Method for removal and stabilization of mercury in mercury-containing gas streams

• US 6,942,840 B1
• Filed: 09/23/2002
• Issued: 09/13/2005
• Est. Priority Date: 09/24/2001
• Status: Expired due to Fees

• Current Assignee: Mercury Control Technologies, LLC
• Original Assignee: ADA Technologies, Inc.
• Inventors: Broderick, Thomas E.
• Primary Examiner(s): GREENE, JASON M
• Application Number:
  US10/253,944
• Time in Patent Office: 1,086 Days
• Field of Search: 422/168, 951/89, 951/95, 951/96, 951/97, 952/05, 952/34, 951/52, 962/34, 962/36, 962/35, 423/210, 423/215.5, 423/99, 423/101, 423/103, 423/104, 423/106, 210/719, 210/721, 210/723, 210/759, 210/914, 210/757, 210/756, 210/758
• US Class Current: 423/101
• CPC Class Codes: B01D 2251/108 Halogens or halogen compounds hydrogen halides B01D2251/50
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: Y10S 210/914 Mercury

Abstract

The present invention is directed to a process and apparatus for removing and stabilizing mercury from mercury-containing gas streams. A gas stream containing vapor phase elemental and/or speciated mercury is contacted with reagent, such as an oxygen-containing oxidant, in a liquid environment to form a mercury-containing precipitate. The mercury-containing precipitate is kept or placed in solution and reacts with one or more additional reagents to form a solid, stable mercury-containing compound.

Claims

1. A scrubber for removing mercury from a gas stream, comprising:

a gas scrubbing zone operable to contact a scrubbing solution with the gas stream to form a mercury-containing precipitate in a mercury-containing solution, wherein the mercury-containing solution comprises at least most of the mercury in the gas stream and the mercury-containing precipitate comprises predominantly mercury and oxygen; and

a collection zone operable to collect the mercury-containing solution, wherein in the mercury-containing solution at least most of the mercury is in the form of a precipitate.

2. The scrubber of claim 1, wherein the mercury in the gas stream comprises speciated mercury.

3. The scrubber of claim 1, wherein the partial pressure of the mercury in the gas stream is at least about 7×

10<sup>−

6</sup> mmHg (100 μ

g/m³).

4. The scrubber of claim 2, wherein the speciated mercury is selected from the group consisting essentially of mercuric chloride, mercuric sulfate, mercuric nitrate and mercuric oxide.

5. The scrubber of claim 1, wherein the scrubbing solution comprises an oxygen-containing oxidant and the precipitate is a compound comprising predominantly HgO.

6. The scrubber of claim 5, wherein the oxidant is selected from the group consisting essentially of a peroxygen compound, a hypochlorite, a chlorate, a perchlorate, a persulfate, iodine, iodide, iodate, hypoiodite, periodate, hydrogen peroxide, and permanganate.

7. The scrubber of claim 5, wherein the oxidant is sodium hypochlorite.

8. The scrubber of claim 5, wherein the concentration of the oxidant in the scrubbing solution ranges from about 0.1 to about 1.0 wt. %.

9. The scrubber of claim 1, wherein the gas scrubbing zone comprises a packing material to provide surface area for the contact of the gas stream with the scrubbing solution.

10. The scrubber of claim 1, wherein the gas stream and the scrubbing solution are introduced into the gas scrubbing zone so as to flow countercurrently therethrough.

11. A process for removing mercury from a gas stream, comprising:

(a) contacting a scrubbing solution with a mercury-containing gas stream to form a mercury-containing precipitate in a mercury-containing solution and a treated gas stream, the mercury-containing precipitate comprising predominantly mercury and oxygen; and

(b) collecting the mercury-containing solution, wherein the mercury-containing solution contains at least most of the mercury from the mercury-containing gas stream and, in the mercury-containing solution, at least most of the mercury is in the form of a precipitate.

12. The process of claim 11, wherein the mercury in the mercury-containing gas stream is selected from the group consisting essentially of elemental mercury, speciated mercury and mixtures thereof.

13. The process of claim 11 wherein the mercury-containing gas stream comprises speciated mercury.

14. The process of claim 13, wherein the speciated mercury is selected from the group consisting essentially of mercuric chloride, mercuric sulfate, mercuric nitrate, mercuric oxide, and mixtures thereof.

