Reducing sulfur gas emissions resulting from the burning of carbonaceous fuels

• US 8,574,324 B2
• Filed: 04/08/2005
• Issued: 11/05/2013
• Est. Priority Date: 06/28/2004
• Status: Active Grant

• Current Assignee: Nox Ii Ltd. (Arthur J Gallagher & Company)
• Original Assignee: Nox Ii Ltd. (Arthur J Gallagher & Company)
• Inventors: Comrie, Douglas C., Vellella, Vincent A.
• Primary Examiner(s): WEISS, PAMELA HL
• Application Number:
  US11/631,046
• Publication Number:
  US 20080286703A1
• Time in Patent Office: 3,133 Days
• Field of Search: 446/28, 446/41, 44620-623, 431/2, 423/210, 423/242.1, 423/244.01, 423/244.07, 422/105, 422/108, 422/111
• US Class Current: 44/641
• CPC Class Codes: B01D 2251/304 of sodium
• CPC Class Codes: B01D 2251/306 of potassium
• CPC Class Codes: B01D 2251/404 of calcium
• CPC Class Codes: B01D 2255/2047 Magnesium
• CPC Class Codes: B01D 2255/20738 Iron
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 53/501 by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
• CPC Class Codes: B01D 53/508 by treating the gases with solids
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• 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 10/02 for reducing smoke development
• CPC Class Codes: C10L 10/04 for minimising corrosion or incrustation
• CPC Class Codes: C10L 9/10 by using additives
• CPC Class Codes: F23J 7/00 Arrangement of devices for supplying chemicals to fire
• CPC Class Codes: F23K 1/00 Preparation of lump or pulverulent fuel in readiness for delivery to combustion apparatus
• CPC Class Codes: F23K 2201/505 with additives

Abstract

A process for burning coal or other carbonaceous fuels captures sulfur and other undesirable compounds are captured and retained in non-reactive ceramic-like form after the combustion phase. The process involves addition of multiple element alkali powders and/or sorbents preferably containing oxidizing anions such as nitrates and nitrites, preferably based on calcium. In various embodiments, the remediation materials when applied in a complex powder and/or liquid containing multiple elements, result in higher sulfur capture than the materials would otherwise achieve on an individual basis. In a preferred embodiment, the sorbents contain elements that minimize or lower the melting point of the ash. This leads to lowered cohesiveness and toughness of the ash so that less ash builds up on the boiler and better heat transfer is obtained.

Claims

1. A method for reducing the amount of sulfur gases released into the atmosphere upon combustion of a sulfur-containing coal in a furnace, the method comprising:

preparing a combustible fuel composition by applying a sorbent composition onto the sulfur-containing coal, wherein the combustible fuel composition consists of the sulfur-containing coal and the applied sorbent;

delivering the combustible fuel composition into the furnace; and

combusting the combustible fuel composition in the furnace to produce heat energy and ash,

wherein the sorbent composition comprises calcium nitrate, calcium nitrite, or both, wherein upon combustion of the coal to release its heat energy, the amount of sulfur in the ash is increased relative to the amount that would be produced by combustion of the coal without applying the sorbent composition.

2. A method according to claim 1, wherein the sorbent composition comprises calcium nitrite and calcium nitrate.

3. A method according to claim 1, wherein the sorbent composition further comprises calcium bromide.

4. A method according to claim 1, comprising applying an aqueous solution comprising calcium nitrate and calcium nitrite onto the fuel.

5. A method according to claim 1, comprising adding up to 6% dry weight of the sorbent composition onto the fuel.

21. A method according to claim 1, comprising applying up to 3% dry weight of the sorbent composition onto the fuel.

22. A method according to claim 1, comprising applying up to 1.5% dry weight of the sorbent composition onto the fuel.

23. A method according to claim 1, wherein the sorbent composition further comprises silicon dioxide, aluminum oxide, calcium oxide, and iron oxide.

24. A method according to claim 23, wherein the sorbent further comprises magnesium oxide.

25. A method according to claim 23, comprising adding a powder composition comprising silicon oxide, aluminum oxide, calcium oxide, and iron oxide onto the carbonaceous fuel.

