar sand particles and the turpentine liquid. In certain embodiments, the contact vessel can be a tilted rotary filter. The extraction mixture containing the liquid to be extracted and the hydrocarbon-containing organic matter extracted from the tar sand is taken out from the contact vessel 110 via the outlet 116, and this outlet together with the extraction mixture containing the extracted hydrocarbon-containing organic matter. A filter 118 may be included to prevent removal of solids. A pump 120 is coupled to the outlet 116 to assist in supplying the extraction mixture to the storage tank 122. Line 124 may be coupled to holding tank 112 to supply the extraction mixture for further processing. After extraction of the hydrocarbon-containing organic matter, the inorganic solid and other materials that do not dissolve in the turpentine liquid can be removed from the contact vessel via the second conveyor 126. Some turpentine liquids include a liquid containing α-terpineol and β-terpineol, but are not limited thereto.

  Referring now to FIG. 2, an apparatus 200 for recovering hydrocarbon-containing organics from oil shale and other sedimentary rock layers containing recoverable hydrocarbon material is provided. The oil shale sample 202 is supplied to a pulverizer or crusher 204 that reduces the size of the oil shale. Preferably, the crusher or crusher 204 reduces the oil shale diameter to about 0.074-0.42 mm. The crushed oil shale may optionally be fed to a filter that ensures uniform and / or qualified particle size. The first conveyor 206 provides particles from the crusher or crusher 204 to the contact container 208. The contact container 208 is coupled to a turpentine liquid supply source 210, which may optionally be coupled to a pump, and at least the turpentine liquid coupled to the contact container 208. Supply to one inlet 212. In certain embodiments, the turpentine liquid source may include means for heating the turpentine liquid. Contact vessel 208 may include a plurality of trays or fins 214 designed to hold the oil shale in the contact vessel for a specified time and to increase or control contact between the oil shale particles and the turpentine liquid. In certain embodiments, the contact vessel can be a tilted rotary filter or a trommel. The extracted mixed stream containing the turpentine liquid and the hydrocarbon-containing organic matter recovered from the oil shale is collected through the outlet 216 and supplied to the storage tank 220. A pump 218 is optionally coupled to the outlet 216 to assist in the supply of the extracted mixture stream to the storage tank 220. The extraction mixture stream may be coupled to line 222 for supplying the extraction mixture for further processing. The second conveyor 224 assists in removing the inorganic or insoluble material from the contact container 208. The terpentine solution can include, but is not limited to, α-terpineol and β-terpineol.

  Referring now to FIG. 3, an apparatus 300 for recovering hydrocarbon-containing organic matter from coal is provided. The coal sample 302 is supplied to a pulverizer or crusher 304 that reduces the size of the coal. Preferably, the pulverizer or crusher 304 reduces the coal diameter to about 0.074-0.84 mm, depending on the quality of the coal sample. In certain embodiments, the pulverizer or crusher 304 can be a wet pulverizer. The crushed coal may optionally be fed to a filter that ensures a uniform and qualified particle size. The crushed coal is supplied to the first contact container 306. The first contact vessel 306 is also coupled to a turpentine liquid supply source 308, which may optionally be coupled to the pump 310, and the turpentine liquid supply is supplied to the first contact container 306. Supply to contact container 306. In certain embodiments, the turpentine liquid source may include means for heating the turpentine liquid. The first contact vessel 306 includes mixing means 312 designed to agitate and enhance or control the contact between the solid coal particles and the turpentine liquid. The extracted mixed stream containing the turpentine liquid and the hydrocarbon-containing organic substance recovered from the coal is collected via the first contact vessel outlet 313 and supplied to the second contact vessel 316. A pump 314 is optionally coupled to the outlet 313 to assist in the supply of the extracted mixture stream to the second contact vessel 316. The second contact vessel 316 may include a series of trays or fins 318 designed to increase or control the separation of solids and turpentine liquid. Optionally, the second contact vessel 316 can be a tilted rotary filter or a trommel. The extraction mixture stream may be collected from a second contact vessel outlet 320, which is optionally coupled to a pump 322 to assist in the supply of the extraction mixture stream to the storage tank 324. May be. Liquid coal and turpentine liquid present in the storage tank 324 may be fed via line 326 to liquid coal refining or other processing steps. A conveyor 328 may be coupled to the second contact vessel 316 for removal and recovery of solids as a by-product of the process. The terpentine solution can include, but is not limited to, α-terpineol and β-terpineol. The apparatus 300 can also be used to process high and low quality oil shale.

  Referring now to FIG. 4, a process 400 is provided for enhanced recovery of hydrocarbon-containing organics from hydrocarbon-containing underground formations. The hydrocarbon-containing reservoir 404 is shown as being located below the ground surface 402. The production well 406 is already in operation. The press-fit well 408 is provided for press-fitting through the line 410 of the turpentine liquid. Turpentine liquid facilitates liquefaction, solubilization and / or extraction of hydrocarbon-containing organic substances present in the reservoir, and also provides driving force to push hydrocarbon-containing organic substances in the formation toward the production well. To do. A hydrocarbon product stream containing the injected turpentine liquid is collected via line 412. The terpentine solution can include, but is not limited to, α-terpineol and β-terpineol.

  In certain embodiments, at least 30% by volume of natural terpineol, synthetic terpineol, mineral terpineol, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpene resin, α-terpene, A terpentine solution for increasing production from petroleum wells comprising β-terpenes, γ-terpenes, or mixtures thereof is provided. In other embodiments, the terpentine solution is at least 30% by volume of geraniol, 3-carene, dipentene (ρ-menta-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpine hydrate, 2 -Pinanol, dihydromicenol, isoborneol, ρ-mentha-8-ol, α-terpinyl acetate, citronellol, ρ-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol or mixtures thereof Including. In still other embodiments, the terpentine solution is at least 30% by volume of anethole, camphene, ρ-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, osmene, alloocimene, Alloocimene alcohol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, or mixtures thereof.

  In certain embodiments, the terpentine solution comprises at least about 40% by volume α-terpineol. In other embodiments, the terpentine solution comprises at least about 25% by volume β-terpineol. In still other embodiments, the terpentine solution comprises at least about 40% by volume α-terpineol and at least about 25% by volume β-terpineol. In other embodiments, the terpentine solution comprises at least about 50% by volume α-terpineol, and in certain embodiments also β-terpineol. In certain embodiments, the terpentine solution comprises at least 20% by volume β-terpineol. In certain embodiments, the terpentine solution comprises about 50-70% by volume α-terpineol and about 10-40% by volume β-terpineol.

  In another aspect, a process is provided for increasing production from an underground hydrocarbon-containing reservoir that undergoes enhanced recovery operations, the process using a terpentine liquid reservoir to facilitate production of hydrocarbon-containing material. Including the step of press-fitting through the press-fit well. Turpentine liquid is natural turpentine, synthetic turpentine, mineral terpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpene resin, α-terpene, β-terpene. At least one compound selected from γ-terpenes, and mixtures thereof. In other embodiments, the terpentine solution is geraniol, 3-carene, dipentene (ρ-menta-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromicelle. At least selected from diol, isoborneol, ρ-menthan-8-ol, α-terpinyl acetate, citronellol, ρ-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof One compound may be included. In still other embodiments, the terpentine solution is anethole, camphene, ρ-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohol, 2 At least one compound selected from -methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, and mixtures thereof May be included. A hydrocarbon-containing organic product stream comprising a turpentine liquid and recovered hydrocarbons is recovered from a production well associated with a hydrocarbon-containing reservoir. The hydrocarbon-containing organic product stream can be separated into a recovered hydrocarbon stream and a terpentine liquid recycle stream. In certain embodiments, the further method further comprises injecting a terpentine recycle stream into the injection well.

