IP Library Granted Patent US 10,767,130
Granted Patent B2
US 10,767,130 · App. 15/941,522 · Granted Sep 8, 2020

Method and additive for controlling nitrogen oxide emissions

Inventors: William J. Morris (Evergreen, CO); Kenneth E. Baldrey (Denver, CO); Constance Senior (Littleton, CO); Ramon Bisque (Golden, CO)
Assignee: ADA-ES, Inc.
C10L5/32C10L9/10C10L10/00F23J7/00C10L2200/0204C10L2200/029C10L2200/0259C10L2230/04C10L2290/02C10L2290/06C10L2290/24F23K2201/505
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Quick Facts
Patent No.
US 10,767,130
App. No.
15/941,522
Granted
Sep 8, 2020
Kind
B2
Abstract

The present disclosure is directed to an additive mixture and method for controlling nitrogen oxide(s) by adding the additive mixture to a feed material prior to combustion.

Claims (54)

1. A method for reducing NO x emissions in a pulverized coal boiler system, comprising:

contacting a feed material comprising coal particles with an additive composition to form an additive-containing feed material, the additive composition comprising: a nitrogenous material comprising one or more of ammonia, an amine, an amide, cyanuric acid, a nitride, and urea; a binder; and a thermal stability agent comprising one or more of a metal hydroxide, a metal carbonate, a metal bicarbonate, a metal hydrate, and a metal nitride, wherein the thermal stability agent is bound by the binder to and substantially surrounds the nitrogenous material and wherein a molar ratio of the thermal stability agent:nitrogenous material ranges from about 1:1 to about 10:1; and

combusting the additive-containing feed material to produce a contaminated gas stream comprising a contaminant produced by combustion of the coal particles and the additive composition or a derivative thereof, wherein the additive composition or the derivative thereof removes or causes removal of the contaminant.

2. The method of claim 1 , wherein the coal particles comprise a high alkali coal, wherein the additive composition is fed to a combustor, wherein the coal particles and the additive composition are mixed together, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, and wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent.

3. The method of claim 1 , wherein the coal particles comprise a high iron coal, wherein the additive composition is fed to a combustor, wherein the coal particles and additive composition are mixed together, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent, and wherein the nitrogenous material is one or more of an amine, an amide, cyanuric acid, and urea.

4. The method of claim 1 , wherein the coal particles comprise a high sulfur coal, wherein the additive composition is fed to a combustor, wherein the coal particles and additive composition are mixed together, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent, and wherein the nitrogenous material is one or more of an amine, an amide, cyanuric acid, and urea.

5. The method of claim 1 , wherein the nitrogenous material comprises urea, wherein an iron content of the coal particles is less than about 10 wt. % (dry basis of the ash) as Fe2O3, wherein an alkali content of the coal particles is at least about 20 wt. % (dry basis of the ash) alkali, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent, and wherein the thermal stability agent comprises one or more of an alkaline earth metal hydroxide, an alkaline earth metal carbonate, and an alkaline earth metal bicarbonate.

6. The method of claim 1 , wherein the coal particles comprise at least about 15 wt. % calcium as CaO (dry basis of the ash), wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the nitrogenous material comprises urea, wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent, and wherein the thermal stability agent comprises one or more of an alkaline earth metal hydroxide and an alkaline earth metal carbonate.

7. The method of claim 1 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent, and wherein the additive composition further comprises one or more of a stabilizing agent and a dispersant.

8. The method of claim 1 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent, and wherein the additive composition comprises prills comprising urea and an alkaline earth metal hydroxide.

9. The method of claim 1 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent, and the additive composition further comprises at least one halogen.

10. The method of claim 9 , wherein the at least one halogen is one or more of iodine and bromine.

11. The method of claim 1 , wherein the thermal stability agent is bound by the binder to and substantially surrounds the nitrogenous material.

12. A method, comprising:

contacting a feed material comprising coal particles with an additive composition to form an additive-containing feed material, the additive composition comprising: a nitrogenous material in the form of particles comprising one or more of ammonia, an amine, an amide, cyanuric acid, a nitride, and urea, wherein the nitrogenous material particles have an exterior surface; and a thermal stability agent bound to and substantially surrounding the exterior surface of the nitrogenous material particles, wherein the thermal stability agent comprises one or more of a metal hydroxide, a metal carbonate, a metal bicarbonate, a metal hydrate, and a metal nitride, and wherein a molar ratio of the thermal stability agent:nitrogenous material ranges from about 1:1 to about 10:1; and

combusting the additive-containing feed material to produce a contaminated gas stream comprising a contaminant produced by combustion of the feed material and the additive composition or a derivative thereof, wherein the thermal stability agent reduces thermal decomposition of the nitrogenous material during combusting of the additive-containing feed material and wherein the additive composition or the derivative thereof removes or causes removal of the contaminant.

