Cleaning stack gas

• US 9,067,837 B2
• Filed: 03/14/2014
• Issued: 06/30/2015
• Est. Priority Date: 03/15/2013
• Status: Active Grant

• Current Assignee: 3 D Clean Coal Emissions Stack, LLC
• Original Assignee: Three D Stack, LLC
• Inventors: Davidson, James Gary
• Primary Examiner(s): VANOY, TIMOTHY C
• Application Number:
  US14/214,247
• Publication Number:
  US 20140260472A1
• Time in Patent Office: 473 Days
• Field of Search: 423/210, 423/239.2, 423/230, 423/244.11, 422/168, 422/169, 422/170, 422/177, 422/180, 71/31, 71/54
• US Class Current: 1/1
• CPC Class Codes: B01D 2255/50 Zeolites
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/404 Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/50 Carbon oxides
• CPC Class Codes: B01D 2257/502 Carbon monoxide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/8609 Sulfur oxides
• CPC Class Codes: B01D 53/8631 Processes characterised by a specific device
• CPC Class Codes: B01D 53/8637 Simultaneously removing sulfur oxides and nitrogen oxides
• CPC Class Codes: B01D 53/864 Removing carbon monoxide or hydrocarbons
• CPC Class Codes: B01D 53/8643 Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
• CPC Class Codes: B01D 53/8665 Removing heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01D 53/8671 Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
• CPC Class Codes: B01D 53/869 Multiple step processes
• CPC Class Codes: B01D 53/8693 After-treatment of removed components
• CPC Class Codes: B01D 53/885 Devices in general for catalytic purification of waste gases
• CPC Class Codes: C05C 5/00 Fertilisers containing other nitrates
• CPC Class Codes: C05D 9/00 Other inorganic fertilisers
• CPC Class Codes: F23J 15/02 : of purifiers, e.g. for removing noxious material traps for solid residues F23J3/04
• CPC Class Codes: F23J 2219/10 : Catalytic reduction devices
• CPC Class Codes: Y02C 20/10 : of nitrous oxide (N2O)
• CPC Class Codes: Y02E 20/32 : Direct CO2 mitigation
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A method and apparatus for cleaning and recycling stack gas from coal-fired power plants, from natural or propane burning heating plants, or from cement kilns by using renewable catalysts of zeolite to separate pollutants into recyclable and reusable materials. The method reduces from the stack gas carbon monoxide (CO), carbon dioxide (CO₂), nitrogen oxide (NOx), sulfur oxide (SOx) as well as halogens such as chloride and fluorides and trace metals particularly, mercury, lead, and zinc. Bauxite compounds can also be separately collected if desired. The method and apparatus also result in production of fertilizer products by purging with gaseous or liquid nitrogen the zeolite beds through which the stack gas flows. The oxygen split in the beds may be recycled to the burners in the plant.

Claims

1. A method of cleaning stack gases comprising the steps of:

(a) providing in a stack adapted to pass stack gases through a first catalytic flow-through bed of calcium zeolite comprising natural zeolite particles of a majority between 44 μ

m and 64 μ

m in size at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce carbon oxides in the stack gases;

(b) providing in the stack adapted to pass stack gases positioned adjacent the first catalytic flow-through bed, a second catalytic flow-through bed of a blend between 25 and 75% of sodium zeolite and calcium zeolite comprising natural sodium and calcium zeolite particles of a majority between 65 μ

m and 125 μ

m in size at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce nitrogen oxides in the stack gases;

(c) providing in the stack adapted to pass stack gases positioned adjacent the second catalytic flow-through bed, a third catalytic flow-through bed of calcium zeolite comprising natural zeolite particles of a majority between 78 μ

m and 204 μ

m at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce sulfur oxides in the stack gases; and

(d) passing stack gases selected from the group consisting of volatiles from combustion of coal or from combustion of natural gas or from a cement kiln sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting materials in the catalytic beds and providing gas exiting the third catalytic bed with at least 70% reduction in sulfur oxides, nitrogen oxides and carbon oxide.

2. The method as set forth in claim 1 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed also remove from the stack gas at least 50% of mercury.

3. The method as set forth in claim 1 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed are each positioned between screens of between 150 and 250 mesh.

4. The method as set forth in claim 1 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on a moving disk.

5. The method as set forth in claim 1 where at least two series of sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided in parallel so stack gas can be cleaned by the method through one series of beds while other series of the beds can be cleaned.