  In another aspect, a method for increasing production from a hydrocarbon-containing underground hydrocarbon layer undergoing enhanced recovery operation is provided. The method includes the step of injecting the terpentine solution into the formation through an injection well. In certain embodiments, the terpentine solution comprises at least 40% by volume α-terpineol and at least 10% by volume β-terpineol. The turpentine liquid liquefies, extracts and / or replaces the hydrocarbon-containing material from the formation, which is then removed from the formation along with the turpentine liquid through the production well. In a more specific embodiment, the method further comprises separating the hydrocarbon from the terpentine liquid. In other embodiments, the method further includes recirculating the turpentine liquid to the injection 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, β-terpineol is present in an amount of about 10-40% by volume. In other embodiments, the terpentine solution further comprises up to about 10% by volume γ-terpineol. In other embodiments, the terpentine solution may comprise up to about 25% by volume organic solvent selected from methanol, ethanol, propanol, toluene, and xylene. This 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 recovery of hydrocarbon-containing organic matter from tar sand is provided. In one embodiment, the terpentine solution comprises at least about 30% by volume α-terpineol and at least about 25% by volume β-terpineol. In another embodiment, the terpentine solution is about 30-70% by volume α-terpineol, about 25-55% by volume β-terpineol, up to about 10% by volume α-terpene, and about 10% by volume. Up to β-terpenes.

  In another aspect, a turpentine solution is provided for recovering hydrocarbon-containing organic matter from a high-grade coal source such as anthracite or bituminous coal. In one embodiment, the terpentine solution comprises at least about 45% by volume α-terpineol and at least about 15% by volume β-terpineol. In another embodiment, the terpentine solution is about 45-80% by volume α-terpineol, about 15-45% by volume β-terpineol, up to about 10% by volume α-terpene, and about 10% by volume. Up to β-terpenes.

  In another aspect, a turpentine solution for recovering hydrocarbon-containing organic matter from a low-grade coal source is provided. In one embodiment, the terpentine solution comprises at least about 60% by volume α-terpineol and up to about 30% by volume β-terpineol. In another embodiment, the terpentine solution is about 60-95% 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 solution for recovering hydrocarbon-containing organic matter from oil shale is provided. As used herein, oil shale generally refers to any sedimentary rock containing bitumen material. In one embodiment, the terpentine solution comprises at least about 60% by volume α-terpineol and up to about 30% by volume β-terpineol. In another embodiment, the terpentine solution is about 60-95% 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 terpentine solution comprises at least about 40 and 70% by volume α-terpineol and at least about 30 and 40% by volume β-terpineol. In yet another embodiment, the terpentine solution is about 40-70% by volume α-terpineol, about 30-40% by volume β-terpineol, up to about 10% by volume α-terpene, and about 10 volumes. % Β-terpene.

  In another aspect, a turpentine liquid for recovering hydrocarbon-containing organic matter from heavy and ultra heavy crude oil is provided. In one embodiment, the terpentine solution comprises at least about 50 and 70% by volume α-terpineol and at least about 30 and 40% by volume β-terpineol. In another embodiment, the terpentine solution comprises about 50-70% by volume α-terpineol, about 30-40% by volume β-terpineol, up to about 10% by volume α-terpene, and about 10% by volume. Β-terpene.

  In another aspect, a method for recovering a hydrocarbon-containing organic material from tar sand is provided. The method includes mining a formation that is rich in tar sand to provide a tar sand sample, the tar sand sample including recoverable hydrocarbon-containing organics and residual inorganic or insoluble materials. The tar sand sample is supplied to a contact vessel, which includes at least one inlet for supplying turpentine liquid for the recovery of hydrocarbons from the tar sand. A tar sand sample is contacted with a turpentine solution to extract hydrocarbon-containing organic matter from the tar sand to produce a residue and an extraction mixture. The extraction mixture includes turpentine liquid and recovered hydrocarbon-containing organic matter, and the residue is separated from turpentine to produce a hydrocarbon product stream and a terpentine liquid recycle stream. In certain embodiments, the method further comprises recirculating the turpentine liquid recycle stream to the contact vessel. In other embodiments, the extraction mixture can be separated by distillation to produce a hydrocarbon product stream and a turpentine liquid recycle stream.

  In certain embodiments, the terpentine solution may include α-terpineol. In other embodiments, the terpentine solution may comprise at least about 40% by volume α-terpineol and 10-40% by weight β-terpineol. In certain embodiments, 0.5 to 4 equivalents of a terpentine solution is used to contact the tar sand and recover hydrocarbons. In certain embodiments, 0.5 to 2.0 equivalents of turpentine liquid is used to contact the tar sand and recover hydrocarbons.

  In another aspect, a method for recovering a hydrocarbon-containing organic substance from an oil shale containing a large amount of hydrocarbon is provided. The method includes mining a rock layer that includes hydrocarbon-containing organics to produce a hydrocarbon-containing oil shale that includes recoverable hydrocarbon material and inorganic or insoluble materials. The oil shale is crushed to produce a crushed hydrocarbon-containing oil shale. The crushed hydrocarbon-containing oil shale is then filtered through a filter screen that prevents excessively large particles from being fed into the extraction process. The crushed hydrocarbon-containing oil shale is sent to a contact vessel that has at least one inlet for supplying turpentine liquid for recovery of hydrocarbons from the crushed hydrocarbon-containing oil shale. Including. The crushed hydrocarbon-containing oil shale is brought into contact with the turpentine liquid, and the hydrocarbon-containing organic matter is extracted from the crushed hydrocarbon-containing oil shale, and the inorganic solid, the turpentine liquid and the recovered hydrocarbon are extracted. An extraction mixture containing. Inorganic or insoluble material is removed from the extraction mixture and the recovered hydrocarbon is separated from the turpentine liquid to produce a hydrocarbon product stream and a terpentine liquid recycle stream. In certain embodiments, the terpentine liquid recycle stream is recirculated to the contact vessel. In other embodiments, the average particle size of the crushed hydrocarbon-containing oil shale is less than about 0.42 mm in diameter. In another embodiment of the method for recovering hydrocarbon-containing organic matter from oil shale, the turpentine liquid is natural turpentine, synthetic turpentine, mineral terpentine, pine oil, α-pinene, β-pinene, α-terpineol, at least one compound selected from β-terpineol, γ-terpineol, terpene resin, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In other embodiments, the terpentine solution is geraniol, 3-carene, dipentene (ρ-menta-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromicelle. At least selected from nor, isoborneol, ρ-menthan-8-ol, α-terpinyl acetate, citronellol, ρ-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof Contains one compound. In other embodiments, the terpentine solution is anethole, camphene, ρ-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, osmene, alloocimene, allocymene alcohol, 2- Including at least one compound selected from methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, and mixtures thereof . In certain embodiments, the terpentine solution may include α-terpineol. In other embodiments, the terpentine solution may comprise 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 the oil shale and recover hydrocarbon-containing organic matter. In certain embodiments, 0.5 to 2.0 equivalents of turpentine liquid is used to contact the oil shale and recover hydrocarbons.

