System and method for increasing the service life and/or catalytic activity of an SCR catalyst and control of multiple emissions
View Patent ↗The present invention relates generally to the field of emission control equipment for boilers, heaters, kilns, or other flue gas-, or combustion gas-, generating devices (e.g., those located at power plants, processing plants, etc.) and, in particular to a new and useful method and apparatus for reducing or preventing the poisoning and/or contamination of an SCR catalyst. In another embodiment, the method and apparatus of the present invention is designed to protect the SCR catalyst. In still another embodiment, the present invention relates to a method and apparatus for increasing the service life and/or catalytic activity of an SCR catalyst while simultaneously controlling various emissions.
1. A method for increasing the active life of an SCR catalyst, the method comprising the steps of:
(a) providing at least one coal-based fuel to a furnace, or boiler;
(b) subjecting the at least one coal-based fuel to a staged combustion process, wherein the staged combustion process produces at least one gaseous phosphorus compound and/or at least one gaseous phosphorus-containing compound;
(c) providing at least one iron-bearing compound to a combustion zone or flue gas stream of the furnace, or boiler, prior to entry of the flue gas into an SCR, wherein the SCR is located upstream of at least one air heater;
(d) permitting the at least one iron-bearing compound to react with the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound present in the combustion zone or flue gas prior to the entry of the flue gas into the SCR to form an iron phosphorus-containing compound;
(e) providing at least one halide-bearing compound to a combustion zone or flue gas stream of a furnace, or boiler, prior to entry of the flue gas into an SCR, with the proviso that halide-bearing compound is not an iron halide; and
(f) permitting the at least one halide-bearing compound to react with and/or oxidize any mercury present in the combustion zone or flue gas,
wherein the method achieves an increase in either one, or both, of a catalytic activity and/or a catalytic lifespan of at least about 10 percent at an operational time of at least about 2,000 hours.
2. The method of claim 1 , wherein the iron-bearing compound is selected from metallic iron, one or more iron oxides, iron carbonate, or mixtures of two or more thereof.
3. The method of claim 1 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, iron (II) oxide, or mixtures of two or more thereof.
4. The method of claim 1 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, or a mixture thereof.
5. The method of claim 1 , wherein the at least one iron-bearing compound is provided to the combustion zone via addition to pulverized coal.
6. The method of claim 1 , wherein the at least one iron-bearing compound is provided to the combustion zone via a dedicated supply line.
7. The method of claim 1 , wherein the halide-bearing compound is selected from potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide, calcium bromide, calcium chloride, calcium fluoride, calcium iodide, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum iodide, transition metal halides with the proviso that the transition metal is not iron, or any mixture of two or more thereof or mixtures of two or more thereof.
8. The method of claim 1 , wherein the iron-bearing compound is selected from iron (II) carbonate and the halide-bearing compound is selected from calcium bromide.
9. The method of claim 1 , wherein the at least one halide-bearing compound is provided to the combustion zone via addition to pulverized coal.
10. The method of claim 1 , wherein the at least one halide-bearing compound is provided to the combustion zone via a dedicated supply line.
11. The method of claim 1 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 2.5:1 to about 10:1.
12. The method of claim 1 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 3.5:1 to about 8:1.
13. The method of claim 1 , wherein the at least one halide-bearing compound is provided at sufficient amount to yield a halide concentration of between about 10 ppm to about 200 ppm.
14. The method of claim 1 , wherein the iron-bearing compound is a water soluble iron-bearing compound.
15. The method of claim 1 , wherein the iron-bearing compound is a water soluble iron-bearing compound that is supplied in the form of an aqueous solution.
16. The method of claim 1 , wherein the iron-bearing compound is a water insoluble iron-bearing compound that is supplied in the form of an aqueous suspension or emulsion.
17. The method of claim 1 , wherein the at least one iron-bearing halide compound is provided to the combustion zone via addition to raw coal which is thereafter pulverized.
18. The method of claim 1 , wherein the staged combustion process utilizes over fire air and the staged combustion process results in an increased amount of the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound and results in the deactivation of the SCR catalyst.
