EXTRACTION OF HYDROCARBONS FROM HYDROCARBON-CONTAINING MATERIALS

• US 20100173806A1
• Filed: 09/17/2008
• Published: 07/08/2010
• Est. Priority Date: 09/20/2007
• Status: Active Grant

• Current Assignee: Green Source Holdings LLC
• Original Assignee: Green Source Energy, LLC
• Inventors: Lee, William Arthur Fitzhugh, Shafie, Mohammad Reza, Tollas, Julius Michael, Fan, Liang-tseng
• Granted Patent: US 8,404,107 B2
• Time in Patent Office: Days
• US Class Current: 507/266
• CPC Class Codes: C10G 1/04 by extraction
• CPC Class Codes: C10G 1/065 in the presence of a solvent
• CPC Class Codes: C10G 21/14 Hydrocarbons
• CPC Class Codes: C10G 21/16 Oxygen-containing compounds
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/1033 Oil well production fluids
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: E21B 43/16 Enhanced recovery methods for obtaining hydrocarbons
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

A method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material includes the steps of providing a first liquid comprising a turpentine liquid; contacting the hydrocarbon-containing material with the turpentine liquid to form an extraction mixture; extracting the hydrocarbon material into the turpentine liquid; and separating the extracted hydrocarbon material from a residual material not extracted.

Claims

1. A method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material, comprising the steps of:

providing a first liquid comprising a turpentine liquid;

contacting the hydrocarbon-containing material with said turpentine liquid such that an extraction mixture is formed and a residual material is formed, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter and the turpentine liquid, the residual material comprising at least a portion of non-soluble material from the hydrocarbon-containing material that are not soluble in the turpentine liquid;

separating the extraction mixture from the residual material; and

separating the extraction mixture into a first portion and a second portion, the first portion of the extraction mixture comprising a hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter, the second portion of the extraction mixture comprising at least a portion of the turpentine liquid.

2. The method of claim 1, wherein said turpentine liquid is selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, α

-pinene, β

-pinene, α

-terpineol, β

-terpineol, γ

-terpineol, terpene resins, α

-terpene, β

-terpene, γ

-terpene, and mixtures thereof.

3. The method of claim 1, wherein said turpentine liquid is selected from the group consisting of geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol, α

-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof;

4. The method of claim 1, wherein said turpentine liquid is selected from the group consisting of anethole, camphene;

p-cymene, anisaldeyde, 3,7-dimethyl-1,6-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.

5. The method of claim 1, wherein said hydrocarbon-containing organic matter is solid or semi-solid, wherein said hydrocarbon-containing material comprises a plurality of particles, the particles having an average particle diameter.

6. The method of claim 5, wherein the average particle diameter is from about 0.74 millimeters to about 25 millimeters.

7. The method of claim 1, further comprising the step of adding a second liquid to the turpentine liquid, the second liquid being selected from the group consisting of lower aliphatic alcohols, lower alkanes, lower aromatics, aliphatic amines, aromatic amines, and mixtures thereof.

8. The method of claim 7, wherein said second liquid is selected from the group consisting of ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane, benzene, toluene, xylene, anathracene, tetraline, triethylamine, aniline, and mixtures thereof.

9. The method of claim 8, wherein the step of contacting the hydrocarbon-containing material with said turpentine liquid further comprising the step of adding water at a temperature around a boiling point of water.

10. The method of claim 1 further comprising the step of heating the turpentine liquid to a temperature to a point above ambient temperature to about 200°

C. before contacting the turpentine liquid with the hydrocarbon-containing material.

11. The method of claim 1, wherein said hydrocarbon-containing material and said turpentine liquid are contacted at a pressure of from about 1.0×

10⁴ Pascals (0.1 atm) to about 5.0×

10⁶ Pascals (50.0 atm).

12. The method of claim 1, further comprising supplying at least a portion of the second portion of the extraction mixture to the contacting step.

13. The method of claim 1, further comprising the step of providing means for contacting said hydrocarbon-containing organic matter and said turpentine liquid in situ in an underground formation containing said hydrocarbon-containing organic matter, and means for extracting said hydrocarbon-containing organic matter from said underground formation.