  In another aspect, a method for recovering hydrocarbon-containing organic matter from coal-rich underground formations is provided. The method includes mining an underground formation to produce coal, the coal including recoverable hydrocarbon-containing organics and inorganic or insoluble materials. The coal is crushed to produce crushed coal and filtered to provide a sample of uniform or desired size. The crushed coal is sent to a contact vessel, the contact vessel includes at least one inlet for supplying turpentine liquid for the recovery of hydrocarbons from the crushed coal, and the crushed coal is crushed It is brought into contact with a terpentine solution for extracting hydrocarbons from the coal produced to produce an inorganic solid and an extraction mixture. The extraction mixture includes terpentine liquid and recovered hydrocarbons. Inorganic or insoluble solids are separated from the extraction mixture and recovered hydrocarbons are separated from the turpentine liquid to produce a liquid coal product stream and a terpentine liquid recycle stream. In certain embodiments, the method further comprises recirculating the turpentine recycle stream to the contact vessel. In yet another embodiment, the liquid coal product stream is fed to a liquid coal refiner. 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 grade coal having an average particle size of less than about 0.84 mm.

  In yet another embodiment of the method for recovering hydrocarbon-containing organic matter from coal, the turpentine liquid is natural turpentine, synthetic terpentine, mineral terpentine, pine oil, α-pinene, β-pinene, α-terpineol, at least one compound selected from β-terpineol, γ-terpineol, terpene resin, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In other embodiments, the terpentine solution is geraniol, 3-carene, dipentene (ρ-menta-1,8-diene), nopol, pinane, 2-pinane hydroxyperoxide, terpin hydrate, 2-pinanol, dihydromicelle. At least selected from the group consisting of nor, isoborneol, ρ-menthane-8-ol, α-terpinyl acetate, citronellol, ρ-menthane-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof. Contains one compound. In other embodiments, the terpentine solution is anethole, camphene, ρ-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, osmene, alloocimene, allocymene alcohol, 2- Including at least one compound selected from methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, and mixtures thereof . In certain embodiments, the terpentine solution comprises at least 60% by volume α-terpineol. In certain embodiments, the terpentine solution comprises at least 45% by volume α-terpineol and at least about 15% by volume β-terpineol. In certain other embodiments, the terpentine solution 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 terpentine liquid is used to contact the oil shale and recover hydrocarbon-containing organic matter. In certain embodiments, 0.5 to 2.0 equivalents of turpentine liquid is used to contact the oil shale and recover the hydrocarbon-containing organic matter.

  In another aspect, a system for recovering hydrocarbon-containing organics from tar sands is provided. The tar sand recovery system includes a tank for supplying turpentine liquid and a contact container, the contact container for recovering the extraction mixture from the contact container with at least one inlet for introducing the turpentine liquid. And at least one outlet. The system also includes a first conveyor for supplying tar sand to the contact vessel. A storage tank is provided that includes a line that connects the storage tank to the contact container, and the line that connects the contact container and the storage tank includes a filter that prevents the passage of solids into the storage tank. Including. The system also includes a second conveyor for solids recovery and transportation.

  In one embodiment, the contact vessel is a rotary tilt filter that includes 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 sand and the turpentine liquid. In certain embodiments, the terpentine solution may include α-terpineol. In other embodiments, the terpentine solution may comprise about 30% to 70% by volume α-terpineol and about 25% to 55% by weight β-terpineol.

  In another aspect, a system is provided for recovering hydrocarbon-containing organics from oil shale. The system includes a tank for supplying turpentine liquid and a pulverizer for finely pulverizing the oil shale to a reduced particle size. At least one inlet for introducing a turpentine liquid, at least one inlet for receiving a crushed oil shale, at least one outlet for recovering solids from the contact vessel, and an extraction mixture from the contact vessel A contact vessel is provided that includes at least one outlet for recovery. A first conveyor is provided to supply the crushed oil shale to the contact container. The system further includes a storage tank, the storage tank including a line connecting the storage tank to the contact vessel, the line including a filter that prevents passage of solids into the storage tank. The system further includes a second conveyor for recovering solids. In certain embodiments, the system further includes a line for supplying the reaction mixture comprising the recovered hydrocarbon and turpentine liquid to a purification apparatus for further separation and / or processing. In certain embodiments, the terpentine solution may include alpha terpineol. In certain embodiments, the terpentine solution may comprise about 60% to 95% by volume alpha terpineol and up to about 30% by weight beta terpineol. In other embodiments, the terpentine solution may comprise about 70% to 90% by volume α-terpineol and about 5% to 25% by weight β-terpineol.

  In another aspect, a system for recovering hydrocarbon-containing organics from coal is provided. The system includes a tank for supplying turpentine liquid and a pulverizer that finely pulverizes coal to produce a particulate material having a reduced size. A contact vessel is provided that includes at least one inlet for introducing the terpentine liquid and at least one outlet for recovering the solid and liquid from the contact vessel. The contact vessel also includes a stirring means for thoroughly mixing the turpentine liquid and the finely pulverized coal. A separator is provided for separating solids and liquids, the separator including an inlet, an outlet, and a line connecting the inlet of the separator to the outlet of the contact vessel. The system also includes a storage tank, which includes a line that connects the storage tank to a separator, which may include a filter that prevents passage of solids into the storage tank.

  In certain embodiments, the system includes a filter to selectively prevent particles having an average diameter greater than about 0.85 mm from being introduced into the contact vessel. In certain other embodiments, the system further includes a line for supplying the liquid coal product to a refiner for further processing. In certain embodiments, the system further includes a first conveyor for supplying crushed coal to the contact vessel. In other embodiments, the system further includes a second conveyor for removing solids from the separator. In certain embodiments, the terpentine solution may include α-terpineol. In embodiments relating to the recovery of hydrocarbons from high grade coal, the terpentine liquid may comprise about 45% to 80% by volume α-terpineol and about 15% to 45% by weight β-terpineol. In embodiments relating to the recovery of hydrocarbons from low grade coal, the turpentine liquid may comprise about 60% to 95% by volume α-terpineol and about 0% to 30% by weight β-terpineol.

  In another aspect, a method for optimizing a terpentine solution for extraction of hydrocarbon-containing organics from hydrocarbon-containing materials is provided. In general, the method includes providing a sample of a hydrocarbon-containing material and analyzing the hydrocarbon material to determine the type of hydrocarbon being extracted. A formulation for extracting hydrocarbon-containing organics from a hydrocarbon material is provided, which 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. Next, the amounts of α-terpineol and β-terpineol in the formulation are adjusted based on the above parameters. In general, the above method provides a good starting point for determining the desired formulation for the extraction of various hydrocarbon-containing materials, but for other hydrocarbon-containing materials and specified operating conditions. Can perform either a series of statistically designed experiments or a series of experiments according to an optimization method to determine the optimal composition of liquid turpentine.

