Mercury removal from flue gas streams using treated sorbents

• US 8,551,431 B1
• Filed: 03/14/2013
• Issued: 10/08/2013
• Est. Priority Date: 01/28/2013
• Status: Active Grant

• Current Assignee: Cabot Norit Americas, Inc. (Cabot Corporation)
• Original Assignee: Cabot Corporation
• Inventors: Adams, Patton, Rester, Dennis O., Williams, Misty
• Primary Examiner(s): VANOY, TIMOTHY C
• Application Number:
  US13/831,053
• Time in Patent Office: 208 Days
• Field of Search: 423/210, 952/34, 502/400, 502/406, 502/415, 502/437, 502/514, 502/516, 502/521, 502/60, 502/64, 502/11
• US Class Current: 423/210
• CPC Class Codes: B01D 2251/108 Halogens or halogen compounds hydrogen halides B01D2251/50
• CPC Class Codes: B01D 2251/304 of sodium
• CPC Class Codes: B01D 2251/60 Inorganic bases or salts
• CPC Class Codes: B01D 2253/108 Zeolites
• 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 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01J 20/027 Compounds of F, Cl, Br, I
• CPC Class Codes: B01J 20/0288 Halides of compounds other than those provided for in B01J20/046
• CPC Class Codes: B01J 20/046 containing halogens, e.g. halides
• CPC Class Codes: B01J 20/18 Synthetic zeolitic molecular sieves
• CPC Class Codes: B01J 20/186 Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
• CPC Class Codes: B01J 20/3021 Milling, crushing or grinding
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3234 Inorganic material layers
• CPC Class Codes: B01J 20/3236 containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 2220/42 Materials comprising a mixture of inorganic materials materials coated or impregnated on a carrier B01J20/32

Abstract

A method for modifying the properties of a sorbent comprising washing a sorbent with a washing solution so as to achieve an exchange of ions between the sorbent and the washing solution, and applying a halogen compound to the sorbent that has been washed with the washing solution to achieve a predetermined concentration of the halogen on the sorbent.

Claims

1. A method for modifying the properties of a sorbent comprising:

washing a sorbent with a washing solution so as to achieve an exchange of ions between the sorbent and the washing solution; and

applying a halogen compound to the sorbent that has been washed with the washing solution to achieve a predetermined concentration of the halogen on the sorbent.

2. The method of claim 1, wherein the sorbent is selected from the group consisting of mineral zeolites, synthetic zeolites, pumice, perlite, fly ash, alumina, diatomaceous earth, silicates, almuninosilicates, phyllosilicates, clay, peat, wood, lignocellulosic materials, biomass, waste, tires, olive pits, peach pits, corn hulls, rice hulls, lignite, brown coal, anthracite coal, bituminous coal, sub-bituminous coal, coconut shells, pecan shells, and walnut shells.

3. The method of claim 1, wherein the sorbent is a zeolite and the zeolite is selected from the group consisting of chabazite, mordenite, erionite, faujasite, clinoptilolite, analcime, phillipsite, zeolite A, zeolite X, zeolite Y, zeolite L, zeolite omega, and ZSM-5.

4. The method of claim 1, wherein the washing solution is an aqueous solution comprising a solute and the solute is selected from the group consisting of ammonium nitrate, ammonium bromide, ammonium carbonate, ammonium bicarbonate, ammonium chloride, ammonium perchlorate, ammonium hydroxide, ammonium sulfate, ammonium iodide, ammonium phosphate, and quarternary ammonium cations.

5. The method of claim 1, wherein the washing solution comprises a greater than or equal to 0.001M ammonium nitrate or ammonium bromide solution.

6. The method of claim 1, wherein washing the granularized zeolite with a washing solution comprises repeating the washing such that the sorbent receives a plurality of washes with the washing solution without reusing the washing solution between any of the plurality of washes.

7. The method of claim 1, wherein the halogen compound is selected from the group consisting of bromine, chlorine, iodine, sodium bromide, calcium bromide, magnesium bromide, copper (II) bromide, iron (II) bromide, iron (III) bromide, zinc bromide, potassium bromide, copper (I) chloride, copper (II) chloride, iron (II) chloride, iron (III) chloride, and zinc chloride.

8. The method of claim 1, wherein applying the halogen compound to the sorbent to achieve the predetermined concentration of the halogen on the sorbent comprises applying an aqueous solution comprising at least 20% sodium bromide by weight so as to achieve a final bromide concentration of at least 0.05% by weight.

9. The method of claim 1, wherein applying the halogen compound to the sorbent to achieve the predetermined concentration of the halogen on the sorbent comprises spraying an aqueous solution onto the sorbent.

10. The method of claim 1, further comprising milling the sorbent.

11. The method of claim 10, wherein the milled sorbent has a median particle diameter of approximately 20 micron on a volume basis.

