KR101458881B1 - Extraction of hydrocarbons from hydrocarbon-containing materials - Google Patents

Abstract

The present invention provides a method of treating a subject comprising: providing a first liquid comprising a liquid of turpentine; Contacting the turpentine fluid with a hydrocarbon containing material to form an extract mixture; Extracting the hydrocarbon material with a turpentine liquid; Containing organic material from the hydrocarbon-containing material, comprising the step of separating the extracted hydrocarbon material from the unextracted residual material.

Description

[0001] EXTRACTION OF HYDROCARBONS FROM HYDROCARBON-CONTAINING MATERIALS [0002]

This application is a continuation-in-part of U.S. Patent Application No. 12 / 174,139, filed July 16, 2008, and U.S. Patent Application No. 12 / 053,126, filed on March 21, 2008, U.S. Provisional Patent Application No. 60 / 973,964, filed September 20, 2007, which is incorporated herein by reference.

The present invention relates to a process for extracting hydrocarbons from a hydrocarbon-containing material.

Liquefaction, dissolution and / or extraction of fossil fuels (individually and collectively referred to below as fossil fuels), called hydrocarbon-containing organic matter, in solid, semi-solid, high viscous or viscous form, It proved challenging and difficult. These fossil fuels used herein include, but are not limited to, coal, oil shale, tar sands and oil sands (hereinafter collectively referred to as tar sand), as well as crude oil, heavy oil crude oil, raw bitumen, kerogen, hydrocarbon-containing organic materials in natural asphalt and / or asphaltene. The difficulty may be due in part to the fact that these fossil fuels often contain complex organic polymers bound by oxygen and sulfur bonds, which are in the matrix of inorganic compounds. As the demand and consumption of hydrocarbon-based materials increases, there is a need to produce additional liquid hydrocarbon feedstocks for the production of various chemicals, pharmaceuticals and processed materials, as well as for the production of liquid and gaseous fuels.

A variety of techniques and processes have been developed to liquefy, dissolve and / or extract fossil fuels. However, no prior art liquefaction, dissolution 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 fact that all the prior art and processes for liquefaction, dissolution or extraction of hydrocarbons developed so far are expensive to deploy and operate. Also, prior art and processes for liquefying, dissolving or extracting hydrocarbons are difficult to scale up, operate and / or control due to one or more of the following reasons: (1) operation at excessively elevated pressure; (2) operating at very high temperatures; (3) the need for expensive process vessels and equipment requiring external supply of hydrogen under extreme conditions; (4) is prone to become a mixture or composition of two or more reagents, catalysts, and / or promoters that are frequently highly toxic, unable to regenerate or recycle; (5) It is required to supply a special type of energy, for example microwave radiation; (6) the long treatment time of partial liquefaction, dissolution or extraction; (7) Excessively finer particles are required, which are excessively difficult and expensive to manufacture and handle, with a size of about 200 mesh (0.074 mm); (8) The required reagents, catalysts and / or promoters can not be recovered and regenerated. Thus, there is a need to provide additional techniques and processes for increased recovery of hydrocarbon materials.

In a primary drilling operation it is desirable to use a process that enhances the dissolution of additional or trapped hydrocarbon-containing organic materials that can be recovered so that the pressure gradient existing through the through-holes exerts a force on the hydrocarbon-containing organic material, Do. In particular, it is generally useful to dissolve the heavy hydrocarbons remaining in the reservoir through a primary drilling operation.

For secondary and tertiary or enhanced oil recovery systems it is desirable to use a process that is cost effective and that enhances the dissolution of the oil to recover the hydrocarbon containing organic material from the reservoir in a manner that does not damage the reservoir. While effective methods and compositions exist for tertiary operation, current methods suffer from operational costs when compared to the value of the resulting hydrocarbon-containing organic material.

According to an embodiment of the present invention, a method for extracting a hydrocarbon-containing organic material from a hydrocarbon-containing material includes providing a first liquid containing a turpentine liquid, contacting the turpentine fluid with a hydrocarbon- But also to form a residual material. The extraction mixture contains at least a portion of the hydrocarbon-containing organic material and the turpentine liquid. The residual material comprises a non-soluble material from the hydrocarbon-containing material. The residual material also includes a reduced portion of the hydrocarbon-containing organic material in an environment where all such hydrocarbon-containing material is not dissolved by the turpentine liquid and is transferred to the extraction mixture. The residual material is then separated from the extraction mixture. The extraction mixture is further separated into a first portion and a second portion. The first portion of the extraction mixture comprises a hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic material extracted from the hydrocarbon-containing material. The second portion of the extraction mixture comprises at least a portion of the solution of the turpentine. In one embodiment, substantially all of the turbine fluid is recovered from the regeneration stream.

In yet another embodiment, substantially all of the hydrocarbon containing organic material is extracted with the extraction mixture. In this embodiment, the residue material is basically oil-free and can be used or disposed further without affecting the environment.

The present invention has an effect of providing a method of extracting hydrocarbon from a hydrocarbon-containing material.

1 is a schematic diagram of one embodiment of an apparatus for recovering hydrocarbons from a tar sand;
2 is a schematic diagram of one embodiment of an apparatus for recovering hydrocarbons from an oil shell.
3 is a schematic diagram of one embodiment of an apparatus for recovering hydrocarbons from coal.
4 is a schematic view for enhanced recovery of hydrocarbons from reservoirs below the surface of the earth;

In one aspect, the present invention relates to a composition that is readily disposed for extraction, liquefaction and / or dissolution of fossil fuels from coal, oil shells, tar sands, etc. as well as from storage.

According to one embodiment, the method of the present invention is used for the storage of coal, oil shells, tar sand, or reservoirs containing heavy oil, crude oil, natural gas (which often coexist with crude oil and other such fossil fuels) Liquefying, dissolving and / or extracting the hydrocarbon-containing organic material from the same hydrocarbon-containing material. Hydrocarbon-containing organic materials include, but are not limited to, heavy oil, crude oil, natural gas, and the like. The hydrocarbon-containing organic material may be in solid, semi-solid, liquid, sludge, viscous liquid, liquid or gaseous form. Other materials that are suitable hydrocarbon containing materials for treatment using the method of the present invention include liquids and solids including hydrocarbon-containing materials as well as residual materials. Exemplary hydrocarbon containing materials may also include oil tank bottoms, oil pits and pond sludge and slurry mixes, abandoned food, manure, sewage sludge or municipal waste. The liquefying, dissolving and / or extracting the hydrocarbon-containing organic material provides a turpentine liquid and the hydrocarbon-containing material is contacted with the turpentine fluid and the hydrocarbon-containing material to extract at least a portion of the hydrocarbon-containing organic material from the hydrocarbon- Generating an extraction mixture comprising a hydrocarbon containing organic material removed from the turpentine liquid and separating the extracted organic material from the turpentine liquid from any remaining material that has not been extracted. The solution of the turpentine may contain a certain amount of terpineol. The naturally occurring turpentine fluid contains a certain amount of terpene. In one embodiment, the turpentine liquid comprises alpha-terpineol.

In certain embodiments, the ratio of the turpentine liquid to the hydrocarbon containing organic material is greater than about 1: 2 and greater than 4: 1, in some embodiments greater than about 1: 1, and in some embodiments greater than 2: 1. In embodiments relating to storage recovery, the ratio may be greater than or equal to about 3: 1, and in other embodiments associated with storage recovery, the ratio may be greater than or equal to about 4: 1. For storage applications, the void content is used to estimate an estimate of the hydrocarbon-containing material. As another aspect of the present invention, the amount of hydrocarbon-containing material can be measured more directly, such as in the use of tar sand and coal and oil shells.

In certain embodiments, the minimum organic content contained in the hydrocarbon-containing material is at least about 1% by weight, in other embodiments at least about 10% by weight, and in yet another embodiment at least about 14% by weight of the hydrocarbonaceous material.

In one embodiment of the invention, the liquefying, dissolving or extracting reagent selected for the hydrocarbon-containing material may comprise alpha-terpineol, or alpha-terpineol itself, as natural, synthetic or mineral turpentine.

In certain embodiments, liquefaction, dissolution and / or extraction of the fossil fuel or hydrocarbon containing organic material may be performed at a temperature in the range of about 2-300 ° C. In certain embodiments, the organic material or material is contacted with the turpentine fluid at a temperature of about 300 캜 or less, or about 60 캜 or less. In other embodiments, the liquefaction, dissolution, and / or extraction temperature may be in the range of about 20 to 200 < 0 > C. The pressure at which liquefaction, dissolution and / or extraction of fossil fuels is performed can generally be within the range of about 1.0 x 10 ⁴ pascals (about 0.1 atm) to about 5.0 x 10 ⁶ pascals (about 50.0 atm). In certain embodiments, the process can be performed at a pressure between about 5.0 x 10 ⁴ pascals (0.5 atm) to about 8.0 x 10 ⁵ pascals (8.0 atm). In certain other embodiments, the fossil fuel or hydrocarbon-containing organic material that is liquefied, dissolved and / or extracted in contact with, or in contact with, one or more turpentine fluids may be liquefied, liquefied and / Lumps, or blocks of fossil fuel within the range of about 0.74 to 10 mm in the melting and / or extraction vessel (hereinafter referred to as the reactor). In a particular embodiment, the size of the particle, piece, lump, or block of fossil fuel is within the range of about 0.149 mm (100 mesh) to 20 mm. In certain embodiments, the particles, flakes, agglomerates, or blocks of the fossil fuel are passed through a liquid, liquefied and / or extracted reagent or reagents in liquid form through the bed of particles, flakes, agglomerates or blocks by boiling reagents or reagents Lt; / RTI > In certain embodiments, the time for liquefaction, dissolution and / or extraction is between about 1 minute and 90 minutes. Fossil fuels may be partially or fully liquefied, dissolved and / or extracted; The degree of liquefaction, dissolution and / or extraction may be controlled by adjusting working conditions such as temperature, pressure, intensity of agitation and operating time and / or adjusting the type, relative amount and concentration of the liquefying, dissolving or extracting reagents or reagents in the reactor .

The basis of one aspect of the present invention is that about 60 grams of about 250 grams of coal from Pittsburgh seam in Washington, When added, the color of the reagent almost immediately turns to pitch black and remains unchanged after several hours. This indicated that the color change was not due to suspension of the coal particles but was an indication of the extraction of hydrocarbon-containing organic materials from coal. Subsequently α- terpineol and two samples of coal: slightly more transferring the mixture to a 1 only (jar) a tight seal with a cap from the tray and about 20 ℃ and 1.01 × 1O for about 25 days ⁵ Pascal (1 atm) It was kept at low atmospheric conditions. The conversion of the coal sample (i.e., degree of liquefaction) was determined to be about 71% by weight after filtration, washing with ethanol, drying and weighing. This 71% by weight conversion is such that almost all soluble < RTI ID = 0.0 >(< / RTI >< RTI ID = 0.0 > It corresponds to bitumen (organic matter). A series of subsequent experiments with coal as well as coal with oil shells and tar sand under various operating conditions have shown that the family of reagents comprising natural and / or synthetic turpentine and pinene's alcohols, i.e. terpineol, containing pinenes, (Organics), bitumen (organics) and / or asphaltenes (organics) in fossil fuels including coal, oil shells, tar sands, heavy oil and / or crude oil without the aid of alkaline metals , ≪ / RTI > dissolves and / or extracts. These reagents, other than mineral derived from petroleum, are renewable and are "green" or low toxic and include fossil fuels such as tetralin, xylene, anthracene and various solutions or mixtures of these reagents and other compounds. Is relatively inexpensive when compared to all other known liquefaction, dissolution, and / or extraction reagents for < RTI ID = 0.0 > Even non-renewable but petroleum-derived mineral turpentines are relatively low toxic and inexpensive. Some of the liquefaction, dissolution and / or extraction reagents penetrate or diffuse into the particles, flakes, blocks or lumps of fossil fuels through their pores at a considerable rate so that these particles, flakes, blocks, Even under much milder conditions than those required in the latest inventions relating to the liquefaction, dissolution and / or extraction of fossil fuels such as oil shells, tar sands, crude oil and heavy oils, for example at room temperature and pressure, Lt; RTI ID = 0.0 > liquefied, dissolved or < / RTI >

One aspect of the present invention provides a method of liquefying, dissolving or extracting a fossil fuel or hydrocarbon containing organic material from a hydrocarbon containing material such as coal, oil shell and tar sand, wherein a portion of the solid or semi-solid fossil fuel Is contacted with the turpentine liquid in an extraction mixture which may be free of alkali metals, catalysts, hydrogen (H ₂ ) and / or carbon monoxide (CO). Hydrogen and CO may be useful as a mixture, but one embodiment of the present invention includes processes and compositions without hydrogen and CO.

