EP2205696A1 - Extraction of hydrocarbons from hydrocarbon-containing materials - Google Patents

Extraction of hydrocarbons from hydrocarbon-containing materials

Info

Publication number
EP2205696A1
EP2205696A1 EP08832082A EP08832082A EP2205696A1 EP 2205696 A1 EP2205696 A1 EP 2205696A1 EP 08832082 A EP08832082 A EP 08832082A EP 08832082 A EP08832082 A EP 08832082A EP 2205696 A1 EP2205696 A1 EP 2205696A1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbon
turpentine liquid
terpineol
turpentine
organic matter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08832082A
Other languages
German (de)
English (en)
French (fr)
Inventor
Liang-Tseng Fan
Mohammad Reza Shafie
Julius Michael Tollas
William Arthur Fitzhugh Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Green Source Energy LLC
Original Assignee
Green Source Energy LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/053,126 external-priority patent/US8101812B2/en
Priority claimed from US12/174,139 external-priority patent/US8272442B2/en
Application filed by Green Source Energy LLC filed Critical Green Source Energy LLC
Publication of EP2205696A1 publication Critical patent/EP2205696A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/14—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to the field of extraction of hydrocarbons from hydrocarbon-containing materials.
  • fossil fuels also called hydrocarbon- containing organic matter
  • hydrocarbon-containing organic matter in solid, semi-solid, highly viscous or viscous form
  • fossil fuels include, but are not limited to, hydrocarbon- containing organic matter within coal, oil shale, tar sands and oil sands (hereinafter jointly called tar sands), as well as crude oil, heavy crude oil, crude bitumen, kerogen, natural asphalt and/or asphaltene.
  • the difficulty can in part be attributed to the fact that these fossil fuels include complex organic polymers linked by oxygen and sulfur bonds, which are often imbedded in the matrices of inorganic compounds.
  • the prior art processes and technologies for the liquefaction, solubilization and/or extraction of hydrocarbons may be difficult to scale up, operate and/or control because of one or more of the following reasons: (1) operating at an inordinately elevated pressure; (2) operating at a very high temperature; (3) the need for expensive processing vessels and equipment that require the external supply of hydrogen under extreme conditions; (4) being subjected to a mixture, or composition, of two or more reagents, catalysts and/or promoters, which are frequently highly toxic and are neither renewable nor recyclable; (5) requiring to supply a special form of energy, e.g., microwave radiation; (6) long process times for partial liquefaction, solubilization or extraction; (7) requiring extraordinarily fine particles with a size of about 200 mesh (0.074 mm), which is profoundly difficult and costly to manufacture and handle; and (8) being incapable of recovering and recycling the necessary reagents, catalysts and/or promoters.
  • a method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material includes the steps of providing a first liquid including a turpentine liquid and contacting the hydrocarbon- containing material with the turpentine liquid such that an extraction mixture is formed, as well as residual material.
  • the extraction mixture contains at least a portion of the hydrocarbon- containing organic matter and the turpentine liquid.
  • the residual material includes non-soluble material from the hydrocarbon-containing material.
  • the residual material can also includes a reduced portion of the hydrocarbon-containing organic matter in the circumstance where all such hydrocarbon-containing material has not been solubilized by the turpentine liquid and moved into the extraction mixture. The residual material is then separated from the extraction mixture.
  • the extraction mixture is further separated into a first portion and a second portion.
  • the first portion of the extraction mixture includes a hydrocarbon product stream that includes at least a portion of the hydrocarbon-containing organic matter 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 of the turpentine liquid is recovered in the recycle stream.
  • substantially all hydrocarbon-containing organic matter is extracted into the extraction mixture.
  • the residual materials are essential oil-free and can be further used or disposed without impact to the environment.
  • Figure 1 is a schematic for one embodiment of an apparatus for the recovery of hydrocarbons from tar sands.
  • Figure 2 is a schematic for one embodiment of an apparatus for the recovery of hydrocarbons from oil shale.
  • Figure 3 is a schematic for one embodiment of an apparatus for the recovery of hydrocarbons from coal.
  • Figure 4 is a schematic for the enhanced recovery of hydrocarbons from a subsurface reservoir. DETAILED DESCRIPTION OF THE INVENTION
  • the present invention relates to a readily deployed composition for the extraction, liquefaction and/or solubilization of fossil fuels from coal, oil shale, tar sands and the like, as well as from reservoirs.
  • a method is providing including the steps of liquefying, solubilizing and/or extracting hydrocarbon-containing organic matter from a hydrocarbon- containing material, such as for example, coal, oil shale, tar sands, or a reservoir containing heavy crude oil, crude oil, natural gas (which frequently coexists with crude oils and other said fossil fuels), or a combination thereof.
  • Hydrocarbon-containing organic matter includes, but is not limited to, heavy crude oil, crude oil, natural gas and the like. Hydrocarbon-containing organic matter can be solid, semi-solid, liquid, sludge, viscous liquid, liquid or gaseous form.
  • exemplary hydrocarbon-containing materials can also include oil tank bottoms, oil pit or pond sludge and slurry mix, discarded foods, manure, sewage sludge or municipal garbage.
  • Liquefying, solubilizing and/or extracting the hydrocarbon-containing organic matter includes the step of providing a turpentine liquid, contacting the hydrocarbon- containing material with the turpentine liquid so as to extract at least a portion of said hydrocarbon-containing organic matter from said hydrocarbon-containing material into said turpentine liquid to create an extraction mixture that includes the hydrocarbon-containing organic matter that has been removed from the hydrocarbon-containing material and the turpentine liquid, and separating the extracted organic matter in the turpentine liquid from any residual material not extracted.
  • Turpentine liquid can include an amount of terpineol.
  • Naturally occurring turpentine liquid includes an amount of terpene.
  • the turpentine liquid includes ⁇ -terpineol.
  • the ratio of turpentine liquid to hydrocarbon-containing material is greater than or equal to about 1:2 and 4:1, in some embodiments greater than or equal to about 1:1, and in some embodiments the ratio can be greater than or equal to 2:1 In embodiments relating the reservoir recovery, the ratio can be greater than or equal to about 3:1, and in other embodiments relating to reservoir recovery the ratio can be greater than or equal to about 4:1.
  • pore volume is used to determine an estimated measure of the hydrocarbon-containing material. In other aspects of this invention, such as in the use of tar sands and coal and oil shale, volume of the hydrocarbon-containing material can be more directly measured.
  • 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 further embodiments greater than or equal to about 14% by weight of the hydrocarbon-containing material.
  • a liquefaction, solubilization or extraction reagent of choice for the hydrocarbon-containing matter is a natural, synthetic or mineral turpentine, which can include ⁇ -terpineol, or ⁇ -terpineol itself.
  • the liquefaction, solubilization and/or extraction of fossil fuels or hydrocarbon-containing organic matter can be carried out at a temperature, which is within the range of about 2°C to about 300°C.
  • the organic matter or material is contacted with a turpentine liquid at a temperature of less than about 300°C, or less than about 60 0 C.
  • the liquefaction, solubilization and/or extraction temperatures can be within the range of about 20 0 C to about 200 0 C.
  • the pressure under which the liquefaction, solubilization and/or extraction of fossil fuels is to be carried out may typically be within the range of about 1.OxIO 4 Pascals (0.1 atm) to about 5.OxIO 6 Pascals (50.0 atm). hi certain embodiments, the process can be conducted at a pressure between about 5.OxIO 4 Pascals (0.5 atm) to about 8.0xl0 5 Pascals (8.0 atm).
  • the fossil fuels or hydrocarbon-containing organic matter to be liquefied, solubilized and/or extracted by immersion in, or contact with, one or more turpentine liquid can be in the form of a bed of particles, pieces, chunks or blocks of fossil fuels whose sizes are within the range of about 0.74 mm to about 10 mm in a liquefaction, solubilization or extraction vessel (reactor hereafter) that contains one or more of the said liquefaction, solubilization and/or extraction reagents.
  • the sizes of the particles, pieces, chunks or blocks of fossil fuels are within the range of about 0.149 mm (100 mesh) to about 20 mm.
  • the bed of particles, pieces, chunks or blocks of fossil fuels is agitated by passing the liquefaction, solubilization and/or extraction reagent or reagents in the form of liquid through the bed of particles, pieces, chunks or blocks by boiling the reagent or reagents.
  • the duration of liquefaction, solubilization and/or extraction is between about 1 minute to about 90 minutes.
  • the fossil fuels can be partially or fully 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 liquefaction, solubilization or extraction reagent or reagents in the reactor.
  • the basis of one aspect of the present invention is the unexpected discovery that when about 500 grams of the reagent, ⁇ -terpineol, were added to about 250 grams of the 60-mesh sample of coal from the Pittsburgh seam in Washington County of Pennsylvania in a tray, the reagent's color turned pitch black almost immediately, and remained so after several hours.
  • this 2:1 mixture of ⁇ -terpineol and the coal sample was transferred from the tray to a capped and tightly sealed jar and was maintained under the ambient conditions of about 20 0 C and slightly less than about 1.0IxIO 5 Pascals (1 atm) for about 25 days.
  • the conversion, (i.e., the degree of liquefaction), of the coal sample was determined to be about 71 wt. % after filtering, washing with ethanol, drying, and weighing. This 71 wt.
  • % conversion corresponds to nearly all the solubilizable bitumen (organic matter) present in the coal sample whose proximate analyses are 2.00 wt. % of as-received moisture, 9.25 wt. % of dry ash, 38.63 wt. % of dry volatile matter, and 50.12 wt. % of dry fixed carbon.
