Carbon dioxide sequestration using alkaline earth metal-bearing minerals

• US 7,722,842 B2
• Filed: 12/30/2004
• Issued: 05/25/2010
• Est. Priority Date: 12/31/2003
• Status: Active Grant

• Current Assignee: Ohio State University
• Original Assignee: Ohio State University
• Inventors: Park, Ah-Hyung, Fan, Liang-Shih
• Primary Examiner(s): Hendrickson; Stuart L.
• Assistant Examiner(s): MCCRACKEN, DANIEL
• Application Number:
  US11/027,368
• Publication Number:
  US 20050180910A1
• Time in Patent Office: 1,972 Days
• Field of Search: 423/165, 4234191-435
• US Class Current: 423/165
• CPC Class Codes: B01D 2251/402 of magnesium
• CPC Class Codes: B01D 53/62 Carbon oxides
• 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

A method for mineral sequestration of pollutant gases resulting from the combustion of carbon-based fuels such as carbon and sulfur dioxides is provided and includes, providing a particulate magnesium-containing mineral and exposing the magnesium-containing mineral to a weak acid to dissolve magnesium from the mineral and form a magnesium-containing solution. The surface of the particulate magnesium-containing mineral is physically activated to expose and dissolve additional magnesium into the solution. Pollutant gases such as carbon dioxide are mixed with the magnesium-containing solution. When the pH of the magnesium-containing solution is increased, solid magnesium carbonate is formed.

Claims

1. A method for mineral carbonation of carbon dioxide comprising,

providing a particulate magnesium-containing mineral;

exposing said magnesium-containing mineral to an aqueous solution containing from about 0.5 to about 5.0% by weight of a weak acid to dissolve magnesium from said mineral and form a magnesium-containing solution;

physically activating the surface of said particulate magnesium-containing mineral by fluidizing said particulate magnesium-containing mineral with grinding media, ultrasonic energy, or microwave energy to expose and dissolve additional magnesium into said solution;

separating the remaining particulate from said magnesium-containing solution;

mixing a gas containing carbon dioxide with said magnesium-containing solution; and

increasing the pH of said magnesium-containing solution to form magnesium carbonate and to remove carbon dioxide from said carbon dioxide containing gas.

2. A method as claimed in claim 1 in which said weak acid is selected from the group consisting of orthophosphoric acid, oxalic acid, citric acid, formic acid, lactic acid ammonium hydrogen sulfate, acetic acid, and mixtures thereof.

3. A method as claimed in claim 1 in which said weak acid comprises a mixture of about 1.0 vol. % orthophosphoric acid and 0.9 wt % oxalic acid.

4. A method as claimed in claim 1 including adding a chelating agent to aid in the dissolution of said magnesium-containing mineral.

5. A method as claimed in claim 4 in which said chelating agent comprises a weak acid or a salt of a weak acid.

6. A method as claimed in claim 5 in which said chelating agent is selected from the group consisting of EDTA, acetic acid, oxalic acid, ascorbic acid, phthalic acid, and salts thereof.

7. A method as claimed in claim 5 in which said chelating agent is selected from compounds that provide anionic groups in aqueous solution selected from the group consisting of ethylene-diamine, acetate, glycolate, S₂O₃⁻

2, F⁻

, SO₄<sup>−

2</sup>, OH⁻

, picolinate, glycine, glutamate, and malonate.

8. A method as claimed in claim 1 in which the surface of said magnesium-containing mineral is physically activated by fluidizing said particulate magnesium-containing mineral with grinding media.

9. A method as claimed in claim 8 in which said magnesium-containing mineral is fluidized in a fluidized bed reactor.

10. A method as claimed in claim 8 in which said magnesium-containing mineral is mixed in a continuous stuffed tank reactor.

11. A method as claimed in claim 8 in which said grinding media is selected from the group consisting of glass, zirconia, alumina, and mixtures thereof.

