MX2012013862A

MX2012013862A - Extraction of hydrocarbons from hydrocarbon-containing materials.

Info

Publication number: MX2012013862A
Application number: MX2012013862A
Authority: MX
Inventors: Lian-Tseng Fan; Mohammad Reza Shafie; Julius Michael Tollas; William Arthur Fitzhugh Lee
Original assignee: Green Source Energy Llc
Priority date: 2007-09-20
Filing date: 2012-11-29
Publication date: 2013-06-25
Also published as: ECSP10010124A; AP2010005221A0; EA201000512A1; JP2015004077A; CA2699764C; AU2008301860A1; MY149974A; AP2769A; UY31345A1; IL204606A; NZ584661A; TWI441909B; JP2010540694A; EA023805B1; AR068497A1; BRPI0817129A2; TW200914599A; CA2699764A1; EP2205696A1; AU2008301860B2

Abstract

Solvents and methods are provided for extracting a hydrocarbon fraction from a solid, semi-solid, liquid or viscous liquid hydrocarbon-containing material.

Description

EXTRACTION OF HYDROCARBONS FROM MATERIALS CONTAINING HYDROCARBONS.

Field of the Invention The present invention relates to the field of hydrocarbon extraction from materials that contain them.

Background of the Invention The present application is a continuation in part of the patent applications of the United States of America numbers 12/174, 139, filed July 16, 2008, and 12 / 053,126, filed on March 21, 2008; and claims for the benefit of the provisional patent application of the United States of America number 60 / 973,964, filed on September 20, 2007; each of which is incorporated herein in its entirety and as a reference.

The liquefaction, solubilization and / or extraction of fossil fuels, also called organic matter containing hydrocarbons, in solid, semi-solid, highly viscous or viscous form (referred to individually and jointly as fossil fuels hereafter) has proved to be Extremely challenging and difficult. As used herein, such fossil fuels include, but are not limited to, organic matter containing hydrocarbons within coal, bituminous, bituminous sands, and asphalt sands (hereinafter collectively referred to as tar sands), as well as crude oil, heavy crude oil, crude bitumen, kerogen, asphaltene and / or natural asphalt. The difficulty can be attributed in part to the fact that these fossil fuels include complex organic polymers linked by oxygen and sulfur bonds, which are often embedded in the matrices of inorganic compounds. There is a need to produce additional liquid hydrocarbon raw material for the manufacture of liquid and gaseous fuels as well as for the production of various chemical products, pharmaceutical materials and design as the demand and consumption of these hydrocarbon-based materials increases.

Several technologies or processes have been developed to liquefy, solubilize and / or extract fossil fuels. None of the technologies or processes of liquefaction, solubilization and extraction of the prior art, however, has proven to be commercially viable on a large scale for all types of fossil fuels known. This is due to the fact that all prior art technologies and processes for hydrocarbon liquefaction, solubilization or extraction developed to date are expensive to use and work. Additionally, processes and technologies of the prior art for liquefaction, solubilization and / or extraction of hydrocarbons can be difficult to scale, operate and / or control due to one or more of the following reasons: (1) operation at unduly high pressure elevated (2) operation at a very high temperature; (3) the need for expensive vessels and processing equipment that require the external supply of hydrogen under extreme conditions; (4) subjecting a mixture, or composition, of two or more reagents, catalysts and / or promoters, which are often highly toxic and are neither renewable nor recyclable; (5) requirement of the supply of a special form of energy, for example, microwave radiation; (6) long processing times for partial liquefaction, solubilization or extraction; (7) requirement of extraordinarily fine particles with a size of approximately 200 mesh (0.074 mm), which is deeply difficult and expensive to manufacture and handle; and (8) inability to recover and recycle the necessary reagents, catalysts and / or promoters. Thus, there is a need to provide additional techniques and processes for the enhanced recovery of hydrocarbon materials.

For primary drilling operations, it would be advantageous to employ a process that improves the solubilization and promotes the movement of organic matter containing additional or trapped hydrocarbons that could then be recovered allowing the existing pressure gradients to force the organic matter containing hydrocarbons to through the drilling hole. In particular, it would be useful to solubilize the heavier hydrocarbons that usually remain in the reserve through primary drilling operations.

For improved secondary and tertiary oil recovery operations, it would be advantageous to employ a process that would improve the solubilization of oil for recover the organic matter that contains hydrocarbons and that is in the reserve, in a way that is profitable and that does not damage the deposit. While there are effective methods and compositions for tertiary operations, current methods suffer due to the cost of operations compared to the value of organic matter containing hydrocarbons produced.

Compendium of the Invention According to one embodiment of the present invention, a method of extracting organic matter containing hydrocarbons from a hydrocarbon-containing material includes the steps of providing a first liquid that includes a turpentine liquid, and contacting the material containing hydrocarbon with the turpentine liquid so that an extraction mixture is formed, as well as residual material. The extraction mixture contains at least a portion of the organic matter containing hydrocarbons and the turpentine liquid. The residual material includes non-soluble material from the hydrocarbon-containing material. The waste material may also include a reduced portion of the organic material containing hydrocarbons in the circumstance where all of said hydrocarbon-containing material has not been solubilized by the turpentine liquid and displaced within the extraction mixture. The residual material is then separated from the extraction mixture. The extraction mixture is then further separated into a first portion and a second portion. The first portion of the extraction mixture includes a stream of hydrocarbon product that includes at least a portion of the hydrocarbon-containing organic material extracted from the hydrocarbon-containing material. The second portion of the extraction mixture includes at least a portion of the turpentine liquid. In one embodiment, substantially all the turpentine liquid is recovered in the recirculation stream.

In another embodiment, substantially all of the organic matter containing hydrocarbons is extracted into the extraction mixture. In such a mode, the waste materials are essentially free of petroleum and can be used additionally or disposed without impact to the environment.

Brief Description of the Drawings Figure 1 is a diagram for an embodiment of an apparatus for the recovery of hydrocarbons from bituminous sands.

Figure 2 is a diagram for an embodiment of an apparatus for the recovery of hydrocarbons from bituminous.

Figure 3 is a diagram for an embodiment of an apparatus for the recovery of hydrocarbons from coal coal.

Figure 4 is a scheme for the improved recovery of hydrocarbons from an underground deposit.

Detailed description of the invention In one aspect, the present invention relates to a composition readily used for the extraction, liquefaction and / or solubilization of fossil fuels from coal, bituminous, bituminous sands and the like, as well as from reservoirs.

According to one embodiment, a method is provided that includes the steps of liquefaction, solubilization and / or extraction of organic matter containing hydrocarbons from a material containing hydrocarbons, such as, for example, carbon, bituminous, bituminous sands. , or a field containing heavy crude oil, crude oil, natural gas (which often coexists with crude oils and other such fossil fuels), or a combination of these. Organic matter containing hydrocarbons includes, but is not limited to, heavy crude oil, crude oil, natural gas and the like. The organic matter that contains hydrocarbons can be solid, semi-solid, liquid, muddy, liquid viscous, liquid or gaseous. Other materials that are hydrocarbon-containing materials suitable for the treatment using the method of this invention include liquid and solids including hydrocarbon-containing materials as well as a waste material. Exemplary materials containing hydrocarbons may also include bottoms of oil tanks, sludge mixtures and sludge from pits or oil tanks, discarded food, manure, sewer sludge or municipal waste. The liquefaction, solubilization and / or extraction of the organic matter containing hydrocarbons includes the step of providing a liquid of turpentine, contacting the hydrogen-containing material with the turpentine liquid in order to extract at least a portion of said organic matter containing hydrocarbons from said hydrocarbon-containing material into said turpentine liquid to create an extraction mixture that it includes the organic matter that contains hydrocarbons that have been removed from the material containing hydrocarbons and the turpentine liquid, and separate the organic matter extracted in the turpentine liquid from any residual material not extracted. The turpentine liquid may include an amount of terpineol. The turpentine liquid that is created naturally includes an amount of terpene. In one embodiment, the turpentine fluid includes α-terpineol.

In certain embodiments, the ratio of turpentine to hydrocarbon-containing material is greater than or equal to about 1: 2 and 4: 1, in some embodiments it is greater than or equal to about 1: 1, and in some embodiments the ratio can be greater than or equal to 2: 1. In modalities that are related to the recovery of deposits, the proportion can be greater than or equal to approximately 3: 1, and in other modalities that are related to the recovery of deposits the proportion it can be greater than or equal to approximately 4: 1. For the purpose of its application in a reservoir, the pore volume is used to determine an estimated measure of the material containing hydrocarbons. In other aspects of this invention, such as in the use of bituminous sands and coal and bituminous shale, the volume of the hydrocarbon-containing material can be measured more directly.

In certain embodiments, the minimum organic matter contained in the hydrocarbon-containing material is greater than or equal to about 1% by weight, in other embodiments greater than or equal to about 10% by weight, and in still other embodiments greater than or equal to to about 14% by weight of the hydrocarbon-containing material.

In one embodiment of the invention, a liquefaction, solubilization or extraction reagent, of choice for the hydrocarbon-containing material is a natural, synthetic or mineral turpentine, which may include a-terpineol, or a-terpineol itself.

In certain embodiments of the invention, the liquefaction, solubilization and / or extraction of the fossil fuels or organic matter containing hydrocarbons can be carried out at a temperature, which is within the range of about 2 ° C to about 300 ° C. . In certain embodiments, the organic material or material is brought into contact with a turpentine liquid at a temperature of less than about 300 ° C, or less than about 60 ° C. In other embodiments, the liquefaction, solubilization and / or extraction temperatures may be within the range of about 20 ° C to about 200 ° C. The pressure under which the liquefaction, solubilization and / or extraction of fossil fuels is carried out may typically be within the range of approximately 1.0x104 Passes (0.1 atm) to approximately 5.0xl06 Passes (50.0 atm). In certain modalities, the process can be carried out at a pressure between approximately 5.0xl04 Paséales (0.5 atm) to approximately 8.0xl05 Paséales (8.0 atm). In certain other embodiments, fossil fuels or organic matter containing hydrocarbons to be subjected to liquefaction, solubilization and / or extraction by immersion in, or by contact with, one or more turpentine liquids may be in the form of a bed. of particles, pieces, pieces, or blocks or fossil fuels whose sizes are within the range of approximately 0.74 mm to approximately 10 mm in a liquefaction, solubilization or extraction container (reactor hereinafter) containing one or more of said reagents of liquefaction, solubilization and / or extraction. In certain modalities, the sizes of the particles, pieces, pieces or blocks of fossil fuels are within the range of approximately 0.149 mm (100 mesh) to approximately 20 mm. In certain embodiments, the bed of particles, pieces, pieces, or blocks of fossil fuels is stirred by passing the reagent or reagents of liquefaction, solubilization and / or extraction in the form of a liquid through the bed of particles, pieces, pieces. or blocks by means of boiling the reagent or reagents. In certain embodiments, the duration of liquefaction, solubilization and / or extraction is between about 1 minute to about 90 minutes. Fossil fuels can be partially or totally liquefied, solubilized and / or extracted; the degree of liquefaction, solubilization and / or extraction can be effected by controlling the operating conditions, such as temperature, pressure, intensity of agitation and duration of operation and / or adjusting the type, relative amount and concentration of the reagent or reagents of liquefaction , solubilization or extraction in the reactor.