15. The process of claim 14, wherein the partial pressure of the mercury-containing compounds in the gas stream is at least about 7×

10<sup>−

6</sup> mmHg (100 μ

g/m³).

16. The process of claim 12, wherein the scrubbing solution comprises an oxygen-containing oxidant and the precipitate is a compound comprising predominantly HgO.

17. The process of claim 16, wherein the oxidant is selected from the group consisting essentially of a peroxygen compound, a chlorate, and mixtures thereof.

18. The process of claim 16, wherein the oxidant is a peroxygen compound and the peroxygen compound is selected from the group consisting essentially of a peroxide, a persulfate, a perchlorate, a periodate, hydrogen peroxide, permanganate and mixtures thereof.

19. The process of claim 16, wherein the oxidant comprises a hypochlorite and the concentration of the oxidant in the scrubbing solution ranges from about 0.1 to about 1.0 percent by weight.

20. The process of claim 11, wherein, in the contacting step (a), the gas stream and the scrubbing solution flow countercurrently through a scrubber.

21. The process of claim 16, wherein in the contacting step (a) the pH of the scrubbing solution is above approximately pH9.

22. The process of claim 21, further comprising:

(c) contacting a base with the scrubbing solution to maintain the pH in the desired range.

23. The process of claim 11, wherein the ratio of the gas stream to the scrubbing solution ranges from about 0.07 to about 0.2.

24. The process of claim 11, further comprising:

(c) removing the mercury-containing precipitates from the mercury-containing solution to form a treated scrubbing solution and a removed mercury-containing slurry.

25. The process of claim 24, further comprising:

(d) recycling the treated scrubbing solution to the contacting step and wherein the slurry comprises at least most of the mercury-containing precipitates in the mercury-containing solution.

26. The process of claim 24, wherein the slurry comprises an oxygen-containing oxidant and further comprising:

(d) contacting the removed mercury-containing slurry with a reductant to neutralize at least most of the oxidant in the slurry to form a reduced slurry.

27. The process of claim 26, wherein the reductant is selected from the group consisting essentially of oxalic acid, sodium sulfite, sodium hydrosulfite, and mixtures thereof.

28. The process of claim 27, wherein the molar ratio of the reductant to the oxidant is at least about 1:

1.

29. The process of claim 26, wherein in contacting step (d) the pH of the slurry ranges from about pH 9 to about pH 11.

30. The process of claim 26, further comprising:

(e) contacting the reduced slurry with a mercury-reactive sulfur-containing material to convert at least most of the mercury into a compound comprising mercury and sulfur and to form a treated slurry.

31. The process of claim 30, wherein the mercury-reactive sulfur-containing material is selected from the group consisting essentially of a polysulfide, a sulfide other than a polysulfide, and mixtures thereof.

32. The process of claim 30, wherein in contacting step (e) the pH of the reduced slurry ranges from about pH 5.5 to about pH 7.5.

33. The process of claim 30, wherein the mercury reactive material is a compound of sulfur and further comprising:

(f) contacting the treated slurry with a sulfide scavenger to convert at least most of the unreacted mercury reactive material into a substantially nonreactive sulfur-containing material and form a further treated slurry.

34. The process of claim 33, wherein the sulfide scavenger is selected from the group consisting essentially of a metal salt, ferrous sulfate, ferric sulfate, cuprous sulfate, cupric sulfate, ferric chloride, ferrous chloride, stannic chloride, stannous chloride, cupric chloride, cuprous chloride and mixtures thereof.

35. The process of claim 34, wherein the treated slurry during contacting step (f) has a pH ranging from about pH 5.5 to about pH 7.5.

36. The process of claim 33, further comprising:

separating at least most of the compounds of mercury and sulfur from the further treated slurry.

37. The process of claim 11, wherein the partial pressure of mercury-containing compounds in the treated gas stream is no more than about 8.9×

10<sup>−

3</sup> mmHg (90 mg/m³).