  As shown in Table 1, the specific formulation for extraction, liquefaction and / or solubilization of hydrocarbon-containing organics from tar sands varies based on particle size. In certain embodiments, a method for preparing a terpentine solution for extracting hydrocarbon-containing organics from tar sands is rich in the hydrocarbons being extracted in the amount of α-terpineol and β-terpineol in the formulation. Adjusting as a function of the size of the solid particles. In other embodiments, when the hydrocarbon-containing organic particulate material comprises low grade coal or oil shale, the amount of α-terpineol in the turpentine solution is increased and the amount of β-terpineol in the terpentine solution is decreased. . In another embodiment, when the hydrocarbon-containing organic particulate material includes tar sand, the amount of α-terpineol in the terpentine solution is decreased and the amount of β-terpineol in the terpentine solution is increased. In other embodiments, when the hydrocarbon-containing organic particulate material comprises tar sand and the particulate material has an average diameter of less than about 4.76 mm, the amount of α-terpineol in the turpentine liquid is reduced, Increase the amount of β-terpineol in the terpentine solution. In other embodiments, the amount of α-terpineol in the turpentine liquid is increased when the hydrocarbon-containing organic particulate material comprises tar sand and the average diameter of the particulate material is greater than about 1 inch (1 mesh). Reducing the amount of β-terpineol in the terpentine solution.

  Similar to that shown above for tar sand extraction, as shown in Tables 2 and 3, the formulation for coal extraction, liquefaction and / or solubilization depends on the particle size of the coal being extracted. Depends on both quality and. In one embodiment of a method for preparing a turpentine solution for extracting hydrocarbon-containing organics, the hydrocarbon-containing material comprises anthracite, bituminous coal, or other high grade coal, and the average diameter of the particulate matter is about 0. When it is less than 15 mm, the amount of α-terpineol in the terpentine solution is decreased, and the amount of β-terpineol in the terpentine solution is increased. In other embodiments, when the hydrocarbon-rich particulate material comprises anthracite, bituminous coal, or other high grade coal, and the average diameter of the particulate material is greater than about 0.84 mm, the terpentine solution Increase the amount of α-terpineol in the medium and decrease the amount of β-terpineol in the terpentine solution. In another embodiment, the amount of α-terpineol in the turpentine liquid is reduced when the hydrocarbon-rich particulate material comprises low grade coal and the average diameter of the particulate material is less than about 0.074 mm. The amount of β-terpineol in the terpentine solution is increased. In other embodiments, the amount of α-terpineol in the turpentine liquid is increased when the hydrocarbon-rich particulate material comprises low grade coal and the average diameter of the particulate material is greater than about 0.42 mm. Increase and decrease the amount of β-terpineol in the terpentine solution.

  Similar to that shown above for tar sand extraction, the formulation for oil shale extraction, liquefaction and / or solubilization depends on particle size, as shown in Table 4. In one embodiment of a method for preparing a composition for extracting a hydrocarbon-containing organic material, the hydrocarbon-rich particulate material comprises oil shale and the average diameter of the particulate material is less than about 0.074 mm. In this case, the amount of α-terpineol in the terpentine solution is decreased and the amount of β-terpineol in the terpentine solution is increased. In another embodiment, when the hydrocarbon-rich particulate material includes oil shale and the average diameter of the particulate material is greater than about 0.42 mm, the amount of α-terpineol in the turpentine liquid is increased. Reducing the amount of β-terpineol in the terpentine solution.

  Crude oil extraction is likewise dependent on the type of crude oil being extracted, liquefied and / or solubilized. As shown in Table 5, the formulation for crude oil extraction, liquefaction and / or solubilization is a function of both the density and quality of the crude oil being extracted. The method includes providing a turpentine liquid formulation comprising at least 50% by volume α-terpineol and at least 20% by volume β-terpineol, and based on the density of the liquid hydrocarbon being extracted. Adjusting the amount of α-terpineol and β-terpineol therein. In one embodiment, when the API gravity of the liquid hydrocarbon being extracted is greater than about 22 °, the amount of α-terpineol in the terpentine solution is decreased and the amount of β-terpineol in the terpentine solution is increased. Let In another embodiment, when the API gravity of the liquid hydrocarbon being extracted is less than about 22 °, the amount of α-terpineol in the terpentine solution is increased and the amount of β-terpineol in the terpentine solution is decreased. . As used herein, the light petroleum API is at least about 31 °, the medium crude API is about 22 ° to about 31 °, and the heavy petroleum API is about 10 ° to about 22 °. And the API of superheavy oil is less than about 10 °.

  In another aspect, a method for preparing a terpentine solution for enhancing recovery of liquid hydrocarbon-containing organic matter from underground formations is provided. The method provides a formulation comprising at least 50% by volume of α-terpineol and at least 20% by volume of β-terpineol, and α-terpineol and β- Adjusting the amount of terpineol.

  In another aspect, a composition is provided for the selection and / or recovery of hydrocarbons from a liquid hydrocarbon-containing vessel, the composition comprising natural turpentine, synthetic turpentine, mineral turpentine, pine oil, α- At least one compound selected from pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpene resin, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In another embodiment, the composition for the selection and / or recovery of hydrocarbons is geraniol, 3-carene, dipentene (ρ-menta-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, Terpin hydrate, 2-pinanol, dihydromicenol, isoborneol, ρ-menthane-8-ol, α-terpinyl acetate, citronellol, ρ-menthane-8-yl acetate, 7-hydroxydihydrocitronellal, menthol And at least one compound selected from mixtures thereof. In yet another embodiment, the composition for the selection and / or recovery of hydrocarbons comprises anethole, camphene, ρ-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate. Osimene, alloocimene, alloocimene alcohol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, citronellal, menthone, and their At least one compound selected from the mixture. In one embodiment, the composition comprises at least one of the following compounds: α-pinene, β-pinene, α-terpineol, and β-terpineol. In another embodiment, the composition comprises at least 25% by volume α-terpineol or β-terpineol.

  In another aspect, a method for selecting and / or recovering hydrocarbons from a liquid hydrocarbon-containing vessel is provided. The method comprises contacting the interior of a container with a hydrocarbon selective composition comprising at least one compound selected from α-pinene, β-pinene, α-terpineol, and β-terpineol to form a mixture. The mixture includes a liquid hydrocarbon residue and a hydrocarbon selective composition. This mixture is recovered from the container and removed. In certain embodiments, the curative composition comprises at least 25% by volume α-terpineol or β-terpineol. In certain other embodiments, the curative composition comprises at least 25% by volume α-terpineol and at least 25% by volume β-terpineol.

Example 1. In this example, coal from Pittsburgh vein in Washington County, Pennsylvania was liquefied with the reagent α-terpineol. Coal samples were obtained from the Coal Bank of Pennsylvania State University, which provided the following industrial analysis: 2.00% by weight moisture as received, 9.25% % Dry ash, 38.63% by weight dry volatiles, and 50.12% by weight dry fixed carbon. The particle size of the coal sample was about 60 mesh. About 60 grams of α-terpineol was gently added to about 30 grams of coal sample placed in the extraction vessel, resulting in a 2: 1 reagent to sample ratio. The resulting extraction vessel with a mixture of α-terpineol and coal, with a lid but not tightly sealed, was maintained at a constant temperature of about 96 ° C. and constantly stirred, without boiling the α-terpineol. In addition, the pressure in the extraction vessel remained at an ambient pressure slightly below about 1.01 × 10 ⁵ Pascal (1 atm). After about 30 minutes, the mixture was filtered, and the coal particles obtained on the filter were selected with ethanol and dried to a constant weight. Based on the weight loss, the degree of conversion or liquefaction of the coal sample was determined to be about 68% by weight.

