IP Library Granted Patent US 10,987,623
Granted Patent B2
US 10,987,623 · App. 15/853,029 · Granted Apr 27, 2021

Sorbents for the oxidation and removal of mercury

Inventors: John H. Pavlish (East Grand Forks, MN); Edwin S. Olson (Grand Forks, ND); Michael J. Holmes (Thompson, ND)
Assignee: Midwest Energy Emission Corp
B01D53/64B01D53/10B01D53/83B01J20/027B01J20/0262B01J20/04B01J20/041B01J20/043B01J20/10B01J20/106B01J20/12B01J20/20B01J20/223B01J20/28004B01J20/3416B01D2251/108B01D2251/206B01D2253/102B01D2257/602B01D2258/0283B01J2220/42
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Quick Facts
Patent No.
US 10,987,623
App. No.
15/853,029
Granted
Apr 27, 2021
Kind
B2
Abstract

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.

Claims (58)

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 iodine (I 2 ), iodide (I − ), or a combination thereof, and

the 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 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, 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 IBr, ICl, FeI x (x=1, 2, 3, or 4), NiI 2 , ZnI 2 , NH 4 I, NaI, I − , KI, CHI 3 , CaI 2 , or a combination thereof.

4. The method of claim I, wherein the halogen or halide promoter comprises HI, a Group V iodide, a Group VI iodide, 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, an ammonium salt, 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 I, 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 6 , wherein the carbon sorbent material is activated carbon.

8. The method of claim 1 , further comprising adding an ammonium salt into the mercury-containing gas.

9. The method of claim 8 , 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.

10. The method of claim 8 , wherein the ammonium salt is ammonium sulfate.

11. The method of claim 8 , wherein the sorbent comprises activated carbon.

12. The method of claim 8 , wherein the sorbent comprises a non-carbon sorbent.

13. The method of claim 8 , wherein the sorbent material added to the mercury-containing gas cornprises a non-promoted non-ammonium salt-protected sorbent.

14. The method of claim 8 , wherein adding the ammonium salt into the mercury-containing gas forms ammonium salt-protected activated carbon sorhent particles comprising

active sites that bind with mercury atoms, wherein the active sites comprise carbocations bound to iodide-promoter anions, and

ammonia, an ammonium salt, or a combination thereof, in at least a surface layer thereof.

15. 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.

16. 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.

17. The method of claim 1 , wherein the 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.

18. The method of claim 1 , wherein the 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.

19. The method of claim 1 , wherein the 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.

20. The method of claim 1 , wherein the 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 promoted-sorbent material added to the mercury-containing gas.

21. The method of claim 1 , wherein the 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 promoted-sorbent material added to the mercury-containing gas.

22. A method of separatirig 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 a combination thereof, added to the coal, added to the combustion chamber, or a combination thereof,

to provide the mercury-containing gas, when

the mercury-containing gas comprises the halogen or halide promoter, and

the halogen or halide promoter and promoter precursor comprises iodine (I 2 ), iodide (I − ), or a combination thereof;

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, wherein the 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;

contacting mercury in the mercury-containing gas with the sorbent, to form a mercury/sorbent composition; and.

separating the mercury/sorbent composition from the mercury-containing gas.

23. The method of claim 22 , wherein the 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 promoted sorbent material added to the mercury-containing gas.

24. The method of claim 22 , wherein the 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 promoted sorbent material added to the mercury-containing gas.

25. 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 31 , 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 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, to form a mercury/sorbent composition; and

separating the mercury/sorbent composition from the mercury-containing gas.

Assignments (3)
CHANGE OF NAME Recorded Nov 7, 2024
From: MIDWEST ENERGY EMISSIONS CORP.
To: BIRCHTECH CORP.
Reel/Frame 069187/0413 →
CORRECTIVE ASSIGNMENT TO CORRECT THE THE ASSIGNEE NAME PREVIOUSLY RECORDED AT REEL: 055474 FRAME: 0305. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded May 17, 2023
From: PAVLISH, JOHN H.; OLSON, EDWIN S.; HOLMES, MICHAEL J.
To: MIDMIDWEST ENERGY EMISSIONS CORP.
Reel/Frame 063694/0782 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 3, 2021
From: PAVLISH, JOHN H.; OLSON, EDWIN S.; HOLMES, MICHAEL J.
To: MIDWEST ENERGY EMISSIONS CORP
Reel/Frame 055474/0305 →
Continuity (19)
Continuation In Part 15295594 · Oct 17, 2016
Continuation 14102896 · Dec 11, 2013
Continuation 12429058 · Apr 23, 2009
Continuation In Part 12201595 · Aug 29, 2008
Division 11209163 · Aug 22, 2005
Division 15853029 · Dec 22, 2017
Continuation In Part 15382114 · Dec 16, 2016
Continuation In Part 14712558 · May 14, 2015
Continuation 13966768 · Aug 14, 2013
Continuation 13427665 · Mar 22, 2012
Continuation 12419219 · Apr 6, 2009
Continuation 12201595 · Aug 29, 2008
Division 11209163 · Aug 22, 2005
Continuation In Part 14195360 · Mar 3, 2014
Continuation In Part 10554018 · Jan 23, 2007
Provisional Application 60605640 · Aug 30, 2004
Provisional Application 61773549 · Mar 6, 2013
Provisional Application 60464868 · Apr 23, 2003
Related Publication 20180133646A1 · May 17, 2018