Carbon Dioxide Capture and Mitigation of Carbon Dioxide Emissions

• US 20080031801A1
• Filed: 05/04/2005
• Published: 02/07/2008
• Est. Priority Date: 05/04/2004
• Status: Active Grant

• Current Assignee: GRDC, LLC (PENN Entertainment, Inc.)
• Original Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Inventors: Lackner, Klaus, Zeman, Frank, Krevor, Samuel, Grimes, Patrick
• Granted Patent: US 7,947,239 B2
• Time in Patent Office: Days
• US Class Current: 423/438
• CPC Class Codes: B01D 2251/404 of calcium
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: C01F 11/18 Carbonates
• CPC Class Codes: C01F 5/24 Magnesium carbonates
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The present invention describes methods and systems for extracting, capturing, reducing, storing, sequestering, or disposing of carbon dioxide (CO₂), particularly from the air. The CO₂ extraction methods and systems involve the use of chemical processes, mineral sequestration, and solid and liquid sorbents. Methods are also described for extracting and/or capturing CO₂ via condensation on solid surfaces at low temperature.

Claims

1. A method of extracting or sequestering carbon dioxide, comprising:

(a) dissolving a magnesium bearing silicate in an aqueous acid to form an acidic solution;

(b) increasing the pH of the solution of step (a) to precipitate one or more magnesium components; and

(c) carbonating the precipitated magnesium components from step (b) to bind carbon dioxide.

3. The method according to claim 1 or claim 2, wherein the magnesium bearing silicate of step (a) comprises peridotite rock.

4. The method according to claim 1 or claim 2, wherein the magnesium bearing silicate of step (a) is selected from serpentine or olivine.

5. The method according to claim 1 or claim 2, wherein the aqueous acid of step (a) is selected from citric acid, acetic acid, chromic acid, sulfuric acid, orthophosphoric acid, oxalic acid, ammonium bisulfate, or a combination of two or more thereof.

6. The method according to claim 1 or claim 2, wherein the pH of the acidic solution is less than or equal to about pH 4.5.

7. The method according to claim 1 or claim 2, further comprising the step of neutralizing the acidic solution of step (a) with a neutralizing agent to precipitate iron and silicate prior to the precipitation of the one or more magnesium components.

8. The method according to claim 7, wherein the neutralizing step comprises a neutralizing agent selected from ammonia or magnesium hydroxide.

9. The method according to claim 7, wherein the pH of the neutralized solution is less than or equal to about pH 8.

10. The method according to claim 1 or claim 2, wherein increasing the pH in step (b) comprises an ammonia-containing reagent.

11. The method according to claim 1 or claim 2, wherein increasing the pH in step (b) comprises a reagent selected from NaOH, KOH, NH₃, NH₄OH, NH₄HCO₃, (NH₄)₂CO₃, Na₂CO₃, or a combination thereof.

12. The method according to claim 10 or claim 11, wherein increasing the pH comprises a reagent that is carbonated prior to precipitating the one or more magnesium components.

13. The method according to claim 10, wherein the ammonia-containing reagent is selected from ammonia, ammonium hydroxide, ammonium carbonate, or ammonium bicarbonate.

14. The method according to claim 13, wherein the ammonia-containing reagent is selected from ammonium carbonate or ammonium bicarbonate.

15. The method according to claim 12, wherein the reagent that is carbonated prior to precipitating the one or more magnesium components is an ammonia-containing reagent.

16. The method according to claim 1 or claim 2, wherein the one or more magnesium components of step (b) is Mg(OH)₂.

17. The method according to claim 1 or claim 2, wherein the one or more magnesium components of step (b) is Mg(CO)₃, or hydrated forms thereof.

18. The method according to claim 1 or claim 2, wherein the one or more precipitated magnesium components is carbonated in step (c) in a gas solid reaction between magnesium components and carbon dioxide at elevated temperature.

19. The method according to claim 18, wherein the temperature is about 300°

C. to less than about 900°

C.

