Method and system for controlling mercury emissions from coal-fired thermal processes
View Patent ↗The present disclosure is directed to the use of elemental or speciated iodine to control total mercury emissions.
1. A method, comprising:
in a mercury-containing gas stream comprising vapor-phase mercury and vapor-phase iodine and having a temperature ranging from about 325 to about 450° C., the vapor-phase iodine being derived, at least in part, from an iodine-containing additive, separating at least about 50% of the vapor-phase mercury from the mercury-containing gas stream, wherein at least one of the following is true:
(i) the mercury-containing gas stream comprises about 3.5 ppmw or less vapor-phase iodine;
(ii) in the mercury-containing gas stream, a molar ratio of vapor-phase iodine to vapor-phase mercury is no more than about 600;
(iii) at an air preheater outlet, a concentration of vapor-phase iodine ranges from about 0.1 to about 10 ppmw; and
(iv) a concentration of the vapor-phase iodine is about 30 ppmw or less relative to a weight of a solid mercury-containing feed material producing the vapor-phase mercury.
2. The method of claim 1 , wherein (i) is true.
3. The method of claim 2 , wherein the mercury-containing gas stream comprises about 1.5 ppmw or less vapor-phase iodine.
4. The method of claim 1 , wherein (ii) is true.
5. The method of claim 4 , wherein the molar ratio is no more than about 250.
6. The method of claim 1 , wherein (iii) is true.
7. The method of claim 6 , wherein the concentration of vapor-phase iodine at the air preheater outlet ranges from about 0.2 to about 2 ppmw.
8. The method of claim 1 , wherein (iv) is true.
9. The method of claim 1 , wherein the feed material natively comprises no more than about 3 ppmw total iodine and no more than about 10 ppmw total bromine, wherein an iodine-containing additive is contacted with the feed material, wherein the iodine-containing additive comprises no more than about 25% of halogens other than iodine, and wherein a total iodine concentration relative to a weight of the feed material is about 15 ppmw or less.
10. The method of claim 6 , wherein the iodine is contacted with vapor-phase mercury upstream of the air preheater.
11. The method of claim 9 , wherein the feed material is combustible, wherein the combustible feed material is combusted to produce the mercury-containing gas stream, wherein the vapor-phase iodine causes removal of at least about 75% of elemental and speciated mercury from the mercury-containing gas stream, and wherein the combustible feed material, when combusted, produces an unburned carbon particulate level of no more than about 20% by weight of the combustible feed material.
12. The method of claim 1 , further comprising:
while vapor phase iodine and mercury are in the mercury-containing gas stream, introducing, into the mercury-containing gas stream, a reactive surface agent to collect at least most of the iodine and mercury.
13. The method of claim 12 , wherein the reactive surface agent is one or more of a zeolite, silica, alumina, silica alumina, gamma-alumina, activated alumina, acidified alumina, a metal oxide particle, aluminosilicate, ion exchange resin, clay, a transition metal sulfate, a ceramic, an alkaline material, trona, an alkali metal bicarbonate, an alkali metal bisulfate, an alkali metal bisulfite, sulfide, elemental sulfur, circulating fluidized bed ash, fluidized catalytic cracker fines, and fumed silicate, and wherein one or more of a mean, median, and P 90 size of the reactive surface agent is no more than about 100 microns.
14. The method of claim 1 , wherein a concentration of the vapor-phase mercury in the mercury-containing gas stream is at least about 0.001 ppmw, wherein a molar ratio, in the mercury-containing gas stream, of vapor phase iodine to total gas-phase mercury is no more than about 250, wherein a concentration of the vapor-phase iodine in the mercury-containing gas stream is about 1.5 ppmw or less, and further comprising:
contacting the mercury-containing gas stream, while the vapor-phase iodine and mercury are in the mercury-containing gas stream, with a selective catalytic reduction catalyst to at least one of catalyze the formation of diatomic iodine and oxidize at least some of the vapor-phase mercury.
15. The method of claim 1 , further comprising:
passing the mercury-containing gas stream through at least one of a baghouse, a spray dryer absorber, and an electrostatic precipitator to form a treated gas stream; and
thereafter passing the treated gas stream through a wet scrubber, the wet scrubber having a scrubber slurry sorbing no more than about 20% of the total mercury.