  • reagents except mineral turpentine that is derived from petroleum, are renewable and "green," i.e., low in toxicity, and relatively inexpensive, as compared to all other known liquefaction, solubilization and/or extraction reagents for the fossil fuels, such as tetraline, 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 is inexpensive.
  • any of the said liquefaction, solubilization and/or extraction reagents penetrates or diffuses into the particles, pieces, blocks or chunks of fossil fuels through their pores at appreciable rates, thus causing these particles, pieces, chunks or blocks to subsequently release the liquefiable, solubilizable or extractable fraction in them often almost nearly completely even under the far milder conditions, e.g., ambient temperature and pressure, than those required by the recent inventions pertaining to the liquefaction, solubilization and/or extraction of the fossil fuels, such as coal, oil shale, tar sands, crude oil and heavy crude oil.
  • An aspect of the present invention provides a method of liquefying, solubilizing and/or extracting the fossil fuels or hydrocarbon-containing organic matter from hydrocarbon- containing material, such as coal, oil shale and tar sands, wherein a portion of solid or semi-solid fossil fuels is contacted with a turpentine liquid in an extraction mixture, which can be in an absence of an alkali metal, catalyst, hydrogen (H 2 ) and/or carbon monoxide (CO). While hydrogen and CO can be useful as a mixing agent, one embodiment of the invention includes the process and the composition in the absence of hydrogen and CO.
  • the turpentine liquid is selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, ⁇ -pinene, ⁇ -pinene, ⁇ -terpineol, ⁇ -terpineol, ⁇ - terpineol, polymers thereof, and mixtures thereof.
  • the turpentine liquid is selected from geraniol, 3-carene, dipentene (p-mentha-l,8-diene), nopol, pinane, 2- pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol, ⁇ -terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof.
  • the turpentine liquid is selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethyl-l,6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal, menthone, and mixtures thereof.
  • solid or semi-solid fossil fuels or other hydrocarbon-containing materials such as coal, oil shale, tar sands and heavy crude oil, or for example oil tank bottoms, oil pit or pond sludge, discarded foods, manure, sewage sludge or municipal garbage, may be provided in any size that facilitates contact with a turpentine liquid.
  • the fossil fuels or hydrocarbon-containing materials can be provided as particles, pieces, chunks, or blocks, for example, large fragments or pieces of coal or oil shale.
  • the fossil fuel or hydrocarbon-containing material is provided as particles.
  • the particles of fossil fuel or hydrocarbon-containing materials have an average particle size of from about 0.074 mm to about 100 mm. In certain other embodiments, the particles of fossil fuel have an average particle size from about 0.074 mm to about 25 mm.
  • a second liquid can be added to the turpentine liquid.
  • the second liquid can be selected from lower aliphatic alcohols, alkanes, aromatics, aliphatic amines, aromatic amines, carbon bisulfide and mixtures thereof.
  • Exemplary mixtures include solvents manufactured in petroleum refining, such as decant oil, light cycle oil and naphtha, or solvents manufactured in dry distilling coal and fractionating liquefied coal.
  • lower aliphatic alcohols refers to primary, secondary and tertiary monohydric and polyhydric alcohols of between 2 and 12 carbon atoms.
  • alkanes refers to straight chain and branched chain alkanes of between 5 and 22 carbon atoms.
  • aromatics refers to monocyclic, heterocyclic and polycyclic compounds.
  • aliphatic amines refers to primary, secondary and tertiary amines having alkyl substituents of between 1 and 15 carbon atoms.
  • benzene, naphthalene, toluene or combinations thereof are used.
  • the lower aliphatic alcohols noted above can be used.
  • the solvent is selected from ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, naphthalene, anthracene, tetraline, triethylamine, aniline, carbon bisulfide, and mixtures thereof, at a temperature and pressure operable to maintain the solvent in liquid form.
  • the ratio of turpentine liquid to any other turpentine-miscible 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 embodiments, the ratio is greater than or equal to about 3:1. In yet other embodiments, the ratio is greater than or equal to 4: 1.
  • the fossil fuel and the turpentine liquid are contacted at a temperature of from about 2 0 C to about 300°C.
  • the fossil fuel is contacted by the turpentine liquid at a temperature of less than about 200 0 C.
  • the fossil fuel and the turpentine liquid are contacted at a pressure of from about 1.0x10 4 Pascals (0.1 atm) to about 5.OxIO 6 Pascals (50 atm).
  • the method is executed at a pressure of from about 0.5 atm to about 8 atm.
  • the method further includes providing an extraction vessel within which the solid or semi-solid fossil fuel is contacted with the turpentine liquid.
  • agitation means can be provided whereby the fossil fuel and the turpentine liquid contained within the reactor or extractor vessel are mixed and agitated.
  • the fossil fuel and turpentine liquid can be incubated in a holding tank so as to prolong their time of contact.
  • the degree of liquefaction, solubilization and/or extraction is controlled by the length of time the solid or semi-solid fossil fuel is in contact with the turpentine liquid and/or the temperature of the mixture of the fossil fuel and turpentine liquid.
  • the fossil fuel is contacted with a heterogeneous liquid including a turpentine liquid and water as an agitant.
  • the ratio of turpentine fluid to water is greater than or equal to about 1 : 1 by volume, to avoid slurry formation, which may render separation of the extracted organic matter in the turpentine liquid-containing fluid difficult.
  • the fossil fuel is contacted by the turpentine liquid in the presence of an energy input selected from thermal energy in excess of about 300 0 C, pressure in excess of 50 arm, microwave energy, ultrasonic energy, ionizing radiation energy, mechanical shear-forces, and mixtures thereof.
  • an energy input selected from thermal energy in excess of about 300 0 C, pressure in excess of 50 arm, microwave energy, ultrasonic energy, ionizing radiation energy, mechanical shear-forces, and mixtures thereof.
  • a liquefaction or solubilization catalyst is provided to the mixture of fossil fuel and turpentine liquid.
  • the reaction or solubilization mixture is supplemented by the addition of a compound selected from hydrogen, carbon monoxide, water, metal oxides, metals, and mixtures thereof.
  • a microorganism is included in the reaction or solubilization mixture.
  • Select chemical bonds for example, sulfur cross-links and oxygen cross-links, in the hydrocarbons of fossil fuels and other hydrocarbon-containing materials are broken by biotreatment with bacillus-type thermophilic and chemolithotrophic microorganisms selected from naturally occurring isolates derived from hot sulfur springs. The breaking of these select chemical bonds facilitates the solubilization of hydrocarbons in fossil fuels and other hydrocarbon-containing materials.
  • a method for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material comprising a viscous liquid, liquid or gaseous 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 as to extract hydrocarbon-containing organic matter into said turpentine liquid and form an extraction liquid.
  • the extraction liquid is removed from said formation, wherein the extraction liquid includes the turpentine liquid containing the extracted hydrocarbon-containing organic matter.
  • the extracted hydrocarbon-containing organic matter is separated from a residual material not extracted.
  • the method can further include separating said extracted hydrocarbon material from the turpentine liquid.
  • the viscous liquid, liquid or gaseous fossil fuel material can be heavy crude oil, crude oil, natural gas, or a combination thereof.
  • the underground formation may be a crude oil reservoir or a natural gas reservoir, for example.
  • the present invention can be deployed readily in- situ to liquefy and/or solubilize directly the 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 physio- chemical affinity with bituminous organic matter, including bitumen, kerogen and/or tar, in solid coal, oil shale and tar sands.
  • bituminous organic matter including bitumen, kerogen and/or tar
  • bituminous organic matter comprising mainly hydrocarbons
  • the organic matter dissolves into the extraction reagent of the present invention, thereby liquefying the organic matters.
  • the hydrocarbons and the extraction reagent of the present invention rapidly form a homogeneous solution, i.e., a one-phase liquid.
  • the present invention takes advantage of the very strong physico-chemical affinity of the turpentine liquid.
  • One method of the present invention injects an extraction reagent of the present invention into an oil or natural gas reservoir through an injection well.
  • Oil is dissolved into the extraction reagent of the present invention when the two come into contact in an oil reservoir, thereby yielding a homogeneous solution, i.e., 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 producer well; dissolution of previously trapped oil into the extraction reagent of the present invention continues until the extraction reagent is fully saturated with oil. Thereafter, the extraction reagent becomes inactive in the additional oil recovery process and simply flows through the pores of the reservoir as a one-phase liquid, eventually reaching a production well.
  • an extraction reagent of the present invention is injected to improve the oil recover from oil reservoirs containing very viscous oil, e.g., the reservoirs of the "Orinoco Oil Belt” in Venezuela.
  • the recovery factor with prior art recovery methods is low, ranging from 10% to 15% of the original oil in such reservoirs.
  • the unexpected increase in the recovery efficiency from these reservoirs with injection of the turpentine liquid extraction reagent of the present invention can be further enhanced by adopting horizontal wells for both producers and injectors, and periodic steam soaking of these wells.
  • Ultimate recovery of natural gas from a large gas reservoir can be increased with the injection of an extraction reagent of the present invention into a reservoir.
  • the gas production form such a reservoir often creates dangerously large-scale subsidence on the surfaces of the gas field, e.g., the "Groeningen” field in the Netherlands. As such, it is necessary that the reservoir pressure be maintained by water injection.
  • the water injected into the reservoir traps about 30% of the gas in-situ at high pressure due to the two-phase flow of water and gas through the reservoir with a low permeability.
  • the trapped gas in the reservoir is dissolved in the reagent and flows to the producer wells. By separating the reagent and gas at the surface, the gas is recovered and the reagent is recycled for reuse.