In certain embodiments, the turpentine fluid is selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, oil, alpha -pinene, beta -pinene, alpha -terpineol, beta -terpineol, ≪ / RTI > In certain other embodiments, the turpentine liquid is selected from the group consisting of geraniol, 3-karen, dipentene (p-menta-1,8-diene), nopol, , Dihydrothiomycenol, isobonole, p-menth-8-ol, a-terpinylacetate, citroneol, p-menth-8-yl acetate, 7-hydroxydihydrocituronol, ≪ / RTI > In another embodiment, the turpent fluid is anethole, camphene; p-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, aloocymene, aloocimene alcohol, 2- 8-epoxyoctane, camphor, citral, 7-methoxydihydro-citroneol, 10-camphorsulfonic acid, synthronelal, menton, mixtures thereof.

According to one embodiment, a solid or semi-solid fossil fuel, such as coal, oil shell, tar sand and heavy oil or a solid or semi-solid fossil fuel such as oil tank bottom, oil pit or pond sludge, abandoned food, manure, sewage sludge or municipal waste, The hydrocarbon-containing material may be provided in such a size as to facilitate contact with the liquid of the turpentine. The fossil fuel or hydrocarbon containing material may be provided as a particle, piece, lump or block, for example a large piece or piece of coal or oil shell. According to certain embodiments of the present invention, the fossil fuel or hydrocarbon containing material may be provided as particles. According to certain embodiments of the present invention, the particles of the fossil fuel or hydrocarbon containing material have an average particle size of about 0.074 to 100 mm. In certain other embodiments, the particles of fossil fuel have an average particle size of about 0.074 to 25 mm.

According to one embodiment of the present invention, a second liquid may be added to the liquid of the turpentine. According to certain embodiments of the present invention, the second liquid is selected from lower aliphatic alcohols, alkanes, aromatics, aliphatic amines, aromatic amines, carbon disulfides, and mixtures thereof. Exemplary mixtures include solvents prepared from crude oil tablets such as decant oil, light cycle oil and naphtha, or solvents prepared to dry distill coal and fractionate liquefied coal, .

As used herein, lower aliphatic alcohols refer to primary, secondary and tertiary monohydric and polyhydric alcohols having from 2 to 12 carbon atoms. As used herein, an alkane refers to straight and branched chain alkanes having from 5 to 22 carbon atoms. As used herein, aromatic streams refer to monocyclic, heterocyclic and polycyclic compounds. As used herein, aliphatic amines refer to primary, secondary and tertiary amines having an alkyl substituent having from 1 to 15 carbon atoms. In certain embodiments, benzene, naphthalene, toluene, or a combination thereof is used. In another embodiment, the lower aliphatic alcohols described above may be used. In one embodiment, the solvent is selected from the group consisting of ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, naphthalene, anthracene, tetralin, Triethylamine, aniline, carbon disulfide, and mixtures thereof.

In certain embodiments, the ratio of the turpentine liquid contained in the fluid to any other turpentine-miscible solvent is greater than 1: 1, in certain embodiments greater than about 9: 4. In certain embodiments, the ratio is at least about 3: 1. In another embodiment, the ratio is 4: 1 or greater.

According to one embodiment of the present invention, the fossil fuel and the turpentine liquid are contacted at a temperature of about 20-300 占 폚. In a particular embodiment, the fossil fuel is contacted by the turpentine liquid at a temperature of about 200 DEG C or less.

According to one embodiment of the present invention, the fossil fuel and the turpentine liquid are contacted at a pressure of about 1.0 x 10 ⁴ pascals (0.1 atm) to 5.O x 10 ⁶ pascals (50 atm). According to one embodiment, the process is carried out at a pressure of about 0.5 to 8 atm.

According to one aspect of the present invention, a method of the present invention includes providing an extraction vessel in which the solid or semi-solid fossil fuel is in contact with the liquid of the turbine. According to one embodiment, an agitating means may be provided to allow mixing and stirring of the fossil fuel and the turpentine liquid contained in the reactor or extractor vessel.

According to one embodiment of the present invention, the fossil fuel and the turpentine liquid can be cultured in a holding tank to extend their contact time. According to a further embodiment, the degree of liquefaction, dissolution and / or extraction is controlled by the length of time the solid or semi-solid fossil fuel is in contact with the liquid and / or the temperature of the mixture of fossil fuel and liquid of the liquid.

According to one aspect of the present invention, the fossil fuel is contacted with a homogenized liquid comprising water as a turpentine liquid and an agitator.

In certain embodiments, the ratio of turpentine to water is greater than about 1: 1 by volume to avoid slurry formation that can make it difficult to separate the organic material extracted from the turpentine fluid-containing fluid.

In accordance with one aspect of the present invention, a fossil fuel is fired in a turbine fluid in the presence of an energy input selected from at least about 300 DEG C heat energy, at least about 50 atm pressure, microwave energy, ultrasonic energy, ionizing radiation energy, mechanical shear forces, .

According to one aspect of the present invention, a liquefying or dissolving catalyst is provided in a mixture of fossil fuel and a liquid of turpentine.

According to one embodiment of the invention, the reaction and lysis mixture is supplemented by the selection of compounds selected from hydrogen, carbon monoxide, water, metal oxides, metals and mixtures thereof.

According to one embodiment of the present invention, microorganisms are included in the reaction and dissolution mixture. Selective chemical bonding of fossil fuels and other hydrocarbon-containing materials in hydrocarbons, for example, sulfur bridges and oxygen bridges, is a Bacillus-type pyrophoric and a chemolithotrophic species selected from naturally occurring isolates derived from hot sulfur springs. It is destroyed by biotreatment with microorganism. The destruction of these selective chemical bonds facilitates the dissolution of hydrocarbons in fossil fuels and other hydrocarbon-containing materials.

Other aspects and advantages of the present invention will become readily apparent to those skilled in the art from this disclosure, and specific embodiments of the invention have been shown and described, simply by way of illustration of the best mode contemplated for carrying out the invention. As can be appreciated, the present invention may have other and various embodiments, some of which may be modified in various obvious forms without departing from the invention. Accordingly, the specification is to be regarded as illustrative in nature, and not as restrictive.

According to one embodiment of the present invention, the process of the present invention provides for the extraction of hydrocarbon-containing organic materials from a hydrocarbon-containing material comprising viscous liquid, liquid or gaseous fossil fuel material. The method provides a first liquid comprising a turpentine liquid. The turpentine liquid contacts the hydrocarbon-containing material in situ in an underground facility containing the fossil fuel material to form an extraction mixture to extract the hydrocarbon-containing organic material into the turpentine fluid and to form an extract. The extract is removed from the facility, the extract comprising a turpentine liquid containing the extracted hydrocarbon-containing organic material. The extracted hydrocarbon-containing organic material is separated from the unextracted residual material. The method may further comprise separating the extracted hydrocarbon material from the terbin fluid. The viscous liquid, liquid and gaseous fossil fuel materials may be heavy oil, crude oil, natural gas or a combination thereof. The underground facility can be, for example, a crude oil reservoir or a natural gas reservoir.

The present invention can be readily deployed in situ to directly liquefy and / or dissolve fossil fuels in underground facilities and extract the resulting liquid product from such facilities.

The extraction reagent of the present invention has very strong physico-chemical affinity with bituminous organic materials including bitumen, kerogen and / or tar in solid coal, oil shell and tar sand as a liquid. When the extraction reagent of the present invention and the bituminous organic material containing mainly hydrocarbon are in direct contact with each other, the organic material is dissolved in the extraction reagent of the present invention to liquefy the organic material. Upon contact, the hydrocarbons and extraction reagents of the present invention rapidly form a homogeneous liquid, i.e., a one-ohase liquid.

It is possible to utilize the physical-chemical affinity between the extraction reagent and the bituminous material of the present invention to enhance oil recovery from the oil reservoir under site conditions. The prior art location recovery techniques currently applied to oil depots are largely dependent on the so-called frontal displacement method. This method is mainly controlled by the characteristics of the multi-phase fluid flow in the porous medium. This tends to leave much of the original oil, often about 40%, which is not recovered even in the "good" low viscosity oil reservoir. The reagents of the present invention overcome the complex nature of an effective multi-step flow under in situ conditions to enhance oil recovery.

The present invention exploits the very strong physico-chemical affinity of the turpentine solution.

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.

The oil is dissolved in the extraction reagent of the present invention upon contact with the extraction reagent of the present invention in the oil reservoir, resulting in a homogenous liquid, i.e., a single liquid. The extraction reagent of the present invention does not simply change the oil when moving from the injection well to the production well; The dissolution of the oil previously trapped with the extraction reagent of the present invention continues until the extraction reagent is completely saturated with the oil. The extraction reagent is then deactivated in the additional oil recovery process and simply flows through the pores of the reservoir as a single phase liquid, eventually reaching the production phase.

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

In the first in-situ embodiment, the water (7,0) porosity at about 3.0 (3.0) of the extraction reagent of the present invention is already water-flooded with residual oil saturation, producing about 51% of the original oil in the reservoir It is injected into the oil reservoir. The injection of the extraction reagent can produce an additional approximately 41% of the original oil in the reservoir unexpectedly. This embodiment of the method was experimentally acknowledged as described in Example 22 below.

In the second in-situ embodiment, a void amount of about 5.0 at about (2.0) of the inventive extraction reagent is injected into the oil reservoir. Initially, this injection causes only oil to be produced until about three-quarters (0.75) of void volume is injected at about one-third (0.3) of the extraction reagent of the present invention; Thereafter, the extraction reagent of the present invention in which the oil is dissolved is produced. Most of the oil present can be recovered when a three point (3.5) void volume is injected at approximately one point (1.5) of the reagent. This method recovers about 90% of the original oil in the reservoir out of the way. An embodiment of this method has also been experimentally proven as described in Example 22 below.

In a third in situ embodiment, the extraction reagent of the present invention is used to improve oil recovery from a reservoir of an oil reservoir containing very viscous oil, for example, "Orinoco Oil Belt" in Venezuela Lt; / RTI > The recovery factor for prior art recovery methods is low, ranging from 10 to 15% of the original oil in these reservoirs. The unexpected increase in the recovery efficiency from this reservoir with the injection of the turpentine extraction reagent of the present invention adopts a horizontal well for the machine and the injector and is further strengthened by periodic steam soaking of these aquifers .

The ultimate recovery of natural gas from a large gas reservoir can be increased by injecting the extraction reagent of the present invention into the reservoir. Gas production from such a gas reservoir often creates a dangerously large scale subsidence on the surface of the gas field, for example the "Groeningen" field in the Netherlands. As such, the reservoir pressure needs to be maintained by water injection. The water injected into the reservoir is low permeability and traps about 30% of the gas at the home pressure due to the two-phase flow of water and gas through the reservoir. With the injection of the extraction reagent of the present invention, the gas trapped in the reservoir is dissolved in the reagent and flows into the production chamber. The gas is recovered by separating the reagent and the gas from the ground, and the reagent is regenerated for reuse.

The extraction process of the present invention can be carried out after one or more known processes for facilitating oil production, for example, CO ₂ and natural gas injection and surfactant addition, have been carried out.