19. A method for increasing the active life of an SCR catalyst, the method comprising the steps of:
(i) providing at least one coal-based fuel to a furnace, or boiler;
(ii) subjecting the at least one coal-based fuel to a staged combustion process, wherein the staged combustion process produces at least one gaseous phosphorus compound and/or at least one gaseous phosphorus-containing compound;
(iii) providing at least one iron-bearing compound to a combustion zone or flue gas stream of the furnace, or boiler, prior to entry of the flue gas into an SCR, wherein the SCR is located upstream of at least one air heater;
(iv) permitting the at least one iron-bearing compound to react with the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound present in the combustion zone or flue gas prior to the entry of the flue gas into the SCR to form an iron phosphorus-containing compound;
(v) providing at least one halide-bearing compound to a combustion zone or flue gas stream of a furnace, or boiler, prior to entry of the flue gas into an SCR, with the proviso that halide-bearing compound is not an iron halide; and
(vi) permitting the at least one halide-bearing compound to react with and/or oxidize any mercury present in the combustion zone or flue gas,
wherein the method achieves an increase in either one, or both, of a catalytic activity and/or a catalytic lifespan of at least about 15 percent at an operational time of at least about 3,000 hours.
20. The method of claim 19 , wherein the iron-bearing compound is selected from metallic iron, one or more iron oxides, iron carbonate, or mixtures of two or more thereof.
21. The method of claim 19 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, iron (II) oxide, or mixtures of two or more thereof.
22. The method of claim 19 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, or a mixture thereof.
23. The method of claim 19 , wherein the at least one iron-bearing compound is provided to the combustion zone via addition to pulverized coal.
24. The method of claim 19 , wherein the at least one iron-bearing compound is provided to the combustion zone via a dedicated supply line.
25. The method of claim 19 , wherein the halide-bearing compound is selected from potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide, calcium bromide, calcium chloride, calcium fluoride, calcium iodide, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum iodide, transition metal halides with the proviso that the transition metal is not iron, or any mixture of two or more thereof or mixtures of two or more thereof.
26. The method of claim 19 , wherein the iron-bearing compound is selected from iron (II) carbonate and the halide-bearing compound is selected from calcium bromide.
27. The method of claim 19 , wherein the at least one halide-bearing compound is provided to the combustion zone via addition to pulverized coal.
28. The method of claim 19 , wherein the at least one halide-bearing compound is provided to the combustion zone via a dedicated supply line.
29. The method of claim 19 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 2.5:1 to about 10:1.
30. The method of claim 19 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 3.5:1 to about 8:1.
31. The method of claim 19 , wherein the at least one halide-bearing compound is provided at sufficient amount to yield a halide concentration of between about 10 ppm to about 200 ppm.
32. The method of claim 19 , wherein the iron-bearing compound is a water soluble iron-bearing compound.
33. The method of claim 19 , wherein the iron-bearing compound is a water soluble iron-bearing compound that is supplied in the form of an aqueous solution.
34. The method of claim 19 , wherein the iron-bearing compound is a water insoluble iron-bearing compound that is supplied in the form of an aqueous suspension or emulsion.
35. The method of claim 19 , wherein the at least one iron-bearing halide compound is provided to the combustion zone via addition to raw coal which is thereafter pulverized.
36. The method of claim 19 , wherein the staged combustion process utilizes over fire air and the staged combustion process results in an increased amount of the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound and results in the deactivation of the SCR catalyst.