38. A system for stabilizing mercury in a mercury-containing gas stream, comprising:

(a) a scrubber having;

(i) a gas scrubbing zone operable to contact a scrubbing solution with the gas stream to form a mercury-containing precipitate in a mercury-containing solution, wherein the mercury-containing solution comprises at least most of the mercury in the gas stream, and the mercury-containing precipitate comprises predominantly a compound of mercury and oxygen; and

(ii) a collection zone operable to collect the mercury-containing solution, wherein, in the mercury-containing solution, at least most of the mercury is in the form of a precipitate;

(b) a solid/liquid separator operable to separate the mercury-containing precipitates from the mercury-containing solution; and

(c) a mercury stabilization reactor operable to convert the recovered mercury-containing precipitates into a compound of mercury and sulfur.

39. The system of claim 38, wherein the mercury in the gas stream is selected from the group consisting essentially of elemental mercury, speciated mercury, and mixtures thereof.

40. The system of claim 39, wherein the partial pressure of the mercury in the gas stream is at least about 3×

10<sup>−

3</sup> mmHg (30 mg/m³).

41. The system of claim 38, wherein the mercury comprises speciated mercury selected from the group consisting essentially of mercuric chloride, mercuric sulfate, mercuric nitrate, and mercuric oxide.

42. The system of claim 38, wherein the scrubbing solution comprises an oxygen-containing oxidant and the precipitate is a compound comprising predominantly HgO.

43. The system of claim 42, wherein the oxidant is at least one of a peroxygen compound, a hypochlorite, a chlorate, a perchlorate, a persulfate, iodine, iodide, iodate, hypoiodite, periodate, hydrogen peroxide, and permanganate.

44. The system of claim 42, wherein the oxidant is a peroxygen compound that is at least one of a peroxide, a persulfate, a perchlorate, a periodate and hydrogen peroxide.

45. The system of claim 42, wherein the oxidant is a hypochlorite and the concentration of the oxidant in the scrubbing solution ranges from about 0.1 to about 1.0 percent by weight.

46. The system of claim 38, wherein the gas scrubbing zone comprises a packing material to provide surface area for the contact of the gas stream with the scrubbing solution.

47. The system of claim 38, wherein the gas stream and the scrubbing solution are introduced into the gas scrubbing zone so as to flow countercurrently therethrough.

48. The system of claim 38, wherein the compound of mercury and sulfur is HgS.

49. The system of claim 48, wherein in the mercury stabilization reactor a mercury-reactive sulfur-containing material is contacted with the mercury-containing precipitates and the mercury-reactive sulfur-containing material is selected from the group consisting essentially of a polysulfide, a sulfide other than a polysulfide, and mixtures thereof.

50. In a scrubber for removing mercury from a mercury-containing gas stream, an aqueous scrubbing solution comprising:

at least about 0.1 percent by weight of an oxygen-containing oxidant in a solution having a pH of over approximately pH 9 to convert the mercury to a substantially insoluble compound of mercury and oxygen.

51. The aqueous scrubbing solution of claim 50, further comprising base solution to maintain the pH over approximately pH 9.

52. The aqueous scrubbing solution of claim 50, wherein the concentration of the oxidant ranges from about 0.1 to about 0.5 percent by weight and wherein the oxidant is selected from the group consisting essentially of a peroxygen compound, a hypochlorite, a chlorate, a perchlorate, a persulfate, iodine, iodide, iodate, hypoiodite, periodate, hydrogen peroxide, and permanganate.

53. A process for stabilizing mercury in a mercury-containing gas stream, comprising:

(a) contacting a mercury-containing gas stream with a scrubbing solution to form a treated gas stream and a mercury-containing solid in a mercury-containing solution, the mercury-containing solution comprising at least most of the mercury in the mercury-containing gas stream and the mercury-containing solid comprising predominantly a compound of mercury and oxygen; and

(b) converting at least most of the mercury in the mercury-containing solution into a compound of mercury and sulfur.

54. The process of claim 53, wherein, after step (a) and before step (b), at least most of the mercury in the mercury-containing solution is in the form of a solid.

55. The process of claim 53, wherein, after step (a) and before step (b), at least most of the mercury in the mercury-containing solution is in the form of HgO.

56. The process of claim 54, further comprising after step (b):

(c) separating at least most of the mercury from the mercury-containing solution to form a mercury-containing slurry and a treated scrubbing solution;

(d) recycling the treated scrubbing solution to step (a); and

(e) contacting the mercury-containing slurry with a mercury reactive material to form the compound of mercury and sulfur.

57. The process of claim 53, wherein the scrubbing solution comprises at least about 0.1 percent by weight of an oxygen-containing oxidant.