Sorbents for the oxidation and removal of mercury
Various embodiments disclosed relate to sorbents for the oxidation and removal of mercury. The present invention includes removing mercury from a mercury-containing gas using a halide-promoted and optionally ammonium-protected sorbent that can include carbon sorbent, non-carbon sorbent, or a combination thereof.
1. A method of separating mercury from a mercury-containing gas, the method comprising:
combusting in a combustion chamber
coal fed to the combustion chamber, and
a halogen or halide promoter, a promoter precursor that transforms into the promoter, or combination thereof, added to the coal, added to the combustion chamber, or a combination thereof,
to provide the mercury-containing gas, wherein
the mercury-containing gas comprises the halogen or halide promoter,
the halogen or halide promoter and promoter precursor comprises chlorine (Cl 2 ), chloride (Cl − ), bromine (Br 2 ), bromide (Br − ), iodine (I 2 ), iodide (I − ), or a combination thereof, and
the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 1 to about 3000 ppmw per weight of the coal fed to the combustion chamber;
adding an ammonium salt into the mercury-containing gas;
adding a sorbent material into the mercury-containing gas downstream of the combustion chamber such that the sorbent material contacts the halogen or halide promoter in the mercury-containing gas;
contacting mercury in the mercury-containing gas with the sorbent material, to form a mercury/sorbent composition; and
separating the mercury/sorbent composition from the mercury-containing gas.
2. The method of claim 1 , comprising adding the promoter into the combustion chamber, placing the promoter on the coal prior to combusting the coal, adding the promoter precursor into the combustion chamber that transforms into the promoter, placing the promoter precursor on the coal prior to combusting the coal, or a combination thereof.
3. The method of claim 1 , wherein at least one of the promoter and the promoter precursor is independently HCl, HBr, HI, Br 2 , Cl 2 , I 2 , BrCl, IBr, ICl, ClF, PBr 3 , PCl 5 , SCl 2 , CuCl 2 , CuBr 2 , Al 2 Br 6 , FeI x (x=1, 2, 3, or 4), FeBr y (y=1, 2, 3, or 4), FeCl z (z=1, 2, 3, or 4), MnBr 2 , MnCl 2 , NiBr 2 , NiCl 2 , NiI 2 , ZnBr 2 , ZnCl 2 , ZnI 2 , NH 4 Br, NH 4 Cl, NH 4 I, NH 4 F, NaBr, NaCl, NaI, Br − , Cl − , I − , KI, KCl, LiCl, LiBr, AgCl, AgBr, CHI 3 , CH 3 Br, AuBr, MgBr 2 , MgCl 2 , CaI 2 , CaBr 2 , CaCl 2 , or a combination thereof.
4. The method of claim 1 , wherein the halogen or halide promoter comprises HI, a Group V iodide, a Group VI iodide, HCl, a Group V chloride, a Group VI chloride, HBr, a Group V bromide, a Group VI bromide, or a combination thereof.
5. The method of claim 1 , further comprising adding a secondary material into the mercury-containing gas downstream of the combustion chamber, wherein the secondary material comprises an alkaline material, a clay, halogen, a compound derived from a halogen, a hydrohalide, a compound comprising a Group V or Group VI element and a molecular halogen, or a combination thereof.
6. The method of claim 1 , wherein the sorbent material added into the mercury-containing gas comprises at least one of a carbon sorbent material and a non-carbon sorbent material.
7. The method of claim 1 , wherein the ammonium salt is ammonium bromide, ammonium iodide, ammonium chloride, an organic halide with a formula of CH 3 NH 3 X (wherein X is Cl, Br or I), ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfite, ammonium hydrogen sulfite, ammonium persulfate, ammonium pyrosulfate, ammonium thiosulphate, ammonium dithionite, ammonium aluminium sulfate, ammonium iron sulfate, ammonium sulfamate, ammonium phosphate, diammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium thiophosate, ammonium nitrate, ammonium nitrite, ammonium carbonate, ammonium thiocyanate, ammonium sulfide, ammonium hydrogen sulfide, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium chlorate, ammonium chromate, ammonium fluoride, ammonium formate, ammonium hydroxide, ammonium perchlorate, or a combination thereof.
