Method and system for controlling mercury emissions from coal-fired thermal processes

• US 9,352,275 B2
• Filed: 06/24/2013
• Issued: 05/31/2016
• Est. Priority Date: 02/04/2010
• Status: Active Grant

• Current Assignee: ARQ Solutions Incorporated
• Original Assignee: ADA-ES, Inc. (Advanced Emissions Solutions, Inc.)
• Inventors: Durham, Michael D., Sjostrom, Sharon, Baldrey, Kenneth E., French, Nina Bergan, Bisque, Ramon
• Primary Examiner(s): VANOY, TIMOTHY C
• Application Number:
  US13/925,311
• Publication Number:
  US 20140072487A1
• Time in Patent Office: 1,072 Days
• Field of Search: 423/210, 951/34, 446/20
• US Class Current: 1/1
• CPC Class Codes: B01D 2251/108 Halogens or halogen compounds hydrogen halides B01D2251/50
• CPC Class Codes: B01D 2253/10 Inorganic adsorbents
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 46/00 Filters or filtering processes specially modified for separating dispersed particles from gases or vapours filtering elements B01D24/00-B01D35/00; filtering material B01D39/00; their regeneration outside the filters B01D41/00
• CPC Class Codes: B01D 53/50 Sulfur oxides B01D53/60 takes precedence
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01D 53/8625 Nitrogen oxides
• CPC Class Codes: C10L 10/00 Use of additives to fuels or fires for particular purposes additives for liquid carbonaceous fuels characterised by their chemical nature C10L1/10; using binders for briquetting solid fuels C10L5/10; using additives to improve the combustion of solid fuels C10L9/10
• CPC Class Codes: C10L 2290/141 of additive or catalyst
• CPC Class Codes: C10L 3/101 Removal of contaminants
• CPC Class Codes: F23J 15/003 for supplying chemicals to fumes, e.g. using injection devices
• CPC Class Codes: F23J 15/02 of purifiers, e.g. for removing noxious material traps for solid residues F23J3/04
• CPC Class Codes: F23J 2215/60 Heavy metals; Compounds thereof
• CPC Class Codes: F23J 7/00 Arrangement of devices for supplying chemicals to fire

Abstract

The present disclosure is directed to the use of elemental or speciated iodine and bromine to control total mercury emissions.

Claims

1. A method, comprising:

providing a mercury-containing gas stream comprising vapor-phase mercury, a vapor-phase iodine, and ash particulates;

introducing a reactive surface agent into the mercury-containing gas stream to form particulates comprising at least part of the vapor-phase mercury and the reactive surface agent; and

thereafter removing particulates from the mercury-containing gas stream to form a treated stream, at least a portion of the vapor-phase mercury being removed from the mercury-containing gas stream with removal of the particulates, wherein at least one of the following is true;

(i) the mercury-containing gas stream comprises about 3.5 ppmw or less vapor-phase iodine;

(ii) in the mercury-containing gas stream, a molar ratio of vapor-phase iodine to vapor-phase mercury is no more than about 600;

(iii) at an air preheater outlet, a concentration of vapor-phase iodine ranges from about 0.1 to about 10 ppmw; and

(iv) a concentration of the iodine is about 30 ppmw or less relative to a weight of a mercury-containing feed material producing the vapor-phase mercury.

2. The method of claim 1, wherein (i) is true.

3. The method of claim 2, wherein the mercury-containing gas stream comprises about 1.5 ppmw or less vapor-phase iodine.

4. The method of claim 1, wherein (ii) is true.

5. The method of claim 4, wherein the molar ratio is no more than about 250.

6. The method of claim 1, wherein (iii) is true.

7. The method of claim 6, wherein a temperature of the mercury-containing gas stream ranges from about 325 to about 450°

C. and wherein the concentration of vapor-phase iodine at the air preheater outlet ranges from about 0.2 to about 2 ppmw.

8. The method of claim 6, wherein the iodine is contacted with vapor-phase mercury upstream of the air preheater, wherein the mercury-containing gas stream is derived from coal combustion, wherein the reactive surface agent is introduced into the mercury-containing gas stream after coal combustion, and wherein the reactive surface agent comprises a zeolite, silica, silica alumina, alumina, gamma-alumina, activated alumina, acidified alumina, amorphous or crystalline aluminosilicate, amorphous silica alumina, ion exchange resin, clay, a transition metal sulfate, porous ceramic, porous carbonaceous material, unburned carbon, charcoal, char, coke, carbon black, trona, alkali metal bicarbonate, alkali metal bisulfate, alkali metal bisulfite, alkali metal sulfide, elemental sulfur, limestone, hydrated or slaked lime, circulating fluidized bed ash, fluidized catalytic cracker (FCC) fines, fumed silicate, metal oxide particles, and mixtures thereof.

