Methods for the treatment of a flue gas stream using catalytically-enhanced sorbent compositions
View Patent ↗A sorbent composition that is useful for injection into a flue gas stream of a coal burning furnace to efficiently remove mercury from the flue gas stream. The sorbent composition may include a sorbent with an associated ancillary catalyst component that is a catalytic metal, a precursor to a catalytic metal, a catalytic metal compound or a precursor to a catalytic metal compound. Alternatively, a catalytic metal or metal compound, or their precursors, may be admixed with the coal feedstock prior to or during combustion in the furnace, or may be independently injected into a flue gas stream. A catalytic promoter may also be used to enhance the performance of the catalytic metal or metal compound.
1. A method for removal of one or more contaminants from a flue gas stream comprising:
combusting a fuel source, the combusting generating a flue gas stream comprising one or more contaminants;
contacting the flue gas stream with a particulate solid sorbent;
maintaining the particulate solid sorbent in contact with the flue gas stream for a period of time sufficient to catalytically oxidize at least a portion of the one or more contaminants and form an oxidized contaminant species; and
sequestering the oxidized contaminant species with the particulate solid sorbent,
wherein the particulate solid sorbent comprises:
a powdered activated carbon sorbent, the powdered activated carbon sorbent having a mean particle diameter (D50) of not greater than about 25 μm, a surface area of at least about 350 m 2 /g, and a total pore volume of at least about 0.20 cc/g; and
an ancillary catalyst component selected from the group consisting of,
(i) a catalytic metal selected from the group consisting of Fe, Cu, Mn, Pd, Au, Ag, Pt, Ir, V, Ni, Zn, Sn, Ti, Ce, and combinations thereof,
(ii) a precursor to the catalytic metal, wherein the precursor to the catalytic metal comprises the catalytic metal and is selected from the group consisting of a metal oxide, a metal halide, a metal hydroxide, a metal sulfate, a metal nitrate, a metal carbonate, and combinations thereof, and
(iii) combinations of the catalytic metal and the precursor to the catalytic metal,
wherein the ancillary catalyst component is coated on a surface of the powdered activated carbon sorbent, and
wherein the amount of the ancillary catalyst component is at least 0.001 wt. % and not greater than about 20 wt. %.
2. The method of claim 1 , wherein the precursor to the catalytic metal is selected from the group consisting of copper (II) oxide (CuO), copper (II) chloride (CuCl 2 ), copper (II) nitrate (Cu(NO 3 ) 2 ), copper (II) hydroxide (Cu(OH) 2 ), copper (II) carbonate (CuCO 3 ), iron (III) oxide (Fe 2 O 3 ), iron (III) chloride (FeCl 3 ), iron (III) nitrate (Fe(NO 3 ) 3 ), iron (III) sulfate Fe 2 (SO 4 ) 3 , cerium (IV) oxide (CeO 2 ), manganese (IV) oxide (MnO 2 ), vanadium (V) oxide (V 2 O 5 ), zinc (II) oxide (ZnO), zinc sulfate (ZnSO 4 ), and combinations thereof.
3. The method of claim 1 , wherein the catalytic metal is selected from the group consisting of Fe, Cu, Mn, Zn, and combinations thereof.
4. The method of claim 1 , wherein the precursor to a catalytic metal is selected from the group consisting of a metal sulfate, a metal nitrate, and combinations thereof.
5. The method of claim 1 , wherein the particulate solid sorbent further comprises a catalytic promoter dispersed on the powdered activated carbon sorbent, wherein the catalytic promoter comprises a promoter metal compound selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and combinations thereof.
6. The method of claim 5 , wherein the catalytic promoter comprises a metal in elemental form or in the form of a metal oxide, a metal hydroxide, or a metal salt, the metal being selected from the group consisting of Li, Na, K, Be, Ca, Sr, Ba, Mg, and combinations thereof.
7. The method of claim 1 , wherein the particulate solid sorbent comprises not greater than about 1 wt. % of the ancillary catalyst component.
8. The method of claim 1 , wherein the particulate solid sorbent comprises not greater than about 5 wt. % of the ancillary catalyst component.
9. The method of claim 1 , wherein the particulate solid sorbent comprises not greater than about 10 wt. % of the ancillary catalyst component.
10. The method of claim 1 , wherein the powdered activated carbon sorbent has a mean particle diameter (D50) of not greater than about 20 μm.
11. The method of claim 1 , wherein the powdered activated carbon sorbent has a mean particle diameter (D50) of not greater than about 15 μm.
12. The method of claim 1 , wherein the particulate solid sorbent further comprises less than about 15 wt. % of a halogen.
13. The method of claim 1 , wherein the particulate solid sorbent further comprises less than about 6 wt. % of a halogen.
14. The method of claim 1 , wherein the particulate solid sorbent further comprises less than about 3 wt. % of a halogen.
15. The method of claim 1 , wherein the particulate solid sorbent comprises substantially no halogens.
16. The method of claim 1 , wherein the particulate solid sorbent further comprises an aqueous solubilizing medium in an amount that is at least about 2 wt. % and not greater than about 12 wt. %.
17. The method of claim 1 , wherein the fuel source comprises coal.
18. The method of claim 1 , wherein the one or more contaminants comprises mercury.
19. The method of claim 1 , wherein a ratio of micropore volume to mesopore volume is at least about 0.7 and not greater than about 1.5.