14. The method of claim 1, wherein said hydrocarbon containing material is contacted by said turpentine liquid at a temperature of less than about 300°

C.

15. The method of claim 1, wherein the hydrocarbon-containing material is contacted by said turpentine liquid at a temperature of less than about 60°

C.

16. The method of claim 1 wherein the hydrocarbon-containing material is in an underground formation and the contacting of the hydrocarbon-containing material with said turpentine liquid occurs in situ in the underground formation;

and further comprising the step of

recovering the extraction mixture through a production well in fluid communication with the underground formation, wherein the residual material remains in situ in the underground formation.

17. The method of claim 16 further comprising the step of reinjecting the recycle stream into the injection well for further extraction of hydrocarbon material.

18. The method of claim 16 wherein the underground formation is undergoing primary recovery of the hydrocarbon material.

19. The method of claim 1 wherein the turpentine liquid comprises at least about 30% by volume α

-terpineol and at least about 15% β

-terpineol.

20. The method of claim 1 wherein the turpentine liquid comprises between about 50% by volume α

-terpineol and at least about 20% by volume β

-terpineol.

21. The method of claim 1 wherein the turpentine further comprises at least one of α

-terpene, terpene or γ

-terpene.

22. The method of claim 1 wherein the turpentine liquid comprises α

-terpineol and β

-terpineol, wherein the ratio of α

-terpineol to β

-terpineol is at least about 1.3;

1.

23. The method of claim 1 wherein the turpentine liquid comprises α

-terpineol and β

-terpineol, wherein the ratio of α

-terpineol to β

-terpineol is at least about 2;

1.

24. The method of claim 1 for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material, said hydrocarbon material comprising tar sands,

wherein the contacting of the hydrocarbon-containing material with said turpentine liquid comprises the step of supplying the tar sands to an interior portion of an extraction vessel and supplying the turpentine liquid to the interior portion of the extraction vessel for a period of time operable to extract a substantial portion of the hydrocarbon-containing organic matter from the hydrocarbon-containing material.

25. The method of claim 1 for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material, said hydrocarbon material comprising oil shale, the method further comprising the steps of:

grinding the hydrocarbon-containing organic matter to create a plurality of particles, the particles defining an average diameter size in the range of 4.8 mm to 25 mm such that the plurality of particles is contacting the turpentine liquid.

26. The method of claim 1 for extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material, said hydrocarbon material comprising coal, the method further comprising the steps of

grinding the hydrocarbon-containing organic matter to create a plurality of particles, the particles defining an average diameter size in the range of 0.8 mm to 0.07 mm such that the plurality of particles is contacting the turpentine liquid.

27. A composition for the extraction of a hydrocarbon-containing organic matter, the composition comprising at least about 30% by volume of α

-terpineol and at least about 10% by volume of β

-terpineol.

28. The composition of claim 27 wherein said composition comprises between about 50 and 70% by volume α

-terpineol and between about 20 and 40% by volume of β

-terpineol.

29. The composition of claim 27 also comprising up to 20% by volume γ

-terpineol.

30. The composition of claim 27 also comprising up to 20% by volume of at least one compound selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, α

-pinene, β

-pinene, α

-terpene, β

-terpene, and γ

-terpene.

31. The composition of claim 27 also comprising at least one compound selected from the group consisting of geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol, α

-terpinyl acetate, citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof.

32. The composition of claim 27 also comprising at least one compound selected from the group consisting of anethole, camphene, p-cymene, anisaldeyde, 3,7-dimethyl-1,6-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.

33. The composition of claim 27 also comprising up to about 10% by volume α

-terpene and up to about 10% by volume β

-terpene.

34. The composition of claim 27 wherein the composition also comprises between about 30 and 70% by volume α

-terpineol and between about 25 and 55% by volume β

-terpineol.

35. The composition of claim 27 wherein the composition also comprises between about 45 and 80% by volume α

-terpineol and between about 15 and 45% by volume β

-terpineol.

36. The composition of claim 27 wherein the composition also comprises between about 40 and 70% by volume α

-terpineol and between about 30 and 40% by volume β

-terpineol.