6. The method as set forth in claim 1 comprising in addition a fourth catalytic flow-through bed of calcium zeolite comprising natural zeolite particles between 44 μ

m and 64 μ

m in size positioned in the stack before the first catalytic bed with an electrical charge on said fourth catalytic flow-through bed to collect bauxite compounds from the stack gases before passing through the first catalytic bed.

7. The method as set forth in claim 1 where the stack gases exiting from third catalytic bed through the stack have at least 95% reduction in sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered to the first catalytic flow-through bed.

8. The method as set forth in claim 6 where the stack gases exiting a stack from the third catalytic bed through the stack is at least 95% reduction in bauxite compound, sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered through the stack to the a fourth catalytic flow-through bed.

9. A method of cleaning stack gases comprising the steps of:

(a) providing in a stack adapted to pass stack gases through a first catalytic flow-through bed of calcium zeolite comprising natural zeolite particles of a majority between 44 μ

m and 64 μ

m in size at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce carbon oxides in the stack gases;

(b) providing in the stack adapted to pass stack gases positioned adjacent the first catalytic flow-through bed, a second catalytic flow-through bed of a blend between 25 and 75% of sodium zeolite and calcium zeolite comprising natural sodium and calcium zeolite particles of a majority between 65 μ

m and 125 μ

m in size at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce nitrogen oxides in the stack gases;

(c) providing in the stack adapted to pass stack gases positioned adjacent the second catalytic flow-through bed, a third catalytic flow-through bed of calcium zeolite comprising natural zeolite particles of a majority between 78 μ

m and 204 μ

m at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce sulfur oxides in the stack gases;

(d) passing stack gases selected from the group consisting of volatiles from combustion of coal or from combustion of natural gas or from a cement kiln sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting materials in the catalytic beds and providing gas exiting the third catalytic bed with at least 70% reduction in sulfur oxides, nitrogen oxides and carbon oxide; and

(e) purging solids and liquids from the first catalytic bed, the second catalytic bed, and the third catalytic bed by intermittently passing nitrogen through the beds to remove solids and liquids collected from the stack gases by the beds.

10. The method as set forth in claim 9 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed also remove from the stack gas at least 50% of mercury.

11. The method as set forth in claim 9 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed are each positioned between screens of between 150 and 350 mesh.

12. The method as set forth in claim 9 where first catalytic bed, second catalytic bed, and third catalytic bed are purged with liquid nitrogen to remove the solids and liquids from collected from stack gas by the beds.

13. The method as set forth in claim 9 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on a moving disk.

14. The method as set forth in claim 9 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on a moving disk such that the stack gases in step (d) can be continuously passed through the first catalytic bed, the second catalytic bed, and the third catalytic bed to provide collection of solids and/or liquids from the stack gases while other portions of the same bed or like beds are purged with nitrogen to remove the solids and liquids from the stack gas by the beds.

15. The method as set forth in claim 9 where at least two series of sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed are provided in parallel so stack gas can be cleaned by the method through one series of beds while other series of the beds can be cleaned.

16. The method as set forth in claim 11 where first catalytic bed, second catalytic bed, and third catalytic bed are purged with liquid nitrogen to remove the solids and liquids from collected from stack gas by the beds.

17. The method as set forth in claim 9 comprising in addition a fourth catalytic flow-through bed of calcium zeolite comprising natural zeolite particles between 44 μ

m and 64 μ

m in size positioned in the stack before the first catalytic bed with an electrical charge beneath said fourth catalytic flow-through bed to collect bauxite compounds from the stack gases before passing through the first catalytic bed.

18. The method as set forth in claim 9 where the fourth catalytic flow-through bed is on a rotating disk so the stack gases are continuously move through the fourth bed while other portions of the same beds or a like bed are purged with nitrogen to remove solids and liquids collected from the stack gas by the fourth bed.

19. The method as set forth in claim 18 where the nitrogen is liquid nitrogen.

20. The method as set forth in claim 9 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed also remove from the stack gas at least 90% of mercury.

21. The method as set forth in claim 9 where the stack gases exiting from third catalytic bed through the stack have at least 95% reduction in sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered to the a first catalytic flow-through bed.

22. The method as set forth in claim 9 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed also remove from the stack gas at least 70% of mercury.

23. The method as set forth in claim 17 where the stack gases exiting from third catalytic bed through the stack have at least 95% reduction in bauxite compounds, sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered through the stack to the fourth catalytic flow-through bed.