Exemplary methods for carrying out the invention Example

Coal

In a particular embodiment, the anthracite or bituminous coal is about 0.841 mm (20 mesh) ~ 0.149 mm (100 mesh) and ground to a size of the range, followed by about 1.O × 1O ⁵ Pascal (1 atm) ~ 2.O × 1O ⁵ Pascal by immersion in turpentine mixture under a pressure in the range (2.0 atm) dissolution and / or extraction, or can be liquefied. In certain other embodiments, the liquid turpentine is a natural, synthetic or mineral containing about 50 to 70% by volume of alpha-terpineol, about 20 to 40% by volume of beta-terpineol and about 10% Lt; / RTI > In certain embodiments, the phase of the ground anthracite coal or bituminous coal may be agitated by passing the turpentine liquid at a temperature in the range of 80 to about 130 DEG C, or possibly below the boiling point of the turpentine liquid. In certain other embodiments, the time for dissolution and / or extraction, i.e., liquefaction, can be within about 10 to 40 minutes. In certain embodiments, the contact time for extraction of the hydrocarbon-containing organic material from coal is no more than 5 minutes.

In some embodiments, lignite, brown coal or some other low grade coal is ground to a size ranging from about 0.419 mm (40 mesh) to 0.074 mm (200 mesh), followed by about 1.0 x 10 ⁵ is immersed in the liquid under turpentine Pascal (1 atm) ~ 2.O × 1O 5 pascal (2.0 atm) range of pressures may be dissolved and / or extracted, i.e. liquefied. In certain other embodiments, the turpentine liquid is a natural, synthetic or mineral containing about 70 to 90% by volume of alpha-terpineol, about 5 to 25% by volume of beta-terpineol and about 5% Lt; / RTI > In another embodiment, the phase of the abraded atom, lignite or any other lower coal may be agitated by passing the turpentine liquid at a temperature in the range of 80 to about 130 占 폚, or possibly below the boiling point of the turpentine liquid. In certain other embodiments, the time of dissolution and / or extraction, i.e., liquefaction, may be within about 20-60 minutes. In certain embodiments, the contact time for extraction of the hydrocarbon-containing organic material from coal is no more than 5 minutes.

Oil shell

In a particular embodiment, the oil shell is about 0.419 mm (40 mesh) - 0.074 mm (200 mesh) and ground to a size of the range, followed by about 1.O × 1O ⁵ Pascal (1 atm) - 2.O × 1O 5 Can be dissolved and / or extracted, i. E., Liquefied by immersion in a solution of turpentine under pressure in the Pascal range (2.0 atm). In certain other embodiments, the turpentine liquid is a natural, synthetic or mineral containing about 70 to 90% by volume of alpha-terpineol, about 5 to 25% by volume of beta-terpineol and about 5% Lt; / RTI > In certain other embodiments, the surface of the polished oil shell may be agitated by passing the turpentine liquid at a temperature in the range of 80 to about 130 占 폚, or possibly below the boiling point of the turpentine liquid. In another embodiment, the time of dissolution and / or extraction, i.e. liquefaction, can be within about 30-60 minutes. In certain embodiments, the contact time for extraction of the hydrocarbon-containing organic material from the oil shell is 5 minutes or less.

tar Sand

In a particular embodiment, the tar sand is pulverized to a size of about 25.4 mm (1 mesh) ~ 4.76 mm (4 mesh) range, is then about 1.O × 1O ⁵ Pascal (1 atm) ~ 2.O × 1O 5 Pascal (I. E., 2.0 atm) and can be dissolved and / or extracted, i. E., Liquefied. In another embodiment, the turpentine liquid comprises about 40-60 vol% alpha -terpineol, about 30-50 vol% beta-terpineol, 5 vol% alpha and / or beta-pinene, % ≪ / RTI > of other components. In yet another embodiment, the ground tar sand bed may be agitated by passing the turpentine liquid at a temperature in the range of about 60-90 DEG C, or possibly below the boiling point of the turpentine liquid. In other embodiments, the time of dissolution and / or extraction, i.e., liquefaction, can be within about 10-30 minutes. In certain embodiments, the contact time for extraction of the hydrocarbon-containing organic material from the tar sand is less than 5 minutes.

crude oil( Crude oil )

In certain embodiments, the hard and medium crude oil is produced at the home site for primary, secondary, or tertiary recovery by injecting a turpentine liquid of about one (1.0) to about five (5.0) . In another embodiment, a solution of turpentine between about 2.0 and 4.0 voids can be injected. In certain embodiments, the turpentine liquid comprises about 40-70 vol% alpha -terpineol, about 30-40 vol% beta-terpineol, about 10 vol% alpha and / or beta -pinene, and about 10 volumes % ≪ / RTI > of other components. In certain embodiments, the injection of the turpentine fluid may lead to the infusion of water at a pore volume of about one (1.0) to about three (3.0) pores.

In certain embodiments, the heavy and superheated oils can be removed from the underground reservoir for production, in-situ, for primary, secondary, or tertiary recovery by injecting a turpentine fluid of about one (1.0) to about five (5.0) voids. In another embodiment, a solution of turpentine between about 2.0 and 4.0 voids can be injected. In certain embodiments, the turpentine liquid comprises about 50-70 vol% alpha-terpineol, about 20-35 vol% beta-terpineol, about 10 vol% alpha and / or beta -pinene, and about 5 vol %, ≪ / RTI > other ingredients, and may be used in combination with steam injection.

In Figure 1 there is provided an apparatus for recovering hydrocarbon containing organic material from a tar sand. The apparatus 100 includes a turpentine fluid supply 102 which may optionally be coupled to a pump 104 for supplying a turpent fluid to the contact or extraction vessel 110. In certain embodiments, the turpentine fluid supply may comprise means for heating the fluid. In certain embodiments, the contact vessel may be a tilted rotary filter or trommel. The tar sand sample 106 is provided in a conveyor 108 or similar transport device for feeding tar sand to the inlet of the contact vessel 110. Optionally, the conveyor 108 may include a filter screen or similar separation device to prevent large particles from entering the process. The contact vessel 110 includes at least one inlet for the turpentine liquid to be introduced and contacted with the tar sand. The contact vessel 110 may include a plurality of trays or fins 114 designed to maintain or increase the contact between the tar sand and the turpentine liquid by maintaining the tar sand in the contact vessel for a specified period of time. In certain embodiments, the contact vessel may be a tilted rotary filter. The extraction mixture containing the hydrocarbon-containing organic material and the extraction liquid extracted from the tar sand is removed from the contact vessel 110 via the outlet 116 with the extraction mixture containing the extracted hydrocarbon- And a filter 118 for preventing the filter 118 from being damaged. The pump 120 may be coupled to the outlet 116 to assist in supplying the extraction mixture to the holding tank 220. Line 124 may be coupled to the holding tank to supply the extraction mixture for further processing. After extraction of the hydrocarbon-containing organic material, inorganic solids and other materials that are not dissolved in the turpentine liquid may be removed from the contact vessel via the second conveyor 126. Some of the solutions of terbinafine include, but are not limited to, solutions containing? -Terpineol and? -Terpineol.

2, there is provided an apparatus 200 for recovering a hydrocarbon-containing organic material from another sedimentary rock structure comprising an oil shell and a recoverable hydrocarbon material. The oil shell sample 202 is fed to a grinder or crusher 204 to reduce the size of the oil shell. Preferably, the grinder or grinder 204 reduces the oil shell to a diameter between about 0.074-0.42 mm. The pulverized oil shell may optionally be fed into a filter to ensure a constant / constant or suitable particle size. The first conveyor 206 provides particles from the grinder or grinder 204 to the contact vessel 208. The contact vessel 208 is optionally connected to a pump 210 for supplying the turpentine fluid to at least one inlet 212 connected to the contact vessel 208. In certain embodiments, the turpentine fluid supply may comprise means for heating the fluid. The contact vessel 208 may include a plurality of trays or fins 214 designed to hold the oil shell in the contact vessel for a specified period of time to increase or regulate the contact between the oil shell particles and the turpentine fluid. In certain embodiments, the contact vessel may be a tilted rotary filter or a trommel. The extraction mixture stream containing the hydrocarbon containing organic material recovered from the oil shell and the turpentine liquid is collected via outlet 216 and fed to holding tank 220. The pump 218 may optionally be coupled to the outlet 216 to assist in feeding the effluent mixture stream to the holding tank 122. The extraction mixture stream may be coupled to line 222 for feeding the extraction mixture stream in an additional process. The second conveyor 224 aids in the removal of inorganic and insoluble materials from the contact vessel. The solution of terbinafine may include, but is not limited to, alpha-terpineol and beta-terpineol.

3, there is provided an apparatus 300 for recovering a hydrocarbon-containing organic material from coal. The coal sample 302 is fed to a grinder or crusher 304 to reduce the size of the coal. Preferably, the grinder or grinder 304 reduces the coal to a diameter of about 0.074 to 0.84 mm, depending on the quality of the coal sample. In a particular embodiment, the grinder or grinder 304 may be a wet grinder. The pulverized coal may be fed as a filter to ensure a constant and / or suitable particle size. The pulverized coal is supplied to the first contact vessel 306. The first contact vessel 306 is optionally connected to the pump 310 and to the turbinic fluid supply 308 for supplying the turpent fluid to the first contact vessel 306. In certain embodiments, the turpentine fluid supply may comprise means for heating the fluid. The first contact vessel 306 includes mixing means 312 designed to agitate to improve or control contact between the solid coal particles and the liquid turpentine. The extraction mixture stream containing the hydrocarbon containing organic material recovered from the coal and the turpentine liquid is collected via the first contact vessel outlet 313 and fed to the second contact vessel 316. The pump 314 may optionally be coupled to the outlet 313 to assist in feeding the extraction mixture stream to the second contact vessel 316. The second contact vessel 316 may include a series of trays or pins 318 designed to increase or control the separation of solids and turpent fluid. Optionally, the second contact vessel 316 may be a tilted rotary filter or a trommel. The extraction mixture stream may be withdrawn from the second contact vessel outlet 320, which may optionally be coupled to the pump 322, to assist in the supply of the extraction mixture stream to the holding tank 324. The liquid coal and some turpent fluid present in the holding tank 324 may be fed to the liquid coal purification or other processing stage via line 326. The conveyor 328 can be coupled to the second contact vessel 316 for removal and recovery of solids as a by-product of the process. The solution of terbinafine may include, but is not limited to, alpha-terpineol and beta-terpineol. Apparatus 300 may also be used to treat advanced or lower oil shells.

FIG. 4 provides a process 400 for enhanced recovery of a hydrocarbon-containing organic material from a hydrocarbon-containing subsurface facility. The hydrocarbon containing reservoir 404 is shown positioned below the surface 402. Production set 406 is already in operation. Injection tab 408 is provided for injecting the turpentine fluid through line 410. The turbine solution not only facilitates the liquefaction, dissolution and / or extraction of the hydrocarbon containing organic material present in the reservoir, but also provides a driving force for pushing the hydrocarbon containing organic material in the facility towards the production well. The hydrocarbon product stream containing the injected turpine fluid is collected via line 412. The solution of terbinafine may include, but is not limited to, alpha-terpineol and beta-terpineol.

In certain embodiments, a turpentine liquid is provided to increase production from the wells, wherein at least 30% by volume of natural turpentine, synthetic turpentine, mineral turpentine, oil, alpha -pinene, beta -pinene, alpha -terpineol, Terpineol,? -Terpineol, terpene resin,? -Terpene,? -Terpene,? -Terpene and mixtures thereof. In another embodiment, the liquid turpentine comprises at least 30% by volume of geraniol, 3-karen, dipentene (p-menta-1,8-diene), nopol, pyrazine, 2-phenanhydroperoxide, P-menthol-8-ol,? -Terpinylacetate, citronellol, p-menth-8-yl acetate, 7-hydroxydihydrocitoloneol , Menthol, and mixtures thereof. In yet another embodiment, the liquid turpentine comprises at least 30 vol% anethole, camphene; p-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, aloocymene, aloocimene alcohol, 2- 8-epoxyoctane, camphor, citral, 7-methoxydihydro-citroneol, 10-camphorsulfonic acid, synthronelal, menton, and mixtures thereof.