37. The composition of claim 27 wherein the composition also comprises between about 50 and 70% by volume α

-terpineol and between about 30 and 40% by volume β

-terpineol.

38. The composition of claim 27 also comprising up to about 5% by volume α

-terpene and up to about 5% by volume β

-terpene.

39. The composition of claim 27 wherein the composition also comprises between about 60 and 95% by volume α

-terpineol and up to about 30% by volume β

-terpineol.

40. The composition of claim 27 wherein the composition also comprises between about 60 and 95% by volume α

-terpineol and up to about 30% by volume β

-terpineol.

41. A method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material, the method comprising the steps of:

providing a first liquid comprising a turpentine liquid, the turpentine liquid comprising α

-terpineol;

contacting the hydrocarbon-containing material with said turpentine liquid such that an extraction mixture is formed and a residual material is formed, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter and the turpentine liquid, the residual material comprising at least a portion of non-soluble material from the hydrocarbon-containing material that are not soluble in the turpentine liquid; and

separating the extraction mixture from the residual material.

42. The method of claim 41 further comprising the step of separating the extraction mixture into a hydrocarbon product stream and a recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter, the recycle stream containing at least a portion of the turpentine liquid.

43. The method of claim 42 further comprising the step of recycling the recycle stream to contact the hydrocarbon-carbon containing material.

44. An apparatus for recovering hydrocarbon-containing organic matter from solid or semi-solid hydrocarbon containing materials, comprising:

a turpentine liquid supply comprising a turpentine liquid containing terpineol for extracting hydrocarbons-containing organic matter from the hydrocarbon containing materials;

a contacting vessel, said contacting vessel having a first inlet and being in fluid communication with the turpentine liquid supply through the first inlet, the contacting vessel being operable to receive the hydrocarbon-containing materials in an interior portion through a second inlet, the contacting vessel being operable to maintain the hydrocarbon-containing materials and the turpentine liquid in the interior portion of the contacting vessel for a predetermined amount of time operable to form an extraction mixture and a residual material, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter and the turpentine liquid, the residual material comprising at least a portion of non-soluble material from the hydrocarbon-containing material that are not soluble in the turpentine liquid;

the contacting vessel comprising a first outlet for recovering the extraction mixture from the contacting vessel and a second outlet for recovering the residual material from the contacting vessel, the contacting vessel being operable to allow for mechanical agitation;

a holding tank, said holding tank being in fluid communication with the contacting vessel through a line, wherein the holding tank is operable to receive the extraction mixture from the contacting vessel, wherein the line includes a filter to prevent the passage of solids to the holding tank; and

collection means for collecting the residual material from the second outlet of the contacting vessel.

45. The apparatus of claim 44 further comprising a separation vessel for receiving the extraction mixture, the separation vessel being operable to substantially separate the hydrocarbon-containing organic matter from the turpentine liquid.

46. The apparatus of claim 44 further comprising a recycle stream for receiving the turpentine liquid from the separation vessel, the recycle stream operable to return the turpentine liquid from the separation vessel to the contacting vessel for reuse.

47. The apparatus of claim 44 further comprising a grinder, said grinder being configured to reduce the size of the hydrocarbon containing materials for contact with the liquid turpentine in the contacting vessel.

48. The apparatus of claim 44 wherein said contacting vessel is a rotary inclined filter further comprising a plurality of fins or trays configured to control contact time between the turpentine liquid and the hydrocarbon containing materials.

49. The apparatus of claim 44 wherein said means for introducing hydrocarbon containing materials to the contacting vessel comprises a conveyor.

50. The apparatus of claim 44 wherein said contacting vessel further comprises means for mixing the hydrocarbon containing material and the turpentine liquid.