  • the extraction methods of the present invention can be implemented after one or more of the known methods for facilitating oil production, e.g., CO 2 or natural gas injection and surfactant addition, are executed.
  • 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, i.e., liquefied, by immersing in a turpentine liquid under a pressure within the range of about 1.OxIO 5 Pascals (1 atm) to about 2.OxIO 5 Pascals (2.0 atm).
  • the turpentine liquid can be natural, synthetic or mineral turpentine that includes up to about 50-70 volume % of ⁇ -terpineol, about 20-40 volume % of ⁇ -terpineol, and about 10 volume % of other components.
  • the bed of ground anthracite or bituminous coal can be agitated by passing said turpentine liquid at a temperature in the range between 80°C and about 130 0 C, or possibly up to the boiling point of said turpentine liquid, hi certain other embodiments, the duration of solubilization and/or extraction, i.e., liquefaction, can be within about 10 minutes to about 40 minutes, hi certain embodiments, the contact time for the extraction of hydrocarbon-containing organic matter from coal is less than 5 minutes.
  • lignite, brown coal, or any other low-rank coals 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, i.e., liquefied, by immersing in a turpentine liquid under a pressure within the range of about 1.OxIO 5 Pascals (1 atm) to about 2.0xl0 5 Pascals (2.0 atm).
  • the turpentine liquid can be natural, synthetic or mineral turpentine that includes about 70-90 volume % of ⁇ -terpineol, about 5-25 volume % of ⁇ -terpineol, and about 5 volume % of other components.
  • the bed of ground lignite, brown coal, or any other low-rank coals can be agitated by passing said turpentine liquid at a temperature in the range between about 80°C and about 130°C, or possibly up to the boiling point of said turpentine liquid.
  • the solubilization and/or extraction, i.e., liquefaction can be within about 20 minutes to about 60 minutes, hi certain embodiments, the contact time for the extraction of hydrocarbon-containing organic matter from coal is less than 5 minutes.
  • oil shale can be ground to sizes ranging from about 0.419 mm (40 mesh) to 0.074 mm (200 mesh), and subsequently be solubilized and/or extracted, i.e., liquefied, by immersing in a turpentine liquid under a pressure within the range of about 1.0x1.0 5 Pascals (1 atm) to about 2.OxIO 5 Pascals (2.0 atm).
  • the turpentine liquid can be natural, synthetic or mineral turpentine that includes about 70-90 volume % of ⁇ - terpineol, about 5-25 volume % of ⁇ -terpineol, and about 5 volume % of other components.
  • the bed ground oil shale can be agitated by passing said turpentine liquid at a temperature in the range between about 80 0 C and about 130°C, or possibly up to the boiling point of said turpentine liquid.
  • the solubilization and/or extraction, i.e., liquefaction can be within about 30 minutes to about 60 minutes.
  • the contact time for the extraction of hydrocarbon-containing organic matter from oil shale is less than 5 minutes.
  • tar sands can be broken up to sizes ranging from about 25.4 mm (1 mesh) to 4.76 mm (4 mesh), and subsequently be solubilized and/or extracted, i.e., liquefied, by immersing in a turpentine liquid under a pressure within the range of about 1.0x1.0 5 Pascals (1 atm) to about 2.0xl0 5 Pascals (2.0 atm).
  • the turpentine liquid can be natural, synthetic or mineral that includes containing about 40-60 volume % of ⁇ -terpineol, about 30-50 volume % of ⁇ -terpineol, 5 volume % of ⁇ and/or ⁇ -pinene and about 5 volume % of other components.
  • a ground oil shale bed can be agitated by passing said turpentine liquid at a temperature in the range between about 60°C and about 90 0 C, or possibly up to the boiling point of said turpentine liquid.
  • the solubilization and/or extraction, i.e., liquefaction can be within about 10 minutes to about 30 minutes.
  • the contact time for the extraction of hydrocarbon-containing organic matter from tar sands is less than 5 minutes.
  • light and medium crude oil can be produced in situ, i.e., removed from an underground reservoir, for primary, secondary or tertiary recovery, by injecting about one (1.0) to about five (5.0) pore volumes of a turpentine liquid. In other embodiments, between about two (2.0) and about four (4.0) pore volumes of a turpentine liquid can be injected.
  • the turpentine liquid can be natural, synthetic or mineral turpentine that includes about 40-70 volume % of ⁇ -terpineol, about 30-40 volume % of ⁇ -terpineol, 10 volume % of ⁇ and/or ⁇ -pinene and about 10 volume % of other components, hi certain embodiments, the injection of a turpentine liquid can be followed by waterflooding with about one (1.0) to about three (3.0) pore volumes of water.
  • heavy and extra heavy crude oil can be produced in situ, i.e., removed from an underground reservoir, for primary, secondary or tertiary recovery, by injecting about one (1.0) to about five (5.0) pore volumes of a turpentine liquid. In other embodiments, between about two (2.0) and about four (4.0) pore volumes of a turpentine liquid can be injected.
  • the turpentine liquid can be natural, synthetic or mineral turpentine that includes about 50-70 volume % of ⁇ -terpineol, about 20-35 volume % of ⁇ -terpineol, 10 volume % of ⁇ and/or ⁇ -pinene and about 5 volume % of other components can be used in conjunction with steam injection.
  • Apparatus 100 includes turpentine liquid supply 102, which can optionally be coupled to a pump 104, to supply a turpentine liquid to contacting vessel or extraction vessel 1 10.
  • the turpentine liquid supply can include means for heating the turpentine liquid.
  • the contacting vessel can be an inclined rotary filter or trommel.
  • Tar sand sample 106 is provided to conveyor 108 or like feeding apparatus for supplying the tar sands to an inlet of contacting vessel 1 10.
  • conveyor 108 can include a filter screen or like separating apparatus to prevent large particles from being introduced into the process.
  • Contacting vessel 110 includes at least one inlet for turpentine liquid to be introduced and contacted with the tar sands.
  • Contacting vessel 110 can include a plurality of trays or fins 114 designed to retain the tar sands in the contacting vessel for a specified amount of time, and to increase or control contact between the tar sand particles and the turpentine liquid.
  • the contacting vessel can be an inclined rotary filter.
  • An extraction mixture that includes the extracting liquid and hydrocarbon-containing organic matter extracted from the tar sands is removed from contacting vessel 110 via outlet 116, which can include filter 118 to prevent the removal of solids with the extraction mixture that includes the extracted hydrocarbon-containing organic matter.
  • Pump 120 can be coupled to outlet 1 16 to assist with supplying the extraction mixture to holding tank 122.
  • Line 124 can be coupled to holding tank 112 for supplying the extraction mixture for further processing.
  • inorganic solids and other materials not soluble in the turpentine liquid can be removed from the contacting vessel via second conveyor 126.
  • Some turpentine liquids include, but are not limited to, liquids that include ⁇ -terpineol and ⁇ -terpineol.
  • apparatus 200 is provided for the recovery of hydrocarbon- containing organic matter from oil shale and other sedimentary rock formations that include recoverable hydrocarbon materials.
  • Oil shale sample 202 is supplied to grinder or crusher 204 to reduce the size of the oil shale.
  • grinder or crusher 204 reduces the oil shale to between about 0.074 and 0.42 mm in diameter.
  • Crushed oil shale may optionally be supplied to a filter to ensure uniform and/or conforming particle size.
  • First conveyor 206 provides particles from grinder or crusher 204 to contacting vessel 208.
  • Contacting vessel 208 is coupled to turpentine liquid supply 210, which may optionally be coupled to a pump, and which supplies a turpentine liquid to at least one inlet 212 coupled to contacting vessel 208.
  • the turpentine liquid supply can include means for heating the turpentine liquid.
  • Contacting vessel 208 can include a plurality of trays or fins 214 designed to retain the tar sands in the contacting vessel for a specified amount of time, and to increase or control contact between the tar sand particles and the turpentine liquid.
  • the contacting vessel can be an inclined rotary filter or trommel.
  • An extraction mixture stream that includes the turpentine liquid and recovered hydrocarbon-containing organic matter from the oil shale is collected via outlet 216 and supplied to holding tank 220.
  • Pump 218 is optionally coupled to outlet 216 to assist with the supply of the extraction mixture stream to holding tank 220.
  • the extraction mixture stream can be coupled to line 222 for supplying the extraction mixture stream to further processing.
  • Second conveyor 224 assists with the removal of inorganic or insoluble materials from contacting vessel 208.
  • Turpentine liquids can include, but are not limited to, ⁇ - terpineol and ⁇ -terpineol.
  • apparatus 300 is provided for the recovery of hydrocarbon- containing organic matter from coal.
  • Coal sample 302 is supplied to grinder or crusher 304 to reduce the size of the coal.
  • grinder or crusher 304 reduces the coal to between about 0.074 and 0.84 mm in diameter, depending upon the quality of the coal sample.
  • the grinder or crusher 304 can be a wet grinder.
  • Crushed coal may optionally be supplied to a filter to ensure uniform and/or conforming particle size.
  • Crushed coal is supplied to first contacting vessel 306.
  • First contacting vessel 306 is also coupled to a turpentine liquid supply 308, which may optionally be coupled to pump 310, and which supplies the turpentine liquid to first contacting vessel 306.
  • the turpentine liquid supply can include means for heating the turpentine liquid.
  • First contacting vessel 306 includes mixing means 312 designed to agitate and improve or control contact between the solid coal particles and the turpentine liquid.
  • An extraction mixture stream that includes the turpentine liquid and recovered hydrocarbon-containing organic matter from the oil shale is collected via first contacting vessel outlet 313 and supplied to second contacting vessel 316.
  • Pump 314 is optionally coupled to outlet 313 to assist with the supply of the extraction mixture stream to the second contacting vessel 316.
  • Second contacting vessel 316 can include a series of trays or fins 318 designed to increase or control separation of the solids and turpentine liquids.
  • the second contacting vessel 316 can be an inclined rotary filter or trommel.
  • the extraction mixture stream can be collected from second contacting vessel outlet 320, which may optionally be coupled to pump 322, to assist with supply of the extraction mixture stream to holding tank 324.