In certain embodiments, the turpentine liquid comprises at least about 40% by volume of alpha -terpineol. In another embodiment, the liquid turpentine comprises at least about 25% by volume of? -Terpineol. In yet another embodiment, the turpentine liquid comprises at least about 40 vol% alpha -terpineol and about 25 vol% beta-terpineol. In another embodiment, the liquid turpentine comprises at least about 50% alpha-terpineol and in certain embodiments beta-terpineol. In certain embodiments, the turpentine liquid comprises at least 20% by volume of? -Terpineol. In certain embodiments, the turpentine liquid comprises 50-70 vol% alpha-terpineol and about 10-40 vol% beta-terpineol.

In another aspect, a process is provided for performing enhanced recovery operations to increase production from an underground hydrocarbon-containing reservoir, the process comprising injecting a turpentine liquid into the reservoir through the injection well to stimulate production of the hydrocarbon- . The turpentine liquid may be at least one selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, oil, alpha -pinene, beta -pinene, alpha -terpineol, beta terpineol, y- terpineol, terpene resin, , gamma-terpene, and mixtures thereof. In another embodiment, the turpentine liquid is selected from the group consisting of geraniol, 3-karen, dipentene (p-menta-1,8-diene), nopol, 8-yl acetate, 7-hydroxydihydrocituronol, menthol, and their derivatives, such as p-menthol-8-ol, And mixtures thereof. In another embodiment, the liquid of the turpentine is anethole, camphene; p-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, aloocymene, aloocimene alcohol, 2- At least one compound selected from 8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, synthronelal, menton, and mixtures thereof. The hydrocarbon-containing organic material production stream comprising the turpentine liquid and the recovered hydrocarbons is recovered from the production process associated with the hydrocarbon-containing reservoir. The hydrocarbon-containing organic material production stream may be separated into a recovered hydrocarbon stream and a turpentine liquid recovery stream. In certain embodiments, an additional method may further comprise injecting the turpentine fluid recovery stream into the infusion well.

In another aspect, a method is provided for performing enhanced recovery operations to increase production from a hydrocarbon facility below a hydrocarbon containing surface. The method includes injecting a solution of the turpentine into the facility through the injection well. In certain embodiments, the turpentine liquid comprises at least 40 vol% alpha -terpineol and at least about 10 vol% beta-terpineol. The turpentine liquid dissolves, extracts and / or extracts the hydrocarbon-containing material from the facility, which is subsequently recovered from the facility along with the liquid turpentine through the production line. In certain embodiments, the method also includes separating the turbine solution and the hydrocarbon. In yet another embodiment, the method further comprises regenerating the turpentine fluid by injection. In certain embodiments, alpha -terpineol is present in an amount of about 40-70 vol%. In certain embodiments, alpha -terpineol is present in an amount of at least 70% by volume. In another embodiment,? -Terpineol is present in an amount of about 10-40% by volume. In another embodiment, the liquid turpentine further comprises less than about 10% by volume of gamma-terpineol. In another embodiment, the turpentine liquid may comprise up to about 25% by volume of an organic solvent selected from methanol, ethanol, propanol, toluene and xylene. This method is useful for the recovery of hydrocarbon-containing organic materials during primary, secondary and tertiary recovery operations, including after secondary recovery operations involving water injection.

In another embodiment, a turpentine liquid is provided for recovering hydrocarbon containing organic material from a tar sand. In one embodiment, the turpentine liquid comprises at least about 30 vol% alpha -terpineol and at least about 25 vol% beta-terpineol. In yet another embodiment, the turpentine liquid comprises about 30-70 vol% alpha -terpineol, about 25-55 vol% beta-terpineol, about 10 vol% alpha-terpene, and about 10 vol% Of [beta] -terpene.

In another aspect, a turpentine liquid is provided for recovering a hydrocarbon-containing organic material from an advanced coal source, such as anthracite or bituminous coal, for example. In one embodiment, the liquid turpentine comprises at least about 45 vol% alpha -terpineol and at least about 15 vol% beta-terpineol. In yet another embodiment, the turpentine liquid comprises about 45-80 vol% alpha -terpineol, about 15-45 vol% beta-terpineol, about 10 vol% alpha-terpene, and about 10 vol% Of [beta] -terpene.

In another embodiment, a turpentine liquid is provided for recovering hydrocarbon containing organic material from a lower coal source. In one embodiment, the liquid turpentine comprises at least about 60 vol% alpha -terpineol and about 30 vol% beta-terpineol. In yet another embodiment, the turpentine liquid comprises about 60-95 vol% alpha -terpineol, about 30 vol% beta -terpineol, about 5 vol% alpha-terpene, and about 5 vol% beta-terpene.

In yet another embodiment, a turpentine liquid is provided for recovering hydrocarbon containing organic material from the oil shell. The oil shell used herein refers to any sedimentary rock that generally contains bituminous materials. In one embodiment, the liquid turpentine comprises at least about 60 vol% alpha -terpineol and up to about 30 vol% beta-terpineol. In yet another embodiment, the turpentine liquid comprises about 60-95 vol% alpha -terpineol, about 30 vol% beta -terpineol, about 5 vol% alpha-terpene, and about 5 vol% beta-terpene.

In another embodiment, a turpentine liquid is provided for recovering hydrocarbon-containing organic materials from light and heavy oils. In one embodiment, the turpentine liquid comprises at least about 40-70% by volume of alpha -terpineol and at least about 30-40% by volume of beta-terpineol. In yet another embodiment, the turpentine liquid comprises about 40-70 vol% alpha -terpineol, about 30-40 vol% beta-terpineol, about 10 vol% alpha-terpene, and about 10 vol% Of [beta] -terpene.

In another embodiment, a turpentine liquid is provided for recovering hydrocarbon-containing organic materials from middle and remaining heavy oil. In one embodiment, the liquid turpentine comprises at least about 50-70% by volume of alpha -terpineol and at least about 30-40% by volume of beta-terpineol. In yet another embodiment, the turpentine liquid comprises about 50-70 vol% alpha -terpineol, about 30-40 vol% beta-terpineol, about 10 vol% alpha-terpene, and about 10 vol% Of [beta] -terpene.

In yet another aspect, a method is provided for recovering hydrocarbon containing organic material from a tar sand. The method includes mining in a tar-sand-rich facility to provide a tar-sand sample, wherein the tar-sand includes recoverable hydrocarbon-containing organic material and residual inorganic and insoluble material. The tar sand sample is fed into the contact vessel, which includes at least one inlet for supplying the turbine fluid for recovery of the hydrocarbon from the tar sand. The tar sand sample is contacted with the turpentine liquid to extract the hydrocarbon containing organic material from the tar sand to produce the residual material and the extraction mixture. The extraction mixture comprises a turpentine liquid and a recovered hydrocarbon containing organic material, wherein the residual material is separated from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recovery stream. In certain embodiments, the method includes regenerating the turpentine fluid recovery stream with a contact vessel. In another embodiment, the extraction mixture may be separated by distillation to produce a hydrocarbon product stream and a turpentine liquid recovery stream.

In certain embodiments, the turpentine liquid may comprise alpha-terpineol. In another embodiment, the liquid turpentine comprises at least about 40 vol% alpha -terpineol and 10-40 vol% beta-terpineol. In certain embodiments, 0.5 to 4 equivalents of a solution of turpentine is used to contact the tar sand and recover the hydrocarbons. In certain embodiments, 0.5 to 2.0 equivalents of a solution of the turpentine is used to contact the tar sand and recover the hydrocarbons.

In yet another aspect, a method is provided for recovering a hydrocarbon-containing organic material from a hydrocarbon-rich oil shell. The method comprises producing a hydrocarbon-containing oil shell comprising a recoverable hydrocarbon material and an inorganic or insoluble material mined from a rock facility comprising a hydrocarbon-containing organic material. The oil shell is ground to produce a crushed hydrocarbon-containing oil shell. The comminuted hydrocarbon-containing oil shell is then filtered through a filter screen to prevent or control excessively large particles from being fed to the extraction process. The comminuted hydrocarbon-containing oil shell is conveyed to a contact vessel, which comprises at least one inlet for feeding the turpentine liquid for recovery of hydrocarbon from the comminuted hydrocarbon-containing oil shell. The comminuted hydrocarbon-containing oil shell is contacted with the turpentine liquid to extract the hydrocarbon-containing organic material from the comminuted hydrocarbon-containing oil shell to produce an extract mixture comprising inorganic solids and a turbine liquid and recovered hydrocarbons and inorganic solids. Inorganic and insoluble materials are recovered from the extraction mixture and the recovered hydrocarbons are separated from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recovery stream. In certain embodiments, the turpentine fluid recovery stream is recycled to the contact vessel. In another embodiment, the comminuted hydrocarbon-containing oil shell has an average particle size of a diameter of about 0.42 mm or less. In another embodiment of the method for recovering a hydrocarbon-containing organic material from an oil shell, the turpent fluid is selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, oil feed, a-pinene,? -Pinene,? -Terpineol, , At least one compound selected from γ-terpineol, terpene resin, α-terpene, β-terpene, γ-terpene and mixtures thereof. In another embodiment, the turpentine liquid is selected from the group consisting of geraniol, 3-karen, dipentene (p-menta-1,8-diene), nopol, 8-yl acetate, 7-hydroxydihydrocituronol, menthol, and their derivatives, such as p-menthol-8-ol, And mixtures thereof. In another embodiment, the turpent fluid is anethole, camphene; p-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, aloocymene, aloocimene alcohol, 2- At least one compound selected from 8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, synthronal, menthone and mixtures thereof. In certain embodiments, the turpentine liquid may comprise alpha-terpineol. In another embodiment, the liquid turpentine comprises at least about 40 vol% alpha -terpineol and 10-40 vol% beta-terpineol. In certain embodiments, 0.5 to 4 equivalents of the turpentine liquid is used to contact the oil shell and recover the hydrocarbon-containing organic material. In certain embodiments, 0.5 to 2.0 equivalents of the turbine fluid is used to contact the oil shell and recover the hydrocarbons.

In yet another aspect, a method is provided for recovering hydrocarbon containing organic material from a facility below the surface of a coal-rich earth. This method produces coal by mining from a facility below the surface of the earth, where the coal contains recoverable hydrocarbon material and inorganic or insoluble material. The coal is polished to produce pulverized coal and filtered to provide a sample of a certain or desirable size. The pulverized coal is conveyed to a contact vessel, wherein the contact vessel comprises at least one inlet for feeding the turpentine liquid for recovery of hydrocarbon from the pulverized coal, wherein the pulverized coal is in contact with the turpentine liquid to produce an extract mixture and an inorganic solids The hydrocarbon is extracted from the pulverized coal. The extraction mixture comprises a turpentine liquid and recovered hydrocarbons. The inorganic and insoluble materials are separated from the extraction mixture and the recovered hydrocarbons are separated from the turpentine liquid to produce a liquid coal product stream and a turpentine liquid recovery stream. In certain embodiments, the method further comprises recirculating the turpentine fluid recovery stream to the contact vessel. In another embodiment, the liquid coal product stream is fed to a liquid coal refinery. In certain embodiments, the coal sample comprises a lower coal having an average particle size of about 0.42 mm or less. In certain embodiments, the coal sample comprises high grade coal having an average particle size of about 0.84 mm or less.