13. The method of claim 12 , wherein the thermal stability agent is in contact with some, but not all, of the exterior surface of the nitrogenous material particles, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, and wherein the thermal stability agent comprises ash.

14. The method of claim 12 , wherein the thermal stability agent is in contact with the exterior surface of the nitrogenous material particles and thermally protects the nitrogenous material from one or more of combustion and thermal breakdown, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, and wherein the thermal stability agent further comprises ash.

15. The method of claim 12 , wherein the thermal stability agent in contact with the exterior surface of the nitrogenous material particles is a heat sink, wherein the thermal stability agent forms, when the composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, and wherein the thermal stability agent further comprises ash.

16. The method of claim 12 , wherein the nitrogenous material particles further comprise a substrate and wherein the substrate is a porous matrix comprising one or more of a zeolite, a char, graphite, and ash.

17. The method of claim 16 , wherein the additive-containing feed material is fed to a combustor, wherein the coal particles and the additive composition are mixed together, and wherein the substrate is one or more of flyash and bottom ash.

18. The method of claim 12 , wherein the additive-containing feed material is fed to a combustor, wherein the coal particles and the additive composition are mixed together, wherein the additive composition further comprises a binder, and wherein the binder binds the thermal stability agent to the nitrogenous material.

19. The method of claim 18 , wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent.

20. The method of claim 19 , wherein the alkaline binding agent comprises one or more of an alkali hydroxide, an alkali carbonate, an alkali bicarbonate, lime, limestone, caustic soda, trona, an alkaline earth metal hydroxide, an alkaline earth metal carbonate, and an alkaline earth bicarbonate.

21. The method of claim 16 , wherein the substrate comprises from about 10 to about 90 wt% of the additive composition.

22. The method of claim 19 , wherein the binder comprises from about 0 to about 5 wt% of the additive composition.

23. The method of claim 12 , wherein the additive composition is in the form of one or more of a slurry and a sludge.

24. The method of claim 12 , wherein the additive composition comprises solid particles, wherein the solid particles have a moisture level, and wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material.

25. The method of claim 12 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material and wherein the thermal stability agent comprises one or more of an alkaline earth metal hydroxide, an alkaline earth metal carbonate, an alkaline earth and metal bicarbonate.

26. The method of claim 12 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material and wherein the coal particles are one or more of a high alkali coal, a high iron coal, and a high sulfur coal.

27. The method of claim 12 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material and wherein the thermal stability agent comprises one or more of an alkaline earth metal hydroxide, an alkaline earth metal carbonate, and an alkaline earth metal bicarbonate.

28. The method of claim 12 , wherein the thermal stability agent, forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material and wherein the additive composition further comprises one or more of a stabilizing agent, a dispersant, and a binder.

29. The method of claim 12 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material and wherein the additive composition further comprises one or more of flyash and bottom ash.

30. The method of claim 12 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material and wherein the thermal stability agent comprises one or more of magnesium hydroxide, magnesium carbonate, and magnesium bicarbonate.

31. The method of claim 12 , wherein the thermal stability agent is bound by a binder to and substantially surrounds the nitrogenous material.

32. A method, comprising:

contacting a feed material comprising particulate coal with an additive composition to form an additive-containing feed material, the additive composition comprising: a nitrogenous material in the form of particles having an exterior particle surface and comprising one or more of ammonia, an amine, an amide, cyanuric acid, a nitride, and urea; and a thermal stability agent comprising an alkaline earth metal hydroxide, an alkaline earth metal carbonate, and/or an alkaline earth metal bicarbonate, wherein the thermal stability agent is bound to and in contact with at least part of the exterior particle surface, wherein a molar ratio of the thermal stability agent:nitrogenous material ranges from about 1:1 to about 10:1, and wherein the additive composition, in the absence of the thermal stability agent, is unstable when the feed material is combusted; and

combusting the additive-containing feed material to produce a contaminated gas stream comprising a contaminant produced by combustion of the feed material and the additive composition or a derivative thereof, wherein the additive composition or the derivative thereof removes or causes removal of the contaminant.

33. The method of claim 32 , wherein the thermal stability agent thermally protects the nitrogenous material from one or more of combustion and thermal breakdown, wherein the thermal stability agent further comprises ash, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, wherein an iron content of the particulate coal is less than about 10 wt. % (dry basis of the ash) as Fe2O3, and wherein an alkali content of the particulate coal is at least about 20 wt. % (dry basis of the ash) alkali.

34. The method of claim 32 , wherein the thermal stability agent is a heat sink, wherein the thermal stability agent further comprises ash, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, wherein an iron content of the particulate coal is less than about 10 wt. % (dry basis of the ash) as Fe2O3, and wherein an alkali content of the particulate coal is at least about 20 wt. % (dry basis of the ash) alkali.

