Sorbents for the oxidation and removal of mercury

• US 7,435,286 B2
• Filed: 08/22/2005
• Issued: 10/14/2008
• Est. Priority Date: 08/30/2004
• Status: Active Grant

• Current Assignee: Midwest Energy Emissions Corp.
• Original Assignee: Energy & Environmental Research Center (GE Aerospace)
• Inventors: Holmes, Michael J., Pavlish, John H., Olson, Edwin S.
• Primary Examiner(s): Griffin; Walter D.
• Assistant Examiner(s): ORLANDO, AMBER ROSE
• Application Number:
  US11/209,163
• Publication Number:
  US 20060048646A1
• Time in Patent Office: 1,149 Days
• Field of Search: 110/345, 423/210, 951/34, 951/42
• US Class Current: 95/142
• 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 reducing mercury in mercury-containing gas to a desired level, the method comprising:

preparing a sorbent having a sorbent composition;

wherein preparing the sorbent comprises reacting a base activated carbon with at least one promoter selected from the group consisting of molecular halogens, halides, and combinations thereof to yield a promoted halogenated carbon comprising active sites wherein the active sites comprise halide covalently-bound to the base-activated carbon;

injecting the sorbent into a mercury-containing gas stream at at least one sorbent injection location and at a sorbent injection rate, wherein the mercury-containing gas stream is a combustion gas or a gasification gas, and wherein the composition of the mercury-containing gas may vary with time;

optionally co-injecting an alkaline sorbent into the mercury-containing gas stream at at least one alkaline injection location and at an alkaline injection rate;

collecting greater than 70 wt % of the mercury in the mercury-containing gas on the sorbent to produce a cleaned gas;

monitoring the mercury content of the cleaned gas; and

controlling, in response to the monitored mercury content of the cleaned gas, which may vary with the composition of the mercury-containing gas and operating conditions, the sorbent injection rate, the alkaline injection rate, the sorbent composition, or a combination thereof so that the mercury content of the cleaned gas is maintained at substantially the desired level with minimal operating cost.

2. The method of claim 1 comprising co-injecting an alkaline sorbent into the mercury-containing gas stream whereby contaminants in the mercury-containing gas are consumed by the alkaline sorbent, thus maintaining active sites on the sorbent, and whereby oxidized mercury is captured from the mercury-containing gas stream.

3. The method of claim 2 wherein the alkaline sorbent is selected from the group consisting of alkali elements, alkaline earth elements, alkali salts, alkaline earth salts, and combinations thereof.

4. The method of claim 3 wherein the alkaline sorbent is selected from the group consisting of sodium carbonate, calcium oxide, lime, and combinations thereof.

5. The method of claim 2 wherein the at least one alkaline injection location is upstream of the at least one sorbent injection location.

6. The method of claim 5 wherein the alkaline sorbent injection into the mercury-containing gas occurs upstream of the halogenated carbon sorbent injection into the mercury-containing gas stream.

7. The method of claim 1 wherein preparing the sorbent further comprises reacting the activated carbon or the promoted carbon with a secondary component to enhance the reactivity and capacity of the sorbent.

8. The method of claim 7 wherein the secondary component is selected from the group consisting of iodine, hydrohalides, Group V halides, Group VI halides, and combinations thereof.

9. The method of claim 8 comprising co-injecting an alkaline sorbent into the mercury-containing gas stream.

10. The method of claim 7 wherein monitoring the mercury content of the cleaned gas is used to control the sorbent composition by controlling the ratio of the secondary component to the activated carbon, the ratio of the at least one promoter to the activated carbon, or a combination thereof to optimize the number of active sites on the sorbent available for oxidizing and capturing the mercury in the mercury-containing gas stream, whereby the desired mercury level in the cleaned gas is substantially continuously maintained.

11. The method of claim 7 wherein the at least one promoter and secondary component are combined with the base activated carbon substantially simultaneously.

12. The method of claim 1 wherein the monitored mercury content of the cleaned gas is used to control the composition of the sorbent.

13. The method of claim 12 further comprising injecting the activated carbon at an activated carbon injection rate and injecting the at least one promoter at a promoter injection rate into a transport tine whereby in-flight reaction produces the promoted halogenated carbon, wherein the promoter is selected from the group consisting of molecular halogens, halides, and combinations thereof, wherein the promoter is reacted in the gas phase or as a vapor, wherein the promoter is added at from about 1 to about 30 grams per 100 grams of activated carbon, and wherein the promoter injection rate and the sorbent injection rate into the gas are determined at least in part on the monitored mercury content of the cleaned gas.

14. The method of claim 12 wherein controlling the sorbent composition comprises controlling at least one of the ratio of the at least one promoter to the activated carbon and the ratio of the alkaline injection rate to the sorbent injection rate

the sorbent injection rate, the alkaline injection rate, the sorbent composition, or a combination thereof.