37. A method for simultaneously sequestering one or more gaseous phosphorus compounds, or gaseous phosphorus-containing compounds, in the form of one or more less reactive iron-phosphorus-containing compounds, and oxidizing mercury, the method comprising the steps of:
(A) providing at least one coal-based fuel to a furnace, or boiler;
(B) subjecting the at least one coal-based fuel to a staged combustion process, wherein the staged combustion process produces at least one gaseous phosphorus compound and/or at least one gaseous phosphorus-containing compound;
(C) providing at least one iron-bearing compound to a combustion of the furnace, or boiler; and
(D) permitting the at least one iron-bearing compound to react with the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound present in the combustion zone or flue gas to form one or more less reactive iron-phosphorus-containing compounds;
(E) providing at least one halide-bearing compound to a combustion zone or flue gas stream of a furnace, or boiler, prior to entry of the flue gas into an SCR, with the proviso that halide-bearing compound is not an iron halide; and
(F) permitting the at least one halide-bearing compound to react with and/or oxidize any mercury present in the combustion zone or flue gas,
wherein the method achieves an increase in either one, or both, of a catalytic activity and/or a catalytic lifespan of at least about 10 percent at an operational time of at least about 4,000 hours.
38. The method of claim 37 , wherein the iron-bearing compound is selected from metallic iron, one or more iron oxides, iron carbonate, or mixtures of two or more thereof.
39. The method of claim 37 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, iron (II) oxide, or mixtures of two or more thereof.
40. The method of claim 37 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, or a mixture thereof.
41. The method of claim 37 , wherein the at least one iron-bearing compound is provided to the combustion zone via addition to pulverized coal.
42. The method of claim 37 , wherein the at least one iron-bearing compound is provided to the combustion zone via a dedicated supply line.
43. The method of claim 37 , wherein the halide-bearing compound is selected from potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide, calcium bromide, calcium chloride, calcium fluoride, calcium iodide, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum iodide, transition metal halides with the proviso that the transition metal is not iron, or any mixture of two or more thereof or mixtures of two or more thereof.
44. The method of claim 37 , wherein the iron-bearing compound is selected from iron (II) carbonate and the halide-bearing compound is selected from calcium bromide.
45. The method of claim 37 , wherein the at least one halide-bearing compound is provided to the combustion zone via addition to pulverized coal.
46. The method of claim 37 , wherein the at least one halide-bearing compound is provided to the combustion zone via a dedicated supply line.
47. The method of claim 37 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 2.5:1 to about 10:1.
48. The method of claim 37 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 3.5:1 to about 8:1.
49. The method of claim 37 , wherein the at least one halide-bearing compound is provided at sufficient amount to yield a halide concentration of between about 10 ppm to about 200 ppm.
50. The method of claim 37 , wherein the one or more less reactive iron-phosphorus-containing compounds further contains oxygen.
51. The method of claim 37 , wherein the iron-bearing compound is a water soluble iron-bearing compound.
52. The method of claim 37 , wherein the iron-bearing compound is a water soluble iron-bearing compound that is supplied in the form of an aqueous solution.
53. The method of claim 37 , wherein the iron-bearing compound is a water insoluble iron-bearing compound that is supplied in the form of an aqueous suspension or emulsion.
54. The method of claim 37 , wherein the staged combustion process utilizes over fire air and the staged combustion process results in an increased amount of the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound and results in an increased acid gas concentration in the flue gas.
55. A method for simultaneously sequestering one or more gaseous phosphorus compounds, or gaseous phosphorus-containing compounds, in the form of one or more less reactive iron-phosphorus-containing compounds, and oxidizing mercury, the method comprising the steps of:
(I) providing at least one coal-based fuel to a furnace, or boiler;
(II) subjecting the at least one coal-based fuel to a staged combustion process, wherein the staged combustion process produces at least one gaseous phosphorus compound and/or at least one gaseous phosphorus-containing compound;
(III) providing at least one iron-bearing compound to a combustion zone of the furnace, or boiler; and
(IV) permitting the at least one iron-bearing compound to react with the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound present in the combustion zone or flue gas to form one or more less reactive iron-phosphorus-containing compounds;
(V) providing at least one halide-bearing compound to a combustion zone or flue gas stream of a furnace, or boiler, prior to entry of the flue gas into an SCR, with the proviso that halide-bearing compound is not an iron halide; and
(IV) (VI) permitting the at least one halide-bearing compound to react with and/or oxidize any mercury present in the combustion zone or flue gas,
wherein the method achieves an increase in either one, or both, of a catalytic activity and/or a catalytic lifespan of at least about 15 percent at an operational time of at least about 3,000 hours.