16. The method of claim 1 , further comprising:
passing the mercury-containing gas stream through at least one of a first particulate removal device to remove at least most of the mercury and form a first gas stream; and
passing the first gas stream through a preheater to form a second gas stream; and
passing the second gas stream through a second particulate removal device to remove at least most of any remaining mercury from the second gas stream and form a treated gas stream.
17. The method of claim 1 , wherein the mercury-containing gas stream is derived from combustion of a combustible feed material and wherein the feed material is one of a high- and medium-sulfur coal and wherein a concentration of at least one of sulfur trioxide and nitrogen dioxide gas in the mercury-containing gas stream is at least about 5 ppmv.
18. The method of claim 1 , wherein the mercury-containing gas stream is derived from combustion of a combustible feed material and wherein the feed material is a high alkali coal.
19. The method of claim 1 , wherein the vapor phase iodine comprises both a hydrogen-iodine species and diatomic iodide and wherein a molecular ratio of diatomic iodide to the hydrogen-iodine species is at least about 10:1.
20. The method of claim 12 , wherein the reactive surface agent is introduced by a dry scrubber and wherein the dry scrubber is located upstream of a particulate removal device.
21. A method, comprising:
contacting a mercury-containing solid feed material with an iodine-containing additive to form a treated feed material, wherein an iodine concentration of the iodine-containing additive relative to a weight of the feed material is about 30 ppmw or less;
thereafter generating, from the treated feed material, a mercury-containing gas stream comprising vapor-phase mercury and iodine; and
removing at least about 50% or more of the mercury from the mercury-containing gas stream.
22. The method of claim 21 , wherein the iodine-containing additive facilitates the vapor-phase mercury to be removed from the mercury-containing gas stream, wherein the feed material natively comprises no more than about 4 ppmw iodine, wherein the iodine-containing additive is substantially free of halogens other than iodine, and wherein the mercury-containing gas stream contains no more than about 1 ppmw vapor-phase bromine.
23. The method of claim 21 , wherein the iodine-containing additive comprises at least about 100 ppmw iodine wherein the iodine-containing additive comprises no more than about 40 wt. % carbon and facilitates the vapor-phase mercury to be removed from the mercury-containing gas stream and wherein at least one of the following is true:
(i) the mercury-containing gas stream comprises about 3.5 ppmw or less vapor-phase iodine;
(ii) in the mercury-containing gas stream, a molar ratio of vapor-phase iodine to vapor-phase mercury is no more than about 600; and
(iii) at an air preheater outlet, a concentration of vapor-phase iodine ranges from about 0.1 to about 10 ppmw.
24. The method of claim 23 , wherein (i) is true.
25. The method of claim 24 , wherein the mercury-containing gas stream comprises about 1.5 ppmw or less vapor-phase iodine.
26. The method of claim 23 , wherein (ii) is true.
27. The method of claim 26 , wherein the molar ratio is no more than about 250 and wherein the mercury-containing gas stream temperature ranges from about 150 to about 600° C.
28. The method of claim 23 , wherein (iii) is true.
29. The method of claim 28 , wherein a temperature of the mercury-containing gas stream ranges from about 325 to about 450° C. and wherein the concentration of vapor-phase iodine at the air preheater outlet ranges from about 0.2 to about 2 ppmw.
30. The method of claim 21 , wherein the feed material is a combustible feed material, wherein the waste gas is derived by combustion, wherein the vapor-phase iodine causes removal of at least about 75% of elemental and speciated mercury from the mercury-containing gas stream, and wherein the feed material, when combusted, has an unburned carbon particulate level of no more than about 30% by weight of the feed material.
31. The method of claim 21 , further comprising:
while iodine and mercury are in the mercury-containing gas stream, introducing, into the mercury-containing gas stream, a reactive surface agent to collect at least most of the iodine and mercury.
32. The method of claim 31 , wherein the reactive surface agent is one or more of a zeolite, silica, alumina, silica alumina, gamma-alumina, activated alumina, acidified alumina, a metal oxide particle, aluminosilicate, ion exchange resin, clay, a transition metal sulfate, a ceramic, an alkaline material, trona, an alkali metal bicarbonate, an alkali metal bisulfate, an alkali metal bisulfite, circulating fluidized bed ash, fluidized catalytic cracker fines, fumed silicate, and wherein one or more of a mean, median, and P 90 size of the reactive surface agent is no more than about 100 microns.