24. A method of cleaning stack gases comprising the steps of:

(a) providing in a stack adapted to pass stack gases of less than 7% oxygen through a first catalytic flow-through bed of calcium zeolite comprising natural zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce carbon oxides from the stack gases and increase oxygen levels in the stack gas;

(b) providing in the stack adapted to pass stack gases positioned adjacent the first catalytic flow-through bed, a second catalytic flow-through bed of a blend between 25 and 75% of sodium zeolite and calcium zeolite comprising natural sodium and calcium zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce nitrogen oxides from the stack gases and increase oxygen levels in the stack gas;

(c) providing in the stack adapted to pass stack gases positioned adjacent the second catalytic flow-through bed, a third catalytic flow-through bed of calcium zeolite comprising natural zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce sulfur oxides in the stack gases and increase oxygen levels in the stack gas; and

(d) passing stack gases of less than 7% oxygen selected from the group consisting of volatiles from combustion of coal or from combustion of natural gas or from a cement kiln sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting materials in the catalytic beds and providing gas exiting the third catalytic bed with at least 70% reduction in sulfur oxides, nitrogen oxides and carbon oxide and greater than 15% oxygen.

25. The method as set forth in claim 24 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed are each positioned between screens of between 150 and 250 mesh.

26. The method as set forth in claim 24 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on a moving disk.

27. The method as set forth in claim 24 where at least two series of sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided in parallel so stack gas can be cleaned by the method through one series of beds while other series of the beds can be cleaned.

28. The method as set forth in claim 24 comprising in addition a fourth catalytic flow-through bed of calcium zeolite comprising natural zeolite particles in the stack before the first catalytic bed with an electrical charge on said fourth catalytic flow-through bed to collect bauxite compounds from the stack gases before passing through the first catalytic bed and increase oxygen levels in the stack gas.

29. The method as set forth in claim 24 where the stack gases exiting from third catalytic bed through the stack have at least 95% reduction in sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered to the first catalytic flow-through bed.

30. The method as set forth in claim 28 where the stack gases exiting a stack from the third catalytic bed through the stack is at least 95% reduction in bauxite compounds, sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered through the stack to the a fourth catalytic flow-through bed.

31. A method of cleaning stack gases comprising the steps of:

(a) providing in a stack adapted to pass stack gases through a first catalytic flow-through bed of calcium zeolite comprising natural zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce carbon oxides from the stack gases and increase oxygen levels in the stack gas;

(b) providing in the stack adapted to pass stack gases positioned adjacent the first catalytic flow-through bed, a second catalytic flow-through bed of a blend between 25 and 75% of sodium zeolite and calcium zeolite comprising natural sodium and calcium zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce nitrogen oxides from the stack gases and increase oxygen levels in the stack gas;

(c) providing in the stack adapted to pass stack gases positioned adjacent the second catalytic flow-through bed, a third catalytic flow-through bed of calcium zeolite comprising natural zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce sulfur oxides in the stack gases and increase oxygen levels in the stack gas;

(d) passing stack gases of less than 7% oxygen selected from the group consisting of volatiles from combustion of coal or from combustion of natural gas or from a cement kiln sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting solids in the catalytic beds and providing gas exiting the third catalytic bed with at least 70% reduction in sulfur oxides, nitrogen oxides and carbon oxide and at least 15% oxygen; and

(e) purging solids and liquids from the first catalytic bed, the second catalytic bed, and the third catalytic bed by intermittently passing nitrogen through the beds to remove solids and liquids collected from the stack gases by the beds.

32. The method as set forth in claim 31 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed are each positioned between screens of between 150 and 350 mesh.

33. The method as set forth in claim 31 where first catalytic bed, second catalytic bed, and third catalytic bed are purged with liquid nitrogen to remove the solids and liquids from collected from stack gas by the beds.

34. The method as set forth in claim 31 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on a moving disk.

35. The method as set forth in claim 31 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on a rotating disk such that the stack gases in step (d) can be continuously passed through the first catalytic bed, the second catalytic bed, and the third catalytic bed to provide collection of solids and/or liquids from the stack gases while other portions of the same bed or like beds are purged with nitrogen to remove solids and liquids from the stack gas by the beds.

36. The method as set forth in claim 31 where at least two series of sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed are provided in parallel so stack gas can be cleaned by the method through one series of beds while other series of the beds can be cleaned.

37. The method as set forth in claim 31 where first catalytic bed, second catalytic bed, and third catalytic bed are purged with liquid nitrogen to remove the solids and liquids from collected from stack gas by the beds.