The basis of one aspect of the present invention is the unexpected discovery that when approximately 500 grams of the reagent, α-terpineol, was added to approximately 250 grams of the 60 mesh sample of coal from the Pittsburgh vein in Washington County Washington in a tray, the color of the reagent became black almost immediately, and it remained that way after several hours. This indicated that the color change was not due to the suspension of the coal particles, but was rather indicative of the extraction of the organic matter containing hydrocarbons, from the coal. Subsequently, this 2: 1 mixture of α-terpineol and the carbon sample was transferred from the tray to a cap and hermetically sealed and kept under ambient conditions of approximately 20 ° C and slightly less than approximately 1.01 × 105 Pases (1 atm. ) for approximately 25 days. The conversion, (that is, the degree of liquefaction) of the carbon sample was determined to be about 71% by weight after filtering, washing with ethanol, drying and weighing. This conversion of 71% by weight corresponds to almost all the soluble bitumen (organic matter) present in the carbon sample whose approximate analysis was 2.00% by weight of received moisture, 9.25% by weight of dry ash, 38.63% by weight of dry volatile matter, and 50.12% by weight of dry fixed carbon. A series of subsequent experiments with charcoal, as well as with bitumen and bituminous sands under various operating conditions, have shown that the family of reagents that includes natural and / or synthetic turpentine containing pinenes, and alcohols from Pinenos, that is, terpineols, are immoderadamente effective in the liquefaction, solubilization and / or extraction of kerogéno (organic matter), bitumen (organic matter) and / or asfalteno (organic matter) in fossil fuels, including coal, bituminous, bituminous sands, crude oil heavy and / or crude oil, without requiring the help of any catalyst or alkali metals. These reagents, except mineral turpentine derived from petroleum, are renewable and "green", that is, low in toxicity, and relatively cheap, in comparison with all other liquefaction, solubilization and / or extraction reagents for fossil fuels. , such as tetralino, xylene, anthracene and various solutions or mixtures of these reagents with other compounds. Even mineral turpentine derived from petroleum, although not renewable, is relatively low in toxicity and cheap. It was also found that any of the liquefaction, solubilization and / or extraction reagents penetrates or diffuses into the particles, pieces, pieces, blocks or pieces of fossil fuels through their pores at appreciable speeds, thereby causing these particles, pieces, pieces or blocks subsequently release the liquefiable, soluble or extractable fraction that is found in these frequently almost completely even under much milder conditions than, for example, the environmental temperature and pressure, than those required by recent inventions. which have to do with the liquefaction, solubilization and / or extraction of fossil fuels, such as coal, bituminous, bituminous sands, crude oil and heavy crude oil.

One aspect of the present invention provides a method of liquefaction, solubilization and / or extraction of fossil fuels or organic matter containing hydrocarbons from hydrocarbon-containing material, such as coal, bituminous and bituminous sands, wherein a portion of Solid or semi-solid fossil fuels are brought into contact with a turpentine liquid in an extraction mixture, which may be in the absence of an alkali metal, catalyst, hydrogen (H2) and / or carbon monoxide (CO). While hydrogen and CO can be useful as mixing agents, one embodiment of the invention includes the process and the composition in the absence of hydrogen and CO.

In certain modalities, the turpentine liquid is selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, a-pinene, ß-pinene, α-terpineol, β-terpineol, β-terpineol, polymers thereof, and mixtures of these. In certain other embodiments, the turpentine liquid is selected from geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinano, 2-pinene hydroperoxide, terpine hydrate, 2-pinanol, dihydromicenol , isoborneol, p-methan-8-ol, a-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In other embodiments, the turpentine liquid is selected from anethole, camfeno, p-cymene, anisaldehyde, 3,7-dimethyl-l, 6-octadiene, isobornyl acetate, ocimene, alloocmene, aloocimeno alcohols, 2-methoxy-2 , 6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, cintronelal, menthone, and mixtures thereof.

According to one aspect, solid or semi-solid fossil fuels or other materials containing hydrocarbons, such as coal, bituminous shale, bituminous sands and heavy crude oil, or for example petroleum tank bottoms, pits sludge or oil ponds , discarded food, manure, sewage sludge or municipal waste, can be provided in any size that facilitates contact with the turpentine liquid. Fossil fuels or materials containing hydrocarbons can be supplied as particles, pieces, pieces, or blocks, for example, large fragments or pieces of coal or bituminous waste. According to a certain aspect of the invention, the fossil fuel or hydrocarbon-containing material is provided as particles. According to a certain aspect of the invention, the fossil fuel particles or the hydrocarbon-containing materials have a particle size of from about 0.074 mm to about 100 mm. In certain other embodiments, the fossil fuel particles have an average particle size of about 0.074 mm to about 25 mm.

According to one aspect of the present invention, a second liquid can be added to the turpentine liquid. According to a certain aspect of the invention, the second liquid can be selected from minor aliphatic alcohols, alénes, aromatics, aliphatic amines, aromatic amines, carbon disulphide and mixtures thereof. Exemplary mixtures include solvents manufactured in petroleum refining , such as decanted petroleum, light cycle oil and naphtha, or solvents manufactured in the dry distillation of coal and the fractionation of liquefied coal.

As used herein, minor aliphatic alcohols refer to monohydric and primary, secondary and tertiary polyhydric alcohols of 2 to 12 carbon atoms. As used herein, the allians refer to straight chain alkanes and a branched chain of between 5 and 22 carbon atoms. As used herein, aromatics refers to monocyclic, heterocyclic and polycyclic compounds. As used herein, aliphatic amines refer to primary, secondary and tertiary amines having alkyl substituents of between 1 and 15 carbon atoms. In certain embodiments, benzene, naphthalene, toluene or combinations of these are used. In another embodiment, the lower aliphatic alcohols noted above may be employed. In one embodiment the solvent is selected from ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, naphthalene, anthracene, tetralin, triethylamine, aniline, carbon disulphide, and mixtures thereof, at a temperature and operable pressure to keep the solvent in liquid form.

In certain embodiments, the ratio of turpentine to any other miscible turpentine solvent contained in said fluid is greater than or equal to 1: 1, in certain embodiments greater than or equal to about 9: 4. In certain modalities, the ratio is greater than or equal to approximately 3: 1. In still other modalities, the ratio is greater than or equal to 4: 1.

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

According to a further aspect of the present invention, the fossil fuel and the turpentine liquid are brought into contact at a pressure of from about 10 × 10O Passes (0.1 atm) to about 5.0 × 0.06 Pascals (50 atm). According to one aspect, the method is executed at a pressure of from about 0.5 atm to about 8 atm.

In accordance with one aspect of the present invention, the method further includes providing an extraction vessel within which the solid or semi-solid fossil fuel is brought into contact with the turpentine liquid. According to one aspect, stirring means may be provided by means of which the fossil fuel and the turpentine contained within the reactor or the extractor vessel are mixed and stirred.

According to one aspect of the present invention, fossil fuel and turpentine liquid can be incubated in a holding tank so that their contact time is prolonged. According to a further aspect, the degree of liquefaction, solubilization and / or extraction is controlled by the length of time that the solid or semi-solid fossil fuel is in contact with the turpentine liquid and / or the temperature of the fuel mixture. fossil and turpentine.

In accordance with one aspect of the present invention, the fossil fuel is brought into contact with a heterogeneous liquid that includes a turpentine liquid and water as a stirrer.

In certain embodiments, the ratio of turpentine fluid to water is greater than or equal to about 1: 1 by volume, to prevent the formation of sludge, which can make it difficult to separate the organic matter extracted in the fluid containing liquid of turpentine.

According to one aspect of the present invention, the fossil fuel is brought into contact with the turpentine liquid in the presence of a selected energy input from thermal energy in excess of about 300 ° C, pressure in excess of 50 atm, microwave energy, ultrasonic energy, ionization radiation energy, mechanical cutting forces, and mixtures of these.

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

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

According to one aspect of the present invention, a microorganism is included in the reaction mixture or solubilization. The selected chemical bonds, for example, sulfur bonds and oxygen bonds, in fossil fuel hydrocarbons and other hydrocarbon-containing materials are broken by biotreatment with thermophilic microorganisms and bacillus-type chemolithotrophs, selected from isolates that are they naturally form and derived from hot sulfur springs. The breaking of these selected chemical bonds facilitates the solubilization of hydrocarbons in fossil fuels and other materials containing hydrocarbons.

Still other aspects and advantages of the present invention will become more readily apparent to those skilled in the art from this description, wherein certain embodiments of the invention are shown and described, simply by way of illustration of the best contemplated way of carrying out the invention. As you may notice, the invention is capable of other and different modalities, and its various details are capable of modifications in several obvious respects, without departing from the invention. Accordingly, the description should be seen as illustrative in nature and not as restrictive.

According to one embodiment of the present invention, a method is provided for extracting organic matter containing hydrocarbon from material containing hydrocarbon comprising a gaseous, liquid or viscous liquid fossil fuel material. The method provides a first liquid that includes a turpentine liquid. The turpentine liquid is contacted with the hydrocarbon-containing material in situ in an underground formation containing said fossil fuel material, thereby forming an extraction mixture so that the organic matter containing hydrocarbons in said liquid is extracted from said liquid. turpentine and form an extraction liquid. The extraction liquid is removed from said formation, where the extraction liquid includes the turpentine liquid containing the extracted organic matter containing hydrocarbons. The organic matter that contains hydrocarbons, extracted is separated from a residual material not extracted. The method may further include separating said hydrocarbon material extracted from the turpentine liquid. The gaseous, liquid or viscous liquid fossil fuel material can be heavy crude oil, crude oil, natural gas, or a combination of these. The underground formation may be a crude oil field or a natural gas field, for example.

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

An extraction reagent of the present invention is a liquid, which has a very strong physical-chemical affinity with the bituminous organic matter, including bitumen, kerogen and / or tars, in solid carbon, bituminous and bituminous sands. When the extraction reagent of the present invention and the bituminous organic material comprising mainly hydrocarbons, are placed in direct contact with one another, the organic matter is dissolved in the extraction reagent of the present invention, thereby liquefying the organic matters . With contact, the hydrocarbons and extraction reagent of the present invention rapidly form a homogeneous solution, that is, a one-phase liquid.

It is possible to take advantage of the physical-chemical affinity between the extraction reagent of the present invention and the bituminous material to improve the recovery of petroleum from petroleum deposits under in situ conditions. The techniques of in situ recovery of prior art applied to date in oil deposits mainly resort to the so-called frontal displacement method. This process is controlled strictly by the characteristics of the fluid flow in multiple phases in a porous medium. This tends to leave a large portion, usually above about 40% of the original oil, not recovered, even for the "good" reserves of low viscosity oil. The extraction reagent of the present invention improves oil recovery by overcoming the complex behavior of the multiple phase flow that prevails under in situ conditions.

The present invention takes advantage of the much stronger physical-chemical affinity of the turpentine liquid.

A method of the present invention injects an extraction reagent of the present invention into a natural gas or oil reservoir through an injection well.

The oil is dissolved in the extraction reagent of the present invention when the two come into contact in an oil field, thereby giving way to a homogeneous solution, that is, a one-phase liquid. The extraction reagent of the present invention does not simply displace the oil as it travels from the injection well to the production well; the oil solution previously trapped in the extraction reagent of the present invention continues until the extraction reagent is completely saturated with petroleum. In this way, the extraction reagent becomes inactive in the process of recovering additional oil and simply flows through the reservoir pores as a one-phase liquid, eventually reaching a production well.

The following illustrates three specific embodiments of in situ methods for oil recovery of the present invention.

In a first in situ mode, approximately three (3.0) to seven (7.0) pore volumes of an extraction reagent of the present invention are injected into a petroleum reservoir that is already flooded with water until the saturation of residual oil while producing approximately 51% of the original oil in the deposit. The injection of the extraction reagent can unexpectedly produce an additional 41% of the original oil in the reservoir. This method modality was experimentally validated, as described in Example 22, which is presented below.

In a second in situ mode, approximately two (2.0) to five (5.0) pore volumes of an extraction reagent of the present invention are injected into an oil reservoir. At the beginning, the injection causes only the oil to be produced until approximately one third (0.3) to three quarters (0.75) pore volume of the extraction reagent of the present invention is injected; after this, the extraction reagent of the present invention in which the oil is dissolved, is produced. The majority of the present oil can be recovered after the injection between approximately one and a half (1.5) to three and a half (3.5) pore volumes of the reagent. The method unexpectedly recovers approximately 90% of the original oil in the deposit. This method modality is also experimentally validated, as described in Example 22, which is presented below.