33. The method of claim 21 , wherein a concentration of the vapor-phase mercury in the mercury-containing gas stream is at least about 0.005 ppmw, wherein a concentration of the vapor-phase iodine in the mercury-containing gas stream is about 1.5 ppmw or less, and further comprising:
contacting the mercury-containing gas stream, while the vapor-phase iodine and mercury are in the mercury-containing gas stream, with a selective catalytic reduction catalyst to at least one of catalyze the formation of diatomic iodine and oxidize at least some of the vapor-phase mercury.
34. The method of claim 21 , further comprising:
passing the mercury-containing gas stream through at least one of a baghouse, a spray dryer absorber, and an electrostatic precipitator to form a treated gas stream; and
thereafter passing the treated gas stream through a wet scrubber, the wet scrubber having a scrubber slurry absorbing no more than about 20% of the total mercury.
35. The method of claim 21 , further comprising:
passing the mercury-containing gas stream through at least one of a first particulate removal device to remove at least most of the vapor-phase mercury and form a first gas stream; and
passing the first gas stream through a preheater to form a second gas stream; and
passing the second gas stream through a second particulate removal device to remove at least most of any remaining mercury from the second gas stream and form a treated gas stream.
36. The method of claim 21 , wherein the feed material is a high sulfur coal and wherein a concentration of at least one of sulfur trioxide and nitrogen dioxide gas in the mercury-containing gas stream is at least about 10 ppmv.
37. The method of claim 21 , wherein the feed material is a high alkali coal and wherein the feed material comprises no more than about 4 ppmw total native iodine and no more than about 10 ppmw total bromine.
38. The method of claim 21 , wherein the feed material is a Powder River Basin Coal.
39. The method of claim 21 , wherein the vapor phase iodine comprises both a hydrogen-iodine species and diatomic iodide and wherein a molecular ratio of diatomic iodide to the hydrogen-iodine species is at least about 25:1.
40. The method of claim 31 , wherein the reactive surface agent is introduced by a dry scrubber and wherein the dry scrubber is located upstream of a particulate removal device.
41. A method, comprising:
contacting a solid mercury-containing feed material with an iodine-containing additive to form a treated feed material;
generating, from the treated feed material, a mercury-containing gas stream comprising vapor-phase mercury and iodine, wherein the vapor-phase iodine comprises both a hydrogen-iodine species and diatomic iodide and wherein a molecular ratio of diatomic iodide to the hydrogen-iodine species is at least about 25:1; and
removing at least most of the mercury from the mercury-containing gas stream.
42. The method of claim 41 , wherein the feed material natively comprises no more than about 4 ppmw iodine, wherein the additive facilitates the vapor-phase mercury to be removed from the mercury-containing gas stream, and wherein at least one of the following is true:
(i) the mercury-containing gas stream comprises about 3.5 ppmw or less vapor-phase iodine;
(ii) in the mercury-containing gas stream, a molar ratio of vapor-phase iodine to vapor-phase mercury is no more than about 600;
(iii) at an air preheater outlet, a concentration of vapor-phase iodine ranges from about 0.1 to about 10 ppmw; and
(iv) the total vapor-phase iodine concentration is about 30 ppmw or less relative to the weight of the mercury-containing feed material.
43. The method of claim 42 , wherein (i) is true.
44. The method of claim 43 , wherein the mercury-containing gas stream comprises about 1.5 ppmw or less vapor-phase iodine.
45. The method of claim 42 , wherein (ii) is true.
46. The method of claim 45 , wherein the molar ratio is no more than about 250 and wherein the mercury-containing gas stream temperature ranges from about 150 to about 600° C.
47. The method of claim 42 , wherein (iii) is true.
48. The method of claim 47 , wherein a temperature of the mercury-containing gas stream ranges from about 325 to about 450° C. and wherein the concentration of vapor-phase iodine at the air preheater outlet ranges from about 0.2 to about 2 ppmw.
49. The method of claim 42 , wherein (iv) is true.