56. The method of claim 55 , wherein the iron-bearing compound is selected from metallic iron, one or more iron oxides, iron carbonate, or mixtures of two or more thereof.
57. The method of claim 55 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, iron (II) oxide, or mixtures of two or more thereof.
58. The method of claim 55 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, or a mixture thereof.
59. The method of claim 55 , wherein the at least one iron-bearing compound is provided to the combustion zone via addition to pulverized coal.
60. The method of claim 55 , wherein the at least one iron-bearing compound is provided to the combustion zone via a dedicated supply line.
61. The method of claim 55 , wherein the halide-bearing compound is selected from potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide, calcium bromide, calcium chloride, calcium fluoride, calcium iodide, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum iodide, transition metal halides with the proviso that the transition metal is not iron, or any mixture of two or more thereof or mixtures of two or more thereof.
62. The method of claim 55 , wherein the iron-bearing compound is selected from iron (II) carbonate and the halide-bearing compound is selected from calcium bromide.
63. The method of claim 55 , wherein the at least one halide-bearing compound is provided to the combustion zone via addition to pulverized coal.
64. The method of claim 55 , wherein the at least one halide-bearing compound is provided to the combustion zone via a dedicated supply line.
65. The method of claim 55 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 2.5:1 to about 10:1.
66. The method of claim 55 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 3.5:1 to about 8:1.
67. The method of claim 55 , wherein the at least one halide-bearing compound is provided at sufficient amount to yield a halide concentration of between about 10 ppm to about 200 ppm.
68. The method of claim 55 , wherein the one or more less reactive iron-phosphorus-containing compounds further contains oxygen.
69. The method of claim 55 , wherein the iron-bearing compound is a water soluble iron-bearing compound.
70. The method of claim 55 , wherein the iron-bearing compound is a water soluble iron-bearing compound that is supplied in the form of an aqueous solution.
71. The method of claim 55 , wherein the iron-bearing compound is a water insoluble iron-bearing compound that is supplied in the form of an aqueous suspension or emulsion.
72. The method of claim 55 , wherein the staged combustion process utilizes over fire air and the staged combustion process results in an increased amount of the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound and results in an increased acid gas concentration in the flue gas.
73. A method for sequestering one or more gaseous phosphorus compounds, or gaseous phosphorus-containing compounds, in the form of one or more less reactive iron-phosphorus-containing compounds while concurrently sequestering mercury, the method comprising the steps of:
providing at least one coal-based fuel to a furnace, or boiler;
subjecting the at least one coal-based fuel to a staged combustion process, wherein the staged combustion process produces at least one gaseous phosphorus compound and/or at least one gaseous phosphorus-containing compound;
providing at least one iron-bearing compound to a combustion zone of the furnace, or boiler; and
permitting the at least one iron-bearing compound to react with the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound present in the combustion zone or flue gas to form one or more less reactive iron-phosphorus-containing compounds;
providing at least one halide-bearing compound to a combustion zone or flue gas stream of a furnace, or boiler, prior to entry of the flue gas into an SCR, with the proviso that halide-bearing compound is not an iron halide; and
permitting the at least one halide-bearing compound to react with and/or oxidize any mercury present in the combustion zone or flue gas,
wherein the method achieves an increase in either one, or both, of a catalytic activity and/or a catalytic lifespan of at least about 15 percent at an operational time of at least about 4,000 hours.
74. The method of claim 73 , wherein the iron-bearing compound is selected from metallic iron, one or more iron oxides, iron carbonate, or mixtures of two or more thereof.
75. The method of claim 73 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, iron (II) oxide, or mixtures of two or more thereof.
76. The method of claim 73 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, or a mixture thereof.
77. The method of claim 73 , wherein the at least one iron-bearing compound is provided to the combustion zone via addition to pulverized coal.
78. The method of claim 73 , wherein the at least one iron-bearing compound is provided to the combustion zone via a dedicated supply line.