In another embodiment of the method for recovering hydrocarbon-containing organic materials from coal, the turpentine liquid may be selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, oil feed, a-pinene, , At least one compound selected from γ-terpineol, terpene resin, α-terpene, β-terpene, γ-terpene and mixtures thereof. In another embodiment, the turpentine liquid is selected from the group consisting of geraniol, 3-karen, dipentene (p-menta-1,8-diene), nopol, 8-yl acetate, 7-hydroxydihydrocituronol, menthol, and their derivatives, such as p-menthol-8-ol, And mixtures thereof. In another embodiment, the turpent fluid is anethole, camphene; p-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, aloocymene, aloocimene alcohol, 2- At least one compound selected from 8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, synthronal, menthone and mixtures thereof. In certain embodiments, the turpentine liquid comprises at least 60% by volume of alpha -terpineol. In certain embodiments, the turpentine liquid comprises at least about 45 vol% alpha -terpineol and at least about 15 vol% beta-terpineol. In certain other embodiments, the turpentine liquid comprises at least 60 vol% alpha -terpineol and no more than 30 vol% beta-terpineol. In a specific embodiment, 0.5-4 equivalents of the turbine fluid is used to contact the oil shell and recover the hydrocarbon-containing organic material. In certain embodiments, 0.5 to 2.0 equivalents of the turpentine liquid is used to contact the oil shell and recover the hydrocarbon-containing organic material.

In yet another aspect, a system for recovering hydrocarbon containing organic material from a tar sand is provided. The tar sand recovery system includes a tank for supplying the turpentine liquid and a contact vessel including at least one inlet for supplying the turpentine fluid and at least one outlet for withdrawing the extraction mixture from the contact vessel. The system also includes a first conveyor for feeding the tar sand to the contact vessel. A holding tank is provided that includes a line for connecting the holding tank to the contact vessel, the line connecting the holding tank to the contact vessel includes a filter to prevent passage of solids into the holding tank. The system also includes a second conveyor for recovery and transport of solids.

In one embodiment, the contact vessel is a rotary bevel filter comprising a series of pins or trays for separating and / or conditioning the tar sand. In yet another embodiment, a pin or tray is provided to increase or adjust the contact time between the tar sand and the turpentine fluid. In certain embodiments, the turpentine liquid may comprise about 30-70 vol% alpha-terpineol and about 25-55 vol% beta-terpineol.

In yet another aspect, a system for recovering hydrocarbon containing organic material from an oil shell is provided. The system includes a tank for supplying the turpentine fluid and a grinder for crushing the oil shell with a reduced particle size. A contact vessel is provided, comprising at least one inlet for introducing a liquid of turpentine, at least one inlet for receiving a crushed oil shell, at least one outlet for withdrawing solids from the contact vessel, At least one outlet for withdrawing the fluid. The first conveyor is provided to supply the crushed oil shell into the contact vessel. The system is provided with a holding tank comprising a line for connecting the holding tank to the contact vessel, the line comprising a filter for preventing the passage of solids into the holding tank; And a second conveyor for recovering the solids. In certain embodiments, the system further comprises a line for supplying a reaction mixture comprising a hydrocarbon and a turpentine liquid recovered to the refinery for further separation and / or treatment. In certain embodiments, the turpentine liquid may comprise alpha-terpineol. In certain embodiments, the turpentine fluid may comprise about 60-95% by volume of alpha -terpineol and up to about 30% by weight of beta-terpineol. In another embodiment, the liquid turpentine may comprise about 70-90% by volume of alpha -terpineol and about 5-25% by weight of beta-terpineol.

In yet another aspect, a system is provided for recovering hydrocarbon containing organic material from coal. The system includes a tank for supplying the turpentine liquid and a grinder for crushing the coal with a reduced particle size. A contact vessel is provided which includes at least one inlet for introducing the liquid of the turbine and at least one outlet for withdrawing solids and liquid from the contact vessel. The contact vessel includes stirring means for thoroughly mixing the turpentine liquid and the ground coal. A separator is provided for separating solids and liquids, the separator comprising a line for connecting the inlet of the separator to the inlet, the outlet and the outlet of the contact vessel. The system includes a holding tank, which includes a line connecting the holding tank to the separator, which may include a filter to prevent passage of solids into the holding tank.

In certain embodiments, the system includes a filter to selectively prevent particles having an average diameter greater than about 0.85 mm from entering the contact vessel. In certain other embodiments, the system further comprises a line for supplying the liquid coal product to the refinery for further processing. In a particular embodiment, the system includes a first conveyor for supplying pulverized coal to a contact vessel. In another embodiment, the system further comprises a second conveyor for removing solids from the separator. In certain embodiments, the turpentine liquid may comprise alpha-terpineol. In embodiments involving the recovery of hydrocarbons from high grade coal, the turpentine liquid may comprise about 45-80% by volume of alpha-terpineol and about 15-45% by weight of beta-terpineol. In embodiments involving the recovery of hydrocarbons from lower coal, the turpentine liquid may comprise about 60-95% by volume of alpha -terpineol and about 0-30% by weight of beta-terpineol.

In yet another aspect, a method is provided for optimizing a turpentine liquid for extraction of a hydrocarbon-containing organic material from a hydrocarbon-containing material. Generally, the method comprises providing a sample of a hydrocarbon-containing material and analyzing the hydrocarbon material to determine the shape of the hydrocarbon being extracted. There is provided a composition for the extraction of a hydrocarbon-containing organic material from a hydrocarbon material, the composition being a function of the size and form of the particulate hydrocarbon material. Generally, the composition comprises at least about 40% by volume of alpha -terpineol and at least about 10% by volume of beta-terpineol. The amount of? -Terpineol and? -Terpineol in the composition is adjusted based on the above parameters. In general, the process described above provides an excellent starting point for the determination of the desired composition for the extraction of various hydrocarbon-containing materials, but it has been found that, in other hydrocarbon-containing materials and under certain working conditions, a series of statistically- Experiments can be performed to determine the optimal composition of the liquid turpentine.

As shown in Table 1, the specific composition for extraction, liquefaction and / or dissolution of the hydrocarbon-containing organic material from the tar sand varies depending on the particle size. In a particular embodiment, the method for preparing a turpentine liquid for extracting a hydrocarbon-containing organic substance from a tar sand comprises the step of contacting the amount of? -Terpineol and? -Terpineol in the composition as a function of the size of the hydrocarbon- . ≪ / RTI > In another embodiment, when the hydrocarbon containing organic particulate material comprises a lower coal or oil shell, the amount of a-terpineol in the turbine fluid is increased and the amount of beta-terpineol in the turbine fluid is reduced. In another embodiment, when the hydrocarbon containing organic particulate material comprises a tar sand, the amount of a-terpineol in the turbine fluid is reduced and the amount of beta-terpineol in the turbine fluid is increased. In another embodiment, when the hydrocarbon containing organic particulate material comprises a tar sand and the mean diameter of the particulate material is less than or equal to about 4.76 mm, the amount of a-terpineol in the turpentic fluid is reduced and the amount of beta-terpineol The amount is increased. In another embodiment, the amount of alpha-terpineol in the turpentine fluid increases when the hydrocarbon-containing organic particulate material comprises a tar sand and the mean diameter of the particulate material is greater than about 1 inch (1 mesh) The amount of terpineol decreases.

Composition for extraction of tar sand based on particle size Particle size (Mesh / mm diameter) alpha-terpineol beta-terpineol α- / β-terpineol Etc ≪ 4 Mesh (4.76 mm) 30-50% vol 35-55% vol 10% vol 5% vol 1mesh (1 inch) ~
4mesh (4.76mm) 40-60% vol 30-50% vol 10% vol 5% vol > 1mesh (1 inch) 50-70% vol 25-45% vol 10% vol 5% vol

Similar to those presented above for the extraction of tar sands, the composition for extraction, liquefaction and / or dissolution of coal, as shown in Tables 2 and 3, depends on the particle size and the quality of the coal being extracted. In an embodiment of the method for preparing a turbine solution for extracting a hydrocarbon containing organic material, the hydrocarbon-containing material comprises anthracite coal, bituminous coal or other fine coal, and the mean diameter of the particulate material is less than about 0.15 mm, the amount of? -terpineol is reduced, and the amount of? -terpineol in the solution of terbinafine is increased. In another embodiment, when the hydrocarbon-rich particulate material comprises anthracite, bituminous coal or other fine coal, and the average diameter of the particulate material is greater than about 0.84 mm, the amount of a-terpineol in the turbine fluid is reduced, - The amount of terpineol is increased. In yet another embodiment, if the hydrocarbon-rich particulate material comprises lower coal and the average diameter of the particulate material is less than about 0.074 mm, the amount of alpha-terpineol in the turbine fluid increases and the amount of beta-terpineol . In another embodiment, if the hydrocarbon-rich particulate material comprises lower coal and the average diameter of the particulate material is greater than about 0.42 mm, the amount of a-terpineol in the turbine fluid increases, .

Composition for the extraction of fine coal based on particle size Particle size
(Mesh / mm diameter) alpha-terpineol beta-terpineol α- / β-terpineol Etc ≪ 100mesh (0.149 mm) 45-65% vol 35-45% vol 10% vol 0% vol 20 mesh (0.841 mm)
100 mesh (0.149 mm) 50-70% vol 20-40% vol 10% vol 0% vol > 20mesh (0.841mm) 60-80% vol 15-35% vol 10% vol 0% vol

Composition for extraction of low grade coal based on particle size Particle size
(Mesh / mm diameter) alpha-terpineol beta-terpineol α- / β-terpineol Etc ≪ 200mesh (0.074mm) 60-80% vol 10-30% vol 5% vol 0% vol 40 mesh (0.420 mm)
200mesh (0.074mm) 70-90% vol 5-25% vol 5% vol 0% vol > 40mesh (0.420mm) 75-95% vol 0-20% vol 5% vol 0% vol

Similar to those presented above for the extraction of tar sands, the composition for extraction, liquefaction and / or dissolution of the oil shell, as shown in Table 4, depends on the particle size. In an embodiment of the method for preparing a composition for the extraction of hydrocarbon-containing organic materials, the hydrocarbon-rich particulate material comprises an oil shell and the mean diameter of the particulate material is less than about 0.074 mm, The amount is decreased, and the amount of? -Terpineol in the solution of the terbinine is increased. In another embodiment, if the hydrocarbon-rich particulate material comprises an oil shell and the average diameter of the particulate material is greater than about 0.42 mm, the amount of alpha-terpineol in the turbine fluid increases and the amount of beta-terpineol The amount decreases.

Composition for extraction of oil shells based on particle size Particle size
(Mesh / mm diameter) alpha-terpineol beta-terpineol α- / β-terpineol Etc ≪ 200mesh (0.074mm) 60-80% vol 10-30% vol 5% vol 0% vol 40 mesh (0.420 mm)
200mesh (0.074mm) 70-90% vol 5-25% vol 5% vol 0% vol > 40mesh (0.420mm) 75-95% vol 0-20% vol 5% vol 0% vol

Extraction of crude oil likewise depends on the type of crude oil to be extracted, liquefied and / or dissolved. As shown in Table 5, formulations for extraction, liquefaction and / or dissolution of crude oil are a function of particle size and quality of crude oil density to be extracted. The method provides a turpentine liquid composition comprising at least 50 vol% alpha -terpineol and at least 20 vol% beta-terpineol; Terpineol and beta-terpineol in the turpentine liquid composition based on the density of the liquid hydrocarbons to be extracted. In one embodiment, when the API gravity of the liquid hydrocarbon being extracted is greater than or equal to about 22 degrees, the amount of alpha-terpineol in the turbine solution is reduced and the amount of beta-terpineol is increased. In yet another embodiment, when the API gravity of the liquid hydrocarbon being extracted is less than about 22, the amount of alpha-terpineol in the liquid of the turbine is increased and the amount of beta-terpineol is reduced. The diesel used herein has an API of at least about 31 °, a middle crude oil having an API of 22-31 °, a heavy oil having an API of 10-22 °, and a superheated oil having an API of about 10 ° or less.