26. A method according to claim 25, wherein the powder composition comprises Portland cement.

27. A method according to claim 25, wherein the powder composition comprises a dolomitic material selected from the group consisting of dolomite and burnt dolomite.

28. A method according to claim 23, comprising applying an aqueous solution comprising calcium nitrate and calcium nitrite onto particulate carbonaceous fuel, and adding the powder composition onto the wetted fuel.

29. A method according to claim 1, wherein the coal comprises lignite coal.

30. A method according to claim 1, wherein the coal comprises bituminous coal.

31. A method according to claim 1, wherein the coal comprises anthracite coal.

53. A method that according to claim 1 wherein the coal being combusted has 2-4.5% by weight sulfur.

54. A method according to claim 1, wherein the coal combusted in the furnace is compliance coal.

6. A method for reducing the amount of sulfur gases released into the atmosphere upon combustion of a sulfur-containing coal in a furnace, the method comprising:

applying a powder sorbent composition onto the sulfur-containing coal;

delivering a combustible fuel composition comprising the applied powder sorbent composition and the sulfur-containing coal into the furnace; and

combusting the sulfur-containing coal with the powder sorbent composition applied to produce heat energy and ash,

wherein the powder sorbent composition comprises

20-50% by weight Portland cement

20-40% by weight calcium oxide

15-25% by weight of a dolomitic material selected from the group consisting of dolomite and burnt dolomite, and

5-15% by weight of an aluminosilicate clay, and

wherein upon combustion of the coal to release its heat energy, the amount of sulfur in the ash is increased relative to the amount that would be produced by combustion of the coal without applying the powder sorbent composition.

7. A method according to claim 6, wherein the clay comprises calcium montmorillonite, kaolin, or a combination thereof.

8. A method according to claim 6, wherein the sorbent composition comprises about 30% by weight Portland cement, about 40% by weight calcium oxide, about 20% by weight dolomite, and about 10% by weight clay.

9. A method according to claim 6, wherein the sorbent composition further comprises at least one oxidizing salt selected from the group consisting of calcium nitrate and calcium nitrite.

10. A method according to claim 9, comprising applying the at least one oxidizing salt in an aqueous solution.

32. A method according to claim 6, wherein the coal comprises <

4% by weight sulfur.

33. A method according to claim 6, wherein the coal comprises <

3% by weight sulfur.

34. A method according to claim 6, wherein the coal comprises ≈

2% by weight sulfur.

35. A method according to claim 6, wherein the coal comprises >

4% by weight sulfur.

36. A method according to claim 6, comprising applying up to 6% weight of the sorbent composition onto the coal.

37. A method according to claim 36, further comprising applying a liquid sorbent comprising water and solids, the solids comprising at least one of calcium nitrate and calcium nitrite.

38. A method according to claim 37, comprising applying up to 3% weight of the powder composition and up to 1.5% weight of the solids in the liquid sorbent, based on the weight of the coal.

55. A method according to claim 6, wherein the coal being combusted has 2-4.5% by weight sulfur.

56. A method according to claim 6, wherein the coal is selected from bituminous coal, anthracite coal, and lignite coal.

11. A method for reducing sulfur gases and/or mercury released into the atmosphere upon combustion of a coal containing sulfur and/or mercury comprising:

applying a powder sorbent composition onto the coal,

delivering a combustible fuel composition consisting of the applied powder sorbent composition and the sulfur-containing coal into the furnace; and

combusting the coal in the furnace with the powder sorbent composition applied to produce heat energy and ash,

wherein the powder sorbent composition comprises

Portland cement,

at least one water soluble chlorine containing inorganic compound,

calcium oxide,

optionally an aluminosilicate clay, and

an alkali metal salt selected from the group consisting of sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, sodium oxide, and potassium oxide,

wherein upon combustion of the coal to release its heat energy, the amount of sulfur in the ash is increased relative to the amount that would be produced by combustion of the coal without applying the powder sorbent composition.

12. A method according to claim 11, wherein the at least one chlorine containing inorganic compound comprises a soluble salt selected from the group consisting of sodium chloride, potassium chloride, sodium chlorate, and potassium chlorate.

13. A method according to claim 11, wherein the clay comprises metakaolin.

14. A method according to claim 11, wherein the powder composition comprises

20-30% by weight Portland cement,

2-5% by weight of the water soluble chlorine containing inorganic compound,

20-40% by weight calcium oxide

20-30% by weight clay, and

1-9% by weight of the alkali metal salt.