In a third in situ mode, an extraction reagent of the present invention is injected to improve the recovery of petroleum from petroleum deposits containing highly viscous oil, for example, the deposits of the "Orinoco Oil Belt" in Venezuela . The recovery factor with the recovery methods of the prior art is low, within the range of from 10% to 15% of the original oil in such deposits. The unexpected increase in the recovery efficiency of these reservoirs with the injection of the turpentine extraction reagent of the present invention can be further improved by means of adopting horizontal wells for both producing and injection wells, and impregnation of the wells. periodic steam from these wells.

The final recovery of natural gas from a large gas reserve can be increased by injecting an extraction reagent of the present invention into a reservoir. The production of gas from such a reservoir usually dangerously creates a large-scale subsidence on the surfaces of the gas field, for example the "Groeningen" field in the Netherlands. As such, it is necessary that the reservoir pressure be maintained by the injection of water. The water injected into the reserve traps approximately 30% of gas in situ at high pressure due to the flow of two phases of water and gas through the reservoir with low permeability. With the injection of an extraction reagent of the present invention, the gas trapped in the reserve is dissolved in the reagent and flows into the production wells. By means of the separation of the reagent and the gas on the surface, the gas is recovered and the reagent is recycled for a new use.

The extraction methods of the present invention can be implemented after one or more of the known methods for facilitating petroleum production, for example after the injection of C02 or natural gas and the surfactant addition is made.

Exemplary Modalities to carry out the Invention Carbon In certain embodiments, the anthracite or bituminous coal can be ground to sizes ranging from about 0.841 mm (20 mesh to about 0.149 mm (100 mesh), and subsequently be solubilized and / or extracted, that is, liquefied, by means of the immersion in a turpentine liquid under pressure within the range of approximately l.OxlO5 Paséales (1 atm) to approximately 2.0xl05 Paséales (2.0 atm). In certain other embodiments, the turpentine liquid may be natural, synthetic or mineral turpentine including up to about 50-70% by volume of a-terpineol, approximately 10-40% by volume of β-terpineol, and approximately 10% by volume of other components. In certain embodiments, the bed of the anthracite or bituminous ground coal can be stirred by the passage of said turpentine liquid at a temperature within the range of 80 ° C to about 130 ° C, or possibly up to the boiling point of said turpentine liquid. In certain other embodiments, the duration of solubilization and / or extraction, that is, liquefaction, may be within about 10 minutes to about 40 minutes. In certain embodiments, the contact time for the extraction of organic matter containing hydrocarbons from coal is less than 5 minutes.

In some embodiments, lignite, brown lignite, or any other low-range coal can be ground to sizes ranging from approximately 0.419 mm (40 mesh) to approximately 0.074 mm (200 mesh), and subsequently be solubilized and / or extracted, this is, liquefied, by means of the immersion in a turpentine liquid under a pressure within the range of approximately lOxlO5 Paséales (1 atm) to approximately 2.0xl05 Paséales (2.0 atm). In certain other modalities, the turpentine liquid may be natural, synthetic or mineral turpentine that includes approximately 70-90% by volume of α-terpineol, approximately 5-25% by volume of β-terpineol, and approximately 5% by volume of other components. In other embodiments, the ground coal bed of lignite, brown lignite or any other low range coal can be stirred by the passage of said turpentine liquid at a temperature within the range of between about 80 ° C and about 130 ° C. , or possibly up to the boiling point of said turpentine liquid. In certain other embodiments, the solubilization and / or extraction, that is, liquefaction, may be within about 20 minutes to about 60 minutes. In certain embodiments, the contact time for the extraction of organic matter containing hydrocarbons from coal is less than 5 minutes.

Little Bituminous In certain embodiments, the bituminous sheet can be ground to sizes ranging from about 0.419 mm (40 mesh) to about 0.074 mm (200 mesh), and subsequently be solubilized and / or extracted, ie, liquefied, by means of immersion in a turpentine liquid under a pressure in the range of approximately l.OxlO5 Paséales (1 atm) to approximately 2.0xl05 Paséales (2.0 atm). In other embodiments, the turpentine liquid may be natural, synthetic or mineral turpentine that includes approximately 70-90% by volume of a-terpineol, approximately 5-25% by volume of β-terpineol, and approximately 5% by volume of other components. In certain other embodiments, the ground bituminous bed can be agitated by passing said turpentine liquid at a temperature in the range of about 80 ° C to about 130 ° C, or possibly up to the boiling point of said bed. Turpentine liquid. In other embodiments, the solubilization and / or extraction, that is, liquefaction, may be within about 30 minutes to about 60 minutes. In certain modalities, the contact time for the extraction of organic matter containing hydrocarbons from bituminous shale is less than 5 minutes.

Bituminous Sands In certain embodiments, bituminous sands can be broken down to sizes ranging from approximately 25.4 mm (1 mesh) to approximately 4.76 mm (4 mesh), and subsequently to be solubilized and / or extracted, that is, liquefied, by means of immersion in a turpentine liquid under a pressure within the range of approximately l.OxlO5 Paséales (1 atm) to approximately 2.0xl05 Paséales (2.0 atm) . In other embodiments, the turpentine liquid may be natural, synthetic or mineral turpentine which includes a content of approximately 40-60% by volume of α-terpineol, approximately 30-50% by volume of β-terpineol, approximately 5% by volume of a and / or ß-pinene and approximately 5% by volume of other components. In another embodiment, a bed of ground bituminous sands can be agitated by passing said turpentine liquid at a temperature within the range of about 60 ° C to about 90 ° C, or possibly up to the boiling point of said liquid. of turpentine. In other embodiments, the solubilization and / or extraction, that is, liquefaction, may be within about 10 minutes to about 30 minutes. In certain modalities, the contact time for the extraction of organic matter containing hydrocarbons from tar sands is less than 5 minutes.

Raw oil In certain modalities, medium and light crude oil may be produced in situ, that is, collected from an underground deposit, by primary, secondary or tertiary recovery, by means of the injection of one (1.0) to approximately five (5.0) volumes of pore of a turpentine liquid. In other embodiments, between approximately two (2.0) and approximately four (4.0) pore volumes of a turpentine liquid can be injected. In certain embodiments, the turpentine liquid may be natural, synthetic or mineral turpentine that includes about 40-70% by volume of < x-terpineol, approximately 30-40% by volume of β-terpineol, 10% by volume of a and / or β-pinene and approximately 10% by volume of other components. In certain embodiments, the injection of a turpentine liquid can be followed by flooding with water with about one (1.0) to about three (3.0) pore volumes of water.

In certain embodiments, heavy and extra-heavy crude oil may be produced in situ, that is, removed from an underground reservoir, by primary, secondary or tertiary recovery, by injection of approximately one (1.0) to approximately five (5.0) pore volumes of a turpentine liquid. In other embodiments, between approximately two (2.0) and approximately four (4.0) pore volumes of a turpentine liquid can be injected. In certain embodiments, the turpentine liquid may be natural, synthetic or mineral turpentine that includes approximately 50-70% by volume of α-terpineol, approximately 20-35% by volume of β-terpineol, 10% by volume a and / or ß-pinene and approximately 5% by volume of other components can be used in conjunction with steam injection.

Referring to Figure 1, an apparatus for the recovery of organic matter containing hydrocarbons from bituminous sands is provided. The apparatus 100 includes a supply 102 of turpentine liquid, which can optionally be coupled to a pump 104, to supply a turpentine liquid to the contact container or extraction vessel 1 10. In certain embodiments, the supply of turpentine liquid it may include means for heating the turpentine liquid. In certain embodiments, the contact container may be a tilted rotary filter or sifter drum. The bituminous sands sample 106 is taken to a conveyor 108 or similar feeding apparatus for supplying the bituminous sands to an inlet of the contact container 1 10. Optionally, the conveyor 108 may include a filter screen or a similar separation apparatus for prevent large particles from being introduced into the process. The contact container 110 includes at least one inlet for the turpentine liquid to be introduced and brought into contact with the bituminous sands. The contact container 1 10 may include a plurality of trays or flaps 1 14 designed to retain the bituminous sands in the contact vessel for a specified amount of time, and to increase or control the contact between the bituminous sands particles and the liquid of turpentine. In certain embodiments, the contact container may be a tilted rotary filter. An extraction mixture that includes the extraction liquid and the organic matter containing hydrocarbons extracted from the tar sands is removed from the contact container 1 10 by means of an outlet 116, which may include a filter 1 18 to prevent the removal of the oil. solids with the extraction mixture that includes the extracted organic matter that contains hydrocarbons. The pump 120 may be coupled to the outlet 1 16 to assist with the supply of the extraction mixture to the holding tank 122. The line 124 may be coupled to the holding tank 112 to provide the extraction mixture for further processing. After extraction of the organic matter containing hydrocarbons, inorganic solids and other materials not soluble in the turpentine liquid can be removed from the contact container by means of a second conveyor 126. Some turpentine liquids include, but are not limited to , liquids that include α-terpineol and β-terpineol.

Referring now to Figure 2, the apparatus 200 is provided for the recovery of organic matter containing hydrocarbons from bituminous and other sedimentary rock formations that include recoverable hydrocarbon materials. The bituminous-shale sample 202 is taken to the mill or shredder 204 to reduce the size of the bituminousish. Preferably, the mill or grinder 204 reduces the bituminous backbone to between about 0.074 and 0.42 mm in diameter. The shredded bituminous sheet can optionally be supplied to a filter to ensure a uniform and / or adjusting particle size. The first conveyor 206 supplies particles from the mill or grinder 204 to the contact container 208. The contact container 208 is coupled to the turpentine liquid supply 210, which may optionally be coupled to a pump, and which supplies a liquid of turpentine to at least one inlet 212 coupled to the contact vessel 208. In certain embodiments, the supply of turpentine liquid may include means for heating the turpentine liquid. The contact container 208 may include a plurality of trays or flaps 214 designed to retain the bituminous esquit in the contact container for a specified amount of time, and to increase or control the contact between the bituminous-shale particles and the turpentine liquid. . In certain embodiments, the contact container may be a tilted rotary filter or sifter drum. A flow of extraction mixture including the turpentine liquid and the organic matter containing hydrocarbons, recovered from the bituminous waste is collected by means of an outlet 216 and supplied to the holding tank 220. The pump 218 is optionally coupled to the outlet 216 to assist with the supply of the flow of the extraction mixture to the holding tank 220. The flow of the extraction mixture may be coupled to the line 222 to provide the flow of the extraction mixture for further processing. The second conveyor 224 helps with the removal of materials Inorganic or insoluble contact container 208. Turpentine liquids may include, but are not limited to a-terpineol and β-terpineol.

Referring now to Figure 3, the apparatus 300 is provided for the recovery of organic matter containing hydrocarbons from coal. The carbon sample 302 is taken to the mill or grinder 304 to reduce the size of the coal. Preferably, the mill or grinder 304 reduces the size of the coal to between about 0.074 and 0.84 mm in diameter, depending on the quality of the carbon sample. In certain embodiments, the mill or shredder 304 can be a wet mill. The crushed carbon can optionally be taken to a filter to ensure a uniform particle size and / or to fit. The crushed coal is supplied to the first contact container 306. The first contact container 306 is also coupled to a supply 308 of turpentine liquid, which may optionally be coupled to the pump 310, and which supplies the turpentine liquid to the liquid. first contact vessel 306. In certain embodiments, the supply of the turpentine liquid may include means for heating the turpentine liquid. The first contact container 306 includes mixing means 312 designed to agitate and improve or control the contact between the solid carbon particles and the turpentine liquid. An extraction mixture flow including the turpentine liquid and the hydrocarbon-containing organic material recovered from the coal is collected via the outlet 313 of the first contact vessel and is supplied to the second contact vessel 316. The pump 314 is optionally coupled to the outlet 313 to assist in supplying the flow of the extraction mixture to the second contact vessel 316. The second contact vessel 316 may include a series of trays or fins 318 designed to increase or control the separation of the solids and turpentine liquids. Optionally, the second contact container 316 can be a tilted rotary filter or sifter drum. The flow of the extraction mixture can be collected from the outlet 320 of the second contact container, which can optionally be coupled to the pump 322, to assist with the supply of the flow of the extraction mixture to the holding tank 324. The Liquid carbon and any turpentine liquid present in the holding tank 324 can be supplied to a liquid coal refinery or other processing step via the line 326. The conveyor 328 can be coupled to a second contact container 316 for the removal and recovery of solids as a sub product of the process. Turpentine liquids may include, but are not limited to, α-terpineol and β-terpineol. The apparatus 300 can also be used to process high and low grade bituminous shale.