38. The method as set forth in claim 31 comprising in addition a fourth catalytic flow-through bed of calcium zeolite comprising natural zeolite particles positioned in the stack before the first catalytic bed with an electrical charge on said fourth catalytic flow-through bed to collect bauxite compounds from the stack gases before passing through the first catalytic bed.

39. The method as set forth in claim 31 where the fourth catalytic flow-through bed is on a rotating disk so the stack gases are continuously move through the fourth bed while other portions of the same beds or a like bed are purged with nitrogen to remove solids and liquids collected from the stack gas by the fourth bed.

40. The method as set forth in claim 39 where the nitrogen is liquid nitrogen.

41. The method as set forth in claim 31 where the stack gases exiting from third catalytic bed through the stack have at least 95% reduction in sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered to the a first catalytic flow-through bed.

42. The method as set forth in claim 38 where the stack gases exiting from third catalytic bed through the stack have at least 95% reduction in bauxite compounds, sulfur oxides, nitrogen oxides, and carbon oxide compared to the stack gases delivered through the stack to the fourth catalytic flow-through bed.

43. A method of cleaning sulfur oxides stack gases comprising the steps of:

(a) positioning a catalytic flow-through bed of natural calcium zeolite with a porosity of a total surface area of not greater than 1200 m²/g adapted to reduce sulfur oxides in a stack gas; and

(b) passing stack gases selected from the group consisting of volatiles from combustion of coal or combustion of natural gas sequential through the catalytic bed with at least 90% reduction in sulfur oxides.

44. The method as set forth in claim 43 where the catalytic bed is positioned between screens each of between 150 and 250 mesh.

45. The method as set forth in claim 43 where the catalytic bed is provided on moving disks.

46. The method as set forth in claim 43 where the catalytic bed is provided on a moving disk such that the stack gases in step (a) can be continually passed through the catalytic bed to provide collection of solids and/or liquids while other portions or beds are purged with nitrogen to collect the solids and/or liquids from the beds.

47. The method as set forth in claim 46 where the catalytic bed is purged with liquid nitrogen to collect the solids and/or liquids from the beds.

48. The method as set forth in claim 43 where in addition the stack gas is pasted through another catalytic flow-through bed before passing through the first catalytic bed with a porosity of a total surface area not greater than 1200 m²/g adapted to collect bauxite compounds before passage through the first catalytic bed.

49. The method as set forth in claim 48 where the other catalytic flow-through bed is on a moving disk so the stack gases are continuously moved through the other bed while another portion of the disk is being purged with nitrogen.

50. The method as set forth in claim 43 where the catalytic bed have a porosity of a total surface area not greater than 800 m²/g.

51. The method as set forth in claim 48 where the other catalytic flow-through bed has a porosity of a total surface area not greater than 800 m²/g.

52. The method as set forth in claim 43 where the gases exiting a stack from catalytic bed has at least 95% reduction in sulfur oxide from the stack gases delivered to the other catalytic flow-through bed.

53. Apparatus for cleaning stack gases comprising:

(a) a first catalytic flow-through bed of natural calcium zeolite with a porosity of a total surface area of not greater than 1200 m²/g adapted to reduce sulfur oxides positioned in an exhaust stack;

(b) a second catalytic flow-through bed of a blend of natural sodium zeolite and natural calcium zeolite of a porosity with a total surface area of not greater than 1200 m²/g adapted to reduce nitrogen oxides positioned in the exhaust stack above the first bed;

(c) a third catalytic flow-through bed of natural calcium zeolite with a porosity of a total surface area not greater than 1200 m²/g adapted to reduce carbon oxides and mercury oxides positioned in the exhaust stack above the second bed; and

(d) the exhaust stack adapted to provide a gas flow selected from the group consisting of volatiles from combustion of coal or combustion of natural gas sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting solids in the catalytic beds and providing gas exiting the third catalytic bed with at least 90% reduction in sulfur oxides, nitrogen oxides, and carbon oxide.

54. The apparatus as set forth in claim 53 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed are each positioned between screens of between 150 and 250 mesh.

55. The apparatus as set forth in claim 53 where the blend of natural sodium zeolite and natural calcium zeolite in the second catalytic bed is between 25 and 75%.

56. The apparatus as set forth in claim 53 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on moving disks.

57. The apparatus as set forth in claim 53 where the first catalytic bed, the second catalytic bed, and the third catalytic bed are each provided on moving disks such that the stack gases in element (d) can be continually passed through the first catalytic bed, the second catalytic bed, and the third catalytic bed to provide collection of solids and/or liquids while other portions or beds of like compositions are purged with nitrogen to collect the solids and/or liquids from the beds.