15. A method according to claim 11, wherein the sorbent composition further comprises at least one oxidizing salt selected from the group consisting of alkali metal nitrates, alkali metal nitrites, alkaline earth metal nitrates, and alkaline earth metal nitrites.

39. A method according to claim 15, wherein the oxidizing salt comprises calcium nitrate, calcium nitrite, or a combination thereof.

40. A method according to claim 11, further comprising applying a liquid sorbent onto the coal, the liquid sorbent comprising at least one oxidizing salt selected from the group consisting of alkali metal nitrates, alkali metal nitrites, and alkaline earth metal nitrates, and alkaline earth metal nitrites.

41. A method according to claim 40, wherein the oxidizing salt is selected from the group consisting of calcium nitrate, calcium nitrite, and combinations thereof.

42. A method according to claim 11, further comprising applying a liquid sorbent to the coal, the liquid sorbent comprising water and at least one alkali metal salt selected from the group consisting of potassium silicate, sodium silicate, potassium hydroxide, and sodium hydroxide.

43. A method according to claim 11, comprising applying up to 6% by weight of the powder composition based on the weight of the coal.

44. A method according to claim 11, wherein the coal comprises lignite coal.

45. A method according to claim 11, wherein the coal comprises bituminous coal.

46. A method according to claim 11, wherein the coal comprises anthracite coal.

47. A method according to claim 11, wherein the coal comprises greater than or equal to 2% by weight sulfur.

48. A method according to claim 11, wherein the coal comprises greater than or equal to 3% by weight sulfur.

49. A method according to claim 11, wherein the coal comprises greater than or equal to 4% by weight sulfur.

57. A method according to claim 11, wherein the coal being combusted has 2-4.5% by weight sulfur.

58. A method according to claim 11, wherein the coal is selected from bituminous coal, anthracite coal, and lignite coal.

16. A method for reducing the sulfur gases released in the atmosphere upon combustion of sulfur-containing coal in a furnace, the method comprising

applying a liquid sorbent and a powder sorbent onto the sulfur-containing coal, wherein the liquid sorbent comprises water and solids, the solids comprising at least one soluble salt selected from the group consisting of soluble metal nitrates and soluble metal nitrites and the powder sorbent comprises calcium to make a combustible fuel composition consisting of the sulfur-containing coal and the applied sorbents;

delivering the combustible fuel composition into the furnace; and

combusting the combustible fuel composition in the furnace to produce heat energy and ash,

wherein upon combustion of the coal to release its heat energy, the amount of sulfur in the ash is increased relative to the amount that would be produced by combustion of the coal without applying the liquid sorbent and powder sorbent.

17. A method according to claim 16, wherein the liquid sorbent comprises alkali metal nitrates, alkali metal nitrites, alkaline earth metal nitrates, alkaline earth metal nitrites, or combinations thereof.

18. A method according to claim 16, wherein the liquid sorbent comprises calcium nitrate and calcium nitrite.

19. A method according to claim 16, comprising applying up to 6% weight of the solids and up to 6% weight of the powder sorbent.

20. A method according to claim 16, comprising applying up to 3% weight of the solids and up to 3% weight of the powder sorbent.

50. A method according to claim 16, wherein the powder sorbent composition comprises silicon, aluminum, calcium, iron, and magnesium.

51. A method according to claim 16, wherein the powder sorbent composition comprises:

Portland cement;

calcium oxide;

optionally an aluminosilicate clay; and

dolomitic material selected from the group consisting of dolomite and burnt dolomite.

52. A method according to claim 16, wherein the powder sorbent composition comprises

Portland cement;

calcium oxide;

at least one water soluble chlorine containing inorganic compound;

aluminosilicate clay; and

at least one alkali metal salt selected from the group consisting of potassium silicate, sodium silicate, potassium hydroxide, sodium hydroxide, potassium oxide, and sodium oxide.

59. A method according to claim 16, wherein the coal being combusted has 2-4.5% by weight sulfur.

60. A method according to claim 16, wherein the sulfur-containing coal is selected from bituminous coal, anthracite coal, and lignite coal.