Referring now to Figure 4, process 400 is provided for the improved recovery of organic matter containing hydrocarbons from an underground formation containing hydrocarbons. Deposit 404 containing hydrocarbons is shown positioned below surface 402. Production well 406 is already in operation. The injection well 408 is provided for the injection of a turpentine liquid by means of line 410. The turpentine liquid facilitates the liquefaction, solubilization and / or extraction of the organic matter containing hydrocarbons present in the deposit, as well as It provides the driving force to push the organic matter that contains hydrocarbons into the production well. A flow of the hydrocarbon product including injected turpentine liquid is collected via line 412. Turpentine liquids may include, but are not limited to, α-terpineol and β-terpineol.

In certain modalities, the turpentine liquid to increase the production of an oil well is provided to include at least 30% by volume of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene , α-terpineol, β-terpineol, α-terpineol, terpene resins, α-terpene, β-terpene, β-terpene, or mixtures thereof. In other embodiments, the turpentine liquid contains at least 30% by volume of geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinano, 2-pinene hydroxyperoxide, terpine hydrate, 2 -pinanol, dihydromicenol, isoborneol, p-mentan-8-ol, a-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In still other embodiments, the turpentine liquid includes at least 30% by volume of anethole, camphene, p-cymene, anisaldehyde, 3,7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocmene, aloocimono alcohols. , 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, cintronelal, menthone, or mixtures thereof.

In certain embodiments, the turpentine liquid includes at least about 40% by volume of α-terpineol. In other embodiments, the turpentine liquid includes at least about 25 volume% of β-terpineol. In still other embodiments, the turpentine liquid includes at least about 40% by volume of a-terpineol and at least about 25% by volume of β-terpineol. In other embodiments, the turpentine liquid includes at least about 50% a-terpineol, and in certain embodiments also includes β-terpineol. In certain embodiments, the turpentine liquid includes at least 20% by volume of β-terpineol. In certain embodiments, the turpentine liquid includes between about 50 and 70% by volume of a-terpineol and between about 10 and 40% by volume of β-terpineol.

In another aspect, a process is provided to increase the production of an underground reservoir containing hydrocarbons that is carrying out improved recovery operations, which includes the injection of a turpentine liquid into the reservoir through an injection well for stimulate the production of hydrocarbon-containing material. The turpentine liquid may include at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, β-terpineol, terpene resins, a -terpene, ß-terpene,? -terpene, and mixtures thereof. In other embodiments, the turpentine liquid may include at least one compound selected from geraniol, 3-camphor, dipentene (p-mentha-1, 8-diene), nopol, pinano, 2-pinene hydroxyperoxide, terpine hydrate, 2 -pinanol, dihydromicenol, isoborneol, p-mentan-8-ol, a-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In still other modalities, the turpentine liquid may include at least one compound selected from anethole, camphene, p-cymene, anisaldehyde, 3,7-dimethyl-l, 6-octadiene, isobornyl acetate, ocimene, aloocimene, aloocimene alcohols, 2-methoxy -2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, cintronelal, menthone, or mixtures thereof. A production stream of organic matter containing hydrocarbons that includes the turpentine liquid and the recovered hydrocarbons is recovered from the production well associated with the reservoir containing hydrocarbons. The production flow of organic matter containing hydrocarbons can be separated into a stream of recovered hydrocarbons and a recycling stream of turpentine liquid. In certain embodiments, the method also includes the step of injecting the recycling stream of the turpentine liquid into the injection well.

In another aspect, a method is provided to increase the production of a hydrocarbon-containing underground hydrocarbon formation that is carrying out improved recovery operations. The method includes the steps of injecting a turpentine liquid into the formation through an injection well. In certain embodiments, the turpentine liquid includes at least 40% by volume of a-terpineol and at least 10% by volume of β-terpineol. The turpentine liquid solubilizes, extracts and / or displaces the materials containing hydrocarbons from the formation, which are subsequently recovered from the formation with the turpentine liquid through a production well. In certain embodiments, the method also includes the separation of hydrocarbons from the turpentine liquid. In still other modalities, the method also includes recycling the turpentine liquid to the injection well. In certain embodiments, a-terpineol is present in an amount between about 40 and 70% by volume. In certain other embodiments, α-terpineol is present in an amount of at least 70% by volume. In still other embodiments, β-terpineol is present in an amount of between about 10 and 40% by volume. In other embodiments, the turpentine liquid further includes up to about 10% by volume of? -terpineol. In other embodiments, the turpentine liquid may include up to about 25% by volume of an organic solvent selected from methanol, ethanol, propanol, toluene and xylenes. The method is useful for the recovery of organic matter containing hydrocarbons during primary, secondary and tertiary recovery operations, including post-secondary recovery operations that include flooding with water.

In another aspect, a turpentine liquid is provided for the recovery of organic matter containing hydrocarbons from bituminous sands. In one embodiment, the turpentine liquid includes at least about 30 volume% of a-terpineol and at least about 25 volume% of β-terpineol. In another embodiment, the turpentine liquid includes between about 30 and 70% by volume of a-terpineol, between about 25 and 55% by volume of β-terpineol, up to about 10% by volume of a-terpene, and up to about 10 % by volume of ß-terpene.

In another aspect, a turpentine liquid is provided for the recovery of organic matter containing hydrocarbons from high grade coal sources, such as, for example, anthracite or bituminous coal. In one embodiment, the turpentine liquid includes at least about 45% by volume of a-terpineol and at least about 15% by volume of β-terpineol. In another embodiment, the turpentine liquid includes between about 45 and 80% by volume of a-terpineol, between about 15 and 45% by volume of β-terpineol, up to about 10% by volume of a-teipineol, and up to about 10 % by volume of β-terpineol.

In another aspect, a turpentine liquid is provided for the recovery of organic matter containing hydrocarbons from low grade carbon sources. In one embodiment, the turpentine liquid includes at least about 60% by volume of a-terpineol and up to about 30% by volume of β-terpineol. In another embodiment, the turpentine liquid includes between about 60 and 95% by volume of a-terpineol, up to about 30% by volume of β-terpineol, up to about 5% by volume of a-terpene, and up to about 5% by volume volume of β-terpene.

In another aspect, a turpentine liquid is provided for the recovery of organic matter containing hydrocarbons from bituminous. As used herein, bituminous shale generally refers to any sedimentary rock containing bituminous materials. In one embodiment, the turpentine liquid includes at least about 60% by volume of a-terpineol and up to about 30% by volume of β-terpineol. In another embodiment, the turpentine liquid includes between about 60 and 95% by volume of a-terpineol, up to about 30% by volume of β-terpineol, up to about 5% by volume of a-terpene, and up to about 5% by volume volume of β-terpene.

In another aspect, a turpentine liquid is provided for the recovery of organic matter containing hydrocarbons from light and medium crude oil. In one embodiment, the turpentine liquid includes at least about 40 and 70% by volume of α-terpineol and at least about 30 and 40% by volume of β- terpineol. In yet another embodiment, the turpentine liquid includes between about 40 and 70% by volume of a-terpineol, between about 30 and 40% by volume of β-terpineol, up to about 10% by volume of a-terpene, and up to about 10% by volume of ß-terpene.

In another aspect, a turpentine liquid is provided to recover organic matter containing hydrocarbons from heavy and extra heavy crude oil. In one embodiment, the turpentine liquid includes at least about 50 and 70% by volume of a-terpineol and at least about 30 and 40% by volume of β-terpineol. In another embodiment, the turpentine liquid includes between about 50 and 70% by volume of a-terpineol, between about 30 and 40% by volume of β-terpineol, up to about 10% by volume of a-terpene, and up to about 10 % by volume of ß-terpene.

In another aspect, a method is provided for the recovery of organic matter containing hydrocarbons from bituminous sands. The method includes the mining of a rich formation in bituminous sands to provide a sample of bituminous sand, where the bituminous sand sample includes organic matter containing recoverable hydrocarbons and insoluble or inorganic residual material. The bituminous sand sample is supplied to a contact container, wherein the contact container includes at least one inlet for the supply of a turpentine liquid for the recovery of hydrocarbons from the bituminous sands. The bituminous sand sample is put in contact with a turpentine liquid to extract the organic matter containing hydrocarbons from the bituminous sands to produce a residual material and an extraction mixture. The extraction mixture includes the turpentine liquid and the recovered organic matter containing hydrocarbons, and the waste material is separated from the turpentine liquid to produce a hydrocarbon product flow and a turpentine liquid recycle stream. In certain embodiments, the method further includes the step of recycling the recycle stream of turpentine liquid to the contact container. In other embodiments, the extraction mixture can be separated by distillation to produce the flow of the hydrocarbon product and the recycle flow of the turpentine liquid.

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

In another aspect, a method is provided for recovering organic matter containing hydrocarbons from a shale oil rich in hydrocarbons. The method includes the exploitation by mining of a rock formation that includes organic matter that contains hydrocarbons to produce a bituminous waste that contains hydrocarbons and that includes recoverable hydrocarbon material and inorganic or insoluble material. The shale is ground to produce shredded bituminous shale containing hydrocarbons. The shredded bituminous slurry containing hydrocarbons is then filtered with a filter screen to prevent or control that excessively large particles are fed to the extraction process. The bituminous shale containing hydrocarbons is fed to a contact container, wherein the contact container includes at least one inlet for the supply of a turpentine liquid for the recovery of hydrocarbons from the crushed bituminous shale containing hydrocarbons. The bituminous shale containing hydrocarbons is placed in contact with the turpentine liquid to extract the hydrocarbon-containing organic material from the crushed bituminous shale containing hydrocarbons to produce inorganic solids and an extraction mixture that includes the turpentine and hydrocarbon liquid. recovered. Inorganic or insoluble materials are removed from the extraction mixture, and the recovered hydrocarbons are separated from the turpentine liquid to produce a hydrocarbon product flow and a turpentine liquid recycle stream. In certain embodiments, the recycle stream of turpentine liquid is recycled to the contact container. In other embodiments, the shredded bituminous shale containing hydrocarbons has an average particle size of less than about 0.42 mm in diameter. In other embodiments of the method for the recovery of organic matter containing hydrocarbons from bituminous wax, the turpentine liquid includes at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, a-pinene, β-pinene, α-terpineol, β-terpineol, α-terpineol, terpene resins, α-terpene, β-terpene, β-terpene, or mixtures thereof. In other embodiments, the turpentine liquid includes at least one compound selected from geraniol, 3-carene, dipentene (p-mentha-1, 8-diene), nopol, pinano, 2-pinene hydroperoxide, terpine hydrate, 2- pinanol, dihydromicenol, isoborneol, p-menthan-8-ol, a-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In still other embodiments, the turpentine liquid includes at least one compound selected from anetola, camphene, p-cymene, anisaldeido, 3,7-dimethyl-l, 6-octadiene, isobornyl acetate, ocimene, aloocimene, aloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, cintronelal, menthone, or mixtures thereof. In certain embodiments, the turpentine liquid may include α-terpineol. In other embodiments, the turpentine liquid may include at least about 40% by volume of a-terpineol and between 10 and 40% by weight of β-terpineol. In certain modalities, between 0.5 and 4 equivalents of the turpentine liquid are used to make contact with the bituminous waste and recover organic matter containing hydrocarbons. In certain modalities, between 0.5 and 2.0 equivalents of the turpentine liquid are used to contact the bituminous waste and recover hydrocarbons.