15. The method of claim 1 further comprising substantially recovering the sorbent from the cleaned gas and regenerating at least a portion of the recovered sorbent particles to substantially remove contaminants therefrom and recover capacity for capturing mercury, wherein the mercury-containing gas comprises ash and substantially recovering the sorbent from the cleaned gas comprises mechanically separating the sorbent particles from the ash.

16. The method of claim 15 wherein the activated carbon has an average particle size greater than that of the components of the mercury-containing gas stream such that substantially recovering the sorbent from the cleaned gas involves separation by physical means.

17. The method of claim 16 wherein the activated carbon has an average particle size greater than 40 μ

m.

18. The method of claim 15 further comprising reinjecting at least a portion of the regenerated sorbent particles into the mercury-containing gas.

19. The method of claim 18 wherein the monitored mercury content is used to control at least one selected from the group consisting of the alkaline injection rate into the mercury-containing gas relative to the base activated carbon injection rate, the promoted carbon injection rate, the secondary components injection rate, the sorbent injection rate, and combinations thereof, to maintain the desired level of mercury in the cleaned gas stream.

20. The method of claim 18 comprising controlling the sorbent composition, the sorbent injection rate, the ratio of the alkaline injection rate to the sorbent injection rate, or a combination thereof to substantially maintain the desired level of mercury in the cleaned gas while minimizing the cost of removing the mercury from the mercury-containing gas stream.

21. The method of claim 1 wherein the mercury-containing gas is a flue gas stream downstream of a boiler.

22. The method of claim 1 wherein monitoring the mercury content of the cleaned gas is performed substantially continuously.

23. The method of claim 1 wherein the promoter is selected from the group consisting of Br₂, HBr, Group V bromides, Group VI bromides, and combinations thereof

24. The method of claim 23 wherein the promoter is selected from the group consisting of Group V bromides. Group VI bromides and combinations thereof.

25. The method of claim 1 wherein the promoter is reacted in the gas phase or as a vapor.

26. The method of claim 1 wherein the sorbent has a composition comprising from about 1 to about 30 grams of promoter per 100 grains of activated carbon.

27. The method of claim 1 wherein at least part of preparing the sorbent comprises at least one of:

injecting the promoted halogenated carbon at a promoted carbon injection rate and injecting at least one secondary component at a secondary component injection rate into a transport line whereby the sorbent is produced in-flight;

injecting the activated carbon at an activated carbon injection rate and injecting the at least one promoter at a promoter injection rate into a transport line whereby in-flight reaction produces the promoted halogenated carbon; and

injecting activated carbon at an activated carbon injection rate, at least one secondary component at a secondary component injection rate, and at least one promoter at a promoter injection rate substantially simultaneously into a transport line whereby in-flight reaction produces the sorbent.

28. The method of claim 27 wherein controlling, the sorbent composition comprises controlling the promoted halogenated carbon injection rate, the promoter injection rate, the alkaline injection rate, the optional secondary component injection rate, the activated carbon injection rate, or a combination thereof.

29. The method of claim 1 wherein injecting the sorbent into a mercury-containing gas stream comprises injecting the sorbent into a mercury-containing gas stream having a temperature less than about 400°

C.

30. A method for removing mercury from a mercury-containing gas stream to produce a cleaned gas stream having a desired mercury level, the method comprising,

reacting an activated carbon with at least one promoter selected from molecular halogens, Group V halides, Group VT halides, hydrohalides, and combinations thereof and optionally at least one secondary component selected from Group V halides, Group VI halides, hydrohalides, and combinations thereof to produce a halogenated carbon sorbent comprising carbocation reactive sites that are capable of accepting electrons from neutral mercury atoms thereby forming oxidized mercury species that bind to the surface of the halogenated sorbent, wherein the halogenated carbon sorbent comprises a promoter to carbon ratio and optionally, a secondary component to carbon ratio;

injecting the halogenated carbon sorbent into a mercury-containing gas stream at a sorbent injection rate, wherein the mercury containing gas comprises flue gas, synthesis gas, fuel gas, or a combination thereof and wherein the composition of the mercury-containing gas stream may vary with time;

injecting an alkaline sorbent into the mercury-containing gas stream at an alkaline injection rate, wherein the alkaline sorbent is capable of adsorbing oxidized mercury gas and of removing contaminants from the mercury-containing gas stream capable of consuming carbocation reactive sites of the halogenated carbon sorbent;

allowing the sorbents to interact with the mercury-containing gas stream for a residence time to produce a cleaned gas;

removing the halogenated sorbent from the cleaned gas;

monitoring the mercury content of the cleaned gas; and

maintaining the desired mercury level of the cleaned gas by optimizing the sorbent injection rate, the promoter to carbon ratio of the sorbent, the optional secondary component to carbon ratio of the sorbent, the alkaline injection rate, or a combination thereof such that operating costs for removing mercury from the mercury-containing gas stream are minimized.