Composition for extraction of crude oil based on API density Crude oil type alpha-terpineol beta-terpineol α- / β-terpineol Etc Light / medium crude oil
(API over 22 °) 40-70% vol 30-40% vol 10% vol 10% vol Heavy / Ultra heavy oil
(API below 22 °) 50-70% vol 25-35% vol 10% vol 5% vol

In yet another aspect, a method is provided for making a turpentine liquid for enhancing the recovery of liquid hydrocarbon containing organic material from a facility below the surface of the earth. The method provides a composition comprising at least 50% by volume of alpha -terpineol and at least 20% by volume of beta-terpineol; Terpineol and beta-terpineol in the composition based on the geometric characteristics of the facility below the surface of the earth.

In another embodiment, there is provided a composition for cleaning and / or recovering hydrocarbons from a liquid hydrocarbon-containing vessel comprising natural turpentine, synthetic turpentine, mineral turpentine, oil, alpha-pinene, beta -pinene, alpha-terpine At least one compound selected from the group consisting of β-terpineol, γ-terpineol, terpene resin, α-terpene, β-terpene, γ-terpene and mixtures thereof. The compositions for cleaning and / or recovering hydrocarbons can be selected from the group consisting of geraniol, 3-karen, dipentene (p-menta-1,8-diene), nopol, Pyranol, dihydroimacenol, isobonole, p-menth-8-ol, a-terpinyl acetate, citroneol, p-menth-8-yl acetate, 7-hydroxydihydrocituronol, menthol And mixtures thereof. In another embodiment, the composition for cleaning and / or recovering hydrocarbons includes anethole, camphene; p-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, aloocymene, aloocimene alcohol, 2- At least one compound selected from 8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, synthronal, menthone and mixtures thereof. In one embodiment, the composition comprises at least one compound from the following: alpha-pinene, beta-pinene, alpha-terpineol, and beta-terpineol. In another embodiment, the composition comprises at least 25% by volume of alpha-terpineol or beta-terpineol.

In another aspect, a method is provided for cleaning and / or recovering hydrocarbons from a liquid hydrocarbon containing vessel. The method comprises contacting the interior of the vessel with a hydrocarbon cleaning compound comprising at least one compound selected from alpha -pinene, beta-pinene, alpha -terpineol, and beta -terpineol to produce a mixture, The mixture comprises a liquid hydrocarbon residue and a hydrocarbon cleaning composition. This mixture is withdrawn from the vessel and removed. In certain embodiments, the cleaning composition comprises at least 25% by volume of alpha-terpineol or beta-terpineol. In certain other embodiments, the cleaning composition comprises at least 25% by volume of alpha -terpineol and at least 25% by volume of beta-terpineol.

Yes

Example 1

In this example, coal from the Pittsburgh paddle located in Washington, Pennsylvania was liquefied with the reagent alpha-terpineol. A coal sample was obtained from Coal Bank at Pensylvania State University, which provided the following proximate analysis: 2.00 wt% intact moisture, 9.25 wt% dry Ash, 38.63% dry volatile matter and 50.12% dry fixed carbon. The particle size of the coal sample was about 60 mesh. About 60 grams of alpha-terpineol was slowly added to a sample of about 30 grams of coal placed in the extraction vessel to give a reagent to sample ratio of 2: 1. An extraction vessel containing a plug, but not completely sealed, containing the resulting mixture of? -Terpineol and coal was kept at a constant temperature of about 96 占 폚 and continued to stir. α- Terre without boiling to terpineol, it was maintained the pressure in the extraction vessel to the slightly lower than the atmospheric pressure of about lO l.Ol × ⁵ Pascal (1 atm). After 30 minutes, the mixture was filtered, and the remaining coal particles on the filter were washed with ethanol and dried to constant weight. Based on the weight loss, the conversion of the coal sample, i.e., the degree of liquefaction, was determined to be about 68 wt%.

Example 2

This example is the same as Example 1 in all respects except for two. As in Example 1, the temperature was maintained at about 96 for 30 minutes and then the extraction vessel containing the coal sample and a-terpineol was maintained at a temperature of about 135 DEG C for an additional time of about 30 minutes. It was maintained at a pressure of the extraction container to slightly less than atmospheric pressure of about lO l.Ol × ⁵ Pascal (1 atm). The conversion of the coal sample, i.e. the degree of liquefaction, was determined to be about 70 wt.%.

Example 3

The coal samples used were from the same circle with the same approximate analytical values as those used in the above two examples. About 31 grams of alpha-terpineol was added to about 31 grams of coal sample in the extraction vessel. The mixture was maintained at about 96 DEG C for 30 minutes and at atmospheric pressure slightly lower than about 1.0 lO < ⁵ > pascals (1 atm). The degree of conversion, i.e. liquefaction, of the coal sample was determined to be about 71% by weight after weighing the sample after filtration, washing and drying, as was done in the two examples above.

Example 4

This example is the same as Example 3, except that about 30 wt% alpha -terpineol is replaced with hexane to provide a reagent comprising 70 wt% alpha-terpineol and 30 wt% hexane. This reduced the conversion, i. E., The degree of liquefaction, to about 1.3% by weight.

Example 5

In this example, the raw and coal industrial analyzes of the coal samples and the experimental conditions such as temperature, pressure and reagent to sample ratios were the same as in Example 3. However, the extraction time was reduced from about 30 minutes to about 20 minutes. In addition, substituting about 30 wt% alpha -terpineol with 1-butanol provided a reagent comprising 70 wt% alpha-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 wt.%.

Example 6

This example is identical to Example 3 in terms of the temperature, pressure and time of the source and coal industrial analysis and extraction of the coal sample. However, the amount of coal sample used was about 25 grams and the reagent contained about 24 grams (80 weight percent) By weight of alpha -terpineol and about 6 grams (20% by weight) of xylene to 70% by weight of alpha-terpineol and 30% by weight of xylene. The liquefied coal was about 10.0 grams, corresponding to a conversion of about 40 wt%.

Example 7

In this example, coal from Wyodak seam, located in Campbell County, Wyoming, was liquefied with reagent alpha-terpineol. Coal samples were obtained from Coal Bank, Pennsylvania State University, which provided the following coal industrial analysis: 26.30 wt% intact moisture, 7.57 wt% dry ash, 44.86 wt% % Dry volatiles and 47.57% dry fixed carbon. The particle size of the coal sample was about 20 mesh. About 60 grams of alpha-terpineol was slowly added to a sample of about 30 grams of coal placed in the extraction vessel to give a reagent to sample ratio of 2: 1. An extraction vessel containing a plug, but not completely sealed, containing the resulting mixture of? -Terpineol and coal was kept at a constant temperature of about 96 占 폚 and continued to stir. α- Terre without boiling to terpineol, it was maintained the pressure in the extraction vessel to the slightly lower than the atmospheric pressure of about lO l.Ol × ⁵ Pascal (1 atm). After 30 minutes, the mixture in the extraction vessel was filtered, and the remaining coal particles on the filter were washed with ethanol and dried to constant weight. Based on the weight loss, the conversion of the coal sample, i. E., The degree of liquefaction, was determined to be about 75% by weight.

Example 8

The experiment in this example was carried out under the same conditions as the above example except for one. Instead of about 60 grams performed in the above example, about 15 grams of alpha-terpineol was added to about 30 grams of coal samples to give a reagent to coal ratio of 0.5 to 1. The conversion of the coal sample, i.e., the degree of liquefaction, was reduced from about 75 wt% to about 69 wt% obtained in the above example.

Example 9

In this example, about 3 grams of oil shell from the Green-river region of Colorado was dissolved in about 9 grams of alpha-terpineol, resulting in a reagent-to-sample ratio of 3 to 1, (Organic material) and / or bitumen (organic material). The organic carbon content, including both volatile and stationary carbon, was determined to be about 22.66 wt% by a certified analysis company. Two experiments were performed in the oil shell, the sample having a particle size of 60 mesh under slightly lower than room temperature and atmospheric pressure and about 25 ℃ l.Ol × lO ⁵ Pascal (1 atm), respectively. The weight loss of the sample was measured by filtration, washing with ethanol and weighing after drying. This loss was about 9% by weight after about 30 minutes and about 17% by weight after about 45 minutes. From this weight loss, the conversion of the organic material, i.e., the kerogen and / or bitumen, i.e. the degree of extraction of the organic material, was calculated to be about 40% by weight for the former and about 75% by weight for the latter.

Example 10

This example was repeated with the exception that a single experiment lasting about 15 minutes was carried out at a temperature of about 96 占 폚 instead of about 25 占 폚. The weight loss of the oil shell sample was about 12% by weight, corresponding to a conversion of about 53% by weight of the kerogen (organic material), i. E.

Example 11

In this example, the bitumen (organic material) in tar sands from Alberta, Canada was dissolved and extracted with commercial grade synthetic turpentine. I got a tar sand sample from the Alberta Research Council and provided the following industrial analysis; 84.4 wt% dry solids, 11.6 wt% dry bitumen and 4.0 wt% intact moisture. 30 grams of synthetic turpentine was added slowly to a sample of about 15 grams of tar sand in a stoppered but not fully sealed extraction vessel to give a reagent to sample ratio of about 2 to 1 by weight. This extraction vessel containing the resulting mixture of synthetic turpentine and tar sand was kept at a constant temperature of about 96 캜 and continued to stir. Without boiling synthetic turpentine, it was maintained in the extraction vessel to the pressure of slightly below atmospheric pressure of less than about lO l.Ol × ⁵ Pascal (1 atm). After about 20 minutes, the mixture in the extraction vessel was filtered, and the remaining solids (tar sand) on the filter was washed with ethanol and dried to constant weight. The conversion of bitumen from tar sand samples, i. E., The degree of extraction, was determined to be about 100% by weight based on weight loss.

Example 12

In this example, about 60 grams of tar sand samples from the same source having the same approximate analytical values as in the above example were mixed with about 60 grams of alpha-terpineol instead of commercial grade synthetic turpentine containing alpha-terpineol . The resulting reagent to sample ratio was 1 to 1 instead of 2 to 1 in the above example. A test under a temperature slightly lower than the atmospheric pressure and about lO l.Ol × ⁵ Pascal (1 atm) for 96 ℃ continued for about 30 minutes. The degree of conversion, i.e., the degree of extraction of the organic component (organic material) in the tar sand sample, was determined to be about 100% by weight.

Example 13

In this example, about 60 grams of tar sand samples from the same circle having the same approximate analytical values as in the above example were extracted with about 60 grams of commercial grade, synthetic turpentine. The resulting reagent to sample ratio was thus 1: 1. A test under a temperature slightly lower than the atmospheric pressure and about lO l.Ol × ⁵ Pascal (1 atm) for 96 ℃ continued for about 30 minutes. The conversion of bitumen (organic material) in the tar sand sample, i.e. the degree of extraction, was determined to be about 70 wt.%.

Example 14

The experiment in this example was the same as Example 8 in all respects except that the reagent-to-sample ratio was reduced from about 2: 1 to about 0.5: 1: about 60 grams of tar sand samples were mixed with about 30 grams Of synthetic turpentine. The conversion of bitumen (organic material), that is, the degree of extraction, was reduced from about 100 wt% to about 70 wt% obtained in Example 9.

Example 15

The experiment in this example was repeated with α-terpineol instead of the commercial grade synthetic turpentine as in the above example. The conversion of the bitumen (organic material) in the tar sand, i.e. the degree of extraction, was about 70% by weight as in the above example.

Example 16

The experiment of this example as a tar sand samples from the same source with the same approximate value analysis in the above example of a tar sands was carried out under atmospheric pressure a little lower than about lO l.Ol × ⁵ Pascal (1 atm). Approximately 60 grams of commercial grade synthetic turpentine was added to approximately 60 grams of tar sand samples to yield a reagent to sample ratio of approximately one to one. The temperature of the sample and commercial grade synthetic turpentine was maintained at about 65 占 폚 for 30 minutes and then cooled to about 15 占 폚 in about 5 minutes. The tar sand samples were subsequently filtered, washed, dried and weighed. Based on the weight loss, the conversion of bitumen (organic material) in the tar sand sample, i.e. the degree of extraction, was determined to be about 70% by weight.

