Sorbents for the oxidation and removal of mercury

• US 10,589,225 B2
• Filed: 05/14/2015
• Issued: 03/17/2020
• Est. Priority Date: 08/30/2004
• Status: Active Grant

• Current Assignee: Midwest Energy Emissions Corp.
• Original Assignee: Midwest Energy Emissions Corp.
• Inventors: Olson, Edwin S., Holmes, Michael J., Pavlish, John Henry
• Primary Examiner(s): Orlando, Amber R
• Application Number:
  US14/712,558
• Publication Number:
  US 20150246315A1
• Time in Patent Office: 1,769 Days
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/10 with dispersed adsorbents
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01J 20/02 comprising inorganic material
• CPC Class Codes: B01J 20/0262 Compounds of O, S, Se, Te
• CPC Class Codes: B01J 20/027 Compounds of F, Cl, Br, I
• CPC Class Codes: B01J 20/04 comprising compounds of alkali metals, alkaline earth metals or magnesium
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: B01J 20/043 Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
• CPC Class Codes: B01J 20/10 comprising silica or silicate
• CPC Class Codes: B01J 20/106 Perlite
• CPC Class Codes: B01J 20/12 Naturally occurring clays or bleaching earth
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 20/22 comprising organic material
• CPC Class Codes: B01J 20/223 containing metals, e.g. organo-metallic compounds, coordination complexes
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28016 Particle form
• CPC Class Codes: B01J 20/3416 : of sorbents or filter aids comprising free carbon, e.g. activated carbon
• CPC Class Codes: B01J 2220/42 : Materials comprising a mixture of inorganic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: Y10S 95/901 : Activated carbon

Abstract

A promoted activated carbon sorbent is described that is highly effective for the removal of mercury from flue gas streams. The sorbent comprises a new modified carbon form containing reactive forms of halogen and halides. Optional components may be added to increase reactivity and mercury capacity. These may be added directly with the sorbent, or to the flue gas to enhance sorbent performance and/or mercury capture. Mercury removal efficiencies obtained exceed conventional methods. The sorbent can be regenerated and reused. Sorbent treatment and preparation methods are also described. New methods for in-flight preparation, introduction, and control of the active sorbent into the mercury contaminated gas stream are described.

Claims

1. A method for treating a mercury-containing gas, the method comprising:

combusting a mixture comprising coal, pyrolysis char, and an additive comprising HBr, a bromide compound, or a combination thereof, to form the mercury-containing, gas; and

adding a particulate sorbent material comprising activated carbon into the mercury-containing gas.

2. The method of claim 1, wherein the pyrolysis char is a promoted pyrolysis char.

3. The method of claim 1, wherein the pyrolysis char and the additive are added prior to a combustor that combusts the mixture, within the combustor, or a combination thereof.

4. The method of claim 1, wherein the pyrolysis char and the additive are added within a combustor that combusts the mixture.

5. The method of claim 1, further comprising using a particle separation device to remove mercury from the flue gas and comprising collecting greater than 70 wt % of the mercury in the mercury-containing gas to produce a cleaned gas.

6. The method of claim 5, further comprising:

measuring the mercury content of the mercury-containing gas; and

modifying, in response to the measured mercury content;

an injection rate of injecting the sorbent into the mercury-containing gas,

an amount of the additive in the mixture, or

a combination thereof.

7. The method of claim 1, wherein the additive further comprises Br₂.

8. The method of claim 1, wherein the sorbent material is chosen from powdered activated carbon, granular activated carbon, carbon black, carbon fiber, aerogel carbon, pyrolysis char, and combinations thereof.

9. The method of claim 1, further comprising adding an alkaline component to the mercury-containing gas, the alkaline component chosen from alkali elements, alkaline earth elements, alkali salts, alkaline earth salts, and combinations thereof.

10. The method of claim 1, further comprising contacting the sorbent material with a mercury-stabilizing reagent chosen from S, Se, H₂S, SO₂, H₂Se, SeO₂, CS₂, P₂S₅, and combinations thereof.

11. The method of claim 1, further comprising contacting the sorbent material with a secondary component chosen from halogens, hydrogen halides, Group V halides, Group VI halides, and combinations thereof.

12. The method of claim 11, wherein the secondary component is chosen from halogens, halide salts, HI, HBr, HCl, and combinations thereof.

13. The method of claim 11, wherein the secondary component is chosen from I₂, HI, and combinations thereof.

18. The method of claim 1, further comprising

modifying, in response to a measured mercury content,

an injection rate of injecting the sorbent into the mercury-containing gas,

an amount of the additive in the mixture, or

a combination thereof.

19. The method of claim 1, wherein the coal comprises added sorbent enhancement additive that comprises the bromide compound.

20. The method of claim 1, wherein the coal is combusted in a combustion chamber at a coal-combustion facility, wherein the HBr, bromide compound, or combination thereof, is added to the coal before the coal enters the combustion chamber, wherein the addition of the HBr, bromide compound, or combination thereof, to the coal is performed at the coal-combustion facility.

21. The method of claim 1, wherein the coal is combusted in a combustion chamber at a coal-combustion facility, wherein the HBr, bromide compound, or combination thereof, is added to the coal before the coal enters the combustion chamber, wherein the addition of the HBr, bromide compound, or combination thereof, to the coal is performed at a site other than the coal-combustion facility.

22. The method of claim 1, wherein the sorbent is contacted with a halogen or halide promoter prior to the addition of the sorbent to the mercury-containing gas.

23. The method of claim 1, wherein the sorbent is free of contact with a halogen or halide promoter prior to the addition of the sorbent to the mercury-containing gas.

24. The method of claim 6, wherein the measurement of the mercury content of the mercury-containing gas comprises continuous measurement.

25. The method of claim 1, wherein the coal comprises subbituminous coal.

26. The method of claim 1, wherein the coal comprises lignite coal.

27. The method of claim 1, wherein the mixture is combusted in a combustion chamber of a coal-combustion facility upstream of a scrubber, a particulate control system, or a combination thereof, wherein the particulate sorbent is added to the mercury-containing gas before the mercury-containing gas encounters the scrubber, the particulate control system, or the combination thereof.

28. The method of claim 26, wherein the particulate control system comprises an electrostatic precipitator, a baghouse, a fabric filter, or a combination thereof.

29. The method of claim 19, wherein the combustion chamber is a coal combustion furnace.

14. A method for treating a mercury-containing gas, the method comprising:

combusting coal in a combustor comprising pyrolysis char and an additive comprising HBr, a bromide compound, or a combination thereof, to form the mercury-containing gas; and

adding a particulate sorbent material comprising activated carbon into the mercury-containing gas.

15. The method of claim 14, wherein the pyrolysis char is a promoted pyrolysis char.

16. A method for treating a mercury-containing gas, the method comprising:

combusting coal in a combustor and adding within the combustor a pyrolysis char promoted by an additive comprising HBr, a bromide compound, or a combination thereof, to form the mercury-containing gas; and

adding a particulate sorbent material comprising activated carbon into the mercury-containing gas.

17. A method for treating a mercury-containing gas, the method comprising:

combusting a mixture comprising coal, pyrolysis char, and an additive comprising HBr, a bromide compound, or a combination thereof, to form the mercury-containing gas; and

adding a sorbent material comprising activated carbon into the mercury-containing gas.