9. The method of claim 8, wherein the reactive surface agent comprises the porous carbonaceous material and wherein the porous carbonaceous material is selected from the group consisting essentially of coke, fly ash, bottom ash, pet coke, carbon black, activated carbon, charcoal, char, beneficiated unburned carbon derived from fly ash, and mixtures thereof.

10. The method of claim 1, wherein (iv) is true.

11. The method of claim 1, wherein the removed particulates comprise the ash particulates and particulates comprising the reactive surface agent and at least part of the vapor-phase mercury, wherein the feed material natively comprises no more than about 3 ppmw total iodine and no more than about 10 ppmw total bromine, wherein the halogen-containing additive is contacted with the feed material, wherein the halogen-containing additive comprises no more than about 25% of halogens other than iodine and/or bromine, and wherein a total halogen concentration relative to a weight of the feed material is about 15 ppmw or less.

12. The method of claim 11, wherein the feed material is combustible, wherein the combustible feed material is combusted to produce the mercury-containing gas stream, wherein the vapor-phase iodine causes removal of at least about 75% of elemental and speciated mercury from the mercury-containing gas stream, and wherein the combustible feed material, when combusted, produces an unburned carbon particulate level of no more than about 20% by weight of the combustible feed material.

13. The method of claim 1, wherein the mercury-containing gas stream is passed through a selective catalytic reduction zone comprising a selective catalyst reduction agent and wherein at least one of the following is true:

(i) the selective catalyst reduction agent has an effective SO₂-to-SO₃ oxidation rate of lower than about 2%;

(ii) an air preheater outlet temperature is no more than about 150°

Celsius;

(iii) an ammonia slip at a stack is no more than about 5 ppmv;

(iv) the mercury-containing gas stream is formed from combustion of a feed material having no more than about 1 wt. % total sulfur (dry basis of the coal);

(v) the mercury-containing gas stream is formed from combustion of a feed material having an alkali content of at least about 20 wt. % (dry basis of ash); and

(vi) the mercury-containing gas stream has, at a particulate control device, a SO₃ concentration of no more than about 7.5 ppmv and further comprising;

while vapor phase iodine and mercury are in the mercury-containing gas stream, introducing, into the mercury-containing gas stream, a reactive surface agent to collect at least most of the iodine and mercury.

14. The method of claim 13, wherein (i) is true, wherein the reactive surface agent is one or more of a zeolite, silica, alumina, silica alumina, gamma-alumina, activated alumina, acidified alumina, a metal oxide particle, aluminosilicate, ion exchange resin, clay, a transition metal sulfate, a ceramic, an alkaline material, trona, an alkali metal bicarbonate, an alkali metal bisulfate, an alkali metal bisulfite, sulfide, elemental sulfur, circulating fluidized bed ash, fluidized catalytic cracker fines, and fumed silicate, and wherein one or more of a mean, median, and P₉₀ size of the reactive surface agent is no more than about 100 microns.

15. The method of claim 13, wherein the reactive surface agent is introduced by a dry scrubber and wherein the dry scrubber is located upstream of a particulate removal device.

16. The method of claim 1, wherein the removed particulates comprise the ash particulates and particulates comprising the reactive surface agent and at least part of the vapor-phase mercury, wherein a concentration of the vapor-phase mercury in the mercury-containing gas stream is at least about 0.001 ppmw, wherein a molar ratio, in the mercury-containing gas stream, of vapor phase iodine to total gas-phase mercury is no more than about 250, wherein a concentration of the vapor-phase iodine in the mercury-containing gas stream is about 1.5 ppmw or less, and wherein the selective catalytic reduction catalyst at least one of catalyzes the formation of diatomic iodine and oxidizes at least some of the vapor-phase mercury.

17. The method of claim 1, wherein the removed particulates comprise the ash particulates and particulates comprising the reactive surface agent and at least part of the vapor-phase mercury and further comprising:

passing the mercury-containing gas stream through at least one of a baghouse, a spray dryer absorber, and an electrostatic precipitator to form a treated gas stream; and

thereafter passing the treated gas stream through a wet scrubber, the wet scrubber having a scrubber slurry sorbing no more than about 20% of the total mercury.

18. The method of claim 1, wherein the removed particulates comprise the ash particulates and particulates comprising the reactive surface agent and at least part of the vapor-phase mercury and further comprising:

passing the mercury-containing gas stream through at least one of a first particulate removal device to remove at least most of the mercury and form a first gas stream; and

passing the first gas stream through a preheater to form a second gas stream; and

passing the second gas stream through a second particulate removal device to remove at least most of any remaining mercury from the second gas stream and form a treated gas stream.

19. The method of claim 1, wherein the removed particulates comprise the ash particulates and particulates comprising the reactive surface agent and at least part of the vapor-phase mercury, wherein the mercury-containing gas stream is derived from combustion of a combustible feed material and wherein the feed material is one of a high- and medium-sulfur coal and wherein a concentration of at least one of sulfur trioxide and nitrogen dioxide gas in the mercury-containing gas stream is at least about 5 ppmv.