12. The method of claim 10, further comprising blending the milled sorbent with a second sorbent, wherein the second sorbent is an activated carbon.

13. The method of claim 1, further comprising, prior to washing the sorbent with a washing solution, pre-washing the sorbent with a pre-washing solution so as to achieve an increase in the volume of pores of the sorbent with a pore size greater than or equal to 2 nanometers.

14. The method of claim 13, wherein the pre-washing solution is an aqueous solution comprising a solute and the solute is selected from a group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and ammonium hydroxide.

15. The method of claim 13, wherein the pre-washing solution comprises a greater than or equal to 0.05M sodium hydroxide solution.

16. A sorbent for the removal of mercury from a gaseous flue stream prepared by a process comprising:

washing a sorbent with a washing solution so as to achieve an exchange of ions between the sorbent and the washing solution; and

applying a halogen compound to the sorbent that has been washed with the washing solution to achieve a predetermined concentration of the halogen on the sorbent.

17. The sorbent of claim 16, wherein the sorbent is selected from the group consisting of mineral zeolites, synthetic zeolites, pumice, perlite, fly ash, alumina, diatomaceous earth, silicates, almuninosilicates, phyllosilicates, clay, peat, wood, lignocellulosic materials, biomass, waste, tires, olive pits, peach pits, corn hulls, rice hulls, lignite, brown coal, anthracite coal, bituminous coal, sub-bituminous coal, coconut shells, pecan shells, and walnut shells.

18. The sorbent of claim 16, wherein the sorbent is a zeolite and the zeolite is selected from the group consisting of chabazite, mordenite, erionite, faujasite, clinoptilolite, analcime, phillipsite, zeolite A, zeolite X, zeolite Y, zeolite L, zeolite omega, and ZSM-5.

19. The sorbent of claim 16, wherein the washing solution is an aqueous solution comprising a solute and the solute is selected from the group consisting of ammonium nitrate, ammonium bromide, ammonium carbonate, ammonium bicarbonate, ammonium chloride, ammonium perchlorate, ammonium hydroxide, ammonium sulfate, ammonium iodide, ammonium phosphate, and quarternary ammonium cations.

20. The sorbent of claim 16, wherein the washing solution comprises a greater than or equal to 0.001M ammonium nitrate or ammonium bromide solution.

21. The sorbent of claim 16, wherein washing the granularized zeolite with a washing solution comprises repeating the washing such that the sorbent receives a plurality of washes with the washing solution without reusing the washing solution between any of the plurality of washes.

22. The sorbent of claim 16, wherein the halogen compound is selected from the group consisting of bromine, chlorine, iodine, sodium bromide, calcium bromide, magnesium bromide, copper (II) bromide, iron (II) bromide, iron (III) bromide, zinc bromide, potassium bromide, copper (I) chloride, copper (II) chloride, iron (II) chloride, iron (III) chloride, and zinc chloride.

23. The sorbent of claim 16, wherein applying the halogen compound to the sorbent to achieve the predetermined concentration of the halogen on the sorbent comprises applying an aqueous solution comprising at least 20% sodium bromide by weight so as to achieve a final bromide concentration of at least 0.05% by weight.

24. The sorbent of claim 16, wherein applying the halogen compound to the sorbent to achieve the predetermined concentration of the halogen on the sorbent comprises spraying an aqueous solution onto the sorbent.

25. The sorbent of claim 16, further comprising milling the sorbent.

26. The sorbent of claim 25, wherein the milled sorbent has a median particle diameter of approximately 20 micron on a volume basis.

27. The sorbent of claim 25, further comprising blending the milled sorbent with a second sorbent, wherein the second sorbent is an activated carbon.

28. The sorbent of claim 16, further comprising, prior to washing the sorbent with a washing solution, pre-washing the sorbent with a pre-washing solution so as to achieve an increase in the volume of pores of the sorbent with a pore size greater than or equal to 2 nanometers.

29. The sorbent of claim 28, wherein the pre-washing solution is an aqueous solution comprising a solute and the solute is selected from a group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and ammonium hydroxide.

30. The sorbent of claim 28, wherein the pre-washing solution comprises a greater than or equal to 0.05M sodium hydroxide solution.

31. A method for removing mercury from a gaseous flue stream comprising:

introducing a sorbent to a gaseous flue stream, wherein the gaseous flue stream contains mercury; and

facilitating removal of mercury from the gaseous flue stream by adsorption of the mercury onto the sorbent;

wherein the sorbent comprises a sorbent washed with a washing solution so as to achieve an exchange of ions between the sorbent and the washing solution, treated with a halogen compound to achieve a predetermined concentration of the halogen on the sorbent, and milled to a size suitable for injection into the gaseous flue stream.