In another aspect, a method is provided for the recovery of organic matter containing hydrocarbons from a coal-rich underground formation. The method includes the mining of the underground formation to produce coal, where the coal includes an organic matter that contains recoverable hydrocarbons and inorganic or insoluble material. The coal is ground to produce crushed and filtered coal to provide a sample of uniform or desired size. The crushed coal is fed to a contact container, wherein the contact container includes at least one inlet for the supply of turpentine liquid for the recovery of hydrocarbons from crushed coal, and put in contact with the turpentine liquid for extract the hydrocarbons from the crushed coal to produce inorganic solids and an extraction mixture. The extraction mixture includes the turpentine liquid and the recovered hydrocarbons. The inorganic or insoluble solids are separated from the extraction mixture, and the recovered hydrocarbons are separated from the turpentine liquid to produce a flow of liquid carbon product and a recycle stream of turpentine liquid. In certain embodiments, the method further includes recycling the recycle stream of turpentine liquid to the contact container. In still other embodiments, the flow of liquid carbon product is supplied to a liquid coal refinery. In certain embodiments, the carbon sample includes a low grade carbon having an average particle size of less than about 0.42 mm. In certain embodiments, the carbon sample includes a high grade carbon having an average particle size of less than about 0.84 mm.

In still other modalities of the method for the recovery of organic matter containing hydrocarbons from coal, the turpentine liquid includes at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, a-pinene, ß- pinene, α-terpineol, β-terpineol, β-terpineol, terpene resins, < x-terpene, β-terpene, β-terpene, or mixtures thereof. In other embodiments, the turpentine liquid includes at least one compound selected from geraniol, 3 -carene, dipentene (p-mentha-1, 8-diene), nopol, pinano, 2-pinene hydroxyperoxide, terpine hydrate, 2- pinanol, dihydromicenol, isoborneol, p-menthan-8-ol, a-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In other embodiments, the turpentine liquid includes at least one compound selected from anetola, camphene, p-cymene, anisaldeido, 3,7-dimethyl-l, 6-octadiene, isobornyl acetate, ocimene, aloocimeno, aloocimeno alcohols, -methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, cintronelal, menthone, and mixtures thereof. In certain embodiments, the turpentine liquid includes at least 60% by volume of a-terpineol. In certain embodiments, the turpentine liquid includes at least 45% by volume of a-terpineol and at least approximately 15% by volume of β-terpineol. In certain other embodiments, the turpentine liquid includes at least 60% by volume of a-terpineol and up to about 30% by volume of β-terpineol. In certain modalities, between 0.5 and 4 equivalents of the turpentine liquid are used to make contact with the bituminous waste and recover the organic matter that contains hydrocarbons. In certain modalities, between 0.5 and 2.0 Turpentine liquid equivalents are used to contact the bituminous waste and recover the organic matter that contains hydrocarbons.

In another aspect, a system is provided to recover organic matter containing hydrocarbons from bituminous sands. The oil sands recovery system includes a tank for the supply of a turpentine liquid and a contact container, wherein the contact container includes at least one inlet for introducing the turpentine liquid and at least one outlet for the recovery of an extraction mixture from the contact container. The system also includes a first conveyor to supply bituminous sands to the contact container. A holding tank is provided which includes a line connecting the holding tank to the contacting vessel, wherein the line connecting the contacting vessel and the holding tank includes a filter to prevent the passage of solids into the holding tank. retention. The system also includes a second conveyor for the recovery and transport of solids.

In one embodiment, the contact container is an inclined rotary filter that includes a series of trays or fins for separating and / or controlling the bituminous sands. In another embodiment, the trays or fins are provided to increase or control the contact time between the tar sands and the turpentine liquid. In certain embodiments, the turpentine liquid may include α-terpineol. In other embodiments, the turpentine liquid may include between about 30% and 70% by volume of a-terpineol and between about 25% and 55% by weight of β-terpineol.

In another aspect, a system is provided for the recovery of organic matter containing hydrocarbons from bituminous waste. The system includes a tank for the supply of a turpentine liquid and a mill to crush the bituminous worm at a reduced particle size. A contact container is provided which includes at least one entry for introducing the turpentine liquid, at least one entry for receiving shredded bituminous shale, at least one exit for the recovery of solids from the contact container and at least one exit for recovering an extraction mixture from the contact container. A first conveyor is provided to provide shredded bituminous shale to a contact container. The system also includes a holding tank, wherein the holding tank includes a line connecting the holding tank with the contact vessel, wherein the line includes a filter to prevent the passage of solids into the holding tank; a second conveyor to recover solids. In certain embodiments, the system further includes a line for supplying a reaction mixture including recovered hydrocarbons and the turpentine liquid to a refinery for further separation and / or processing. In certain embodiments, the turpentine liquid may include between about 60% and 95% by volume of a-terpineol and up to about 30% by weight of β-terpineol. In other embodiments, the turpentine liquid may include between about 70% and 90% by volume of a-terpineol and between about 5 and 25% by weight of β-terpineol.

In another aspect, a system for the recovery of organic matter containing hydrocarbons from coal is provided. The system includes a tank to supply a turpentine liquid and a mill to crush the coal to produce particulate matter of a reduced size. A contact container is provided which includes at least one entry for introducing the turpentine liquid and at least one outlet for recovering solids and liquids from the contact container. The contact container also includes stirring means for completely mixing the turpentine liquid and the crushed coal. A separator is provided for separating solids and liquids, wherein the separator includes an inlet, an outlet and a line connecting the inlet of the separator with the outlet of the contact container. The system also includes a holding tank, wherein the holding tank includes a line connecting the holding tank to the separator, where the line may include a filter to prevent the passage of solids into the holding tank.

In certain embodiments, the system further includes a filter to selectively prevent particles having an average diameter larger than about 0.85 mm from being introduced into the contact container. In certain other embodiments, the system also includes a line for supplying a liquid coal product to a refinery for further processing. In certain embodiments, the system further includes a first conveyor for supplying crushed coal to the contact container. In other embodiments, the system also includes a second conveyor for the removal of solids from the separator. In certain modalities, the turpentine liquid may include a-terpineol, In modalities aimed at the recovery of hydrocarbons from high grade coal, the turpentine liquid may include between approximately 45% and 80% volume of a-terpineol and between approximately 15% and 45% by weight of β-terpineol. In embodiments directed to the recovery of hydrocarbons from high grade coal, the turpentine liquid may include between about 60% and 95% by volume of a-terpineol and between about 0% and 30% by weight of β-terpineol.

In another aspect, a method is provided for optimizing a turpentine liquid for the extraction of organic matter containing hydrocarbons from hydrocarbon-containing material. Generally, the method includes providing a sample of the hydrocarbon-containing material and analyzing the hydrocarbon material to determine the type of hydrocarbon being extracted. A formulation is provided for the extraction of organic matter containing hydrocarbons from the hydrocarbon material, wherein the formulation is a function of the type of formation and the size of the particles of the hydrocarbon material. Generally, the formulation includes at least about 40% volume of a-terpineol and at least about 10% by volume of β-terpineol. The amount of a-terpineol and β-terpineol in the formulation is then adjusted based on the parameters noted above. In general, although the above-mentioned method provides a good starting point to determine the desired formulation for the extraction of various hydrocarbon-containing materials, for other hydrocarbon-containing materials and under specific operating conditions, either a series of experiments designed statistically or a series of experiments according to an optimization method can in order to determine the optimal composition of the turpentine liquid.

As shown in Table 1, the specific formulation for the extraction, liquefaction and / or solubilization of the organic matter containing hydrocarbons from bituminous sands varies depending on the particle size. In certain embodiments, the method for preparing a turpentine liquid to extract organic matter containing hydrocarbons from bituminous sands includes adjusting the amount of α-terpineol and β-terpineol in the formulation as a function of the size of the solid particles rich in hydrocarbons that are being extracted. In other modalities, if the particulate organic matter containing hydrocarbons includes low grade carbon or a small bituminous, the amount of a-terpineol in the turpentine liquid is increased and the amount of β-terpineol in the turpentine liquid is decreased. In other embodiments, if the particulate organic matter containing hydrocarbons includes tar sands, the amount of a-terpineol in the turpentine liquid is decreased and the amount of β-terpineol in the turpentine liquid is increased. In other embodiments, if the particulate organic matter containing hydrocarbons includes bituminous sands and the average diameter of the particulate matter is less than about 4.76 mm, then the amount of a-terpineol in the turpentine liquid is decreased and the amount of β-terpineol in the turpentine liquid is increased. In other embodiments, if particulate organic matter containing hydrocarbons includes tar sands and the average diameter of the particulate matter is greater than about 2.54 centimeters [1 inch] (mesh 1), then the amount of a-terpineol in the liquid of turpentine is increased and the amount of β-terpineol in the turpentine liquid is decreased.

Table 1. Formulations for the extraction of bituminous sands based on Similar to what was shown above with respect to the extraction of tar sands, as shown in Tables 2 and 3, the formulation for the extraction, liquefaction and / or solubilization of coal depends on both the particle size and the quality of the coal that is being extracted. In one embodiment of the method for preparing a turpentine liquid for extracting organic matter containing hydrocarbons, if the hydrocarbon-containing material includes anthracite, bituminous coal, or other high-grade coal and the average diameter of the particulate matter is less than about 0.15 mm, then decreases the amount of a-terpineol in the turpentine liquid and increases the amount of β-terpineol in the turpentine liquid. In other embodiments, if the particulate matter rich in hydrocarbons includes anthracite, bituminous coal, or other high grade carbon and the average diameter of the particulate matter is greater than about 0.84 mm, then the amount of α-terpineol in the Turpentine liquid and decreases the amount of ß-terpineol in the turpentine liquid. In another embodiment, if the particulate matter rich in hydrocarbons includes low grade carbon and the average diameter of the particle size is less than about 0.074 mm, then the amount of a-terpineol in the turpentine liquid decreases and the amount of β-terpineol in the turpentine liquid. In another embodiment, if the particulate matter rich in hydrocarbons includes low grade carbon and the average diameter of the particulate matter is greater than about 0.42 mm, then the amount of a-terpineol in the turpentine liquid increases and the amount decreases. of ß-terpineol in the turpentine liquid.

Table 2. Formulations for High Grade Coal Extraction based on the Size of the Particle Table 3. Formulations for the extraction of Low Grade Coal based on the particle size.

Particle size α-terpineol ß-terpineol A- / p-terpene Others (Mesh / diameter, mm) < Mesh 200 (0.074 mm) 60-80% vol. 10-30% vol. 5% vol. 0% vol.

Mesh 40 (0.420 mm) - 70-90% vol. 5-25% vol. 5% vol. 0% vol. 200 mesh (0.074 mm) > Mesh 40 (0.420 mm) 75-95% vol. 0-20% vol. 5% vol. 0% vol.

Similar to what was shown above with respect to the extraction of tar sands, as shown in Table 4, the formulation for the extraction, liquefaction and / or solubilization of bituminous shale depends on the particle size. In one embodiment of the method for preparing a composition for extracting organic matter containing hydrocarbons, if the particulate matter rich in hydrocarbons includes a bituminous waste and the average diameter of the particulate matter is less than about 0.074 mm, then the amount of a -terpineol in the turpentine liquid is decreased and the amount of β-terpineol in the turpentine liquid is increased. In another embodiment, if the particulate matter rich in hydrocarbons includes bituminous ridges and the average diameter of the particulate matter is greater than about 0.42 mm, then the amount of a-terpineol in the turpentine liquid is increased and the amount of ß -terpineol in turpentine is diminished.