51. The apparatus of claim 44 further comprising a second contacting vessel coupled to the first contacting vessel, wherein the second contacting vessel comprises an inlet for receiving a turpentine liquid and a coal sample material, a first outlet for recovery of at least a portion of the extraction mixture and a second outlet for removing at least a portion of the residual material from the mixing vessel, wherein the second contacting vessel is located between and coupled to the first contacting vessel and the holding tank

52. The apparatus of claim 44 further comprising a filter located at the inlet of the contacting vessel.

53. A method for recovering hydrocarbon-containing organic matter from tar sands, the method comprising:

obtaining tar sands comprising recoverable hydrocarbon-containing organic matter;

providing a first liquid comprising a turpentine liquid, the turpentine liquid containing terpineol;

supplying the tar sand sample to a contacting vessel, said contacting vessel comprising at least one inlet for supplying the turpentine liquid;

contacting the tar sand sample with the turpentine liquid in a contacting vessel and agitating the tar sand sample with the turpentine liquid such that an extraction mixture is formed and a residual material is formed, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter and the turpentine liquid, the residual material comprising at least a portion of non-soluble material from the tar sands that is not soluble in the turpentine liquid, said contacting vessel comprising at least one inlet for supplying a turpentine liquid;

separating the extraction mixture from the residual material;

separating the extraction mixture into a hydrocarbon product stream and a turpentine liquid recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter from the tar sands; and

recycling at least a portion of the turpentine liquid recycle stream to the contacting step;

wherein said turpentine liquid comprises α

-terpineol and β

-terpineol.

54. A method for recovering hydrocarbon-containing organic matter from comminuted hydrocarbon-containing oil shale, the method comprising:

providing the comminuted hydrocarbon-containing oil shale;

providing a first liquid comprising a turpentine liquid;

filtering the comminuted hydrocarbon-containing oil shale;

feeding the crushed hydrocarbon-containing oil shale to a contacting vessel, the contacting vessel comprising at least one inlet for supplying the turpentine liquid to the contacting vessel;

contacting the comminuted hydrocarbon-containing oil shale with turpentine liquid such that an extraction mixture is formed and a residual material is formed, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter and the turpentine liquid, the residual material comprising at least a portion of non-soluble material from the oil shale that is not soluble in the turpentine liquid

separating the extraction mixture from the residual material; and

separating the hydrocarbon-containing organic matter from the turpentine liquid in the extraction mixture to produce a hydrocarbon product stream and a turpentine liquid recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter from the comminuted hydrocarbon containing oil shale; and

recycling at least a portion of the turpentine liquid recycle stream to the contacting step.

55. A method for recovering hydrocarbon-containing organic matter from hydrocarbon-containing coal rich sub-surface formation, the method comprising:

obtaining coal, said coal comprising a recoverable hydrocarbon-containing organic matter;

grinding the coal to produce crushed coal;

filtering the crushed coal;

feeding the crushed coal to a contacting vessel, said contacting vessel comprising at least one inlet for supplying a turpentine liquid to the contacting vessel;

contacting the crushed coal with turpentine liquid such that an extraction mixture is formed and a residual material is formed, the extraction mixture comprising at least a portion of the hydrocarbon-containing organic matter and the turpentine liquid, the residual material comprising at least a portion of non-soluble material from the coal that is not soluble in the turpentine liquids;

separating the residual material from the extraction mixture; and

separating the hydrocarbon-containing organic matter from the turpentine liquid to produce a hydrocarbon product stream and a turpentine liquid recycle stream, the hydrocarbon product stream comprising at least a portion of the hydrocarbon-containing organic matter from the coal; and

recycling at least a portion of the turpentine liquid recycle stream to the contacting step.

56. A method for increasing recovery of hydrocarbon-containing organic matter from a production well coupled to a hydrocarbon-containing sub-surface formation, the subsurface formation comprising hydrocarbon-containing material, the method comprising:

providing an injection well, said injection being in fluid communication with the sub-surface formation;

providing a first liquid, the first liquid comprising a turpentine liquid comprising terpineol;

injecting the turpentine liquid through the injection well and into the formation, wherein the turpentine liquid and the hydrocarbon-containing organic matter from the hydrocarbon containing sub-surface formation form an extraction mixture comprising at least a portion of the extraction mixture hydrocarbon-containing organic matter and at least a portion of the turpentine liquid;

recovering the extraction mixture from the formation through the production well; and

separating the extraction mixture to produce a hydrocarbon product stream and a turpentine liquid stream.