  • Liquid coal and any turpentine liquid present in holding tank 324 can be supplied to a liquid coal refinery or other processing step via line 326.
  • Conveyor 328 can be coupled to second contacting vessel 316 for removal and recovery of the solids as a by-product of the process.
  • Turpentine liquids can include, but are not limited to, ⁇ -terpineol and ⁇ -terpineol.
  • the apparatus 300 can also be used to process high and low grade oil shale.
  • process 400 is provided for the enhanced recovery of hydrocarbon-containing organic matter from a hydrocarbon-containing subsurface formation.
  • Hydrocarbon-containing reservoir 404 is shown positioned below the surface 402.
  • Production well 406 is already in operation.
  • Injection well 408 is provided for the injection of a turpentine liquid via line 410.
  • the turpentine liquid facilitates the liquefaction, solubilization and/or extraction of hydrocarbon-containing organic matter present in the reservoir, as well as providing the driving force to push the hydrocarbon-containing organic matter in the formation toward the production well.
  • a hydrocarbon product stream that includes injected turpentine liquid is collected via line 412.
  • Turpentine liquids can include, but are not limited to, ⁇ -terpineol and ⁇ - terpineol.
  • the turpentine liquid for increasing production from an oil well includes at least 30% by volume of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, ⁇ -pinene, ⁇ -pinene, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, terpene resins, ⁇ - terpene, ⁇ -terpene, ⁇ -terpene, or mixtures thereof.
  • the turpentine liquid includes at least 30% by volume geraniol, 3-carene, dipentene (p-mentha-l,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p- menthan-8-ol, ⁇ -terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7- hydroxydihydrocitronellal, menthol, or mixtures thereof.
  • the turpentine liquid includes at least 30% by volume anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethyl-l,6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2- methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10- camphorsulphonic acid, cintronellal, menthone, or mixtures thereof.
  • the turpentine liquid includes at least about 40% by volume ⁇ - terpineol. In other embodiments, the turpentine liquid includes at least about 25% by volume ⁇ - terpineol. In yet other embodiments, the turpentine liquid includes at least about 40% by volume ⁇ -terpineol and at least about 25% by volume ⁇ -terpineol. In other embodiments, the turpentine liquid includes at least about 50% ⁇ -terpineol, and in certain embodiments also includes ⁇ - terpineol. In certain embodiments, the turpentine liquid includes at least 20% by volume of ⁇ - terpineol. In certain embodiments, the turpentine liquid includes between about 50 and 70% by volume of ⁇ -terpineol and between about 10 and 40% by volume of ⁇ -terpineol.
  • a process for increasing production from a sub-surface hydrocarbon- containing reservoir undergoing enhanced recovery operations includes injecting a turpentine liquid into the reservoir through an injection well to stimulate production of the hydrocarbon-containing material.
  • the turpentine liquid can include at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, ⁇ -pinene, ⁇ - pinene, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, terpene resins, ⁇ -terpene, ⁇ -terpene, ⁇ -terpene, and mixtures thereof.
  • the turpentine liquid can include at least one compound selected from geraniol, 3-carene, dipentene (p-mentha-l,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol, ⁇ - terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof.
  • the turpentine liquid can include at least one compound selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethyl-l,6- octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2-methoxy-2,6- dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal, menthone, and mixtures thereof.
  • a hydrocarbon-containing organic matter production stream that includes the turpentine liquid and recovered hydrocarbons is recovered from the production well associated with the hydrocarbon-containing reservoir.
  • the hydrocarbon-containing organic matter production stream can be separated into a recovered hydrocarbons stream and a turpentine liquid recycle stream.
  • the method of further can further include the step of injecting the turpentine liquid recycle stream into the injection well.
  • a method for the increasing production from a hydrocarbon-containing sub-surface hydrocarbon formation undergoing enhanced recovery operations includes the steps of injecting a turpentine liquid into the formation through an injection well, hi certain embodiments, the turpentine liquid includes at least 40% by volume ⁇ -terpineol and at least 10% by volume ⁇ -terpineol.
  • the turpentine liquid solubilizes, extracts and/or displaces the hydrocarbon-containing materials from the formation, which are subsequently recovered from the formation with the turpentine liquid through a production well.
  • the method further includes separating the hydrocarbons from the turpentine liquid, hi yet other embodiments, the method further includes recycling the turpentine liquid to the injection well.
  • ⁇ -terpineol is present in an amount between about 40 and 70% by volume. In certain other embodiments, ⁇ -terpineol is present in an amount of at least 70% by volume. In yet other embodiments, ⁇ -terpineol is present in an amount between about 10 and 40% by volume, hi other embodiments, the turpentine liquid further includes up to about 10% by volume ⁇ -terpineol.
  • the turpentine liquid can 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 hydrocarbon-containing organic matter during primary, secondary and tertiary recovery operations, including after secondary recovery operations that include waterflooding.
  • a turpentine liquid for the recovery of hydrocarbon-containing organic matter from tar sands includes at least about 30% by volume ⁇ -terpineol and at least about 25% by volume ⁇ -terpineol. In another embodiment, the turpentine liquid includes between about 30 and 70% by volume ⁇ -terpineol, between about 25 and 55% by volume ⁇ -terpineol, up to about 10% by volume ⁇ -terpene, and up to about 10% by volume ⁇ -terpene.
  • a turpentine liquid for recovering hydrocarbon-containing organic matter from high grade coal sources, such as for example, anthracite or bituminous coal.
  • the turpentine liquid includes at least about 45% by volume ⁇ - terpineol and at least about 15% by volume ⁇ -terpineol.
  • the turpentine liquid includes between about 45 and 80% by volume ⁇ -terpineol, between about 15 and 45% by volume ⁇ -terpineol, up to about 10% by volume ⁇ -terpene, and up to about 10% by volume ⁇ - terpene.
  • a turpentine liquid for recovering hydrocarbon-containing organic matter from low grade coal sources includes at least about 60% by volume ⁇ -terpineol and up to about 30% by volume ⁇ -terpineol. In another embodiment, the turpentine liquid includes between about 60 and 95% by volume ⁇ - terpineol, up to about 30% by volume ⁇ -terpineol, up to about 5% by volume ⁇ -terpene, and up to about 5% by volume ⁇ -terpene.
  • a turpentine liquid for recovering hydrocarbon-containing organic matter from oil shale is provided.
  • oil shale generally refers to any sedimentary rock that contains bituminous materials.
  • the turpentine liquid includes at least about 60% by volume ⁇ -terpineol and up to about 30% by volume ⁇ -terpineol.
  • the turpentine liquid includes between about 60 and 95% by volume ⁇ -terpineol, up to about 30% by volume ⁇ -terpineol, up to about 5% by volume ⁇ -terpene, and up to about 5% by volume ⁇ -terpene.
  • a turpentine liquid for recovering hydrocarbon-containing organic matter from light and medium crude oil.
  • the turpentine liquid includes at least about 40 and 70% by volume ⁇ -terpineol and at least about 30 and 40% by volume ⁇ -terpineol.
  • the turpentine liquid includes between about 40 and 70% by volume ⁇ -terpineol, between about 30 and 40% by volume ⁇ -terpineol, up to about 10% by volume ⁇ -terpene, and up to about 10% by volume ⁇ -terpene.
  • a turpentine liquid for recovering hydrocarbon-containing organic matter from heavy and extra heavy crude oil.
  • the turpentine liquid includes at least about 50 and 70% by volume ⁇ -terpineol and at least about 30 and 40% by volume ⁇ -terpineol.
  • the turpentine liquid includes between about 50 and 70% by volume ⁇ -terpineol, between about 30 and 40% by volume ⁇ -terpineol, up to about 10% by volume ⁇ -terpene, and up to about 10% by volume ⁇ -terpene.
  • a method for recovering hydrocarbon-containing organic matter from tar sands includes mining a formation rich in tar sands to provide a tar sand sample, wherein the tar sand sample includes a recoverable hydrocarbon-containing organic matter and residual inorganic or insoluble material.
  • the tar sand sample is supplied to a contacting vessel, wherein the contacting vessel includes at least one inlet for supplying a turpentine liquid for recovery of hydrocarbons from the tar sands.
  • the tar sand sample is contacted with a turpentine liquid to extract the hydrocarbon-containing organic matter from the tar sands to produce a residual material and an extraction mixture.
  • the extraction mixture includes the turpentine liquid and recovered hydrocarbon-containing organic matter, and the residual material is separated from the turpentine liquid to produce hydrocarbon product stream and a turpentine liquid recycle stream.
  • the method further includes the step of recycling the turpentine liquid recycle stream to the contracting vessel.
  • the extraction mixture can be separated by distillation to produce the hydrocarbon product stream and the turpentine liquid recycle stream.
  • the turpentine liquid can include ⁇ -terpineol. In other embodiments, the turpentine liquid can include at least about 40% by volume ⁇ -terpineol and between 10 and 40% by weight ⁇ -terpineol. In certain embodiments, between 0.5 and 4 equivalents of the turpentine liquid is used to contact the tar sands and recover hydrocarbons. In certain embodiments, between 0.5 and 2.0 equivalents of the turpentine liquid is used to contact the tar sands and recover hydrocarbons.
  • a method for recovering hydrocarbon-containing organic matter from a hydrocarbon rich oil shale includes mining a rock formation that includes hydrocarbon-containing organic matter to produce a hydrocarbon containing oil shale that includes a recoverable hydrocarbon material and inorganic or insoluble material.
  • the oil shale is ground to produce crushed hydrocarbon-containing oil shale.
  • the crushed hydrocarbon- containing oil shale is then filtered with a filter screen to prevent or control the excessively large particles from being supplied to the extraction process.
  • the crushed hydrocarbon-containing oil shale is fed to a contacting vessel, wherein the contacting vessel includes at least one inlet for supplying a turpentine liquid for recovery of hydrocarbons from the crushed hydrocarbon- containing oil shale.