Table 4. Formulations for Bituminous Estrus Extraction based on The extraction of crude oil in a similar way depends on the type of crude oil that is being extracted, liquefied and / or solidified. As shown in Table 5, the formulation for the extraction, liquefaction and / or solubilization of the crude oil depends on a function of both the particle size and the quality of the density of the crude oil being extracted. The method includes providing a turpentine liquid formulation that includes at least 50% by volume of a-terpineol and at least 20% by volume of β-terpineol; Adjust the amount of a-terpineol and β-terpineol in the turpentine liquid formulation based on the density of the liquid hydrocarbon you are being extracted. In one embodiment, if the API gravity of the liquid hydrocarbon being extracted is greater than about 22 °, then the amount of terpineol in the turpentine liquid is decreased and the amount of β-terpineol in the turpentine liquid is increased. . In another embodiment, if the API gravity of the liquid hydrocarbon being extracted is less than about 22 °, then the amount of a-terpineol in the turpentine liquid is increased and the amount of β-terpineol in the turpentine liquid is decreased . As used herein, light oils have an API of less than about 3 Io, medium crude oils have an API of between about 22 ° and about 31 °, heavy oil has an API of between about 10o and about 22 °, and extra heavy oil has an API of less than about 10 °.

Table 5. Formulations for Crude Oil Extraction based API density In another aspect, a method is provided for preparing a turpentine liquid to improve the recovery of organic matter containing liquid hydrocarbons from an underground formation. The method includes providing a formulation comprising at least 50% by volume of a-terpineol and at least 20% by volume of β-terpineol, and adjusting the amount of a-terpineol and β-terpineol in the formulation based on the geological characteristics of the underground formation.

In another aspect, a composition for cleaning and / or recovering hydrocarbons from a container containing liquid hydrocarbons is provided, wherein the composition includes at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, a -pinene, ß-pinene, α-terpineol, β-terpineol, α-terpineol, terpene resins, α-terpene, β-terpene, β-terpene, or mixtures thereof. In other modalities, the composition for cleaning and / or recovering hydrocarbons includes at least one compound selected from geraniol, 3-camphor, dipentene (p-mentha-1, 8-diene), nopol, pinano, 2-pentane hydroxyperoxide, terpine hydrate, 2-pentanol, dihydromicenol, isoborneol, p- mentan-8-ol, a-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In still other embodiments, the composition for cleaning and / or recovering hydrocarbons includes at least one compound selected from anetola, camphene, p-cymene, anisaldeido, 3,7-dimethyl-1, 6-octadiene, isobornyl acetate, ocimene, alloocmene. , aloocimeno alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, cintronelal, menthone, and mixtures thereof. In one embodiment, the composition includes at least one compound of the following: α-pinene, β-pinene, α-terpineol, and β-terpineol. In another embodiment, the composition includes at least 25% by volume of α-terpineol or β-terpineol.

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

Examples Example 1.

In this example, coal from the Pittsburgh vein in Washington County, Pennsylvania was lique with a-terpineol reagent. The coal sample was obtained from Coal Bank at the Pennsylvania State University, which provided the following approximate analysis for this; 2.00% by weight of received moisture, 9.25% by weight of dry ash, 38.63% by weight of dry volatile matter, and 50.12% of dry fixed carbon. The particle size of the carbon sample was approximately 60 mesh.

Approximately 60 grams of α-terpineol were gently added to approximately 30 grams of the carbon sample placed in an extraction vessel, thereby giving a ratio of reagent to sample of 2 to 1. The extraction vessel closed but not hermetically sealed containing the resulting mixture of α-terpineol and carbon was maintained at a constant temperature of about 96 ° C and was continuously stirred. Without boiling the α-terpineol, the pressure in the extraction vessel remained at ambient pressure of slightly less than about l .OlxlO5 Paséales (1 atm). After 30 minutes, the mixture was filtered and the carbon particles retained in the filter were washed with ethanol and dried at a constant weight. Based on the weight loss, it was determined that the conversion, that is, the degree of liquefaction, of the carbon sample was approximately 68% by weight.

Example 2 This example is identical to Example 1 in all aspects except two. After maintaining the temperature at about 96 ° C, for about 30 minutes, as was done in Example 1, the extraction vessel containing the carbon sample and the α-terpineol was maintained at a temperature of approximately 135 ° C. an additional period of approximately 30 minutes. The pressure in the extraction vessel remained at ambient pressure of slightly less than approximately 1.01x10s Paséales (1 atm). The conversion, ie, the degree of liquefaction, of the carbon sample was determined to be about 70% by weight.

Example 3 The carbon sample was from the same source with the same approximate analyzes as those used in the two preceding examples. Approximately 31 grams of α-terpineol were added to approximately 31 grams of the carbon sample in an extraction vessel. The mixture was maintained at about 96 ° C and an ambient pressure of slightly less than about 1.01x105 Pases (1 atm) for about 30 minutes. It was determined that the conversion, that is, the degree of liquefaction, of the carbon sample obtained was about 71% by weight by weighing the sample after filtering it, washing it, and drying it as was done in the two previous examples.

Example 4 This example is identical to Example 3, except that about 30% by weight of α-terpineol was replaced with hexane, providing a reagent including 70% by weight of α-terpineol and 30% by weight of hexane. This reduced the conversion, that is, the degree of liquefaction to approximately 1.3% by weight.

Example 5 The source and approximate analysis of the carbon sample and the experimental conditions in terms of temperature, pressure and ratio of reagent to sample for this example were the same as those of Example 3. The duration of the extraction, however, was reduced from about 30 minutes to about 20 minutes. Additionally, about 30% by weight of α-terpineol was replaced with 1-butanol, providing a reagent including 70% by weight of α-terpineol and 30% by weight of 1-butanol. The amount of liquefied coal was only about 0.30 grams, corresponding to the conversion of about 1.0% by weight.

Example 6 This example is the same as Example 3 in terms of the source and the approximate analyzes of the carbon sample and temperature, pressure and duration of extraction. The amount of the carbon sample used was, however, approximately 25 grams and the reagent comprised approximately 24 grams (80% by weight) of a-terpineol and approximately 6 grams (20% by weight) of xylenes, providing a reagent that it included 70% by weight of a-terpineol and 30% by weight of xylenes. The liquefied carbon was approximately 10.0 grams, corresponding to the conversion of approximately 40% by weight.

Example 7 In this example, coal from the Wyodak vein in Campbell County, Wyoming was liquefied with the a-terpineol reagent. The coal sample was obtained from Coal Bank at the Pennsylvania State University, which provided the following approximate analyzes for this: 26.30% by weight of moisture received, 7.57% by weight of dry ash, 44.86% of dry volatile matter, and 47.57% by weight of dry fixed carbon. The particle size of the carbon sample was approximately 20 mesh. Approximately 60 grams of α-terpineol were added gently to approximately 30 grams of the carbon sample placed in an extraction vessel, a ratio of reagent to sample of approximately 2. a 1. The closed, but not hermetically sealed extraction vessel containing the resulting mixture of α-terpineol and carbon was maintained at a constant temperature of about 96 ° C and was continuously stirred. Without boiling the α-terpineol, the pressure in the extraction vessel remained at ambient pressure of slightly less than approximately 1.01 × 10 5 Paséales (1 atm). After about 30 minutes, the mixture in the extraction vessel was filtered and the carbon particles retained in the filter were washed with ethanol and dried to constant weight. Based on the weight loss, it was determined that the conversion, that is, the degree of liquefaction, of the carbon sample was 75% weight.

Example 8 The experiment in this example was carried out under conditions identical to those of the previous example except one. Approximately 15 grams of α-terpineol were added, instead of approximately 60 grams, as was done in the previous example, to approximately 30 grams of the carbon sample, thus a 0.5 to 1 ratio of carbon reactant was achieved. The conversion, that is, the degree of liquefaction, of the obtained carbon sample decreased from about 75% by weight achieved in the previous example to about 69% by weight.

Example 9 In this example, approximately 3 grams of bituminous shale from the Colorado River Verde region were solubilized with approximately 9 grams of a-terpineol, in this way giving rise to a ratio of reagent to sample of 3 to 1, to extract kerogen (organic matter) and / or bitumen (organic matter) of this. The content of organic carbon, including both volatile and fixed carbon, was determined to be approximately 22.66% by weight by a certified analytical company. Two experiments with bituminous-shale samples, with a 60-mesh particle size, were carried out under ambient conditions of pressure and temperature of about 25 ° C and slightly less than about 1.01x105 Pases (1 atm), respectively. The weight losses of the samples were determined by weighing the samples after filtering them, washing them with ethanol, and drying them. These losses were approximately 9% by weight after 30 minutes and approximately 17% by weight after 45 minutes. From these weight losses, it was estimated that the conversion, that is, the degree of extraction of the organic matter, that is, kerogen and / or bitumen, was approximately 40% by weight for the former and approximately 75% by weight. in weight for the last one.

Example 10 The example duplicated the previous example with the exception that a single experiment, which lasted approximately 15 minutes, was carried out at a temperature of about 96 ° C instead of about 25 ° C. The weight loss of the bituminous-shale sample was approximately 12% by weight, corresponding to the conversion, that is, the degree of extraction, of kerogen (organic matter) of approximately 53% by weight.

Example 11 In this example, bitumen (organic matter) in the tar sands of Alberta, Canada was solubilized and extracted with commercial grade synthetic turpentine. The bituminous sands sample was obtained from the Alberta Research Council, which provided the following approximate analysis for this; 84.4% by weight of dry solids, 1.6% by weight of dry bitumen, and 4.0% by weight of moisture received. Approximately 30 grams of synthetic turpentine was gently added to approximately 15 grams of the bituminous sands sample in a closed extraction vessel, but not sealed hermetically, using a ratio of reactant to sample of approximately 2 to 1 by weight. This extraction vessel, which contains the resulting mixture of synthetic turpentine and bituminous sands was maintained at a constant temperature of about 96 ° C and was continuously agitated. Without boiling the synthetic turpentine, the pressure in the extraction vessel remained at room temperature of slightly less than about l .OlxlO5 Paséales (1 atm). After 20 minutes, the mixture in the extraction vessel was filtered and the solids (bituminous sands) retained in the filter were washed with ethanol and dried at a constant weight. Based on the weight loss, it was determined that the conversion, that is, the degree of extraction, of the bitumen from the bituminous sand sample was approximately 100% by weight.

Example 12 In this example, approximately 60 grams of the bituminous sands sample from the same source with the same approximate analysis as that of the previous example was extracted by approximately 60 grams of a-terpineol, instead of commercial-grade synthetic turpentine, which includes α-terpineol. The resulting ratio of reagent to sample was 1 to 1 instead of 2 to 1 as in the previous example. The experiment lasted about 30 minutes at a temperature of about 96 ° C under the ambient pressure of slightly less than about l .OlxlO5 Paséales (1 atm). It was determined that the conversion, that is, the degree of extraction, of the bitumen (organic matter) in the bituminous sands sample was approximately 100% by weight.

Example 13 In this example, approximately 60 grams of the bituminous sands sample from the same source with the same analysis as that of the two previous examples were extracted by approximately 60 grams of synthetic turpentine, which is of commercial grade. The resulting ratio of reagent to sample, in this way, was about 1 to 1. The experiment was carried out for about 30 minutes at a temperature of about 96 ° C under ambient pressure conditions of slightly less than about l .OlxlO5 Pass (1 atm). HE determined that the conversion, that is, the degree of extraction, of the bitumen (organic matter) in the bituminous sands sample was approximately 70% by weight.

Example 14 The experiment in this example doubled that of Example 8 in all respects except that the ratio of reagent to sample was reduced from approximately 2 to 1 to approximately 0.5 to 1: Approximately 60 grams of the tar sands sample were extracted by approximately 30 grams of synthetic turpentine, which is of commercial grade. It was determined that the conversion, that is, the degree of extraction, of bitumen (organic matter) decreased from about 100% by weight achieved in Example 9 to about 70% by weight.

Example 15 The experiment in this example repeated that of the previous example with a-terpineol instead of commercial-grade synthetic turpentine. The conversion, that is, the degree of extraction, of bitumen (organic matter) in the bituminous sands sample was approximately 70% by weight as in the previous example.