79. The method of claim 73 , wherein the halide-bearing compound is selected from potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide, calcium bromide, calcium chloride, calcium fluoride, calcium iodide, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum iodide, transition metal halides with the proviso that the transition metal is not iron, or any mixture of two or more thereof or mixtures of two or more thereof.
80. The method of claim 73 , wherein the iron-bearing compound is selected from iron (II) carbonate and the halide-bearing compound is selected from calcium bromide.
81. The method of claim 73 , wherein the at least one halide-bearing compound is provided to the combustion zone via addition to pulverized coal.
82. The method of claim 73 , wherein the at least one halide-bearing compound is provided to the combustion zone via a dedicated supply line.
83. The method of claim 73 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 2.5:1 to about 10:1.
84. The method of claim 73 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 3.5:1 to about 8:1.
85. The method of claim 73 , wherein the at least one halide-bearing compound is provided at sufficient amount to yield a halide concentration of between about 10 ppm to about 200 ppm.
86. The method of claim 73 , wherein the one or more less reactive iron-phosphorus-containing compounds further contains oxygen.
87. The method of claim 73 , wherein the iron-bearing compound is a water soluble iron-bearing compound.
88. The method of claim 73 , wherein the iron-bearing compound is a water soluble iron-bearing compound that is supplied in the form of an aqueous solution.
89. The method of claim 73 , wherein the iron-bearing compound is a water insoluble iron-bearing compound that is supplied in the form of an aqueous suspension or emulsion.
90. The method of claim 73 , wherein the staged combustion process utilizes over fire air and the staged combustion process results in an increased amount of the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound and results in an increased acid gas concentration in the flue gas.
91. A method for increasing the active life of an SCR catalyst, the method comprising the steps of:
providing at least one coal-based fuel to a furnace, or boiler;
subjecting the at least one coal-based fuel to a staged combustion process, wherein the staged combustion process produces at least one gaseous phosphorus compound and/or at least one gaseous phosphorus-containing compound;
providing at least one iron-bearing compound to a combustion zone or flue gas stream of the furnace, or boiler, prior to entry of the flue gas into an SCR, wherein the SCR is located upstream of at least one air heater; and
permitting the at least one iron-bearing compound to react with the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound present in the combustion zone or flue gas prior to the entry of the flue gas into the SCR to form an iron phosphorus-containing compound,
wherein the method achieves an increase in either one, or both, of a catalytic activity and/or a catalytic lifespan of at least about 10 percent at an operational time of at least about 2,000 hours.
92. The method of claim 91 , wherein the iron-bearing compound is selected from metallic iron, one or more iron oxides, iron carbonate, or mixtures of two or more thereof.
93. The method of claim 91 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, iron (II) oxide, or mixtures of two or more thereof.
94. The method of claim 91 , wherein the iron-bearing compound is selected from iron (III) oxide, iron (II) carbonate, or a mixture thereof.
95. The method of claim 91 , wherein the at least one iron-bearing compound is provided to the combustion zone via addition to pulverized coal.
96. The method of claim 91 , wherein the at least one iron-bearing compound is provided to the combustion zone via a dedicated supply line.
97. The method of claim 91 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 2.5:1 to about 10:1.
98. The method of claim 91 , wherein the at least one iron-bearing compound is provided at an excess stoichiometric ratio of iron to phosphorus is in the range of about 3.5:1 to about 8:1.
99. The method of claim 91 , wherein the iron-bearing compound is a water soluble iron-bearing compound.
100. The method of claim 91 , wherein the iron-bearing compound is a water soluble iron-bearing compound that is supplied in the form of an aqueous solution.
101. The method of claim 91 , wherein the iron-bearing compound is a water insoluble iron-bearing compound that is supplied in the form of an aqueous suspension or emulsion.
102. The method of claim 91 , wherein the at least one iron-bearing compound is provided to the combustion zone via addition to raw coal which is thereafter pulverized.
103. The method of claim 91 , wherein the staged combustion process utilizes over fire air and the staged combustion process results in an increased amount of the at least one gaseous phosphorus compound and/or the at least one gaseous phosphorus-containing compound and results in the deactivation of the SCR catalyst.