Example 2. This embodiment is the same as the first embodiment in all aspects except for two. As done in Example 1, after maintaining the temperature at about 96 ° C. for about 30 minutes, the extraction vessel containing the coal sample and α-terpineol was maintained at a temperature of about 135 ° C. for an additional about 30 minutes. The pressure in the extraction vessel remained at an ambient pressure slightly below about 1.01 × 10 ⁵ Pascal (1 atm). The degree of conversion, or liquefaction, of the coal sample was determined to be about 70% by weight.

Example 3. The coal samples used were from the same source as used in the previous two examples and from the same industrial analysis. About 31 grams of α-terpineol was added to about 31 grams of coal sample in the extraction vessel. The mixture was maintained at about 96 ° C. and ambient pressure slightly below about 1.01 × 10 ⁵ Pascal (1 atm) for about 30 minutes. The degree of conversion, or liquefaction, of the resulting coal sample was determined to be about 71 wt% by weighing the sample after filtration, coal preparation and drying as was done in the previous two examples.

  Example 4. This example is the same as Example 3 except that about 30% by weight of α-terpineol was replaced with hexane to provide a reagent comprising 70% by weight of α-terpineol and 30% by weight of hexane. is there. This reduced the degree of conversion, ie liquefaction, to about 1.3% by weight.

  Example 5. The coal sample source and industrial analysis and the experimental conditions for temperature, pressure and reagent to sample ratio for this example were the same as in Example 3. However, the duration of extraction was reduced from about 30 minutes to about 20 minutes. In addition, about 30 wt% α-terpineol was replaced with 1-butanol to provide a reagent comprising 70 wt% α-terpineol and 30 wt% 1-butanol. The amount of liquefied coal was only about 0.30 grams, corresponding to a conversion of about 1.0% by weight.

  Example 6. This example is the same as Example 3 with respect to the source and industrial analysis of the coal sample and the temperature, pressure and duration of extraction. However, the amount of coal sample used was about 25 grams and the reagent contained about 24 grams (80 weight percent) α-terpineol and about 6 grams (20 weight percent) xylene, 70 weight percent. Of α-terpineol and 30% by weight of xylene. The liquefied coal was about 10.0 grams, corresponding to about 40% by weight conversion.

Example 7. In this example, coal from the Wyodak vein in Campbell County, Wyoming was liquefied with the reagent α-terpineol. Coal samples were obtained from the Pennsylvania State University coal bank to which the following industrial analysis provided: 26.30 wt% as-received 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 α-terpineol was gently added to about 30 grams of coal sample placed in the extraction vessel, resulting in a reagent to sample ratio of about 2: 1. The resulting extraction vessel with a lid containing a mixture of α-terpineol and coal but not tightly sealed was maintained at a constant temperature of about 96 ° C. and constantly stirred. Without the α-terpineol boiling, the pressure in the extraction vessel remained at an ambient pressure slightly below about 1.01 × 10 ⁵ Pascal (1 atm). After about 30 minutes, the mixture in the extraction vessel was filtered, and the coal particles obtained on the filter were selected with ethanol and dried to a constant weight. Based on the weight loss, the degree of conversion or liquefaction of the coal sample was determined to be 75% by weight.

  Example 8. The experiment in this example was performed under the same conditions as in the previous example except for one. Instead of about 60 grams performed in the previous example, about 15 grams of α-terpineol was added to about 30 grams of coal sample to give a reagent to coal ratio of 0.5 to 1. The degree of conversion, or liquefaction, of the resulting coal sample was reduced from about 75% by weight obtained in the previous example to about 69% by weight.

Example 9. In this example, about 3 grams of Green River, Colorado oil shale is solubilized with about 9 grams of α-terpineol to produce a 3: 1 reagent to sample ratio from the oil shale. (Organic) and / or bitumen (organic) were extracted. The organic carbon content, including both volatile and fixed carbon, was determined to be about 22.66% by weight by a recognized analytical company. Two experiments with oil shale samples having a particle size of 60 mesh were performed at ambient temperatures and pressures slightly below about 25 ° C. and about 1.01 × 10 ⁵ pascals (1 atm), respectively. Sample weight loss was determined by filtration, ethanol preparation, and weighing after drying. These losses were about 9% by weight after about 30 minutes and about 17% by weight after about 45 minutes. From these weight losses, the degree of conversion of organics, ie kerogen and / or bitumen, ie extraction, was estimated to be about 40% by weight for the former and about 75% by weight for the latter.

  Example 10. This example reproduced the previous example, except that a single experiment lasting about 15 minutes was conducted at a temperature of about 96 ° C. instead of about 25 ° C. The weight loss of the oil shale sample was about 12% by weight, corresponding to about 53% by weight of kerogen (organic) conversion, ie extraction.

Example 11. In this example, bitumen (organic) in tar sands from Alberta, Canada was solubilized and extracted with a commercial grade synthetic turpentine. The tar sand sample was obtained from the Alberta Research Council, which provided the following industrial analysis: 84.4 wt% dry solids, 11.6 wt% dry bitumen, and 4.0% by weight moisture as received. About 30 grams of synthetic terpentine was added to about 15 grams of tar sand sample in a capped but not tightly sealed extraction vessel, and a reagent to sample ratio of about 2 to 1 by weight was utilized. This extraction vessel containing the resulting mixture of synthetic terpentine and tar sand was maintained at a constant temperature of about 96 ° C. Without the synthetic turpentine boiling, the pressure in the extraction vessel remained at an ambient pressure slightly below about 1.01 × 10 ⁵ Pascal (1 atm). After about 20 minutes, the mixture in the extraction container was filtered, and the solid (tar sand) obtained on the filter was selected with ethanol and dried to a constant weight. Based on the weight loss, the degree of bitumen conversion, ie extraction, from the tar sand sample was determined to be about 100% by weight.

Example 12. In this example, about 60 grams of tar sand sample from the same source as in the previous example and from the same industrial analysis was replaced by about 60 grams of commercial grade synthetic turpentine containing α-terpineol. Extracted with α-terpineol. The resulting reagent to sample ratio was 1 to 1 instead of 2 to 1 as in the previous examples. The experiment lasted about 30 minutes at ambient temperature slightly below about 1.01 × 10 ⁵ Pascal (1 atm) at a temperature of about 96 ° C. The degree of bitumen (organic) conversion, ie extraction, in the tar sand sample was determined to be about 100% by weight.

Example 13. In this example, about 60 grams of tar sand sample from the same source as in the previous two examples and the same industrial analysis was extracted with about 60 grams of commercial grade synthetic turpentine. Therefore, the resulting reagent to sample ratio was approximately 1 to 1. This experiment was conducted at a temperature of about 96 ° C. under an ambient pressure slightly below about 1.01 × 10 ⁵ Pascals (1 atm) for about 30 minutes. The degree of bitumen (organic) conversion, ie extraction, in the tar sand sample was determined to be about 70% by weight.

  Example 14. Experiments in this example reproduced Example 8 in all aspects, except that the reagent to sample ratio was reduced from about 2 to 1 to about 0.5 to 1. About 60 grams of tar sand sample was extracted with about 30 grams of commercial grade synthetic turpentine. The degree of bitumen (organic) conversion or extraction was reduced from about 100 wt% obtained in Example 9 to about 70 wt%.