Example 16 The experiment in this example was carried out under conditions of environmental pressure of slightly less than approximately 1.01x105 Paséales (1 atm) with the bituminous sands sample from the same source and with the same approximate analysis as that in the previous examples with bituminous sands. Approximately 60 grams of commercial grade synthetic turpentine was added to approximately 60 grams of the bituminous sands sample, thus resulting in a ratio of reagent to sample of approximately 1 to 1. The sample temperature and the synthetic turpentine commercial grade was maintained at about 65 ° C for about 30 minutes followed by cooling to about 15 ° C within about 5 minutes. Subsequently, the bituminous sand sample was filtered, washed, dried and weighed. Based on the weight loss, it was determined that the conversion, that is, the degree of extraction, of bitumen (organic matter) in the bituminous sands sample was approximately 70% by weight.

Example 17 The experiment in this example repeated that of the previous example with a-terpineol instead of commercial-grade synthetic turpentine. The conversion, that is, the degree of extraction, of bitumen (organic matter) increased to about 90% by weight from about 70% by weight of the above examples.

Example 18 In this example, a sample of bituminous sands, weighing approximately 30 grams, from the same source and with the same approximate analysis as those of Examples 1 to 17, was extracted with a liquid that included approximately 20 grams (80% in weight) of α-terpineol and about 5 grams (20% by weight) of toluene at a temperature of about 96 ° C under ambient pressure of slightly less than about 0.1 L × 10 × 5 Paséales (1 atm). The duration of the experiment (reaction or extraction time) was approximately 30 minutes. The weight loss of the sample was approximately 10.2 grams. From this weight loss, it was estimated that the conversion, that is, the degree of extraction, of bitumen (organic matter) was approximately 33% by weight.

Example 19 Three samples of bituminous sands, all from the same source and with the same Approximate analysis of those used in all the above examples with tar sands were extracted by reagents comprising various amounts of α-terpineol and ethanol at a temperature of about 15 ° C under the ambient pressure of slightly less than about l .Ol × 1 O 5 Pasεales ( 1 atm). The duration of each experiment (reaction or extraction time) was approximately 15 minutes for each sample of bituminous sand. The first sample was extracted with a mixture comprising approximately 0 grams (0% by weight) of a-terpineol and approximately 15 grams (100% by weight) of ethanolAv. , that is, with pure ethanol. The second sample was extracted with a mixture comprising approximately 7.5 grams (50% by weight) of a-terpineol and approximately 7.5 grams (50% by weight) of ethanol. The third sample was extracted with a mixture comprising approximately 12 grams (80% by weight) of a-terpineol and approximately 3 grams (20% by weight) of ethanol. The weight losses and estimated conversions, that is, the extraction grades, of bitumen (organic matter) in the three samples were approximately 0.2 grams (1.0% by weight), 0.6 grams (3.0% by weight) and 0.9 grams (4.5% by weight), for the first, second and third samples, respectively.

Example 20 Perdigones of irregular forms of commercial grade asphalt whose average size was about 15 mm were solubilized and extracted with a-terpineol and at room temperature of about 22 ° C under an environmental pressure of slightly less than about 1.01x105 Paséales (1 atm) . The first sample, weighing approximately 20 grams, was solubilized and extracted with approximately 40 grams of α-terpineol, and the second sample, which also weighed approximately 20 grams, was solubilized and extracted with approximately 20 grams of α-terpineol. Both samples were completely dissolved after 30 minutes. These experiments were carried out to simulate the solubilization and extraction of heavy crude oil, which tends to be rich in asphaltenes such as asphalt.

Example 21 In this example, bitumen (organic matter) in bituminous sands from the same source and with the same approximate analysis of those used in all previous examples with tar sands was solubilized and extracted with two varieties of vegetable oils, soybean oil. and corn oil. Vegetable oils are completely miscible with turpentine. In the first experiment, a bituminous sands sample weighing approximately 15 grams was mixed and stirred continuously with approximately 30 grams of soybean oil for approximately 20 minutes at a temperature of approximately 96 ° C under a slightly ambient air pressure. less than about l .OlxlO5 Pases (1 atm).

The weight loss was approximately 0.5 grams from which it was estimated that the conversion, that is, the degree of extraction, of the bitumen in the sample was approximately 3.3% by weight. In the second experiment, a sample of bituminous sand weighing approximately 30 grams was mixed and stirred continuously with approximately 60 grams of corn oil for approximately 30 minutes at a temperature of approximately 175 ° C under ambient pressure of slightly less than approximately 1.01x105 Paséales (1 atm). The weight loss was approximately 4.8 grams from which it was estimated that the conversion, that is, the degree of extraction, of the bitumen in the sample was approximately 12% by weight.

Example 22 Two tests were performed on core samples of Berean sandstone plug to determine the effect of reagent injection on oil recovery from the core. The first test was designed to determine the increase in oil recovery due to the injection of a-terpineol after a field had already been flooded with water to the limit. The selected core contained 9.01 mL of laboratory oil that simulates crude oil. Flooding with water with an aqueous solution containing 3.0% potassium chloride produced 4.6 mL of oil. Five (5) pore volumes of the a-terpineol injection produced an additional 3.61 mL of oil, thus leaving the core with less than 8.0% of the oil remaining in the original volume. The second test was designed to represent the increase in recovery that could be expected from a virgin reservoir with a-terpineol injection. The selected core contained 8.85 mL of laboratory oil that simulated crude oil. Oil production began after approximately 0.5 pore volumes of a-terpineol injection, which continued to 3.5 pore volumes; however, most of the oil was recovered after only 2.5 pore volumes of the α-terpineol injection. A total of 7.94 mL of laboratory oil were recovered, thus leaving the core with less than 7.5% of oil remaining in the original volume.

In one experiment, several different proportions of a turpentine liquid to tar sands sample were tested. The turpentine liquid for each of the experiments provided below had the same formulation, wherein the composition included about 60 volume% of a-terpineol, about 20 volume% of β-terpineol, and about 20 volume% of β-terpineol. The tar sands were a different mix of minerals from Alberta, Canada, which had a bitumen content of about 12% by weight and a water content of between about 4-5% by weight. The experiments were all carried out at atmospheric temperature.

As shown in Table 6 below, the recovery of hydrocarbons from bituminous sands through all of the proportions given below (ie, proportions of turpentine to tar sands within the range of 1: 2 to 2: 1) resulted in a good hydrocarbon recovery and little discernible difference. With respect to the temperature at which the extraction is carried out, it is believed that the optimum temperature for the extraction, solubilization and / or liquefaction of hydrocarbons from bituminous sands is 65 ° C. As shown in the table, at approximately 130 ° C, the amount of hydrocarbons recovered is reduced. It can be noted, however, that for certain solids from which it is particularly difficult to recover hydrocarbons, increasing the temperature of the extraction solvent can increase the amount of hydrocarbons that are recovered. Finally, it is shown that the exposure time had very little effect on the amount of materials that were extracted. This is probably due to the fact that the smallest extraction time was 20 minutes, which is believed to be more than adequate for the extraction of hydrocarbons from tar sands.

Table 6 Additional experiments were carried out using alternative solvents, such as ethanol and corn oil, which was compared to the composition which included approximately 60 vol.% A-terpineol, approximately 20 vol.% Β-terpineol, and approximately 20 vol. % by volume of? -terpineol. As noted in Table 7 below, the performance of ethanol and corn oil were unexpected and substantially less than the composition which included 60% by volume of a terpineol, approximately 20% by volume of β-terpineol, and about 20% by volume of? -terpineol. For example, while the terpineol composition achieved a complete or almost complete extraction of extractable hydrocarbons, ethanol resulted in only 10% of the recovered hydrocarbons and the heated corn oil gave rise to only 33% of the recoverable hydrocarbons.

Table 7 As shown in Table 8 below, the function of various turpentine liquid formulations is provided, including turpentine liquid formulations including only α-terpineol and α-terpineol in combination with various known organic solvents. The first three compositions presented in the table include a-terpineol, β-terpineol, and β-terpineol. For example, the same primer includes about 60 volume% of a-terpineol, about 30 volume% of β-terpineol, and about 10 volume% of β-terpineol. The results showed unexpectedly that as the concentration of a-terpineol increases, the turpentine function increases to the point that when the turpentine liquid includes approximately 70% of a-terpineol, the complete extraction of the hydrocarbon material from the bituminous sands sample is achieved.

The second data set is presented for the extraction of oil sands containing hydrocarbons with pure a-terpineol. As shown, extraction of more than 100% is achieved, probably due to inconsistencies in the hydrocarbon content of the samples. However, the results generally show the unexpected result that a-terpineol is capable of extracting substantially all of the recoverable hydrocarbon from a sample of bituminous sand.

Finally, the latest data provided in Table 8 illustrates the effectiveness of mixed systems of α-terpineol and known organic solvents. As shown, the substantially complete recovery of the recoverable hydrocarbons is achieved with a composition that includes a 1: 1 ratio of a-terpineol to ethanol. This is unexpected since pure ethanol only removed approximately 10% of the total recoverable hydrocarbons. Additionally, blended systems that include either a 1: 1 or a 3: 1 ratio of a-terpineol to toluene still resulted in the recovery of 77% and 92% of the total recoverable hydrocarbons. This is an unexpected result.

Table 8 The results of the extraction of organic matter containing hydrocarbons from the hydrocarbon-containing material described in the specification, and especially in the previous Examples, were unexpected.

As used herein, the terms "first," "second," "third," and the like should be interpreted solely to identify elements and not imply or restrict any particular sequence of elements or steps.

As used herein, the terms around and approximately should be interpreted as including any value that is within 5% of the value recited. Additionally, the recitation of the term around and approximately with respect to a range of values should be interpreted to include both the upper and lower end of the recited range. As used herein, the terms "first", "second", "third" and the like must be interpreted to identify elements only and do not imply or restrict any particular sequence of elements or steps.

While the invention has been shown or described in only some of its embodiments, it should be clear to those skilled in the art that it is not limited, but is susceptible to several changes without departing from the scope of the invention.

Claims

1. A method of extracting organic matter containing hydrocarbons from a material containing hydrocarbons, which comprises the steps of: provide a first liquid consisting essentially of a turpentine liquid alone or a combination of a turpentine liquid and a second miscible liquid in turpentine wherein the proportion of said turpentine liquid to said miscible liquid in turpentine is greater than or equal to 1 : 1; contacting a hydrocarbon containing material with said first liquid to form an extraction mixture; extracting said hydrocarbon material in said turpentine liquid; Y separating said hydrocarbon material extracted from a residual material not extracted.

2. The method of claim 1, wherein said turpentine liquid is selected from the group consisting of: natural turpentine, synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, 3-carene, anethole, dipentene (p-mentha-l, 8-diene), terpene resins, nopol, pineane, camphene, p-cymene, anisaldehyde, 2-pinene hydroperoxide, 3,7-dimethyl-l, 6 -octadiene, isobornyl acetate, terpine hydrate, ocimene, 2-pinanol, dihydromicenol, isoborneol, a-terpineol, aloocimeno, alcohols aloocimeno, geraniol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camfor, p-mentan-8-ol, a-terpinyl acetate, citral, citronellol, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, p-methane, p-menthan-8-yl acetate, cintronelal, 7-hydroxydihydro-citronellal , menthol, menthone, polymers of these, and mixtures of these.

3. The method of claim 1, wherein said turpentine liquid is selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, polymers of these, and mixtures of these.

4. The method of claim 1, wherein said hydrocarbon-containing material is a solid, semi-solid, liquid or viscous liquid fossil fuel material.

5. The method of claim 4, wherein said material Solid or semi-solid fossil fuel is in the form of particles.

6. The method of claim 5, wherein said solid or semi-solid fossil fuel has an average particle size of from about 0.074 millimeters to about 100 millimeters.

7. The method of claim 1, wherein said contacting step further comprises contacting said reaction mixture with a third liquid which is immiscible with said turpentine liquid.

8. The method of claim 1, wherein said second liquid is selected from the group consisting of lower aliphatic alcohols, lower alkanes, lower aromatics, aliphatic amines, aromatic amines, carbon disulphide, or vegetable oils, and mixtures thereof.

9. The method of claim 8, wherein said second liquid is selected from the group consisting of ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, anthracene, tetralin, triethylamine, aniline, carbon disulfide. , soybean oil, palm oil, rapeseed oil, corn oil, sunflower oil, and canola oil, and mixtures of these.