20. The method of claim 1, wherein the removed particulates comprise the ash particulates and particulates comprising the reactive surface agent and at least part of the vapor-phase mercury and wherein the mercury-containing gas stream is derived from combustion of a combustible feed material and wherein the feed material is a high alkali coal.

21. The method of claim 1, wherein the removed particulates comprise the ash particulates and particulates comprising the reactive surface agent and at least part of the vapor-phase mercury, wherein the vapor phase iodine comprises both a hydrogen-iodine species and diatomic iodide, and wherein a molecular ratio of diatomic iodide to the hydrogen-iodine species is at least about 10:

1.

22. A method, comprising:

providing a mercury-containing gas stream comprising vapor-phase mercury and a vapor-phase halogen;

contacting the mercury-containing gas stream with a reactive surface agent upstream of an air preheater to form particulates comprising at least part of the vapor-phase mercury; and

removing the particulates from the mercury-containing gas stream.

23. The method of claim 22, wherein the reactive surface agent is one or more of a porous carbonaceous material, activated alumina, ceramic, clay, silica, silica-alumina, silicates, zeolites, fine fraction fly ash, FCC fines, and fluidized bed combustor ash.

24. The method of claim 22, wherein the reactive surface agent is a porous carbonaceous material that is selected from the group consisting essentially of activated carbon, charcoal, coke, fly ash, bottom ash, carbon black, activated pet coke and mixtures thereof and wherein a P₈₅ size of the reactive surface agent particulates is no more than about 1 mm and an average diameter of the reactive surface agent particulates is between about 0.10 to about 0.75 mm.

25. The method of claim 22, wherein the mercury-containing gas stream is derived from coal combustion, wherein the reactive surface agent is introduced into the mercury-containing gas stream after coal combustion, and wherein the reactive surface agent comprises a zeolite, silica, silica alumina, alumina, gamma-alumina, activated alumina, acidified alumina, amorphous or crystalline aluminosilicate, amorphous silica alumina, ion exchange resin, clay, a transition metal sulfate, porous ceramic, porous carbonaceous material, unburned carbon, charcoal, char, coke, carbon black, trona, alkali metal bicarbonate, alkali metal bisulfate, alkali metal bisulfite, alkali metal sulfide, elemental sulfur, limestone, hydrated or slaked lime, circulating fluidized bed ash, fluidized catalytic cracker (FCC) fines, fumed silicate, metal oxide particles, and mixtures thereof, wherein the mercury-containing gas stream is derived from coal combustion, wherein the coal comprises no more than about 30% UBC'"'"'s, and wherein a mean, median and P₉₀ size of the reactive surface agent particulates is no more than about 100 microns.

26. The method of claim 22, wherein the mercury active agent is contacted with the mercury-containing gas stream downstream of an economizer.

27. The method of claim 22, wherein the reactive surface agent is in the form of a particulate and wherein at least a portion of the vapor-phase mercury collects on and is removed with the particulate reactive surface agent.

28. The method of claim 22, wherein the vapor-phase halogen is one or more of iodine and bromine.

29. The method of claim 28, wherein the vapor-phase halogen is iodine and wherein at least one of the following is true:

(i) the mercury-containing gas stream comprises about 3.5 ppmw or less vapor-phase iodine;

(ii) in the mercury-containing gas stream, a molar ratio of vapor-phase iodine to vapor-phase mercury is no more than about 600;

(iii) at an air preheater outlet, a concentration of vapor-phase iodine ranges from about 0.1 to about 10 ppmw;

(iv) a concentration of the iodine is about 30 ppmw or less relative to a weight of a mercury-containing feed material producing the vapor-phase mercury.

30. The method of claim 29, wherein (i) is true.

31. The method of claim 29, wherein (ii) is true.

32. The method of claim 29, wherein (iii) is true.

33. The method of claim 29, wherein (iv) is true.

34. The method of claim 29, wherein the reactive surface agent is a porous carbonaceous material that is selected from the group consisting essentially of activated carbon, charcoal, coke, fly ash, bottom ash, carbon black, activated pet coke and mixtures thereof and wherein a P₈₅ size of the reactive surface agent particulates is in the range of from about 1 mm to about 2.5 mm in size and an average diameter of the reactive surface agent particulates is between about 0.75 to about 1.25 mm.

35. The method of claim 22, wherein the reactive surface agent is a porous carbonaceous material that is selected from the group consisting essentially of activated carbon, charcoal, coke, fly ash, bottom ash, carbon black, activated pet coke and mixtures thereof, wherein the reactive surface agent has a surface area of at least about 500 but no more than about 2,500 m²/g, and wherein the reactive surface agent has an ash content in the range of from about 10 to about 95%.