  Example 15. The experiment in this example was repeated with α-terpineol replacing the previous example with a commercial grade synthetic terpentine. The degree of bitumen (organic) conversion or extraction in the tar sand sample was about 70% by weight as in the previous examples.

Example 16. The experiment in this example is the same industrial analysis tar sand sample from the same source as in the previous example with tar sand under ambient pressure slightly below about 1.01 × 10 ⁵ pascals (1 atm). Made in About 60 grams of commercial grade synthetic terpentine was added to about 60 grams of tar sand sample, resulting in a reagent to sample ratio of about 1: 1. The temperature of the sample and the commercial grade synthetic terpentine was maintained at about 65 ° C. for about 30 minutes, followed by cooling to about 15 ° C. within about 5 minutes. The tar sand sample was then filtered, selected, dried and weighed. Based on weight loss, the degree of bitumen (organic) conversion, or extraction, in the tar sand sample was determined to be about 70% by weight.

  Example 17. The experiment in this example was repeated with α-terpineol replacing the previous example with a commercial grade synthetic terpentine. The degree of bitumen (organic) conversion, or extraction, increased from about 70% by weight of the previous example to about 90% by weight.

Example 18. In this example, a tar sand sample from the same source as in Example 11 to Example 17 and weighing about 30 grams of the same industrial analysis was added with about 20 grams (80% by weight) of α-terpineol. A liquid containing about 5 grams (20% by weight) of toluene was extracted at a temperature of about 96 ° C. under an ambient pressure slightly below about 1.01 × 10 ⁵ pascals (1 atm). The duration of the experiment (reaction or extraction time) was about 30 minutes. The sample weight loss was about 10.2 grams. From this weight loss, the degree of bitumen (organic) conversion, ie extraction, was estimated to be about 33% by weight.

Example 19. Three tar sand samples from the same source, all used in all previous examples in tar sands and of the same industrial analysis, were added at about 15 ° C. with reagents containing various amounts of α-terpineol. Extraction was performed under ambient pressure slightly below about 1.01 × 10 ⁵ pascals (1 atm) at temperature. The duration of each experiment (reaction or extraction time) was about 15 minutes for each tar sand sample. The first sample was extracted with a mixture containing about 0 grams (0 wt%) of α-terpineol and about 15 grams (100 wt%) of ethanol, ie pure ethanol. The second sample was extracted with a mixture containing about 7.5 grams (50% by weight) α-terpineol and about 7.5 grams (50% by weight) ethanol. The third sample was extracted with a mixture containing about 12 grams (80% by weight) α-terpineol and about 3 grams (20% by weight) ethanol. The weight loss of bitumen (organic matter) and the estimated conversion, ie extraction, in the three samples is about 0.2 grams (1.0 wt%) for the first, second and third samples, 0.6 grams (3.0 weight percent) and 0.9 grams (4.5 weight percent).

Example 20. Commercial grade asphalt irregular shaped pellets with an average size of about 15 mm, with α-terpineol, at an ambient temperature of about 22 ° C., under an ambient pressure slightly below about 1.01 × 10 ⁵ Pascals (1 atm) Liquefied and extracted. A first sample weighing about 20 grams was liquefied and extracted with about 40 grams of α-terpineol. The second sample also weighed about 20 grams and was liquefied and extracted with about 20 grams of α-terpineol. Both samples were completely dissolved after 30 minutes. These experiments were conducted to simulate the solubilization and extraction of heavy crudes that tend to be rich in asphaltenes, such as asphalt.

Example 21. In this example, bitumen (organic matter) in tar sand of the same industrial analysis from the same source as used in all previous examples in tar sand, two vegetable oils, soybean oil and corn oil Solubilized and extracted. Vegetable oil is completely miscible with the terpentine solution. In a first experiment, a tar sand sample weighing about 15 grams with about 30 grams of soybean oil, at a temperature of about 96 ° C. for about 20 minutes, and slightly below about 1.01 × 10 ⁵ pascals (1 atm) Mix under pressure and constantly stir. Since the weight loss was about 0.5 gram, the degree of bitumen conversion, ie extraction, in the sample was estimated to be about 3.3% by weight. In a second experiment, a tar sand sample weighing about 30 grams was subjected to about 16 grams of corn oil for about 30 minutes at a temperature of about 175 ° C. and an ambient pressure slightly below about 1.01 × 10 ⁵ pascals (1 atm). Mixed under and stirred. Since the weight loss was about 4.8 grams, the degree of bitumen conversion, ie extraction, in the sample was estimated to be about 12% by weight.

  Example 22. Two tests were performed on the Berea sandstone plug core sample to determine the effect of reagent injection on oil recovery from the core. The first test was designed to determine incremental oil recovery by injecting α-terpineol after the oil field was already flooded to the limit. The selected core contained 9.01 mL of laboratory oil simulating crude oil. Water flooding with an aqueous solution containing 3.0% potassium chloride produced 4.6 mL of petroleum. 5 (5) Pore volume α-terpineol injection produced an additional 3.61 mL of petroleum, leaving the core with less than 8.0% of the original volume of petroleum remaining. . The second test was designed to represent the increased recovery that could be expected from unmined reservoirs with α-terpineol injection. The selected core contained 8.85 mL of laboratory oil simulating crude oil. Petroleum production began after the injection of approximately 0.5 pore volume of α-terpineol, and this injection continued to 3.5 pore volume, but most oils were only 2.5 pore volume. It was recovered after α-terpineol injection. A total of 7.94 mL of laboratory oil was recovered, leaving the core with less than 7.5% of the original volume of oil remaining.

  In one experiment, various different ratios of turpentine liquid and tar sand samples were tested. For each of the experiments described below, the terpentine solution has the same formulation, and the composition comprises about 60% by volume α-terpineol, about 20% by volume β-terpineol, and about 20% by volume. % Γ-terpineol. Tar sand was a different mixture of Canadian Alberta ores with a bitumen content of approximately 12% by weight and a water content of approximately 4-5% by weight. All experiments were conducted at ambient temperature.

  As shown in Table 6 below, the recovery of hydrocarbons from tar sand over all of the ratios noted below (ie, the ratio of turpentine liquid to tar sand in the range of 1: 2 to 2: 1). As a result, hydrocarbon recovery was good with little discernable difference. For the temperature at which the extraction was carried out, the optimum temperature for extraction, solubilization and / or liquefaction of hydrocarbons from tar sands would be 65 ° C. As shown in the table, at about 130 ° C., the amount of recovered hydrocarbon was reduced. However, for certain solids where it is particularly difficult to recover hydrocarbons, increasing the temperature of the extraction solvent can increase the amount of hydrocarbons recovered. Finally, the exposure time had little effect on the amount of material extracted. This is probably because the shortest extraction time is 20 minutes, which is considered more than sufficient for extraction from hydrocarbon tar sands.

  Further experiments were performed with alternative solvents, ie ethanol and corn oil, and contained about 60% by volume α-terpineol, about 20% by volume β-terpineol, and about 20% by volume γ-terpineol. Compared to the composition. As described in Table 7 below, the performance of ethanol and corn oil unexpectedly was found to be 60% by volume α-terpineol, about 20% by volume β-terpineol, and about 20% by volume γ- It was considerably lower than the composition containing terpineol. For example, terpineol compositions achieved complete or nearly complete extraction of extractable hydrocarbons, whereas ethanol yielded only 10% of recoverable hydrocarbons, and heated corn oil was recoverable Only 33% of fresh hydrocarbons were produced.