20. The method according to claim 18, wherein the temperature elevation is performed in an autoclave under pressure.

21. The method according to claim 20, wherein the pressure is about 1 to about 50 atmospheres or greater.

22. The method according to claim 1 or claim 2, further comprising following step (c):

(i) washing the precipitated magnesium component to remove residual salt; and

(ii) exposing the precipitated and washed magnesium component to carbon dioxide at elevated temperature and pressure.

23. The method according to claim 22, wherein the elevated temperature comprises about 300°

C. to 500°

C. or above.

24. The method according to claim 22, wherein the elevated pressure comprises about 1 to about 50 atmospheres.

25. The method according to claim 22, wherein the precipitated magnesium component is magnesium hydroxide or magnesium oxide.

26. The method according to claim 1, further comprising recovering ammonia gas and acid following step (c) by thermal decomposition or by electrodialysis.

28. The method according to claim 1 or claim 2, wherein carbon dioxide is extracted or sequestered from air.

29. The method according to claim 1 or claim 2, wherein the acid of step (a) is present in an amount at least 10% in excess of a stoichiometric amount for neutralizing magnesium in the magnesium bearing silicate.

2. A method of extracting or sequestering carbon dioxide, comprising:

(a) dissolving a magnesium bearing silicate in an aqueous acid to form an acidic solution;

(b) increasing the pH of the solution of step (a) to precipitate one or more magnesium components;

(c) carbonating the precipitated magnesium components from step (b) to bind carbon dioxide; and

(d) recovering ammonia gas and acid by thermal decomposition or by electrodialysis.

27. The method according to claim 2 or claim 26, comprising recovering ammonia gas and acid following step (c) by electrodialysis.

30. A method of extracting, reducing, or sequestering carbon dioxide, comprising:

(a) dissolving a magnesium bearing silicate in an aqueous acid to form an acidic solution;

(b) increasing the pH of the acidic solution to remove dissolved silica and produce a dissolved magnesium component;

(c) precipitating a solid magnesium component from the neutralized solution with an ammonia containing reagent, thereby producing an ammonium salt in the solution;

(d) precipitating the ammonium salt from the solution; and

(e) carbonating the precipitated magnesium component to sequester or reduce carbon dioxide from the air.

31. The method according to claim 30, wherein, in step (d) the ammonium salt is precipitated by reducing the volume of the solution.

32. The method according to claim 31, wherein the volume is reduced by at least about 33%.

33. The method according to claim 31, wherein the volume is reduced by evaporation or membrane separation.

34. The method according to claim 30, wherein the carbonating step (e) is performed at elevated temperature.

35. The method according to claim 34, wherein the elevated temperature is about 300°

C. to less than about 900°

C.

36. The method according to claim 35, wherein the elevated temperature results from autoclaving under pressure.

37. The method according to claim 36, wherein the pressure is about 1 to about 50 atmospheres or greater.

38. The method according to claim 30, further optionally comprising the step of recovering ammonia gas and acid following step (e).

39. The method according to claim 38, wherein the recovered acid is solid and anhydrous.

40. The method according to claim 38, wherein the ammonia gas and acid are recovered by thermal decomposition or by electrodialysis.

41. A method for extracting, reducing, or sequestering carbon dioxide, comprising:

(a) dissolving a magnesium bearing silicate in an aqueous acid to form an acidic solution;

(b) increasing the pH of the solution of step (a) to neutralize the acid solution of step (a);

(c) introducing an ammonia reagent selected from ammonium carbonate or ammonium bicarbonate into the solution of step (b) to precipitate magnesium carbonate or hydrated forms thereof; and

(d) carbonating the ammonia to form ammonium carbonate or bicarbonate so as to bind carbon dioxide.

42. The method according to claim 41, further comprising the step of recovering ammonia gas and acid following step (c) and prior to step (d).

43. The method according to claim 41, wherein the magnesium bearing silicate of step (a) comprises peridotite rock.

44. The method according to claim 41, wherein the magnesium bearing silicate of step (a) is selected from serpentine or olivine.