12. A method as claimed in claim 11 in which the pH of said solution is increased in two stages, said first stage increasing the pH to from about 8.4 to about 8.8 to cause the formation and precipitation of iron oxides, and said second stage increasing the pH to from about 9.3 to about 9.7 to cause the formation of said magnesium carbonate.

13. A method as claimed in claim 1 in which the surface of said magnesium-containing mineral is activated by the application of ultrasonic energy.

14. A method as claimed in claim 1 in which the surface of said magnesium-containing mineral is activated by the application of microwave energy.

15. A method as claimed in claim 1 in which said magnesium-containing mineral also contains iron.

16. A method as claimed in claim 1 in which said magnesium-containing mineral is heated during said exposure and physical activation steps.

17. A method as claimed in claim 16 in which said magnesium-containing mineral is heated to a temperature of from about 50°

C. to about 100°

C.

18. A method as claimed in claim 1 in which said magnesium containing mineral is selected from the group consisting of serpentine, olivine, brucite, chondrodite, talc, peridotite, dunite, harzburgite, lherzolite, and mixtures thereof.

19. A method as claimed in claim 1 in which the magnesium-containing mineral particles are from about 100 to about 500 microns in initial size.

20. A method for mineral sequestration of captured carbon dioxide comprising,

providing particulate serpentine and grinding media to a fluidized, heated reactor;

exposing said serpentine to an aqueous solution containing from about 0.5 to about 5.0% by weight of a weak acid and a chelating agent to dissolve magnesium from said mineral and form a magnesium-containing solution;

physically activating the surface of said particulate serpentine with said grinding media in said fluidized bed to expose and dissolve additional magnesium into said solution;

separating the remaining particulate from said magnesium-containing solution;

increasing the pH of said magnesium-containing solution to cause formation and precipitation of iron oxides;

mixing an acidic gas stream containing at least one of carbon dioxide and sulfur dioxide with said magnesium-containing solution; and

increasing the pH of said magnesium-containing solution to form magnesium carbonate and to remove carbon dioxide and/or sulfur dioxide from said gas stream.

21. A method for the sequestration of acid gases from flue gas comprising,

providing a particulate magnesium-containing mineral;

exposing said magnesium-containing mineral to a weak acid to dissolve magnesium from said mineral and form a magnesium-containing solution;

physically activating the surface of said particulate magnesium-containing mineral by fluidizing said particulate magnesium-containing mineral with grinding media, ultrasonic energy, or microwave energy to expose and dissolve additional magnesium into said solution;

separating the remaining particulate from said magnesium-containing solution;

flowing flue gas through said magnesium-containing solution to sequester carbon and sulfur-containing gases; and

increasing the pH of said magnesium-containing solution to form magnesium carbonates and sulfites as precipitates.

22. A method for mineral carbonation of carbon dioxide comprising,

providing a particulate magnesium-containing mineral;

exposing said magnesium-containing mineral to a weak acid selected from the group consisting of orthophosphoric acid, oxalic acid, citric acid, formic acid, lactic acid, acetic acid, and mixtures thereof, to dissolve magnesium from said mineral and form a magnesium-containing solution;

physically activating the surface of said particulate magnesium-containing mineral by fluidizing said particulate magnesium-containing mineral with grinding media, ultrasonic energy, or microwave energy to expose and dissolve additional magnesium into said solution;

separating the remaining particulate from said magnesium-containing solution;

mixing a gas containing carbon dioxide with said magnesium-containing solution; and

increasing the pH of said magnesium-containing solution to form magnesium carbonate and to remove carbon dioxide from said gas.

23. A method as claimed in claim 22 in which said weak acid comprise from about 0.5 to about 5.0% by weight of an aqueous solution.

24. A method as claimed in 22 in which said weak acid comprises a mixture of about 1.0 vol. % orthophosphoric acid and 0.9 wt % oxalic acid.