35. The method of claim 32 , wherein the nitrogenous material particulates further comprise a substrate, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, and wherein the substrate is a porous matrix comprising one or more of a zeolite, a char, graphite, and ash.

36. The method of claim 35 , wherein the composition is fed to a combustor, wherein the coal particles and additive composition are mixed together, and wherein the substrate is one or more of flyash and bottom ash.

37. The method of claim 35 , wherein the substrate comprises from about 10 to about 90 wt% of the additive composition.

38. The method of claim 32 , wherein the additive-containing feed material is fed to a combustor, wherein the particulate coal and the additive composition are mixed together, wherein the additive composition further comprises a binder, and wherein the binder adheres the thermal stability agent to the nitrogenous material.

39. The method of claim 38 , wherein the binder is one or more of a wax, a wax derivative, a gum, a gum derivative, and an alkaline binding agent.

40. The method of claim 39 , wherein the alkaline binding agent comprises one or more of an alkali hydroxide, an alkali carbonate, an alkali bicarbonate, lime, limestone, caustic soda, trona, an alkaline earth metal hydroxide, an alkaline earth metal carbonate, and an alkaline earth bicarbonate.

41. The method of claim 38 , wherein the binder comprises from about 0 to about 5 wt% of the additive composition.

42. The method of claim 32 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, and wherein the additive composition is in the form of one or more of a slurry and a sludge.

43. The method of claim 32 , wherein the additive composition comprises solid particles, wherein the solid particles have a moisture level, wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, and wherein the thermal stability agent substantially surrounds the exterior particle surface.

44. The method of claim 32 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, and wherein the thermal stability agent comprises one or more of magnesium hydroxide, magnesium carbonate, and magnesium bicarbonate.

45. The method of claim 32 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, and wherein the particulate coal is one or more of a high alkali coal, a high iron coal, and a high sulfur coal.

46. The method of claim 32 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, and wherein the additive composition further comprises one or more of a stabilizing agent, a dispersant, and a binder.

47. The method of claim 32 , wherein the thermal stability agent forms, when the additive composition is combusted, one or more of a thermally protective barrier and heat sink around the nitrogenous material to reduce thermal degradation of the nitrogenous material, wherein the thermal stability agent substantially surrounds the exterior particle surface, and wherein the additive composition further comprises one or more of flyash and bottom ash.

48. The method of claim 32 , wherein the thermal stability agent is bound by a binder to and substantially surrounds the nitrogenous material.

Assignments (8)
SECURITY INTEREST Recorded Jan 3, 2025
From: ARQ SOLUTIONS, LLC; ARQ SOLUTIONS (ES), INC.
To: MIDCAP FUNDING IV TRUST
Reel/Frame 069817/0645 →
RELEASE OF SECURITY INTEREST Recorded Dec 27, 2024
From: CF GLOBAL CREDIT, LP, AS ADMINISTRATIVE AGENT
To: ARQ SOLUTIONS, LLC (F/K/A ADA CARBON SOLUTIONS, LLC); ARQ SOLUTIONS (ES), INC. (F/K/A ADA-ES, INC.)
Reel/Frame 069791/0980 →
CHANGE OF NAME Recorded Feb 21, 2024
From: ADA-ES, INC.
To: ARQ SOLUTIONS (ES), INC.
Reel/Frame 066643/0579 →
PATENT SECURITY AGREEMENT Recorded Feb 1, 2023
From: ADA CARBON SOLUTIONS, LLC; ADA-ES, INC.
To: CF GLOBAL CREDIT, LP
Reel/Frame 062622/0051 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jun 4, 2021
From: THE BANK OF NEW YORK MELLON, AS ADMINISTRATIVE AGENT
To: ADA-ES, INC.
Reel/Frame 056483/0657 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 4, 2019
From: MORRIS, WILLIAM J.; BALDREY, KENNETH E.; SENIOR, CONSTANCE; BISQUE, RAMON
To: ADA-ES, INC.
Reel/Frame 049365/0855 →
NOTICE OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Dec 7, 2018
From: ADA-ES, INC.
To: THE BANK OF NEW YORK MELLON, AS ADMINISTRATIVE AGENT
Reel/Frame 047742/0652 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 30, 2018
From: MORRIS, WILLIAM J.; BALDREY, KENNETH E.; SENIOR, CONSTANCE; BISQUE, RAMON
To: ADA ES, INC.
Reel/Frame 045397/0065 →
Continuity (6)
Division 13964441 · Aug 12, 2013
Provisional Application 61792827 · Mar 15, 2013
Provisional Application 61724634 · Nov 9, 2012
Provisional Application 61704290 · Sep 21, 2012
Provisional Application 61682040 · Aug 10, 2012
Related Publication 20180223206A1 · Aug 9, 2018
Cited By (1)
US 12,636,611