45. The method according to claim 41, wherein the aqueous acid of step (a) is selected from citric acid, acetic acid, chromic acid, sulfuric acid, orthophosphoric acid, oxalic acid, ammonium bisulfate, or a combination of two or more thereof.

46. The method according to claim 41, wherein the pH of the acidic solution is less than or equal to about pH 4.5.

47. The method according to claim 41, wherein iron and silicate precipitate in the neutralized solution of step (b).

48. The method according to claim 41, wherein the pH is increased using a neutralizing agent selected from ammonia or magnesium hydroxide.

49. The method according to claim 41, wherein the pH of the neutralized solution is less than or equal to about pH 8.

50. The method according to claim 41, wherein increasing the pH in step (b) comprises an ammonia-containing reagent.

51. The method according to claim 41, wherein increasing the pH in step (b) comprises a reagent selected from NaOH, KOH, NH₃, NH₄OH, NH₄HCO₃, (NH₄)₂CO₃, Na₂CO₃, or a combination thereof.

52. The method according to claim 50, wherein the ammonia-containing reagent is selected from ammonia, ammonium hydroxide, ammonium carbonate, or ammonium bicarbonate.

53. A method for extracting, capturing, or sequestering carbon dioxide from air, comprising:

and (d) releasing the captured carbon dioxide to a system for collection, storage, or transport

(a) exposing the air to a solid sorbent material comprising a large absorption surface so as to saturate the sorbent material with carbon dioxide;

(b) removing remnant air from the saturated sorbent material under reduced pressure;

(c) condensing the carbon dioxide onto a cold surface to capture the carbon dioxide in solid form; and

(d) releasing the captured carbon dioxide to a system for collection, storage, or transport.

54. The method according to claim 53, wherein the solid sorbent material comprises material moving along surfaces exposed to air.

55. The method according to claim 54, wherein the moving material is selected from beads, rods, fabric, or moveable objects comprising rough surfaces.

56. The method according to claim 53, wherein the solid sorbent material is inert.

57. The method according to claim 53, wherein the solid sorbent material is hydrophobic.

58. The method according to claim 53, wherein the solid sorbent material is selected from activated carbon, activated alumina, silicalites, or zeolites.

59. The method according to claim 53, wherein the carbon dioxide sorbent is a material coated with one or more different sorbents.

60. The method according to claim 53, wherein step (b) is performed in a first vacuum chamber.

61. The method according to claim 53, wherein step (c) is performed in a second vacuum chamber comprising a temperature colder than that of the first chamber.

62. The method according to claim 53, wherein the cold surface of step (c) comprises a cold trap suitable for dry ice formation.

63. The method according to claim 53, wherein solid carbon dioxide generated in step (c) is held in a confined volume and warmed so as to become a pressurized gas.

64. The method according to claim 63, wherein captured carbon dioxide sublimates in a containment vessel.

65. The method according to claim 63, wherein the carbon dioxide is released under high pressure for storage, collection, or transport.

66. A cryogenic system for capturing carbon dioxide and recovering a solid sorbent, comprising:

(a) a first chamber for housing a carbon dioxide-laden sorbent material and removal of carbon dioxide from said sorbent material;

(b) a vacuum system for removing air from said first chamber and attachable thereto; and

(c) a second chamber connected to said first chamber and comprising a temperature suitable for condensation and collection of carbon dioxide from said first chamber as solid carbon dioxide onto one or more surfaces of said second chamber, said second chamber comprising a reduced partial pressure of carbon dioxide relative to said first chamber.

67. The system according to claim 66, wherein said temperature in said second chamber is about −

80°

C. to about −

100°

C. or lower.

68. The system according to claim 66, wherein the pressure of the second chamber comprises about 0.001 psi.

69. The system according to claim 66, wherein the sorbent material comprises silicalites, zeolites, activated carbon, activated alumina, or a combination thereof.

70. The system according to claim 66, wherein the cold surfaces of the second chamber capture cold carbon dioxide as dry ice.

71. The system according to claim 70, wherein the cold carbon dioxide is captured as dry ice from about 15 minutes to several hours.