Example 17

The experiment in this example was repeated with α-terpineol instead of the commercial grade synthetic turpentine as in the above example. The conversion of the bitumen (organic material), i. E. The degree of extraction, was increased from about 70% to about 90% by weight of the above example.

Example 18

In this example, a temperature of about 96 ℃ the tar sands sample of about 30 grams from the same circle having the same approximate analytical values as in Examples 11 to 17 under atmospheric pressure slightly lower than about lO l.Ol × ⁵ Pascal (1 atm) Was extracted with a solution containing 20 grams (80 wt.%) Of alpha -terpineol and about 5 grams (20 wt.%) Of toluene. The experiment time (reaction or extraction time) was about 30 minutes. The weight loss of the sample was about 10.2 grams. From this weight loss, the conversion of bitumen (organic material), i. E. The degree of extraction, was calculated to be about 33% by weight.

Example 19

All of the various amounts to a temperature of about 15 ℃ under slightly lower than the atmospheric pressure of about three l.Ol the tar sands sample × lO ⁵ Pascal (1 atm) from the same source with the same industrial analysis and all the clerical script of a tar sands α -Terpineol and ethanol. ≪ / RTI > The experiment time (reaction or extraction time) was about 15 minutes for each tar sand sample. The first sample was extracted with a mixture comprising about 0 grams (0 weight percent) of alpha-terpineol and about 15 grams (100 weight percent) of ethanol, i.e., pure ethanol. The second sample was extracted with a mixture containing about 7.5 grams (50 weight percent) of alpha-terpineol and about 7.5 grams (50 weight percent) of ethanol. The third sample was extracted with a mixture containing about 12 grams (80 weight percent) of alpha-terpineol and about 3 grams (20 weight percent) of ethanol. The calculated conversion of weight loss and bitumen (organic material) in three samples, i.e. the degree of extraction, was about 0.2 grams (1.0 wt%), 0.6 grams (3.0 wt%) for each of the first, And 0.9 grams (4.5 wt%).

Example 20

Dissolving an average size of the irregular shape of the asphalt pellet of a commercial grade of about 15 mm in α- terpineol and under slightly below atmospheric pressure of less than about lO l.Ol × ⁵ Pascal (1 atm) to a temperature of about 22 ℃ and extraction did. A first sample weighing about 20 grams was dissolved and extracted with about 40 grams of alpha -terpineol and a second sample weighed about 20 grams was dissolved and extracted with about 20 grams of alpha-terpineol. Both samples were completely dissolved after 30 minutes. These experiments were conducted to simulate the dissolution and extraction of heavy oil with a tendency to asphaltenes such as asphalt.

Example 21

In this example, bitumen (organic material) in the tar sand from the same source with the same industrial analysis as the tar sand used in all the examples above was dissolved and extracted into two types, vegetable oil, soybean oil and corn oil. This vegetable oil was completely miscible with the turpentine solution. In the first experiment, a tar sands sample was weighed into about 15 grams of about lO l.Ol × ⁵ Pascal (1 atm) than the slightly lower under atmospheric pressure at a temperature of 96 ℃ blended with about 30 grams of soybean oil for about 20 minutes and continued And stirred. The weight loss was about 0.5 grams, from which the conversion of bitumen in the sample, i.e. the degree of extraction, was calculated to be about 3.3% by weight. The second experiment, a tar sands sample was weighed into about 30 grams to about lO l.Ol × ⁵ Pascal (1 atm) than the slightly lower under atmospheric pressure at a temperature of 175 ℃ blending corn oil of about 60 g for about 30 minutes and continued Lt; / RTI > The weight loss was about 4.8 grams, from which the conversion of the bitumen in the sample, i.e. the degree of extraction, was calculated to be about 12% by weight.

Example 22

Two tests were performed on the Berea sandstone plug core samples to determine the effect of reagent injection on oil recovery from the core. The first test was designed to measure the increase in oil recovery due to α-terpineol after the oil has already been pressurized to the limit. The selected core contained 9.01 mL of laboratory natural oil simulated crude oil. Induction of water into an aqueous solution containing 3.0% potassium chloride produced 4.6 mL of oil. The (5) porosity α-terpineol injection produces an additional 3.61 mL of oil leaving a core with less than 8.0% of the original amount of oil remaining in the core. The second test was designed to show an increased number of anticipations from the original store with α-terpineol injection. The selected core contained 8.85 mL of laboratory oil simulated crude oil. Oil production started after the alpha-terpineol injection of about 0.5 voids, which continued to 3.5 voids; However, most of the oil was recovered only after the injection of 2.5 porosity a-terpineol. A total of 7.94 mL of laboratory oil is recovered leaving a core with less than 7.5% of the original amount of oil remaining.

In one experiment, a variety of different rates of turpentine versus tar sand samples were tested. In each of the experiments provided below, the liquid turpentine had the same composition: about 60 vol% alpha -terpineol, about 20 vol% beta-terpineol, and about 20 vol% gamma-terpineol . The tar sand was multiple mixes of ores from Canada, Alberta, with a bitumen content of about 12 wt% and a water content of about 4-5 wt%. All experiments were performed at ambient temperature.

Recovery of hydrocarbons from the tar sand over all ratios provided below (i.e., the ratio of turpentine to tar sand was in the range of 1: 2-2: 1), as shown in Table 6 below, Almost no separation has brought about the difference. With regard to the temperature at which the extraction is carried out, it is believed that the optimum temperature for extraction, dissolution and / or liquefaction of hydrocarbons from the tar sand is 65 ° C. As shown in the table, at 130 DEG C, the amount of recovered hydrocarbons was reduced. However, for certain solids which are particularly difficult to recover hydrocarbons, it has been shown that increasing the temperature of the extraction solvent can increase the amount of hydrocarbon recovered. Finally, exposure time had little effect on the amount of material being extracted. This seems to be due to the shortest extraction time of 20 minutes, which is believed to be more suitable for the extraction of hydrocarbons from tar sands.

Tar sand weight, g Extractable HC weight, g Weight of extraction solvent Tar sands vs solvent ratio Extracted
The amount of HC, g Extracted
HC percent Temperature,
℃ Exposure time, minutes 15 2.0 30.0 1: 2 3.2 161 96 20 60 7.8 120.0 1: 2 5.4 69 96 30 60 7.8 31.6 2: 1 9.6 123 96 30 60 7.8 60.0 1: 1 7.6 97 65 30 60 7.8 60.0 1: 1 4.0 51 130 30 60 7.8 60.0 1: 1 6.3 80 65 30

Additional experiments were performed using alternative solvents, ethanol and corn oil, which were mixed with about 60% by volume of alpha-terpineol, about 20% by volume of beta-terpineol and about 20% by volume of gamma-terpineol ≪ / RTI > As can be seen in Table 7 provided below, the performance of ethanol and corn oil is expected to be about 60% by volume of? -Terpineol, about 20% by volume of? -Terpineol and about 20% by volume of? ≪ / RTI > phenone. For example, the terpineol composition produced completely or nearly completely the extraction of extractable hydrocarbons, whereas ethanol produced only 10% of the recoverable hydrocarbons and the heated corn oil produced only 33% of the recoverable hydrocarbons did.

chemical substance Tar sand weight, g Weight of extractable HC, g Extraction solvent weight Tar sands vs solvent ratio Extracted
HC amount, g Extracted
HC percent Temperature,
℃ Exposure time,
minute ethanol 15 2.0 15.0 1: 1 0.2 10 15 15 Corn oil 30 3.9 60.0 2: 1 1.3 33 175 30 60/20/20 terpineol 60 7.8 60.0 1: 1 7.6 97 65 30 60/20/20 terpineol 60 7.8 31.6 2: 1 9.6 123 96 30

As shown in Table 8 below, the performance of various turpentine liquid compositions comprising a turpentine liquid composition comprising alpha -terpineol alone or alpha-terpineol in combination with various known organic solvents was provided. The first three compositions presented in the table include? -Terpineol,? -Terpineol and? -Terpineol. For example, the first comprises about 60% by volume of alpha-terpineol, about 30% by volume of beta-terpineol and about 10% by volume of gamma-terpineol. The result is that when the concentration of a-terpineol is increased to an unexpected level, the performance of the turpentine liquid is achieved when complete extraction of the hydrocarbon material from the tar sand material sample is achieved when the turpentine liquid contains about 70% alpha-terpineol Respectively.

The second set of data is presented for the extraction of pure α-terpineol hydrocarbons containing tar sand. As shown, over 100% extraction was achieved due to inconsistencies in the hydrocarbon content of the sample. However, the results have generally demonstrated unexpected results that alpha-terpineol can extract almost all recoverable hydrocarbons from tar sand samples.

Finally, the last data provided in Table 8 illustrates the efficacy of a mixed system of? -Terpineol and a known organic solvent. As shown, almost complete recovery of the recoverable hydrocarbons was achieved with a composition comprising a 1: 1 ratio of alpha-terpineol to ethanol. This is unexpected because pure ethanol removed only about 10% of the total recoverable hydrocarbons. Also, a mixing system comprising a 1: 1 or 3: 1 ratio of alpha-terpineol to toluene resulted in 77% and 92% recovery of total recoverable hydrocarbons. This was an unexpected result.

chemical substance Tar sand weight, g Weight of extractable HC, g Extraction solvent weight Tar sands vs solvent ratio Extracted
HC amount, g Extracted
HC percent Temperature,
℃ Exposure time, minutes 60/30/10 terpineol 60 2.0 60.0 1: 1 7.1 91 96 30 40/30/20 terpineol 60 7.8 60.0 1: 1 4.7 60 96 30 70/20/10 terpineol 60 7.8 60.0 1: 1 7.9 101 96 30 100/0/0 terpineol 60 7.8 60.0 1: 1 10.0 128 96 30 100/0/0 terpineol 60 7.8 120.0 1: 2 8.7 111 96 30 100/0/0 terpineol 60 7.8 31.0 2: 1 9.6 123 96 30 50% alpha-terpineol /
50% ethanol 15 2.0 15.0 1: 1 8.1 103 65 30 80% alpha-terpineol / 20% ethanol 15 2.0 15.0 1: 1 1.2 62 15 15 75% alpha-terpineol / 25% toluene 30 3.9 25.0 1: 0.8 1.8 92 15 15 50% alpha-terpineol / 50% toluene 30 3.9 26.0 1: 0.9 3.0 77 96 30 50% alpha-terpineol / 50% xylene 30 3.9 26.0 1: 0.9 2.4 61 96 30

In the specification, the results for the extraction of hydrocarbon-containing organic materials from hydrocarbon-containing materials, particularly those described in the above example, were unexpected.

The terms first, second, third, etc. used herein should be construed as uniquely identifying the elements and not limiting the particular order of elements or steps.

As used herein, the term "about" should be interpreted to include a value that is within 5% of the recited value. Also, the term "about" in relation to a range of values should be interpreted to include both the upper and lower limits of the recited range. The terms first, second, third, etc. used herein should be interpreted as uniquely identifying the element and not limiting the specific order of the element or step.

It will be apparent to those skilled in the art that various changes may be made and equivalents which fall within the true spirit and scope of the invention.