  • the crushed hydrocarbon-containing oil shale is contacted with the turpentine liquid to extract the hydrocarbon-containing organic matter from the crushed hydrocarbon-containing oil shale to produce inorganic solids and an extraction mixture that includes the turpentine liquid and recovered hydrocarbons.
  • the inorganic or insoluble materials are removed from the extraction mixture, and the recovered hydrocarbons are separated from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recycle stream.
  • the turpentine liquid recycle stream is recycled to the contracting vessel.
  • the crushed hydrocarbon-containing oil shale has a mean particle size of less than about 0.42 mm in diameter.
  • the turpentine liquid includes at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, ⁇ - pinene, ⁇ -pinene, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, terpene resins, ⁇ -terpene, ⁇ -terpene, ⁇ - terpene, or mixtures thereof, hi other embodiments, the turpentine liquid includes at least one compound selected from geraniol, 3-carene, dipentene (p-mentha-l,8-diene), nopol, pinane, 2- pinane hydroperoxide, terpin hydrate,
  • the turpentine liquid includes at least one compound selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethyl-l,6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal, menthone, and mixtures thereof.
  • the turpentine liquid can include ⁇ - terpineol.
  • the turpentine liquid can include at least about 40% by volume ⁇ -terpineol and between 10 and 40% by weight ⁇ -terpineol. In certain embodiments, between 0.5 and 4 equivalents of the turpentine liquid is used to contact the oil shale and recover hydrocarbon-containing organic matter. In certain embodiments, between 0.5 and 2.0 equivalents of the turpentine liquid is used to contact the oil shale and recover hydrocarbons.
  • a method for recovering hydrocarbon-containing organic matter from a coal rich sub-surface formation includes mining the sub-surface formation to produce coal, wherein the coal includes a recoverable hydrocarbon-containing organic matter and inorganic or insoluble material.
  • the coal is ground to produce crushed coal and filtered to provide a sample of uniform or desired size.
  • the crushed coal is fed to a contacting vessel, wherein the contacting vessel includes at least one inlet for supplying a turpentine liquid for recovery of hydrocarbons from crushed coal, and contacted with the turpentine liquid to extract the hydrocarbons from the crushed coal to produce inorganic solids and an extraction mixture.
  • the extraction mixture includes the turpentine liquid and recovered hydrocarbons.
  • the method further includes recycling the turpentine liquid recycle stream to the contracting vessel, hi yet other embodiments, the liquid coal product stream is supplied to a liquid coal refinery.
  • the coal sample includes a low grade coal having a mean particle size of less than about 0.42 mm. hi certain embodiments, the coal sample includes a high grade coal having a mean particle size of less than about 0.84 mm.
  • the turpentine liquid includes at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, ⁇ -pinene, ⁇ -pinene, ⁇ -terpineol, ⁇ - terpineol, ⁇ -terpineol, terpene resins, ⁇ -terpene, ⁇ -terpene, ⁇ -terpene, or mixtures thereof.
  • the turpentine liquid includes at least one compound selected from geraniol, 3-carene, dipentene (p-mentha-l,8-diene), nopol, pinane, 2-pinane hydroperoxide, te ⁇ in hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol, ⁇ -te ⁇ inyl acetate, citronellol, p- menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof, hi other embodiments, the turpentine liquid includes at least one compound selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethyl-l,6-octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2-methoxy-2
  • the turpentine liquid includes at least 60% by volume ⁇ - terpineol. In certain embodiments, the turpentine liquid includes at least 45% by volume ⁇ - terpineol and at least about 15% by volume ⁇ -terpineol. In certain other embodiments, the turpentine liquid includes at least 60% by volume ⁇ -terpineol and up to about 30% by volume ⁇ - terpineol. In certain embodiments, between 0.5 and 4 equivalents of the turpentine liquid is used to contact the oil shale and recover hydrocarbon-containing organic matter. In certain embodiments, between 0.5 and 2.0 equivalents of the turpentine liquid is used to contact the oil shale and recover hydrocarbon-containing organic matter.
  • a system for recovering hydrocarbon-containing organic material from tar sands includes a tank for supplying a turpentine liquid and a contacting vessel, wherein the contacting vessel includes at least one inlet for introducing the turpentine liquid and at least one outlet for recovering an extraction mixture from the contacting vessel.
  • the system also includes a first conveyor for supplying tar sands to the contacting vessel.
  • a holding tank that includes a line connecting the holding tank to the contacting vessel is provided, wherein the line connecting the contacting vessel and the holding tank includes a filter to prevent the passage of solids to the holding tank.
  • the system also includes a second conveyor for the recovery and transport of the solids.
  • the contacting vessel is a rotary inclined filter that includes a series of fins or trays for separating and or controlling the tar sands.
  • the fins or trays are provided to increase or control the contact time between the tar sands and the turpentine liquid, hi certain embodiments, the turpentine liquid can include ⁇ -terpineol. In other embodiments, the turpentine liquid can include between about 30% and 70% by volume ⁇ - terpineol and between about 25% and 55% by weight ⁇ -terpineol.
  • a system for recovering hydrocarbon-containing organic matter from oil shale includes a tank for supplying a turpentine liquid and a grinder for comminuting the oil shale to a reduced particle size.
  • a contacting vessel is provided that includes at least one inlet for introducing the turpentine liquid, at least one inlet for receiving crushed oil shale, at least one outlet for recovering solids from the contacting vessel and at least one outlet for recovering an extraction mixture from the contacting vessel.
  • a first conveyor is provided for supplying crushed oil shale to a contacting vessel.
  • the system further includes a holding tank, wherein the holding tank includes a line connecting the holding tank to the contacting vessel, wherein the line includes a filter to prevent the passage of solids to the holding tank; a second conveyor for recovering solids.
  • 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.
  • the turpentine liquid can include ⁇ -terpineol.
  • the turpentine liquid can include between about 60% and 95% by volume ⁇ -terpineol and up to about 30% by weight ⁇ - terpineol.
  • the turpentine liquid can include between about 70% and 90% by volume ⁇ -terpineol and between about 5% and 25% by weight ⁇ -terpineol.
  • a system for recovering hydrocarbon-containing organic matter from coal includes a tank for supplying a turpentine liquid and a grinder for comminuting coal to produced particulate matter of a reduced size.
  • a contacting vessel is provided that includes at least one inlet for introducing the turpentine liquid and at least one outlet for recovering solids and liquids from the contacting vessel.
  • the contacting vessel includes also stirring means for thoroughly mixing the turpentine liquid and the comminuted coal .
  • a separator is provided for separating the solids and liquids, wherein the separator includes an inlet, an outlet and a line connecting the inlet of the separator to the outlet of the contacting vessel.
  • the system also includes a holding tank, wherein the holding tank includes a line that connects the holding tank to the separator, wherein the line can include a filter to prevent the passage of solids to the holding tank.
  • the system further includes a filter for selectively preventing particles having a mean diameter greater than about 0.85 mm from being introduced to the contacting vessel.
  • the system further includes a line for supplying a liquid coal product to a refinery for further processing.
  • the system further includes a first conveyor for supplying crushed coal to the contacting vessel.
  • the system further includes a second conveyor for removing solids from the separator.
  • the turpentine liquid can include ⁇ -terpineol.
  • the turpentine liquid can include between about 45% and 80% by volume ⁇ -terpineol and between about 15% and 45% by weight ⁇ -terpineol. In embodiments directed to the recovery of hydrocarbons from low grade coal, the turpentine liquid can include between about 60% and 95% by volume ⁇ - terpineol and between about 0% and 30% by weight ⁇ -terpineol.
  • a method for optimizing a turpentine liquid for extraction of hydrocarbon-containing organic matter from hydrocarbon containing matter includes providing a sample of the hydrocarbon-containing material and analyzing the hydrocarbon material to determine the type ofhydrocarbon being extracted.
  • a formulation for extraction of hydrocarbon-containing organic matter from the hydrocarbon material is provided, wherein the formulation is a function of the type of formation and the size of the particulate hydrocarbon material.
  • the formulation includes at least about 40% by volume ⁇ -terpineol and at least about 10% by volume ⁇ -terpineol.
  • the amount of ⁇ -terpineol and ⁇ -terpineol in the formulation is then adjusted based upon the parameters noted above, hi general, while the above noted method provides a good starting point for determining the desired formulation for extraction of various hydrocarbon containing materials, for other hydrocarbon- containing materials and under specified operating conditions, either a series of statistically designed experiments or a series of experiments according to an optimization method can be performed to determine the optimum composition of the liquid turpentine.
  • the specific formulation for extraction, liquefaction and/or solubilization of hydrocarbon-containing organic matter from tar sands varies based upon the particle size.
  • the method for preparing a turpentine liquid for extracting hydrocarbon-containing organic matter from tar sands includes adjusting the amount of ⁇ - terpineol and ⁇ -terpineol in the formulation as a function of the size of the hydrocarbon rich solid particulate being extracted.
  • the amount ⁇ -terpineol in the turpentine liquid is increased and the amount of ⁇ -terpineol in the turpentine liquid is decreased.
  • the hydrocarbon-containing organic particulate matter includes tar sands, the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased.
  • the hydrocarbon-containing organic particulate matter includes tar sands and the mean diameter of the particulate matter is less than about 4.76 mm, then the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased, hi other embodiments, if the hydrocarbon-containing organic particulate matter includes tar sands and the mean diameter of the particulate matter is greater than about 1 inch (1 mesh), then the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased.
