Sorbents for the oxidation and removal of mercury

• US 8,652,235 B2
• Filed: 04/23/2009
• Issued: 02/18/2014
• Est. Priority Date: 08/30/2004
• Status: Active Grant

• Current Assignee: Midwest Energy Emissions Corp.
• Original Assignee: Energy & Environmental Research Center (GE Aerospace)
• Inventors: Olson, Edwin S., Holmes, Michael J., Pavlish, John H.
• Primary Examiner(s): ORLANDO, AMBER ROSE
• Application Number:
  US12/429,058
• Publication Number:
  US 20090297413A1
• Time in Patent Office: 1,762 Days
• Field of Search: 951/34, 951/42, 110/345, 423/210
• US Class Current: 95/142
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• 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 20/223 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

Abstract

A promoted carbon and/or non-carbon base sorbent are described that are highly effective for the removal of mercury from flue gas streams. The promoted sorbent comprises a carbon and/or non-carbon base sorbent that has reacted with and contains forms of halogen and halides. Optional components may be added to increase and/or preserve reactivity and mercury capacity. These may be added directly with the base sorbent, or in-flight within a gas stream (air, flue gas, etc.), to enhance base sorbent performance and/or mercury capture. Mercury removal efficiencies obtained exceed conventional methods. The promoted sorbent can be regenerated and reused. Base sorbent treatment and preparation methods are also described. Methods for in-flight preparation, introduction, and control of the active base sorbent into the mercury contaminated gas stream are described.

Claims

1. A method for separating mercury from a mercury containing gas comprising:

(a) providing a carbon sorbent material and a non-carbon sorbent material, wherein the carbon sorbent material comprises activated carbon;

(b) providing a halogen or halide promoter;

(c) promoting at least a portion of the carbon sorbent material and the non-carbon sorbent material by chemically reacting the carbon sorbent material and the non-carbon sorbent material with the halogen or halide promoter to form a promoted halogenated carbon sorbent and a promoted halogenated non-carbon sorbent;

(d) chemically reacting elemental mercury in the mercury containing gas with the promoted halogenated carbon sorbent and the promoted halogenated non-carbon sorbent to form a mercury/sorbent chemical composition; and

(e) separating particulates from the mercury containing gas to form a cleaned gas, the particulates including ash and the mercury/sorbent chemical composition.

2. The method of claim 1, further comprising the step of injecting the non-carbon sorbent material and the halogen or halide promoter into the mercury containing gas.

3. The method of claim 2, wherein said halogen or halide promoter and the non-carbon sorbent material are injected into the mercury containing gas at the same location.

4. The method of claim 2, wherein said halogen or halide promoter and the non-carbon sorbent material are injected into the mercury containing gas at separate locations.

5. The method of claim 4, wherein said halogen or halide promoter is injected into the mercury-containing gas upstream of the injection of said non-carbon sorbent material.

6. The method of claim 5, wherein said halogen or halide promoter is injected into a combustion chamber that produces a mercury-containing gas, and the non-carbon sorbent material is injected downstream of the combustion chamber.

7. The method of claim 6, wherein said halogen or halide promoter is additionally injected downstream of the combustion chamber.

8. The method of claim 6, wherein said combustion chamber is a boiler and the mercury-containing gas is a flue gas.

9. The method of claim 3, wherein said halogen or halide promoter and non-carbon sorbent material are injected downstream of a chamber that produces a mercury-containing gas.

10. The method of claim 9, wherein said chamber is a boiler and the mercury-containing gas is a flue gas.

11. The method of claim 2, wherein the rate at which said non-carbon sorbent material is injected or the rate at which said promoter is injected or combination thereof is adjusted according to a monitored mercury content in the cleaned gas so that the mercury content of the cleaned gas is maintained at substantially a desired level.

12. The method of claim 1, wherein said non-carbon sorbent material is selected from the group consisting porous felsic materials, vesicular felsic materials, porous basaltic materials, vesicular basaltic materials, clay-based compounds, alkaline compounds, calcium hydroxide compounds, sodium acetate compounds, bicarbonate compounds, and combinations thereof.

13. The method of claim 12, wherein said non-carbon sorbent material is a material that reacts with oxidized mercury in the mercury-containing gas to form a second mercury/sorbent chemical composition.

14. The method of claim 1, wherein said non-carbon sorbent material comprises Lewis basic groups.

15. The method of claim 12, wherein said non-carbon sorbent material comprises amorphous forms of tectosilicates comprising nanoscale cavities lined with Lewis basic oxygen associated with alkaline-earth metals.

16. The method of claim 15, wherein said alkaline-earth metals comprise Group I and Group II alkaline-earth metals.

17. The method of claim 1 wherein said non-carbon sorbent material comprises amorphous forms of phyllosilicates comprising nanoscale cavities lined with Lewis basic oxygen.

18. The method of claim 1, wherein said promoted non-carbon sorbent comprises metastable complexes formed between said promoter and inorganic species on the non-carbon sorbent.

19. The method of claim 18 wherein said inorganic species is selected from the group consisting of sodium compounds, calcium compounds, magnesium compounds, aluminum compounds, iron compounds, and combinations thereof.

20. The method of claim 1, wherein said promoted non-carbon sorbent comprises metastable complexes formed between said promoter and metal-oxygen-metal structures on the non-carbon sorbent.

21. The method of claim 20, wherein said promoter after being complexed with the metal-oxygen-metal structures is in the form selected from the group consisting of a dihalogen group, a halogen atom, a hydrohalogen group, a Group V halide, a Group VI halide, and combinations thereof.

22. The method of claim 1, wherein said promoted non-carbon sorbent comprises activated Lewis basic groups or activated Lewis acid groups or combination thereof.

23. The method of claim 1, wherein said interaction between promoted non-carbon sorbent and said mercury-containing gas stream comprises:

mercury diffusing from the gas phase onto a surface of said non-carbon promoted sorbent; and

reacting with activated Lewis basic groups or activated Lewis acid groups or combination thereof to cause chemisorption on a sorbent surface.

24. The method of claim 1 further comprising pretreating said non-carbon sorbent to increase the number of Lewis basic groups or Lewis acid groups or combination thereof on said sorbent.

25. The method of claim 24, wherein pretreating said non-carbon sorbent comprises chemical treatment, thermal treatment, vacuum treatment, and combinations thereof.

26. The method of claim 25, wherein said chemical treatment comprises acid treatment and alkaline treatment.

27. The method of claim 1 further comprising introducing an alkali component into the mercury-containing gas.

28. The method of claim 1, wherein said carbon sorbent or said promoter or combination thereof are introduced into the mercury-containing gas at one or more locations.

29. The method of claim 28, wherein the rate at which said carbon sorbent is introduced or the rate at which said promoter is introduced or combination thereof is adjusted according to a monitored mercury content in the cleaned gas so that the mercury content of the cleaned gas is maintained at substantially a desired level.

30. The method of claim 1, where the promoted halogenated carbon sorbent and the promoted halogenated non-carbon sorbent comprise about 1 to about 30 grams of the halogen or halide promoter per 100 grams of the carbon sorbent and the non-carbon sorbent.