58. The apparatus as set forth in claim 53 where first catalytic bed, second catalytic bed, and third catalytic bed are adapted to be purged with liquid nitrogen to collect the solids and/or liquids from the beds.

59. The apparatus as set forth in claim 53 where a fourth catalytic flow-through bed is provided in the exhaust below the first catalytic bed with a porosity of a total surface area not greater than 1200 m²/g adapted to collect bauxite compounds before passage through the first catalytic bed.

60. The apparatus as set forth in claim 59 where the fourth catalytic flow-through bed is a moving disk so the stack gases are continuously move there through while another portion of the disk is being purged with nitrogen.

61. The apparatus as set forth in claim 60 where the nitrogen is liquid nitrogen.

62. The apparatus as set forth in claim 53 where the beds providing first catalytic bed, second catalytic bed, and third catalytic bed each have a porosity of a total surface area not greater than 800 m²/g.

63. The apparatus as set forth in claim 59 where the fourth catalytic flow-through bed has a porosity of a total surface area not greater than 800 m²/g.

64. The apparatus as set forth in claim 53 where the fourth catalytic flow-through bed has a porosity of a total surface area not greater than 800 m²/g.

65. The apparatus as set forth in claim 53 where the exhaust is adapted to exit gases from third catalytic bed having at least 95% reduction in sulfur oxides, nitrogen oxides, mercury oxide and carbon oxide compared to the stack gases delivered to the a first catalytic flow-through bed.

66. The apparatus as set forth in claim 59 where the stack is adapted to exit gases from third catalytic bed with at least 95% reduction in bauxite compounds, sulfur oxides, nitrogen oxides, mercury oxides, and carbon oxide from the stack gases delivered to the a fourth catalytic flow-through bed.

67. An apparatus of cleaning sulfur oxides from stack gases comprising:

(a) a stack adapted to provide for exit of stack gases;

(b) a catalytic flow-through bed of natural calcium zeolite with a porosity with a total surface area of not greater than 1200 m²/g adapted to reduce sulfur oxides positioned in the stack; and

(c) the stack adapted to provide for flow-through gases selected from the group consisting of volatiles from combustion of coal or combustion of natural gas the catalytic bed to provide for at least 90% reduction in sulfur oxides exiting from the stack compared to the sulfur oxide content in the stack gases delivered to the catalytic flow-through bed.

68. The apparatus as set forth in claim 67 where the catalytic bed is positioned between screens each of between 150 and 250 mesh.

69. The apparatus as set forth in claim 67 where the catalytic bed is provided on rotating disk.

70. The apparatus as set forth in claim 67 where the catalytic bed is provided on a rotating disk such that the stack gases in step (c) can be continually passed through the catalytic bed to provide collection of solids and/or liquids while other portions or beds is purged with nitrogen to collect the solids and/or liquids from the beds.

71. The apparatus as set forth in claim 70 where the catalytic bed is purged with liquid nitrogen to collect the solids and/or liquids from the beds.

72. The apparatus as set forth in claim 67 where in addition positioned in the stack another catalytic flow-through bed below the first catalytic bed with a porosity of a total surface area not greater than 1200 m²/g adapted to collect bauxite compounds before passage through the first catalytic bed.

73. The apparatus as set forth in claim 72 where the other catalytic flow-through bed is on a moving disk so the stack gases continuously move through said other bed while another portion of the disk is being purged with nitrogen.

74. The apparatus in claim 67 where the catalytic bed have a porosity of a total surface area not greater than 800 m²/g.

75. The apparatus as set forth in claim 72 where the other catalytic flow-through bed has a porosity of a total surface area not greater than 800 m²/g.

76. The apparatus method as set forth in claim 67 where the gases exiting the stack from catalytic bed has at least 95% reduction in sulfur oxide compared to the stack gases delivered to the catalytic flow-through bed.