  • the formulation for extraction, liquefaction and/or solubilization of coal depends both on particle size and on the quality of the coal being extracted, hi one embodiment of the method for preparing a turpentine liquid for extracting hydrocarbon-containing organic matter, if the hydrocarbon-containing matter includes anthracite, bituminous coal, or other high grade coal and the mean diameter of the particulate matter is less than about 0.15 mm, then the amount ⁇ - terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased.
  • the hydrocarbon rich particulate matter includes anthracite, bituminous coal, or other high grade coal and the mean diameter of the particulate matter is greater than about 0.84 mm, then the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased. In another embodiment, if the hydrocarbon rich particulate matter includes low grade coal and the mean diameter of the particulate matter is less than about 0.074 mm, then the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased.
  • the hydrocarbon rich particulate matter includes low grade coal and the mean diameter of the particulate matter is greater than about 0.42 mm, then the amount ⁇ - terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased.
  • the formulation for extraction, liquefaction and/or solubilization of oil shale depends on particle size.
  • the hydrocarbon rich particulate matter includes an oil shale and the mean diameter of the particulate matter is less than about 0.074 mm, then the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased.
  • the hydrocarbon rich particulate matter includes oil shale and the mean diameter of the particulate matter is greater than about 0.42 mm, then the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ -terpineol in the turpentine liquid is increased.
  • Table 4 Formulations for Extraction of Oil Shale based upon Particle Size
  • the extraction of crude oil similarly depends on the type of crude oil being extracted, liquefied, and/or solubilized. As shown in Table 5, the formulation for the extraction, liquefaction and/or solubilization of crude oil depends is a function of both 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 ⁇ -terpineol and at least 20% by volume ⁇ -terpineol; adjusting the amount of ⁇ -terpineol and ⁇ -terpineol in the turpentine liquid formulation based upon the density of the liquid hydrocarbon being extracted.
  • the API gravity of the liquid hydrocarbon being extracted is greater than about 22°, then the amount ⁇ -terpineol in the turpentine liquid is decreased and the amount of ⁇ - 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 ⁇ -terpineol in the turpentine liquid is increased and the amount of ⁇ -terpineol in the turpentine liquid is decreased.
  • light oils have an API of at least about 31°
  • medium crude oils have an API of between about 22° and about 31°
  • heavy oil has an API of between about 10° and about 22°
  • extra heavy oil has an API of less than about 10°.
  • a method for preparing a turpentine liquid for enhancing recovery of liquid hydrocarbon-containing organic matter from a sub-surface formation includes providing a formulation comprising at least 50% by volume ⁇ -terpineol and at least 20% by volume ⁇ -terpineol, and adjusting the amount of ⁇ -terpineol and ⁇ -terpineol in the formulation based upon the geological features of the sub-surface formation.
  • a composition for cleaning and/or recovering hydrocarbons from a liquid hydrocarbon-containing vessel includes at least one compound selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, ⁇ - pinene, ⁇ -pinene, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, terpene resins, ⁇ -terpene, ⁇ -terpene, ⁇ - terpene, or mixtures thereof.
  • the composition for cleaning and/or recovering hydrocarbons includes at least one compound selected from geraniol, 3-carene, dipentene (p-mentha-l,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2- pinanol, dihydromycenol, isobomeol, p-menthan-8-ol, ⁇ -terpinyl acetate, citronellol, p-menthan- 8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof.
  • the composition for cleaning and/or recovering hydrocarbons includes at least one compound selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethyl-l,6- octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2-methoxy-2,6- dimethyl-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal, menthone, and mixtures thereof, hi one embodiment, the composition includes at least one compound from the following: ⁇ -pinene, ⁇ -pinene, ⁇ -terpineol, and ⁇ -terpineol. In another embodiment, the composition includes at least 25% by volume ⁇ -terpineol or ⁇ - terpineol.
  • a method for cleaning and/or recovering hydrocarbons from a liquid hydrocarbon-containing vessel includes contacting the interior of vessel with a hydrocarbon cleaning composition that includes at least one compound selected from ⁇ -pinene, ⁇ -pinene, ⁇ -terpineol, and ⁇ -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 vessel.
  • the cleaning composition includes at least 25% by volume of ⁇ -terpineol or ⁇ -terpineol.
  • the cleaning composition includes at least 25% by volume of ⁇ -terpineol and at least 25% by volume ⁇ -terpineol.
  • Example 1 coal from the Pittsburgh seam in Washington County, Pennsylvania was liquefied with reagent ⁇ -terpineol.
  • the coal sample was obtained from the Coal Bank at Pennsylvania State University, which provided the following proximate analyses for it; 2.00 wt. % of as-received moisture, 9.25 wt. % of dry ash, 38.63 wt. % of dry volatile matter, and 50.12 wt. % of dry fixed carbon.
  • the particle size of coal sample was about 60 mesh.
  • About 60 grams of ⁇ -terpineol was gently added to about 30 grams of the coal sample placed in an extraction vessel, thus giving rise to the reagent-to-sample ratio of 2 to 1.
  • the capped, but not tightly sealed, extraction vessel containing the resultant mixture of ⁇ -terpineol and coal was maintained at the constant temperature of about 96°C and continually agitated. Without boiling the ⁇ -terpineol, the pressure in the extraction vessel remained at the ambient pressure of slightly less than about l.OlxlO 5 Pascals (1 arm). After about 30 minutes, the mixture was filtered and the coal particles retained on the filter were washed with ethanol and dried to a constant weight. On the basis of weight loss, the conversion, i.e., the extent of liquefaction, of the coal sample was determined to be about 68 wt. %.
  • Example 2 This example is identical to Example 1 in all aspects except two. After maintaining the temperature at about 96 0 C, for about 30 minutes, as done in Example 1, the extraction vessel containing the coal sample and ⁇ -terpineol was maintained at a temperature at about 135 0 C for an additional period of about 30 minutes. The pressure in the extraction vessel remained at the ambient pressure of slightly less than about l .OlxlO 5 Pascals (1 atm). The conversion, i.e., the degree of liquefaction, of the coal sample was determined to be about 70 wt. %.
  • Example 3 The coal sample used was from the same source with the same proximate analyses as those used in the preceding two examples. About 31 grams of ⁇ -terpineol were added to about 31 grams of the coal sample in an extraction vessel . The mixture was maintained at about 96 0 C and an ambient pressure of slightly less than about l .OlxlO 5 Pascals (1 atm) for about 30 minutes. The conversion, i.e., the degree of liquefaction, of the coal sample attained was determined to be about 71 wt. % by weighing the sample after filtering, washing, and drying as done in the preceding two examples.
  • Example 4 This example is identical to Example 3, except that about 30 wt. % of ⁇ - terpineol was replaced with hexane, providing a reagent that includes 70 wt.% ⁇ -terpineol and 30 wt. % hexane. This reduced the conversion, i.e., the degree of liquefaction to about 1.3 wt. %.
  • Example 5 The source and proximate analyses of coal sample and experimental conditions in terms of temperature, pressure and reagent-to-sample ratio 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 wt. % of the ⁇ -terpineol was replaced with 1-butanol, providing a reagent that includes 70 wt.% ⁇ -terpineol and 30 wt. % 1- butanol. The amount of coal liquefied was only about 0.30 gram, corresponding to conversion of about 1.0 wt. %.
  • Example 6 This example is the same as Example 3 in terms of the source and proximate analyses of coal sample and temperature, pressure and duration of the extraction.
  • the amount of the coal sample used was, however, about 25 grams and the reagent comprised about 24 grams (80 wt. %) of ⁇ -terpineol and about 6 grams (20 wt. %) of xylenes, providing a reagent that includes 70 wt.% ⁇ -terpineol and 30 wt. % xylenes.
  • the coal liquefied was about 10.0 grams, corresponding to conversion of about 40 wt. %.
  • Example 7 coal from the Wyodak seam in Campbell County, Wyoming was liquefied with reagent ⁇ -terpineol.
  • the coal sample was obtained from the Coal Bank at Pennsylvania State University, which provided the following proximate analyses for it; 26.30 wt. % of as-received moisture, 7.57 wt. % of dry ash, 44.86 wt. % of dry volatile matter, and 47.57 wt. % of dry fixed carbon.
  • the coal sample's particle size was about 20 mesh.
  • About 60 grams of ⁇ -terpineol was gently added to about 30 grams of the coal sample placed in an extraction vessel , a reagent-to-sample ratio of about 2 to 1.
  • the capped, but not tightly sealed, extraction vessel containing the resultant mixture of ⁇ -terpineol and coal was maintained at a constant temperature of about 96°C and continually agitated. Without boiling of the ⁇ -terpineol, the pressure in the extraction vessel remained at the ambient pressure of slightly less than about 1.0IxIO 5 Pascals (1 atm). After about 30 minutes, the mixture in the extraction vessel was filtered and the coal particles retained on the filter were washed with ethanol and dried to a constant weight. On the basis of weight loss, the conversion, i.e., the degree of liquefaction, of the coal sample was determined to be 75 wt. %.
  • Example 8 The experiment in this example was carried out under the conditions identical to those of the preceding example except one. About 15 grams of ⁇ -terpineol were added, instead of about 60 grams, as done in the preceding example, to about 30 grams of the coal sample, thus attaining the reagent-to-coal ratio of 0.5 to 1. The conversion, i.e., the degree of liquefaction, of the coal sample attained decreased from about 75 wt. %, attained in the preceding example, to about 69 wt. %.
  • Example 9 In this example, about 3 grams of oil shale from the Green-river region of Colorado was solubilized with about 9 grams of ⁇ -terpineol, thus giving rise to the reagent-to-sample ratio of 3 to 1 , to extract kerogen (organic matter) and/or bitumen (organic matter) from it.