  As shown in Table 8 below, the performance of various terpentine liquid formulations is provided, including terpentine liquid formulations including α-terpineol alone and α-terpineol combined with various known organic solvents. The The first three compositions shown in the table include α-terpineol, β-terpineol, and γ-terpineol. For example, the first 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 the performance of the turpentine liquor improves as the concentration of α-terpineol increases, and when the turpentine liquor contains approximately 70% α-terpineol, the hydrocarbon material from the tar sand sample Indicates that full extraction is reached.

  Figure 2 shows a second data set for extraction of hydrocarbon-containing tar sand with pure α-terpineol. As shown, over 100% extraction was achieved, possibly due to variations in hydrocarbon content in the sample. However, the results generally indicate the unexpected result that α-terpineol can extract substantially all of the recoverable hydrocarbons from the tar sand sample.

  Finally, the last data listed in Table 8 illustrates the effectiveness of the mixed system of α-terpineol and a known organic solvent. As shown, substantially complete recovery of recoverable hydrocarbons is achieved with a composition comprising α-terpineol to ethanol in a 1: 1 ratio. This is unexpected as pure ethanol only extracted about 10% of the total recoverable hydrocarbons. In addition, even mixed systems containing either α-terpineol to toluene in either a 1: 1 or 3: 1 ratio also resulted in 77% and 92% recovery of total recoverable hydrocarbons. This was an unexpected result.

  The results for the recovery of hydrocarbon-containing organics from the hydrocarbon-containing materials described in the examples, particularly in the specification, were unexpected.

  As used herein, terms such as first, second, third, etc. are to be construed as uniquely identifying the element and not implying or limiting any particular ordering of the elements or steps. It should be.

  The terms about and approximately as used in this specification should be construed as including any value within 5% of the stated value. Further, terms relating to a range of values, about and approximate descriptions should be construed as including both the upper and lower limits of the stated range. The terms first, second, third, etc. used in this specification are to be construed as uniquely identifying the elements and not implying or limiting any particular ordering of the elements or steps. Should be.

  Although the invention has been shown or described in only a few of its embodiments, the invention is not so limited and various modifications can be made without departing from the scope of the invention. It should be apparent to those skilled in the art.

Claims (32)