77. A fertilizer product produced by the steps of:

(a) providing in a stack adapted to pass stack gases through a first catalytic flow-through bed of calcium zeolite comprising natural zeolite particles of a majority between 44 μ

m and 64 μ

m in size at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce carbon oxides in the stack gases;

(b) providing in the stack adapted to pass stack gases positioned adjacent the first catalytic flow-through bed, a second catalytic flow-through bed of a blend between 25 and 75% of sodium zeolite and calcium zeolite comprising natural sodium and calcium zeolite particles of a majority between 65 μ

m and 125 μ

m in size at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce nitrogen oxides in the stack gases;

(c) providing in the stack adapted to pass stack gases positioned adjacent the second catalytic flow-through bed, a third catalytic flow-through bed of calcium zeolite comprising natural zeolite particles of a majority between 78 μ

m and 204 μ

m at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce sulfur oxides in the stack gases;

(d) passing stack gases selected from the group consisting of volatiles from combustion of coal or from combustion of natural gas or from a cement kiln sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting materials in the catalytic beds and providing gas exiting the third catalytic bed with at least 70% reduction in sulfur oxides, nitrogen oxides and carbon oxide; and

(e) purging solids and liquids from the first catalytic bed, the second catalytic bed, and the third catalytic bed by intermittently passing nitrogen through the beds to remove solids and liquids collected from the stack gases by the beds.

78. A fertilizer product produced by the steps of:

(a) providing in a stack adapted to pass stack gases of less than 7% oxygen through a first catalytic flow-through bed of calcium zeolite comprising natural zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce carbon oxides from the stack gases and increase oxygen levels in the stack gas;

(b) providing in the stack adapted to pass stack gases positioned adjacent the first catalytic flow-through bed, a second catalytic flow-through bed of a blend between 25 and 75% of sodium zeolite and calcium zeolite comprising natural sodium and calcium zeolite particles of at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce nitrogen oxides from the stack gases and increase oxygen levels in the stack gas;

(c) providing in the stack adapted to pass stack gases positioned adjacent the second catalytic flow-through bed, a third catalytic flow-through bed of calcium zeolite comprising natural zeolite particles at a temperature above the dew point between 125 and 500°

F. and a pressure between 3 and 200 psi adapted to reduce sulfur oxides in the stack gases and increase oxygen levels in the stack gas; and

(d) passing stack gases of less than 7% oxygen selected from the group consisting of volatiles from combustion of coal or from combustion of natural gas or from a cement kiln sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting materials in the catalytic beds and providing gas exiting the third catalytic bed with at least 70% reduction in sulfur oxides, nitrogen oxides and carbon oxide and greater than 15% oxygen.

79. A fertilizer product produced by the steps of:

(a) providing a first catalytic flow-through bed of natural calcium zeolite with a porosity of a total surface area of not greater than 1200 m²/g adapted to reduce sulfur oxides in a stack gas;

(b) providing a second catalytic flow-through bed of a blend of natural sodium zeolite and natural calcium zeolite with a porosity of a total surface area not greater than 1200 m²/g adapted to reduce nitrogen oxides in a stack gas and the blend of sodium zeolite and calcium zeolite is between 25 and 75%;

(c) providing a third catalytic flow-through bed of natural calcium zeolite with a porosity of a total surface area not greater than 1200 m²/g adapted to reduce carbon oxides and mercury oxides in a stack gas;

(d) passing stack gases selected from the group consisting of volatiles from combustion of coal or combustion of natural gas sequential through the first catalytic bed, the second catalytic bed, and the third catalytic bed each collecting solids and liquids in the catalytic beds and providing gas exiting the third catalytic bed with at least 90% reduction in sulfur oxides, nitrogen oxides, and carbon oxide; and

(e) purging the solids and liquids collected from the first catalytic bed, the second catalytic bed, and the third catalytic bed and collecting said solids and liquids purged from the first catalytic bed, the second catalytic bed, and the third catalytic bed to provide a fertilizer product.

80. The fertilizer product as set forth in claim 79 where the beds providing the first catalytic bed, the second catalytic bed, and the third catalytic bed are each positioned between screens of between 150 and 250 mesh.

81. The fertilizer product as set forth in claim 79 where in addition the stack gas is pasted through a fourth catalytic flow-through bed before passage through the first catalytic bed with a porosity of a total surface area not greater than 1200 m²/g adapted to collect bauxite compounds before passage through the first catalytic bed.

82. The fertilizer product set forth in claim 79 where the fourth catalytic flow-through bed is being purged with nitrogen.

83. The fertilizer product as set forth in claim 82 where the nitrogen is liquid nitrogen.

84. The fertilizer product as set forth in claim 79 where the gases exiting a stack from third catalytic bed have at least 95% reduction in sulfur oxides, nitrogen oxides, mercury oxide and carbon oxide from the stack gases delivered to the a first catalytic flow-through bed.

85. The fertilizer product as set forth in claim 81 where the gases exiting the stack from third catalytic bed is at least 95% reduction in bauxite compounds, sulfur oxides, nitrogen oxides, mercury oxides, and carbon oxide from the stack gases delivered to the a fourth catalytic flow-through bed.