  • the organic carbon content including both volatile and fixed carbon, was determined to be about 22.66 wt. % by a certified analysis company.
  • the weight losses of the samples were determined by weighing after filtering, washing with ethanol, and drying. These losses were about 9 wt. % after about 30 minutes and about 17 wt. % after about 45 minutes. From these weight losses, the conversion, i.e., the degree of extraction of organic matter, i.e., kerogen and/or bitumen, was estimated to be about 40 wt. % for the former and was about 75 wt. % for the latter.
  • Example 10 duplicated the preceding example with the exception that a single experiment, lasting about 15 minutes, was carried out at the temperature of about 96 0 C, instead of about 25°C.
  • the weight loss of the oil shale sample was about 12 wt. %, corresponding to the conversion, i.e., the degree of extraction, of kerogen (organic matter) of about 53 wt. %
  • Example 11 bitumen (organic matter) in tar sands from Alberta,
  • the tar- sands sample was obtained from Alberta Research Council, which provided the following proximate analyses for it; 84.4 wt. % of dry solids, 11.6 wt. % of dry bitumen, and 4.0 wt. % of as-received moisture.
  • About 30 grams of synthetic turpentine were gently added to about 15 grams of the tar-sands sample in a capped, but not tightly sealed, extraction vessel , utilizing a reagent-to-sample ratio of about 2 to 1 by weight.
  • This extraction vessel containing the resultant mixture of synthetic turpentine and tar sands, was maintained at a constant temperature of about 96 0 C and continually agitated. Without boiling of the synthetic turpentine, the pressure in the extraction vessel remained at the ambient pressure of slightly less than about 1.01x10 5 Pascals (1 atm). After about 20 minutes, the mixture in the extraction vessel was filtered and the solids (tar sands) retained on the filter were washed with ethanol and dried to a constant weight. On the basis of weight loss, the conversion, i.e., the degree of extraction, of bitumen from the tar-sands sample was determined to be about 100 wt. %.
  • Example 12 In this example, about 60 grams of the tar-sands sample from the same source with the same proximate analyses as those of the preceding example were extracted by about 60 grams of ⁇ -terpineol, instead of commercial-grade synthetic turpentine, which includes ⁇ -terpineol. The resultant reagent-to-sample ratio was 1 to 1 instead of 2 to 1 as in the preceding example. The experiment lasted about 30 minutes at the temperature of about 96°C under the ambient pressure of slightly less than about 1.01 xlO 5 Pascals (1 atm). The conversion, i.e., the extent of extraction, of bitumen (organic matter) in the tar-sands sample was determined to be about 100 wt. %.
  • Example 13 In this example, about 60 grams of the tar-sands sample from the same source with the same proximate analyses as those of the preceding two examples were extracted by about 60 grams of synthetic turpentine, which is of the commercial grade. The resultant reagent-to-sample ratio, therefore, was about 1 to 1. The experiment was carried out for about 30 minutes at the temperature of about 96°C under the ambient pressure of slightly less than about l.OlxlO 5 Pascals (1 atm). The conversion, i.e., the degree of extraction, of bitumen (organic matter) in the tar-sands sample was determined to be about 70 wt. %.
  • Example 14 The experiment in this example duplicated that in Example 8 in all aspects except that the reagent-to-sample ratio was reduced from about 2 to 1 to about 0.5 to 1 : About 60 grams to the tar-sands sample was extracted by about 30 grams of synthetic turpentine, which is of the commercial grade. The conversion, i.e., the degree of extraction, of bitumen (organic matter) decreased from about 100 wt. % attained in Example 9 to about 70 wt. %. [00106] Example 15. The experiment in this example repeated that of the preceding example with ⁇ -terpineol instead of the commercial-grade synthetic turpentine. The conversion, i.e., the degree of extraction, of bitumen (organic matter) in the tar-sands sample was about 70 wt. % as in the preceding example.
  • Example 16 The experiment in this example was carried out under the ambient pressure of slightly less than about 1.01x10 5 Pascals (1 atm) with the tar-sands sample from the same source with the same proximate analyses as those in the preceding examples with tar sands.
  • About 60 grams of commercial-grade synthetic turpentine was added to about 60 grams of the tar-sands sample, thus giving rise to the reagent-to-sample ratio of about 1 to 1.
  • the temperature of the sample and commercial-grade synthetic turpentine was maintained at about 65°C for about 30 minutes followed by cooling to about 15 0 C within about 5 minutes.
  • the tar- sands sample was filtered, washed, dried and weighed.
  • the conversion, i.e., the degree of extraction, of bitumen (organic matter) in the tar-sands sample was determined to be about 70 wt. %.
  • Example 17 The experiment in this example repeated that of the preceding example with ⁇ -terpineol instead of commercial grade synthetic turpentine.
  • the conversion, i.e., the degree of extraction, of bitumen (organic matter) increased to about 90 wt. % from about 70 wt. % of the preceding examples.
  • Example 18 In this example, a tar-sands sample, weighing about 30 grams, from the same source with the same proximate analyses as those in Examples 11 through 17, was extracted with a liquid that included about 20 grams (80 wt. %) of ⁇ -terpineol and about 5 grams (20 wt. %) of toluene at the temperature of about 96°C under the ambient pressure of slightly less than about 1.0IxIO 5 Pascals (1 atm). The duration of the experiment (reaction or extraction time) was about 30 minutes. The weigh loss of the sample was about 10.2 grams. From this weigh loss, the conversion, i.e., the degree of extraction, of bitumen (organic matter) was estimated to be about 33 wt. %.
  • Example 19 Three tar-sands samples, all from the same source with the same proximate analyses as those used in all preceding examples with tar sands were extracted by reagents comprising various amounts of ⁇ -terpineol and ethanol at the temperature of about 15 0 C under the ambient pressure of slightly less than about 1.01x10 5 Pascals (1 atm). The duration of each experiment (reaction or extraction time) was about 15 minutes for each tar-sands sample. The first sample was extracted with a mixture comprising about 0 gram (0 wt. %) of ⁇ -terpineol and about 15 grams (100 wt. %) of ethanol, i.e., with pure ethanol.
  • the second sample was extracted with a mixture comprising about 7.5 grams (50 wt. %) of ⁇ -terpineol and about 7.5 grams (50 wt. %) of ethanol.
  • the third sample was extracted with a mixture comprising about 12 grams (80 wt. %) of ⁇ -terpineol and about 3 grams (20 wt. %) of ethanol.
  • the weight losses and the estimated conversions, i.e., the degrees of extraction, of bitumen (organic matter) in the three samples were about 0.2 gram (1.0 wt. %), 0.6 gram (3.0 wt. %) and 0.9 gram (4.5 wt. %), for the first, second and third sample, respectively.
  • Example 20 Irregular-shaped pellets of commercial-grade asphalt whose average size was about 15 mm were solubilized and extracted with ⁇ -terpineol and at the ambient temperature of about 22°C under the ambient pressure of slightly less than about 1.01x10 5 Pascals (1 atm). The first sample weighing about 20 grams was solubilized and extracted with about 40 grams of ⁇ -terpineol, and the second sample also weighing about 20 grams was solubilized and extracted with about 20 grams of ⁇ -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 like asphalt.
  • Example 21 bitumen (organic matter) in tar-sands from the same source with the same proximate analyses as those used in all previous examples with tar sands was solubilized and extracted with two varieties of vegetable oils, soybean oil and corn oil. The vegetable oils are completely miscible with turpentine liquid.
  • a tar- sands sample weighing about 15 grams was blended and agitated continually with about 30 grams of soybean oil for about 20 minutes at the temperature of about 96°C under the ambient pressure of slightly less than about 1.01x10 5 Pascals (1 atm).
  • the weight loss was about 0.5 gram from which the conversion, i.e., the degree of extraction, of bitumen in the sample was estimated to be about 3.3 wt. %.
  • a tar-sands sample weighing about 30 grams was blended and agitated continually with about 60 grams of corn oil for about 30 minutes at the temperature of about 175°C under the ambient pressure of slightly less than about l.OlxlO 5 Pascals (latm).
  • the weight loss was about 4.8 grams from which the conversion, i.e., the degree of extraction, of bitumen in the sample was estimated to be about 12 wt. %.
  • Example 22 Two tests were performed on Berea sandstone plug core samples to determine the effect of reagent injection on oil recovery from core. The first test was designed to determine the increment oil recovery due to ⁇ - terpineol injection after a field had already undergone waterflooding to the limit.
  • the selected core contained 9.01 mL of laboratory oil simulating crude oil. The waterflooding with aqueous solution containing 3.0% of potassium chloride produced 4.6 mL of oil. Five (5) pore volumes of ⁇ -terpineol injection produced additional 3.61 mL of oil, thereby leaving the core with less than 8.0% of oil remaining in the original volume.
  • the second test was designed to represent the increased recovery that could be expected from a virgin reservoir with ⁇ -terpineol injection.
  • the selected core contained 8.85 mL of laboratory oil simulating crude oil. Oil production began after approximately 0.5 pore volumes of ⁇ -terpineol injection, which was continued until 3.5 pore volumes; however, the majority of the oil was recovered after only 2.5 pore volumes of ⁇ -terpineol injection. A total of 7.94 mL of laboratory oil was recovered, thereby leaving the core with less than 7.5% of oil remaining in the original volume.
  • the performance of various turpentine liquid formulations including turpentine liquid formulations that include only ⁇ -terpineol and ⁇ - terpineol in combination with various known organic solvents, are provided.
  • the first three compositions presented in the table include ⁇ -terpineol, ⁇ -terpineol, and ⁇ -terpineol.
  • the first same includes about 60% by volume ⁇ -terpineol, about 30% by volume ⁇ - terpineol, and about 10% by volume ⁇ -terpineol.
  • the terms about and approximately should be interpreted to include any values which are within 5% of the recited value. Furthermore, recitation of the term about 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 should be interpreted to uniquely identify elements and do not imply or restrict to any particular sequencing of elements or steps.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
EP08832082A 2007-09-20 2008-09-17 Extraction of hydrocarbons from hydrocarbon-containing materials Withdrawn EP2205696A1 (en)