Claims (57)

A method for extracting a hydrocarbon-containing organic substance from a hydrocarbon-containing substance using a homogeneous single-phase hydrocarbon extract essentially composed of a turpentine liquid,
Comprising contacting said hydrocarbon-containing material with a homogeneous single phase hydrocarbon extract which is essentially composed of a turpentine liquid to form a homogeneous single phase extraction mixture and a residue material, said homogeneous single phase extraction mixture comprising said hydrocarbon containing A contact step comprising at least a portion of an organic material, wherein the remnant material comprises at least a portion of a non-solubilizing material from a hydrocarbon-containing material that is not soluble in the turpentine liquid;
Separating the extract mixture from the residue material;
Separating the extraction mixture into a first portion and a second portion, wherein the first portion of the extraction mixture comprises a hydrocarbon product stream comprising at least a portion of the hydrocarbon containing organic material, A separating step comprising at least a part of said turpentic liquid;
Containing organic material from the hydrocarbon-containing material. The method according to claim 1, wherein the turpent fluid is selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil,? -Pinene,? -Pinene,? -Terpineol,? -Terpineol, Olefin, terpene resin,? -Terpene,? -Terpene,? -Terpene, and mixtures thereof. The method of claim 1, wherein the turpent fluid is selected from the group consisting of geraniol, 3-karen, dipentene (p-menta-1,8-diene), nopol, Pyranol, dihydroimacenol, isobonole, p-menth-8-ol, a-terpinyl acetate, citroneol, p-menth-8-yl acetate, 7-hydroxydihydrocituronol, menthol ≪ / RTI > and mixtures thereof. The method according to claim 1, wherein the turpentine liquid is selected from the group consisting of anethole, camphene, p-cymene, anisaldehyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, Cymene alcohol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10- camphorsulfonic acid, ≪ / RTI > and mixtures thereof. The method of claim 1, wherein the hydrocarbon-containing organic material is solid or semi-solid, and the hydrocarbon-containing material comprises a plurality of particles having an average particle diameter. The extraction method according to claim 5, wherein the average particle diameter is 0.74 mm to 25 mm. The method of claim 1 further comprising the step of contacting the hydrocarbon containing material with a second liquid selected from the group consisting of lower aliphatic alcohols, lower alkanes, lower aromatics, aliphatic amines, aromatic amines, and mixtures thereof during the contacting step Lt; / RTI > 8. The method of claim 7, wherein the second solution is selected from the group consisting of ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, anthracene, tetraline, triethylamine, aniline, ≪ / RTI > 9. The method of claim 8, wherein contacting the hydrocarbon-containing material with the turpentine liquid further comprises stirring the extraction mixture using water at a temperature near the boiling point of the water as an agitant. . 2. The method of claim 1, further comprising heating the turpentine fluid to a temperature above room temperature of up to 200 < 0 > C before contacting the turpentine fluid with the hydrocarbonaceous material. The extraction method according to claim 1, wherein the hydrocarbon-containing material and the turpentine liquid are contacted at a pressure of 1.0 × 10 ⁴ pascals (0.1 atm) to ⁵ × 10 ⁶ pascals (50 atm). 2. The method of claim 1, further comprising feeding at least a portion of the second portion of the extraction mixture to the contacting step after separating the extraction mixture into a first portion and a second portion. 2. The method of claim 1, further comprising, prior to said contacting step, providing means for contacting said hydrocarbon containing organic material with said turpentine liquid at an in situ formation of an underground formation containing said hydrocarbon containing organic material, Further comprising providing the means for extracting the hydrocarbon-containing organic material from the underground facility. The extraction method according to claim 1, wherein the hydrocarbon-containing organic material is contacted by the turpentine liquid at a temperature of less than 300 캜. The extraction method according to claim 1, wherein the hydrocarbon-containing organic material is contacted by the turpentine liquid at a temperature of less than 60 캜. The method of claim 1, wherein the hydrocarbon-containing material is in an underground facility prior to and during the contacting step, the contacting step occurs at an in-
Further comprising the step of recovering the extracted mixture through a production well in fluid communication with the underground facility after separating the extracted mixture from the residual material, Lt; / RTI > 17. The method of claim 16, further comprising the step of re-injecting the second portion into the production well for further extraction of the hydrocarbon material after separating the extraction mixture into a first portion and a second portion, Way. 17. The method of claim 16, wherein the underground facility undergoes a primary recovery of the hydrocarbon material. The extraction method according to claim 1, wherein the turpentine liquid comprises at least 30% by volume of? -Terpineol and at least 15% by volume of? -Terpineol. 2. The method of claim 1, wherein the turpentine liquid comprises at least 50% by volume of alpha -terpineol and at least 20% by volume of beta-terpineol. The extraction method according to claim 1, wherein the turpent fluid further comprises at least one of? -Terpene,? -Terpene or? -Terpene. 2. The method of claim 1, wherein the turpentine liquid comprises alpha -terpineol and beta -terpineol and the ratio alpha -terpineol to beta -terpineol is at least 1.3: 1. 3. The method of claim 1, wherein the turpentine liquid comprises alpha -terpineol and beta -terpineol and the ratio alpha -terpineol to beta -terpineol is at least 2: 1. A method for extracting a hydrocarbon-containing organic material from a hydrocarbon-containing material, the hydrocarbon material comprising a tar sand,
Prior to the contacting step, the method includes feeding the tar sand into the interior of the extraction vessel, wherein the contacting step includes contacting the inside of the extraction vessel to extract a portion of the hydrocarbon containing organic material from the hydrocarbon- And supplying the turpentine liquid to the turpentine. 7. A method for extracting a hydrocarbon-containing organic material from a hydrocarbon-containing material comprising an oil shale, the method comprising:
Further comprising polishing the hydrocarbon-containing organic material to produce a plurality of particles defining an average diameter size in the range of 4.8 mm to 25 mm so that the plurality of particles are in contact with the turpentine fluid prior to the contacting step Way. A method for extracting a hydrocarbon-containing organic material from a hydrocarbon-containing material comprising coal, the method comprising:
Further comprising, prior to the contacting step, polishing the hydrocarbon-containing organic material to produce a plurality of particles defining an average diameter size in the range of 0.8 mm to 0.07 mm such that the plurality of particles contact the liquid turpentine . A method for extracting a hydrocarbon-containing organic material from a hydrocarbon-containing material selected from coal, oil shale, tar sand, crude oil, heavy oil, natural gas, or a combination thereof,
Containing material is contacted with? -Terpineol so that an extraction mixture is formed and a residual material is formed, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic material extracted with the? -Terpineol, Comprises a contacting step comprising at least a portion of a non-solubilizing material from a hydrocarbon containing material that is not soluble in the alpha -terpineol;
Separating said extract mixture from said residue material;
Lt; / RTI > 28. The method of claim 27, further comprising separating the extraction mixture into a hydrocarbon product stream and a recycle stream, wherein the hydrocarbon product stream comprises at least a portion of the hydrocarbon containing organic material , Said regeneration stream comprising at least a portion of said alpha-terpineol. 29. The method of claim 28, further comprising regenerating the regeneration stream to contact the hydrocarbon carbon containing material. A method for recovering a hydrocarbon-containing organic material from a tar sand,
Obtaining a tar sand sample comprising a recoverable hydrocarbon containing organic material;
Supplying the tar sand sample to a contact vessel comprising at least one inlet for supplying a solution of the turbine;
Contacting the tar sand sample with a homogeneous single phase hydrocarbon extract consisting essentially of? -Terpineol and? -Terpineol in a contact vessel and stirring the tar sand sample with the hydrocarbon extract to obtain a homogeneous single phase extraction mixture Wherein the extraction mixture comprises at least a portion of the hydrocarbon containing organic material extracted with the hydrocarbon extract and wherein the residual material comprises at least a portion of the non-soluble material from the tar sand sample that is not soluble in the hydrocarbon extract, The contact vessel including at least one inlet for supplying a hydrocarbon extract;
Separating the extract mixture from the residue material;
Separating the extraction mixture into a hydrocarbon product stream and a hydrocarbon extract recovery stream, wherein the hydrocarbon product stream comprises at least a portion of the hydrocarbon containing organic material from the tar sand sample;
Regenerating at least a portion of the hydrocarbon extractive recycle stream into the contacting step;
≪ / RTI > wherein the hydrocarbon-containing organic material is recovered from the tar sand. A method for recovering a hydrocarbon-containing organic material from a pulverized hydrocarbon-containing oil shell,
Providing said pulverized hydrocarbon-containing oil shale;
Providing a first liquid which is essentially composed of a solution of the turpentine;
Filtering the pulverized hydrocarbon-containing oil shell;
Supplying a contact vessel with the pulverized hydrocarbon-containing oil shell, the contact vessel comprising at least one inlet for supplying the contact vessel with the turpentine liquid;
Containing oil shell is contacted with a turpentine liquid to form a homogeneous single phase extraction mixture and a residual material is formed and the extraction mixture comprises at least a portion of the hydrocarbon containing organic material and the turpentine liquid, Wherein the residual material comprises at least a portion of the non-degradable material from the oil shell that is not soluble in the turpentic liquid;
Separating the extract mixture from the residue material;
Separating said hydrocarbon-containing organic material from said turpentine liquid in said extraction mixture to produce a hydrocarbon product stream and a turpentine liquid recovery stream, said hydrocarbon product stream comprising at least a portion of said hydrocarbon-containing organic material from said comminuted hydrocarbon- A separation step including a part;
Regenerating at least a portion of the turpentine fluid recovery stream into the contacting step;
≪ / RTI > wherein the hydrocarbon-containing oil shell comprises at least one hydrocarbon-containing oil shell. A method for recovering a hydrocarbon-containing organic material from a hydrocarbon-rich coal-rich sub-surface formation,
Obtaining a coal comprising a recoverable hydrocarbon containing organic material;
Pulverizing the coal to produce pulverized coal;
Filtering the pulverized coal;
Feeding the pulverized coal to a contact vessel, wherein the contact vessel comprises at least one inlet for supplying a turpentine fluid essentially composed of a turpentine to the contact vessel;
Contacting the pulverized coal with a turpentine liquid to form a homogeneous single phase extraction mixture and forming a residue material, wherein the extraction mixture comprises at least a portion of the hydrocarbon containing organic material and the turpentine liquid, A contact step comprising at least a portion of the non-solubilizing material from the coal that is not soluble in the turpentine liquid;
Separating the residual material from the extraction mixture;
Separating the hydrocarbon-containing organic material from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recovery stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic material from the coal;
Regenerating at least a portion of the turpentine fluid recovery stream into the contacting step;
Wherein the hydrocarbon-containing organic material is recovered from a coal-rich sub-sur-face formation containing hydrocarbon. A method for increasing the recovery of a hydrocarbon-containing organic material from a production well coupled to a hydrocarbon-containing sub-surfa-ce formation comprising a hydrocarbon-containing material,
Providing an underfloor formation and an injection well in fluid communication therewith;
Providing a first liquid essentially consisting of a turpentine solution comprising terpineol;
Wherein the turpentine fluid and the hydrocarbon-containing organic material from the hydrocarbon-containing surface under-formation comprise at least a portion of the hydrocarbon-containing organic material and at least a portion of the turpentine fluid To form a homogeneous single phase extraction mixture;
Recovering the extracted mixture from the formation through the production well;
Separating the extraction mixture to produce a hydrocarbon product stream and a turpentine fluid stream
A method for increasing the recovery of a hydrocarbon-containing organic material from a production well coupled to a hydrocarbon-containing sub-surface formation comprising a hydrocarbon-containing material. 2. The method of claim 1, further comprising adding a surfactant to the hydrocarbon-containing material prior to the contacting step,
Wherein the extraction takes place only after addition of any surfactant to the organic material. 2. The method of claim 1, wherein the hydrocarbon-containing material is contacted with a turpentine liquid of at least 0.5 pore volume. The extraction method according to claim 1, wherein the hydrocarbon extract is? -Terpineol or synthetic turpentine. The extraction method according to claim 1, wherein the hydrocarbon extract liquid is water-free. The method of claim 1, wherein the hydrocarbon extract contacting the hydrocarbon-containing material contains at least 70% of the turpentine liquid. The method of claim 1, further comprising stirring the extraction mixture during the contacting step. 2. The method of claim 1, further comprising contacting the hydrocarbon-containing material with a second liquid of turpentine miscibility during the contacting step, wherein the ratio of the turpentine liquid to the turpentine miscible liquid is at least 1: 1. The method of claim 1, further comprising contacting the hydrocarbon-containing material with a turpentine-miscible solvent during the contacting step. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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