A method for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material using a homogeneous single-phase hydrocarbon extract containing a terpentine solution,
Contacting the hydrocarbon-containing material with a homogeneous single-phase hydrocarbon extract containing a terpentine solution to form a homogeneous single-phase extraction mixture and residue, the homogeneous single-phase extraction The mixture includes at least a portion of the hydrocarbon-containing organics extracted into the terpentine liquid, and the residue includes at least a portion of the insoluble material from the hydrocarbon-containing material that is not soluble in the turpentine liquid;
Separating the extraction mixture from the residue;
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 part comprises at least a part of the terpentine liquid,
The terpentine solution is natural turpentine, synthetic terpentine, mineral terpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpene resin, α-terpene, β- Terpene, γ-terpene, geraniol, 3-carene, dipentene (ρ-menta-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromicenol, isoborneol, ρ-menthane-8-ol, α-terpinyl acetate, citronellol, ρ-menthane-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, anethole, camphene, ρ-cymene, anisaldehyde, 3,7 -Dimethyl-1,6-octadiene, Sobornyl acetate, ocimene, alloocimene, allocymene alcohol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, citronellal, A method selected from the group consisting of mentone, and mixtures thereof.   The hydrocarbon-containing organic material is a solid or semi-solid, and the hydrocarbon-containing material includes a plurality of particles, the particles having an average particle size from 0.74 millimeters to 25 millimeters. the method of.   Adding a second liquid to the terpentine liquid, wherein the second liquid is from the group consisting of a lower aliphatic alcohol, a lower alkane, a lower aromatic compound, an aliphatic amine, an aromatic amine, and mixtures thereof. The method of claim 1, which is selected.   The method of claim 1, further comprising heating the turpentine liquid to a temperature up to a point above ambient temperature up to 200 ° C. prior to contacting the turpentine liquid with the hydrocarbon-containing material.   The method of claim 1, further comprising supplying at least a portion of the second portion of the extraction mixture to the contacting step.   Means for contacting the hydrocarbon-containing organic substance and the terpentine solution in situ in an underground formation containing the hydrocarbon-containing organic substance; and means for extracting the hydrocarbon-containing organic substance from the underground formation The method of claim 1, further comprising:   The method of claim 1, wherein the hydrocarbon-containing material is contacted by the turpentine liquid at a temperature of less than 300 ° C. The hydrocarbon-containing material is in the underground formation, and the step of contacting the hydrocarbon-containing material with the terpentine solution occurs in situ in the underground formation,
The method of claim 1, further comprising recovering the extraction mixture through a production well in fluid communication with the underground formation, the residue remaining in situ in the underground formation.   9. The method of claim 8, further comprising injecting a recycle stream into an injection well for further extraction of hydrocarbon material.   9. The method of claim 8, wherein the underground formation is undergoing primary recovery of hydrocarbon material.   The method of claim 1, wherein the terpentine solution comprises at least 30% by volume α-terpineol and at least 15% β-terpineol. Turpentine is
The method of claim 1, further comprising at least one of α-terpene, β-terpene, or γ-terpene.   The method of claim 1, wherein the terpentine solution comprises α-terpineol and β-terpineol, wherein the ratio of α-terpineol to β-terpineol is at least 1.3: 1. The hydrocarbon material includes tar sand,
The step of contacting the hydrocarbon-containing material with the turpentine liquid is to remove the tar sand from the interior of the extraction vessel for a period of time that serves to extract a substantial portion of the hydrocarbon-containing organic material from the hydrocarbon-containing material into the turpentine liquid. The method according to claim 1 for extracting hydrocarbon-containing organic matter from the hydrocarbon-containing material, comprising the step of supplying to the interior of the extraction vessel with a terpentine solution. The hydrocarbon material includes oil shale;
The method further comprises the step of grinding the hydrocarbon-containing organic material to produce a plurality of particles, wherein the particles define an average diameter size in the range of 4.8 mm to 25 mm such that the plurality of particles are in contact with the turpentine liquid. The method of claim 1 for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material. The hydrocarbon material includes coal;
Crushing the hydrocarbon-containing organics to produce a plurality of particles, wherein the particles have an average diameter size in the range of 0.8 mm to 0.07 mm such that the plurality of particles are in contact with the terpentine solution. The method of claim 1 for extracting hydrocarbon-containing organics from a hydrocarbon-containing material as defined. A method for extracting hydrocarbon-containing organic matter from hydrocarbon-containing materials selected from coal, oil shale, tar sand, crude oil, heavy crude oil, natural gas or mixtures thereof to α-terpineol,
Contacting the hydrocarbon-containing material with α-terpineol such that an extraction mixture is formed and a residue is formed, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic material extracted into α-terpineol. And the residue includes at least a portion of an insoluble material from the hydrocarbon-containing material that is not soluble in α-terpineol;
Separating the extraction mixture from the residue.   The method further comprises separating the extraction mixture into a hydrocarbon product stream and a recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter, the recycle stream comprising at least a portion of the α-terpineol. The method of claim 17 comprising.   The method of claim 18, further comprising recycling the recycle stream into contact with the hydrocarbon-containing material. An apparatus for recovering hydrocarbon-containing organic matter from a solid or semi-solid hydrocarbon-containing material,
A terpentine liquid supply source comprising a terpentine liquid containing terpineol for extracting hydrocarbon-containing organic matter into terpineol from a hydrocarbon-containing material;
A contact vessel, wherein the contact vessel has a first inlet and is in fluid communication with a turpentine liquid source through the first inlet, the contact vessel passing the hydrocarbon-containing material through the second inlet. The contact container serves to contain the hydrocarbon-containing material and the turpentine liquid in the contact container for a predetermined period of time which serves to form an extraction mixture and a residue. The extraction mixture includes at least a portion of the hydrocarbon-containing organic material and the terpentine liquid, and the residue includes at least a portion of the insoluble material that does not dissolve in the turpentine liquid from the hydrocarbon-containing material. The contact container includes a first outlet for recovering the extraction mixture from the contact container and a second outlet for recovering the residue from the contact container, the contact container allowing mechanical stirring. And acts,
A storage tank is further provided, wherein the storage tank is in fluid communication with the contact vessel through a line, the storage tank serves to receive the extraction mixture from the contact vessel, and the line prevents solids from passing into the storage tank. Including a filter to make and
An apparatus further comprising collecting means for collecting the residue from the second outlet of the contact container.   21. The apparatus of claim 20, further comprising a separation container for containing the extraction mixture, wherein the separation container serves to separate the hydrocarbon-containing organic matter from the terpentine liquid.   21. The apparatus of claim 20, further comprising a recycle stream for receiving the turpentine liquid from the separation vessel, the recirculation stream serving to return the turpentine liquid from the separation vessel to the contact vessel for reuse.   21. The apparatus of claim 20, further comprising a pulverizer, wherein the pulverizer is configured to reduce the size of the hydrocarbon-containing material for contact within the contact container with liquid turpentine. .   21. The apparatus of claim 20, wherein the contact vessel is a rotary tilt filter further comprising a plurality of fins or trays configured to control contact time between the turpentine liquid and the hydrocarbon-containing material.   21. The apparatus of claim 20, wherein the means for introducing a hydrocarbon-containing material into a contact vessel includes a conveyor.   21. The apparatus of claim 20, wherein the contact vessel further comprises means for mixing the hydrocarbon-containing material and the terpentine liquid.   A second contact container coupled to the first contact container, the second contact container having an inlet for receiving the turpentine liquid and the coal sample material; and for recovering at least a portion of the extraction mixture. A first outlet and a second outlet for removing at least a portion of the residue from the mixing container, the second contact container being located between the first contact container and the storage tank; 21. The device of claim 20, wherein the device is coupled.   21. The apparatus of claim 20, further comprising a filter located at the inlet of the contact vessel. A method for recovering hydrocarbon-containing organic matter from tar sand,
Obtaining a tar sand sample comprising recoverable hydrocarbon-containing organic matter;
Further comprising supplying a tar sand sample to the contact vessel, the contact vessel including at least one inlet for supplying a turpentine solution;
The tar sand sample is contacted in a contact vessel with a homogeneous single-phase hydrocarbon extract containing α-terpineol and β-terpineol so that a homogeneous single-phase extraction mixture and residue are formed. Stirring the sample with a hydrocarbon extract, wherein the extraction mixture comprises at least a portion of the hydrocarbon-containing organics extracted into the hydrocarbon extract, and the residue is a hydrocarbon extract from the tar sand sample. Including at least a portion of an insoluble material that does not dissolve in the liquid, the contact vessel including at least one inlet for supplying a hydrocarbon extract;
Separating the extraction mixture from the residue;
Separating the extraction mixture into a hydrocarbon product stream and a hydrocarbon extract recycle stream, the hydrocarbon product stream comprising at least a portion of hydrocarbon-containing organics from a tar sand sample;
Recycling at least a portion of the hydrocarbon extract recycle stream to the contacting step. A method for recovering hydrocarbon-containing organic matter from finely crushed hydrocarbon-containing oil shale, comprising:
Providing a finely crushed hydrocarbon-containing oil shale;
Providing a first liquid comprising a terpentine liquid;
Filtering the finely crushed hydrocarbon-containing oil shale;
Sending the crushed hydrocarbon-containing oil shale to the contact vessel, the contact vessel comprising at least one inlet for supplying turpentine liquid to the contact vessel;
Contacting a finely divided hydrocarbon-containing oil shale with a turpentine liquid to form a homogeneous single-phase extraction mixture and a residue, wherein the extraction mixture is a hydrocarbon extracted into the turpentine liquid Including at least a portion of the organic material containing, the residue including at least a portion of the insoluble material from the oil shale that does not dissolve in the turpentine liquid;
Separating the extraction mixture from the residue;
Separating hydrocarbon-containing organics from the terpentine liquid in an extraction mixture to produce a hydrocarbon product stream and a turpentine liquid recycle stream, wherein the hydrocarbon product stream is a finely divided hydrocarbon Including at least a portion of hydrocarbon-containing organic matter from the containing oil shale;
Recycling at least a portion of the terpentine recycle stream to the contacting step. A method for recovering hydrocarbon-containing organic matter from an underground formation rich in hydrocarbon-containing coal,
Obtaining coal containing recoverable hydrocarbon-containing organic matter;
Crushing the coal to produce crushed coal;
Filtering the crushed coal;
A step of sending crushed coal to a contact container, wherein the contact container supplies a terpentine solution containing 45 to 80% by volume of α-terpineol and 15 to 45% by volume of β-terpineol to the contact container. Including at least one inlet for:
Contacting the crushed coal with a turpentine solution such that a homogeneous single-phase extraction mixture and residue are formed, the extraction mixture comprising at least one of the hydrocarbon-containing organics extracted into the terpentine solution. The residue includes at least a portion of a portion of the insoluble material from coal that does not dissolve in the turpentine liquid;
Separating the residue from the extraction mixture;
Separating the hydrocarbon-containing organic matter from the terpentine liquor to produce a hydrocarbon product stream and a terpentine liquor recycle stream, wherein the hydrocarbon product stream is at least a portion of the hydrocarbon-containing organic matter from coal. Including steps,
Recycling at least a portion of the terpentine recycle stream to the contacting step. A method for increasing the recovery of hydrocarbon-containing organic matter from a production well coupled to a hydrocarbon-containing subterranean formation containing hydrocarbon-containing material comprising:
Providing a press-fit well in fluid communication with the underground formation;
Providing a first liquid comprising a terpentine liquid comprising terpineol;
A step of injecting a turpentine solution into a formation through an injection well, wherein the turpentine solution and the hydrocarbon-containing organic matter from the hydrocarbon-containing underground formation are at least one of the extraction mixture hydrocarbon-containing organic matter extracted into the terpentine solution. Forming a homogeneous single-phase extraction mixture comprising parts;
Recovering the extraction mixture from the formation through production wells;
Separating the extraction mixture to produce a hydrocarbon product stream and a terpentine liquid stream.

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