Applications Claiming Priority (4)

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

Publications (1)

Publication Number Publication Date
EP2205696A1 true EP2205696A1 (en) 2010-07-14

Family

ID=56291090

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08832082A Withdrawn EP2205696A1 (en) 2007-09-20 2008-09-17 Extraction of hydrocarbons from hydrocarbon-containing materials

Country Status (24)

Country Link
EP (1) EP2205696A1 (he)
JP (2) JP2010540694A (he)
KR (1) KR101458881B1 (he)
CN (1) CN101868517B (he)
AP (1) AP2769A (he)
AR (1) AR068497A1 (he)
AU (1) AU2008301860B2 (he)
BR (1) BRPI0817129B1 (he)
CA (1) CA2699764C (he)
CL (1) CL2008002819A1 (he)
CO (1) CO6321173A2 (he)
EA (1) EA023805B1 (he)
EC (1) ECSP10010124A (he)
HK (1) HK1146732A1 (he)
IL (1) IL204606A (he)
MA (1) MA32182B1 (he)
MX (2) MX2010002915A (he)
MY (1) MY149974A (he)
NZ (1) NZ584661A (he)
PE (1) PE20090918A1 (he)
TN (1) TN2010000127A1 (he)
TW (1) TWI441909B (he)
UY (1) UY31345A1 (he)
WO (1) WO2009038728A1 (he)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8404108B2 (en) 2007-09-20 2013-03-26 Green Source Energy Llc Extraction of hydrocarbons from hydrocarbon-containing materials and/or processing of hydrocarbon-containing materials
WO2009114145A2 (en) * 2008-03-11 2009-09-17 Verutek Technologies, Inc. Ex-situ low-temperature hydrocarbon separation from tar sands
MA33192B1 (fr) * 2009-03-13 2012-04-02 Green Source Energy Llc Extraction d'hydrocarbures à partir de matières contenant des hydrocarbures et/ou traitement de matières contenant des hydrocarbures
EP2366759A1 (de) * 2010-03-17 2011-09-21 Siemens Aktiengesellschaft Verfahren und Vorrichtungen zur Extraktion von Kohlenwasserstoffen aus Ölsand
JP5504536B2 (ja) * 2010-06-04 2014-05-28 国立大学法人秋田大学 高周波の超音波を使用したオイルサンド由来のビチューメンの抽出方法
US9150776B2 (en) * 2011-06-13 2015-10-06 Nalco Company Additives for improving hydrocarbon recovery
US9884997B2 (en) * 2011-09-30 2018-02-06 Mcw Energy Group Limited Oil from oil sands extraction process
MX353391B (es) 2012-02-02 2018-01-10 Green Source Energy Llc Composiciones y metodos para recuperacion y/o eliminacion de reactivos desde un medio poroso.
US9365777B2 (en) * 2012-06-13 2016-06-14 Red Leaf Resources, Inc. Methods of operation for reduced residual hydrocarbon accumulation in oil shale processing
CN102784493B (zh) * 2012-08-21 2014-03-26 无锡市华立石化工程有限公司 一种自动连续提取松脂液的浸提器
AU2014236331B2 (en) * 2013-03-14 2017-08-31 Flotek Chemistry, Llc Methods and compositions for stimulating the production of hydrocarbons from subterranean formations
CN104420860A (zh) * 2013-08-19 2015-03-18 国润金华（北京）国际能源投资有限公司 一种油砂分离器
CN106977064B (zh) * 2017-03-30 2019-05-24 柴海林 一种生物萃取剂处理含油污泥的方法及其应用
CN109621475B (zh) * 2018-12-18 2021-01-08 江西开源香料有限公司 一种α-蒎烯制备别罗勒烯的方法及应用设备
CN115260002B (zh) * 2022-05-26 2023-10-20 北京工业大学 金属有机框架材料在龙脑/异龙脑混合物中的吸附分离应用

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB322749A (en) * 1928-09-06 1929-12-06 Ig Farbenindustrie Ag Improvements in the extraction of bituminous materials by means of solvents
US2191767A (en) 1934-12-15 1940-02-27 Pennsylvania Petroleum Res Cor Process for treating mineral oils
US2324980A (en) 1940-04-30 1943-07-20 Firestone Tire & Rubber Co Method of reclaiming synthetic rubber
US2356254A (en) 1942-10-21 1944-08-22 Petrolite Corp Process for preventing and/or removing accumulation of solid matter in oil wells, pipelines, and flow lines
US2549438A (en) 1949-09-28 1951-04-17 Petrolite Corp Process for breaking petroleum emulsions
US3061097A (en) * 1958-12-24 1962-10-30 Philip A Mallinckrodt Flotation process for separating bituminous matter from associated gangue minerals
NL169490C (nl) * 1969-03-11 1982-07-16 Owens Illinois Inc Werkwijze voor het bereiden van een bekledingsmateriaal en voortbrengselen, vervaardigd onder toepassing van dit materiaal.
US4029567A (en) * 1976-04-20 1977-06-14 Canadian Patents And Development Limited Solids recovery from coal liquefaction slurry
US4272356A (en) * 1980-04-07 1981-06-09 Stiller Alfred H Coal extraction process
US4576708A (en) * 1984-08-06 1986-03-18 Cities Service Oil & Gas Corp. Beneficiation of shale kerogen and its conversion into shale oil
US4968413A (en) * 1985-08-22 1990-11-06 Chevron Research Company Process for beneficiating oil shale using froth flotation
US5102566A (en) * 1987-10-02 1992-04-07 Exxon Chemical Patents Inc. Low ash lubricant compositions for internal combustion engines (pt-727)
US5328518A (en) * 1991-12-06 1994-07-12 Golden Technologies Company, Inc. Method for separating components of liquids in industrial process
US5634984A (en) * 1993-12-22 1997-06-03 Union Oil Company Of California Method for cleaning an oil-coated substrate
US5454878A (en) * 1994-02-17 1995-10-03 Lockheed Idaho Technologies Company Method for removing hydrocarbon contaminants from solid materials
EP0669151B1 (en) * 1994-02-24 2003-03-26 Matsushita Electric Industrial Co., Ltd. Method for extracting organic substance, solvent for use in said method, and method for measuring content of organic substance
US5868202A (en) * 1997-09-22 1999-02-09 Tarim Associates For Scientific Mineral And Oil Exploration Ag Hydrologic cells for recovery of hydrocarbons or thermal energy from coal, oil-shale, tar-sands and oil-bearing formations
NZ330283A (en) * 1998-04-21 2001-01-26 Organic Interceptor Products L herbicide containing monoterpene derivatives and fatty acid soaps
CA2276944A1 (en) * 1998-10-13 2000-04-13 Venanzio Di Tullio A process for the separation and isolation of tars, oils, and inorganic constituents from mined oil bearing sands and a further process for the extraction of natural resins from plant matter and kerogens from oil shale
FR2828064B1 (fr) * 2001-08-01 2004-05-21 Action Pin Utilisation de derives terpeniques comme agent anti-rebond augmentant la retention
US7594996B2 (en) * 2004-01-23 2009-09-29 Aquatech, Llc Petroleum recovery and cleaning system and process
JP2006075533A (ja) * 2004-09-13 2006-03-23 Olympus Corp 被検体内導入システム、受信装置および被検体内導入装置
CA2578873C (en) * 2004-10-15 2012-12-11 Earth Energy Resources Inc. Removal of hydrocarbons from particulate solids
US7334641B2 (en) * 2005-07-05 2008-02-26 Nicholas Castellano Composition and method to enhance recovery from oil wells

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2009038728A1 *

Also Published As

Publication number Publication date
JP2015004077A (ja) 2015-01-08
EA201000512A1 (ru) 2010-10-29
CN101868517B (zh) 2014-09-17
WO2009038728A1 (en) 2009-03-26
CN101868517A (zh) 2010-10-20
TW200914599A (en) 2009-04-01
JP5858449B2 (ja) 2016-02-10
UY31345A1 (es) 2009-04-30
CO6321173A2 (es) 2011-09-20
IL204606A0 (en) 2010-11-30
KR20100100761A (ko) 2010-09-15
AP2010005221A0 (en) 2010-04-30
AU2008301860A1 (en) 2009-03-26
AR068497A1 (es) 2009-11-18
CL2008002819A1 (es) 2008-10-24
CA2699764A1 (en) 2009-03-26
AP2769A (en) 2013-09-30
BRPI0817129B1 (pt) 2017-05-23
MY149974A (en) 2013-11-15
ECSP10010124A (es) 2010-09-30
HK1146732A1 (en) 2011-07-08
AU2008301860B2 (en) 2012-07-26
MA32182B1 (fr) 2011-04-01
TN2010000127A1 (en) 2011-09-26
TWI441909B (zh) 2014-06-21
EA023805B1 (ru) 2016-07-29
NZ584661A (en) 2012-09-28
PE20090918A1 (es) 2009-07-04
IL204606A (he) 2013-07-31
MX2010002915A (es) 2010-06-02
BRPI0817129A2 (pt) 2015-03-31
JP2010540694A (ja) 2010-12-24
MX2012013862A (es) 2013-06-25
KR101458881B1 (ko) 2014-11-07
CA2699764C (en) 2015-02-17

Similar Documents

Publication Publication Date Title
US8926832B2 (en) Extraction of hydrocarbons from hydrocarbon-containing materials
CA2699764C (en) Extraction of hydrocarbons from hydrocarbon-containing materials
US9416645B2 (en) Extraction of hydrocarbons from hydrocarbon-containing materials and/or processing of hydrocarbon-containing materials
US8522876B2 (en) In situ extraction of hydrocarbons from hydrocarbon-containing materials
CA2755215C (en) Extraction of hydrocarbons from hydrocarbon-containing materials and/or processing of hydrocarbon-containing materials
AU2012244185B2 (en) Extraction of Hydrocarbons from Hydrocarbon-Containing Materials

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100419

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEE, WILLIAM ARTHUR FITZHUGH

Inventor name: FAN, LIANG-TSENG

Inventor name: SHAFIE, MOHAMMAD REZA

Inventor name: TOLLAS, JULIUS MICHAEL

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20111215

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20181018

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190301