Additives for mercury oxidation in coal-fired power plants

• US 8,293,196 B1
• Filed: 08/04/2011
• Issued: 10/23/2012
• Est. Priority Date: 10/27/2005
• Status: Active Grant

• Current Assignee: ARQ Solutions Incorporated
• Original Assignee: ADA-ES, Inc. (Advanced Emissions Solutions, Inc.)
• Inventors: Baldrey, Kenneth E., Sjostrom, Sharon, French, Nina Bergan, Durham, Michael D.
• Primary Examiner(s): Michener, Jennifer
• Assistant Examiner(s): Chan, Heng
• Application Number:
  US13/198,381
• Time in Patent Office: 446 Days
• Field of Search: 423/99, 423/210, 423/213.2, 423/107, 423/462, 951/33, 951/34
• US Class Current: 423/99
• CPC Class Codes: B01D 2251/60 Inorganic bases or salts
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: C01G 13/04 Halides
• CPC Class Codes: C01G 9/00 Compounds of zinc
• CPC Class Codes: C22B 43/00 Obtaining mercury
• CPC Class Codes: Y02P 20/129 Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The present invention is directed to an additive, primarily for combustion of low sulfur and high alkali coals, that includes a transition metal to impact positively bottom ash slag and optionally a halogen to effect mercury oxidation and collection in the flue gas.

Claims

1. A flue gas treatment method, comprising:

(a) providing a coal feed, the coal feed having a Loss on Ignition (“

LOI”

) of at least about 10% and comprising mercury, alkali, and iron, wherein an iron content of the coal feed is less than about 10 wt. % (dry basis of the ash) as Fe₂O₃, the alkali content of the coal feed is at least about 20 wt. % (dry basis of the ash) alkali, and wherein the coal feed comprises no more than about 500 ppm halogens;

(b) contacting the coal feed, prior to combustion, with an additive, the additive comprising a transition metal and a halogen, wherein the additive promotes oxidation of elemental mercury wherein the additive comprises no more than about 1 wt. % carbon and no more than about 0.5 wt. % (dry basis) sulfur;

(c) combusting, by a wet bottom boiler, the coal feed to form a flue gas comprising elemental mercury derived from the mercury in the coal feed and fly ash; and

(d) collecting the oxidized mercury and fly ash to provide a treated flue gas, wherein;

the additive further comprises a mineralizer;

the mineralizer is zinc oxide; and

the additive comprises at least about 1 wt. % (dry basis) mineralizer.

2. The method of claim 1, wherein the coal feed comprises at least about 20 wt. % (dry basis of the ash) alkali, and no more than about 25 ppm (dry basis of the coal) bromine.

3. The method of claim 1, wherein the coal feed comprises no more than about 100 ppm (dry basis of the coal) chlorine and no more than about 10 ppm (dry basis of the coal) bromine.

4. The method of claim 1, wherein the coal feed has a phosphorus content ranging from about 0.1 to about 1.5 wt. % (dry basis of the ash) and wherein the coal feed is a low sulfur coal.

5. The method of claim 1, wherein the coal feed comprises at least about 15 wt. % calcium as CaO (dry basis of the ash), and wherein the coal feed comprises no more than about 100 ppm halogens.

6. The method of claim 1, wherein step (b) comprises the sub-steps:

redirecting a portion of the flue gas stream;

contacting the redirected portion of the flue gas stream with the additive, wherein the

additive is transported by the redirected portion of the flue gas stream; and

thereafter contacting the coal feed with the redirected portion of the flue gas stream, the redirected portion of the flue gas stream comprising the additive, wherein the additive is combined with the coal feed.

7. The method of claim 6, wherein the temperature of the redirected flue gas portion, in the thereafter contacting step, is greater than a temperature of the coal feed prior to the thereafter contacting step and wherein the redirected flue gas portion is input into a furnace along with the coal feed and additive.

8. The method of claim 6, wherein the redirected flue gas portion has a temperature, in the contacting step, greater than a sublimation temperature of at least one component of the additive and wherein at least one component of the additive sublimes into the redirected flue gas portion in the thereafter contacting step.

9. The method of claim 8, wherein a temperature of the redirected flue gas portion is less than an auto-ignition temperature of the coal feed.

10. The method of claim 9, wherein the sublimation temperature is the sublimation temperature of the halogen.

11. A flue gas treatment method, comprising:

(a) providing a coal feed, the coal feed having a Loss on Ignition (“

LOI”

) of at least about 10% and comprising mercury and iron, wherein an iron content of the coal feed is less than about 10 wt. % (dry basis of the ash);

(b) combusting the coal feed to form a flue gas comprising elemental mercury derived from the mercury in the coal feed and fly ash;

(c) contacting an additive with (i) the coal feed, prior to step (b), and/or (ii) the flue gas resulting from step (b), the additive comprising a transition metal and at least one of a halogen, wherein the additive comprises no more than about 1 wt. % carbon, wherein the additive comprises no more than about 0.5 wt. % (dry basis) sulfur, wherein, in either option (i) or (ii), the additive promotes post-combustion oxidation of the elemental mercury; and

(d) collecting the oxidized mercury and fly ash to provide a treated flue gas, wherein;

the additive comprises;

(a) at least about 50 wt. % (dry basis) iron;

(b) at least about 1 wt. % (dry basis) halogens; and

(c) a mineralizer.

12. The method of claim 11, wherein at least some of the halogens are present as inter-halogen compounds.

13. The method of claim 11, wherein at least some of the halogens are present as halides, the halides comprising iron.

14. The method of claim 11, wherein the additive composition is in contact with the coal feed and wherein the coal feed is a high alkali and low sulfur coal.

15. The method of claim 11, wherein the coal feed comprises at least about 20 wt. % (dry basis of the ash) alkali, and no more than about 25 ppm (dry basis of the coal) bromine.

16. The method of claim 11, wherein the coal feed comprises no more than about 100 ppm (dry basis of the coal) chlorine and no more than about 10 ppm (dry basis of the coal) bromine.

17. The method of claim 11, wherein the coal feed has a phosphorus content ranging from about 0.1 to about 1.5 wt. % (dry basis of the ash) and wherein the coal feed is a low sulfur coal.

18. The method of claim 11, wherein the coal feed comprises at least about 15 wt. % calcium as CaO (dry basis of the ash), and wherein the coal feed comprises no more than about 100 ppm halogens.

19. The method of claim 11, wherein step (c) comprises the sub-steps:

redirecting a portion of the flue gas stream;

contacting the redirected portion of the flue gas stream with the additive, wherein the additive is transported by the redirected portion of the flue gas stream; and

thereafter contacting the coal feed with the redirected portion of the flue gas stream, the redirected portion of the flue gas stream comprising the additive, wherein the additive is combined with the coal feed.

20. The method of claim 19, wherein the temperature of the redirected flue gas portion, in the thereafter contacting step, is greater than a temperature of the coal feed prior to the thereafter contacting step and wherein the redirected flue gas portion is input into a furnace along with the coal feed and additive.

21. The method of claim 19, wherein the redirected flue gas portion has a temperature, in the contacting step, greater than a sublimation temperature of at least one component of the additive and wherein at least one component of the additive sublimes into the redirected flue gas portion in the thereafter contacting step.

22. The method of claim 21, wherein a temperature of the redirected flue gas portion is less than an auto-ignition temperature of the coal feed.

23. The method of claim 22, wherein the sublimation temperature is the sublimation temperature of the halogens.