20. A method comprising:
receiving a flue gas stream generated by combustion of a fuel source, the flue gas stream comprising mercury;
contacting the flue gas stream with a particulate solid sorbent to catalytically oxidize at least a portion of the mercury; and
collecting the oxidized at least a portion of the mercury on the particulate solid sorbent,
wherein the particulate solid sorbent comprises:
a powdered activated carbon sorbent, the powdered activated carbon sorbent having a mean particle diameter (D50) of not greater than about 25 μm, a surface area of at least about 350 m 2 /g, and a total pore volume of at least about 0.20 cc/g; and
an ancillary catalyst component associated with a surface of the powdered activated carbon sorbent and selected from the group consisting of,
(i) a catalytic metal selected from the group consisting of Cu, Mn, Pd, Au, Ag, Pt, Ir, V, Ni, Zn, Sn, Ti, Ce, and combinations thereof,
(ii) a precursor to the catalytic metal, wherein the precursor to the catalytic metal comprises the catalytic metal and is selected from the group consisting of a metal oxide, a metal halide, a metal hydroxide, a metal sulfate, a metal nitrate, a metal carbonate, and combinations thereof, and
(iii) combinations of the catalytic metal and the precursor to the catalytic metal,
wherein the amount of the ancillary catalyst component is at least 0.001 wt. % and not greater than about 20 wt. %.
21. The method of claim 20 , wherein the precursor to the catalytic metal precursor is selected from the group consisting of copper (II) oxide (CuO), copper (II) chloride (CuCl 2 ), copper (II) nitrate (Cu(NO 3 ) 2 ), copper (II) hydroxide (Cu(OH) 2 ), copper (II) carbonate (CuCO 3 ), [iron (III) oxide (Fe 2 O 3 ), iron (III) chloride (FeCl 3 ), iron (III) nitrate (Fe(NO 3 ) 3 ), iron (III) sulfate Fe 2 (SO 4 ) 3, ] cerium (IV) oxide (CeO 2 ), manganese (IV) oxide (MnO 2 ), vanadium (V) oxide (V 2 O 5 ), zinc (II) oxide (ZnO), zinc sulfate (ZnSO 4 ), and combinations thereof.
22. The method of claim 20 , wherein the particulate solid sorbent further comprises a catalytic promoter dispersed on the powdered activated carbon sorbent, wherein the catalytic promoter comprises a metal in elemental form or in the form of a metal oxide, metal hydroxide, or metal salt, the metal being selected from the group consisting of Al, Li, Na, K, Be, Ca, Sr, Ba, Sc, Y, Mg, and combinations thereof.
23. The method of claim 20 , wherein the particulate solid sorbent comprises not greater than about 1 wt. % of the ancillary catalyst component.
24. The method of claim 20 , wherein the particulate solid sorbent comprises not greater than about 5 wt. % of the ancillary catalyst component.
25. The method of claim 20 , wherein the particulate solid sorbent comprises not greater than about 10 wt. % of the ancillary catalyst component.
26. The method of claim 20 , wherein the particulate solid sorbent further comprises less than about 15 wt. % of a halogen.
27. The method of claim 20 , wherein the particulate solid sorbent composition further comprises an aqueous solubilizing medium in an amount that is at least about 2 wt. % and not greater than about 12 wt. %.
28. A method comprising:
receiving a flue gas stream comprising one or more contaminants; and
contacting the flue gas stream with a particulate solid sorbent to form an oxidized contaminant species collected on the particulate solid sorbent,
wherein the particulate solid sorbent comprises:
a powdered activated carbon sorbent, the powdered activated carbon sorbent having a mean particle diameter (D50) of not greater than about 25 μm, a surface area of at least about 350 m 2 /g, and a total pore volume of at least about 0.20 cc/g; and
an ancillary catalyst component comprising,
(i) a catalytic metal selected from the group consisting of Fe, Cu, Mn, Pd, Au, Ag, Pt, Ir, V, Ni, Zn, Sn, Ti, Ce, and combinations thereof,
(ii) a precursor to the catalytic metal, wherein the precursor to the catalytic metal comprises the catalytic metal and is selected from the group consisting of a metal oxide, a metal halide, a metal hydroxide, a metal sulfate, a metal nitrate, a metal carbonate, and combinations thereof, and
(iii) combinations of the catalytic metal and the precursor to the catalytic metal,
wherein the amount of the ancillary catalyst component is at least 0.001 wt. % and not greater than about 20 wt. %, and wherein the particulate solid sorbent comprises substantially no halogens.
29. The method of claim 28 , wherein the precursor to the catalytic metal is selected from the group consisting of copper (II) oxide (CuO), copper (II) chloride (CuCl 2 ), copper (II) nitrate (Cu(NO 3 ) 2 ), copper (II) hydroxide (Cu(OH) 2 ), copper (II) carbonate (CuCO 3 ), iron (III) oxide (Fe 2 O 3 ), iron (III) chloride (FeCl 3 ), iron (III) nitrate (Fe(NO 3 ) 3 ), iron (III) sulfate Fe 2 (SO 4 ) 3 , cerium (IV) oxide (CeO 2 ), manganese (IV) oxide (MnO 2 ), vanadium (V) oxide (V 2 O 5 ), zinc (II) oxide (ZnO), zinc sulfate (ZnSO 4 ), and combinations thereof.
30. The method of claim 28 , wherein the particulate solid sorbent comprises not greater than about 1 wt. % of the ancillary catalyst component.
31. The method of claim 28 , wherein the particulate solid sorbent comprises not greater than about 5 wt. % of the ancillary catalyst component.
32. The method of claim 28 , wherein the particulate solid sorbent comprises not greater than about 10 wt. % of the ancillary catalyst component.
33. The method of claim 28 , wherein the ancillary catalyst component is coated on a surface of the powdered activated carbon sorbent.