8. The method of claim 1 , wherein the sorbent material comprises activated carbon.
9. The method of claim 1 , wherein the sorbent material comprises a non-carbon sorbent.
10. The method of claim 1 , wherein the sorbent material added to the mercury-containing gas comprises a non-promoted non-ammonium salt-protected sorbent.
11. The method of claim 1 , wherein adding the ammonium salt into the mercury-containing gas forms ammonium salt-protected activated carbon sorbent particles comprising
active sites that bind with mercury atoms, wherein the active sites comprise carbocations bound to chloride-, bromide-, and/or iodide-promoter anions, and
ammonia, an ammonium salt, or a combination thereof, in at least a surface layer thereof.
12. The method of claim 1 , comprising adding the promoter into the combustion chamber, placing the promoter on the coal prior to combusting the coal, or a combination thereof.
13. The method of claim 1 , comprising adding the promoter precursor into the combustion chamber that transforms into the promoter, placing the promoter precursor on the coal prior to combusting the coal, or a combination thereof.
14. The method of claim 1 , wherein the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 1 to about 1000 ppmw per weight of the coal fed to the combustion chamber.
15. The method of claim 1 , wherein the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 1 to about 500 ppmw per weight of the coal fed to the combustion chamber.
16. The method of claim 1 , wherein the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 0.001 wt % to about 30 wt % of the sorbent material added to the mercury-containing gas.
17. The method of claim 1 , wherein the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 0.1 wt % to about 30 wt % of the sorbent material added to the mercury-containing gas.
18. The method of claim 1 , wherein the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 1 wt % to about 30 wt % of the sorbent material added to the mercury-containing gas.
19. A method of separating mercury from a mercury-containing gas, the method comprising:
combusting in a combustion chamber
coal fed to the combustion chamber, and
a halogen or halide promoter, a promoter precursor that transforms into the promoter, or combination thereof, added to the coal, added to the combustion chamber, or a combination thereof,
to provide the mercury-containing gas, wherein
the mercury-containing gas comprises the halogen or halide promoter,
the halogen or halide promoter and promoter precursor comprises chlorine (Cl 2 ), chloride (Cl − ), bromine (Br 2 ), bromide (Br − ), iodine (I 2 ), iodide (I − ), or a combination thereof, and
the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 0.001 wt % to about 30 wt % of a sorbent material added to the mercury-containing gas;
adding an ammonium salt into the mercury-containing gas;
adding the sorbent material into the mercury-containing gas downstream of the combustion chamber such that the sorbent material contacts the halogen or halide promoter in the mercury-containing gas;
contacting mercury in the mercury-containing gas with the sorbent material, to form a mercury/sorbent composition; and
separating the mercury/sorbent composition from the mercury-containing gas.
20. A method of separating mercury from a mercury-containing gas, the method comprising:
combusting in a combustion chamber
coal fed to the combustion chamber, and
a halogen or halide promoter, a promoter precursor that transforms into the promoter, or combination thereof, added to the coal, added to the combustion chamber, or a combination thereof,
to provide the mercury-containing gas, wherein
the mercury-containing gas comprises the halogen or halide promoter,
the halogen or halide promoter and promoter precursor comprises chlorine (Cl 2 ), chloride (Cl − ), bromine (Br 2 ), bromide (Br − ), iodine (I 2 ), iodide (I − ), or a combination thereof, and
the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 1 to about 3000 ppmw per weight of the coal fed to the combustion chamber, or
the Cl 2 , Cl − , Br 2 , Br − , I 2 , I − , or the combination thereof added to the combustion chamber, added to the coal, or a combination thereof is about 0.001 wt % to about 30 wt % of a sorbent material added to the mercury-containing gas, or
a combination thereof;
adding an ammonium salt into the mercury-containing gas;
adding the sorbent material into the mercury-containing gas downstream of the combustion chamber such that the sorbent material contacts the halogen or halide promoter in the mercury-containing gas;
contacting mercury in the mercury-containing gas with the sorbent material, to form a mercury/sorbent composition; and
separating the mercury/sorbent composition from the mercury-containing gas.