10. The method of claim 7, wherein said liquid immiscible with the turpentine liquid comprises water.

The method of claim 10, wherein said water is boiling.

12. The method of claim 4, wherein said solid, semi-solid, liquid or viscous liquid fossil fuel material and said turpentine liquid are contacted at a temperature of from about 2 ° C to about 200 ° C.

13. The method of claim 4, wherein said solid, semi-solid, liquid or viscous liquid fossil fuel material and said turpentine liquid are brought into contact at a pressure of from about 1.0x104 Passes (0.1 atm) to about 5.0xl06 Passes (50.0 atm).

14. The method of claim 4, which further comprises providing means for contacting said solid, semi-solid, liquid or viscous liquid fossil fuel material and said turpentine liquid in situ in an underground formation containing said fossil fuel material, and to extract said hydrocarbon material from said formation.

15. The method of claim 4, which further comprises a first step of providing a reactor vessel, reactor vessel within which said solid or semi-solid fossil fuel material is contacted with said turpentine liquid, providing a means for stirring said solid or semi-solid fossil fuel material and said turpentine liquid into said reactor vessel; Y stirring said solid or semi-solid fossil fuel material and said turpentine liquid.

16. The method of claim 15, wherein said solid or semi-solid fossil fuel material is contacted with said turpentine liquid at a temperature of less than about 300 ° C.

17. The method of claim 15, wherein said solid or semi-solid fossil fuel material is contacted with said turpentine liquid at a temperature of less than about 60 ° C.

18. The method of claim 1, further comprises providing an energy input to said extraction mixture during said contact, selected from the group consisting of thermal energy in excess of about 250 ° C; pressure in excess of 20.0x105 Paséales (20 atm), microwave energy, ultrasonic energy, ionizing radiation, mechanical cutting forces, and mixtures of these.

19. The method of claim 1 further comprises providing said extraction mixture during said contact with a compound selected from the group consisting of hydrogen, carbon monoxide, water, metal oxides, metals, and mixtures thereof.

20. The method of claim 1 further comprises providing a chemilolytic or thermophilic bacillus-like microorganism to said reaction mixture during said contact.

21. The method of claim 1, wherein said hydrocarbon-containing material is contacted with at least 0.5 pore volume of turpentine liquid.

22. The method of claim 1, wherein said first liquid is a-terpineol or synthetic turpentine.

23. The method of claim 1, wherein said first liquid does not contain water.

24. The method of claim 1, wherein said first liquid contains at least about 70% of said turpentine liquid.

25. The method of claim 1 further comprises the step of stirring said extraction mixture during said contacting step.

26. The method of claim 25, wherein said stirring is effected by contacting said reaction mixture with the boiling water.

27. The method of claim 26, wherein said reaction mixture is immersed in boiling water.

28. The method of claim 1, wherein said hydrocarbon-containing material is coal, bituminous shale, bituminous sand, crude oil, heavy crude oil, or a combination thereof.

29. The method of claim 28, wherein said hydrocarbon-containing material is carbon.

30. A method of extracting organic matter containing hydrocarbons from a material containing hydrocarbons, which comprises the steps of: provide a hydrocarbon extraction liquid which is a turpentine liquid or a combination of a turpentine liquid and a second turpentine miscible liquid. contacting a hydrocarbon containing material with said hydrocarbon extraction liquid to form an extraction mixture; extracting said organic matter containing hydrocarbons in said hydrocarbon extraction liquid; Y separating said extracted organic matter containing hydrocarbons from a residual material not extracted.

31. A method of extracting organic matter containing hydrocarbons from a hydrocarbon-containing material, comprising the steps of: provide a turpentine liquid selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, a-pinene, ß-pinene, α-terpineol, β-terpineol, 3-carene, anethole, dipentene (p- mint-l, 8-diene), terpene resins, nopol, pinano, camphene, p-cymene, anisaldehyde, 2-pinene hydroperoxide, 3,7-dimethyl-l, 6-octadiene, isobornyl acetate, terpine hydrate , ocimeno, 2-pinanol, dihydromicenol, isoborneol, a-terpineol, aloocimeno, alcohols aloocimeno, geraniol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camfor, p-menthan-8-ol, acetate a-terpinyl, citral, citronellol, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, p-methane, p-menthan-8-yl acetate, cintronelal, 7-hydroxydihydro-citronellal, menthol, menthone, polymers thereof, and mixtures of these. contacting a hydrocarbon containing material with said turpentine liquid to form an extraction mixture; extracting said hydrocarbon material in said turpentine liquid; Y separating said hydrocarbon material extracted from a residual material not extracted.

32. A method of extracting organic matter containing hydrocarbons from a hydrocarbon-containing material, comprising a gaseous or liquid or viscous liquid fossil fuel material, selected from heavy crude oil, crude oil, natural gas, or a combination thereof, The method includes: provide a hydrocarbon extraction liquid which essentially consists of turpentine liquid alone or a combination of a turpentine liquid and a second turpentine miscible liquid. contacting heavy crude oil, crude oil, natural gas, or a combination of these in situ in an underground formation containing said fossil fuel material, with said hydrocarbon extraction liquid, to form an extraction mixture in order to extract matter organic containing hydrocarbons from said heavy crude oil, crude oil, natural gas, or a combination thereof in said hydrocarbon extraction liquid and forming an extraction liquid; withdrawing said extraction liquid from said formation, the extraction liquid comprises said turpentine liquid containing the extracted organic matter containing hydrocarbons; Y separating said organic matter extract containing hydrocarbons from a residual material not extracted.

33. The method of claim 32 further comprises separating said extracted organic matter containing hydrocarbons from said hydrocarbon extraction liquid.

34. The method of claim 33, wherein said hydrocarbon extraction liquid separated from said extracted organic material containing hydrocarbons is recycled to be reused in said method.

35. The method of claim 32, wherein said second turpentine miscible liquid is a miscible solvent in turpentine.

36. The method of claim 32, wherein said underground formation is a reservoir of crude oil or a natural gas reservoir.

37. The method of claim 32, wherein said turpentine liquid is selected from the group consisting of: natural turpentine, synthetic turpentine, mineral turpentine, pine oil, a-pinene, ß-pinene, a-terpineol, ß-terpineol, 3-carene, anethole, dipentene (p-mentha-l, 8-diene), resins terpene, nopol, pinano, camphene, p-cymene, anisaldehyde, 2-pinene hydroperoxide, 3,7-dimethyl-l, 6-octadiene, isobornyl acetate, terpine hydrate, ocimene, 2-pinanol, dihydromicenol, isobomeol, a-terpineol, aloocimeno, alcohols aloocimeno, geraniol, 2-methoxy-2,6-dimetil-7,8-epoxioctano, camfor, p-menthan-8-ol, a-terpinyl acetate, citral, citronellol, 7-methoxydihydro -cellular, 10-camphorsulfonic acid, p-methane, p-menthan-8-yl acetate, cintronelal, 7-hydroxydihydro-citronellal, menthol, menthone, polymers thereof, and mixtures thereof.

38. The method of claim 32, wherein said turpentine liquid is selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, polymers of these, and mixtures of these.

39. The method of claim 32 further comprises the additional step of contacting said extraction mixture with a liquid which is immiscible with said turpentine liquid.

40. The method of claim 39, wherein said liquid immiscible with the turpentine liquid comprises water.

41. The method of claim 32, wherein said second liquid is selected from the group consisting of lower aliphatic alcohols, lower alkanes, lower aromatics, aliphatic amines, aromatic amines, carbon disulphide, or vegetable oils, and mixtures thereof.

42. The method of claim 41, wherein said second liquid is selected from the group consisting of ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, anthracene, tetralin, triethylamine, aniline, carbon disulfide. , soybean oil, palm oil, rapeseed oil, corn oil, sunflower oil, and canola oil, and mixtures of these.

43. The method of claim 32, wherein said heavy crude oil, crude oil, natural gas, or a combination thereof and said hydrocarbon extraction liquid are brought into contact at a temperature of from about 2 ° C, to about 200 ° C. ° C.

44. The method of claim 32, wherein said heavy crude oil, crude oil, natural gas, or a combination thereof and said hydrocarbon extraction liquid are brought into contact at a pressure of from about 1.0x10 4 Pases (0.1 atm) to around 5.0x106 Paséales (50.0 atm).

45. The method of claim 32 further comprises providing said extracting mixture with a compound selected from the group consisting of hydrogen, carbon monoxide, metal oxides, metals, and mixtures thereof.

46. The method of claim 32, wherein said heavy crude oil, crude oil, natural gas, or a combination thereof is contacted with at least 0.5 pore volume of turpentine liquid.

47. The method of claim 32, wherein said hydrocarbon extraction liquid is a-teipineol or synthetic turpentine.

48. The method of claim 32, wherein said hydrocarbon extraction liquid contains no added water.

49. The method of claim 32, wherein said hydrocarbon extraction liquid contains at least about 70% of said turpentine liquid.

50. The method of claim 32, wherein the ratio of said turpentine liquid to said turpentine miscible liquid in said hydrocarbon extraction liquid is greater than or equal to 1: 1.

51. The method of claim 32, wherein when said heavy crude oil, crude oil, natural gas, or a combination thereof is put in contact with said hydrocarbon extraction liquid, an extraction liquid of a homogeneous phase is formed.

52. A method of extracting organic matter containing hydrocarbons from a hydrocarbon-containing material, comprising a gaseous or liquid or viscous liquid fossil fuel material, selected from heavy crude oil, crude oil, natural gas, or a combination thereof, The method includes: contact heavy crude oil, crude oil, natural gas, or a combination of these in itself in an underground formation containing said fossil fuel material with a hydrocarbon extraction liquid comprising a turpentine liquid and a second liquid miscible in turpentine, said hydrocarbon extraction liquid contains no added water, to form an extraction mixture to extract organic matter containing hydrocarbons from said heavy crude oil, crude oil, natural gas, or a combination thereof, into said turpentine liquid and forming an extraction liquid; withdrawing said extraction liquid from said formation, the extraction liquid comprises said turpentine liquid that the extracted organic matter containing hydrocarbons; Y separating said extracted organic matter containing hydrocarbons from a residual material not extracted, wherein the proportion of said turpentine liquid to said second miscible turpentine liquid is greater than or equal to 1: 1.

53. The method of claim 21, wherein said hydrocarbon extraction liquid consists of a turpentine liquid and a second turpentine miscible liquid.

54. A method of dissolving heavy crude oil, crude oil, natural gas, or a combination of these in situ in an underground formation, inside a turpentine liquid, the method comprises the steps of: provide a turpentine liquid selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol, 3-carene, anethole, dipentene (p-mentha-1,8-diene), terpene resins, nopol, pinano, camphene, p-cymene, anisaldehyde, 2-pinene hydroperoxide, 3,7-dimethyl-l, 6-octadiene, isobornyl acetate , terpine hydrate, ocimene, 2-pinanol, dihydromicenol, isoborneol, a-terpineol, aloocimeno, aloocimeno alcohols, geraniol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camfor, p-mentan-8- ol, a-terpinyl acetate, citral, citronellol, 7-methoxydihydro-citronellal, 10-camphorsulfonic acid, p-methane, p-menthan-8-yl acetate, cintronelal, 7-hydroxydihydro-citronellal, menthol, menthone, polymers of these, and mixtures of these. contacting a heavy crude oil, crude oil, natural gas, or a combination of these in situ in an underground formation containing said heavy crude oil, crude oil, natural gas, or a combination thereof, with said turpentine liquid for forming an extraction mixture to dissolve heavy crude oil, crude oil, natural gas, or a combination thereof into said turpentine liquid and form an extraction liquid; withdrawing said extraction liquid from said formation, the extraction liquid comprises said turpentine liquid containing the dissolved heavy crude oil, crude oil, natural gas, or a combination thereof and at least one non-extracted residual material; Y separating said heavy crude oil, crude oil, natural gas, or a combination thereof from said waste material.