MULTI-FUNCTIONAL COMPOSITION OF MATTER FOR RAPID REMOVAL OF MERCURY FROM A FLUE GAS

• US 20130109562A1
• Filed: 08/16/2012
• Published: 05/02/2013
• Est. Priority Date: 10/28/2011
• Status: Active Grant

• Current Assignee: ARQ Solutions LLC
• Original Assignee: ADA Carbon Solutions, LLC (Advanced Emissions Solutions, Inc.)
• Inventors: Vizcaino, Christopher, Cannon, Frederick S., Wong, Joseph M., Huston, Robert B.
• Granted Patent: US 9,539,538 B2
• Time in Patent Office: Days
• US Class Current: 502/181
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2253/304 Linear dimensions, e.g. particle shape, diameter
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 2253/31 Pore size distribution
• CPC Class Codes: B01D 2253/311 Porosity, e.g. pore volume
• CPC Class Codes: B01D 2255/2022 Potassium
• CPC Class Codes: B01D 2255/2045 Calcium
• CPC Class Codes: B01D 2255/2047 Magnesium
• CPC Class Codes: B01D 2255/20738 Iron
• CPC Class Codes: B01D 2255/20792 Zinc
• CPC Class Codes: B01D 2255/2094 Tin
• CPC Class Codes: B01D 2255/702 Carbon
• CPC Class Codes: B01D 2255/9202 Linear dimensions
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01D 53/83 with moving reactants
• CPC Class Codes: B01D 53/8665 Removing heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: F23J 15/003 : for supplying chemicals to fumes, e.g. using injection devices
• CPC Class Codes: F23J 2215/60 : Heavy metals; Compounds thereof
• CPC Class Codes: F23J 2219/30 : Sorption devices using carbon, e.g. coke

Abstract

A multi-functional composition of matter that is useful for injection into a flue gas stream to rapidly and efficiently remove mercury from the flue gas stream. The multi-functional composition of matter may include a fixed carbon sorbent and minerals, halogens in the form of halide salts, as well as other physical and chemical properties to enhance (1) the oxidation reaction kinetics for the oxidation of mercury species and (2) the mass diffusion kinetics of the mercury species.

Claims

1. A multi-functional composition of matter, comprising at least about 20 wt. % and not greater than about 75 wt. % fixed carbon, at least about 20 wt. % and not greater than about 50 wt. % minerals, at least about 1 wt. % and not greater than about 15 wt. % of a halogen, and at least about 3 wt. % and not greater than about 12 wt. % aqueous-based solubilizing medium, wherein:

the multi-functional composition of matter has a median particle size of not greater than about 15 micron;

the multi-functional composition of matter has a sum of micropore volume plus mesopore volume that is at least about 0.2 cc/g; and

the ratio of micropore volume to mesopore volume is at least about 0.7 and is not greater than about 1.5.

8. The multi-functional composition of matter recited in claim 1, wherein when injected at a coal-fired power plant combusting high rank coal will result in emissions of mercury of less than 1.2 lbs/Tbtu at composition injection rates (in lbs/MMacf) of at least approximately 30% less as compared to Comparative Sample C under comparable operating conditions.

9. The multi-functional composition of matter recited in claim 1, wherein when injected at a coal-fired power plant combusting high rank coal will result in emissions of mercury of less than 1.2 lbs/Tbtu at composition injection rates (in lbs/MMacf) of at least approximately 60% less as compared to Comparative Sample C under comparable operating conditions.

10. The multi-functional composition of matter recited in claim 1, wherein when injected in a beta test at a coal-fired power plant combusting high rank coal and when the mercury emission rate (lb Hg/Tbtu) is plotted as a function of the composition injection rate (in lbs/MMacf), the slope of the curve with the highest R² value at 1.2 lbs Hg/Tbtu will be more negative than about −

0.6.

11. The multi-functional composition of matter recited in claim 1, when injected in a beta test at a coal-fired power plant combusting high rank coal and when the mercury emission rate (lb Hg/Tbtu) is plotted as a function of the composition injection rate (in lbs/MMacf), the slope of the curve with the highest R² at 1.2 lbs Hg/Tbtu will be more negative than about −

1.5.

12. The multi-functional composition of matter recited in claim 1, which when injected at a coal-fired power plant combusting low rank coal will result in emissions of mercury of less than 4.0 lbs/Tbtu at composition injection rates (in lbs/MMacf) of at least approximately 40% less as compared to Comparative Sample D under comparable operating conditions.

13. The multi-functional composition of matter recited in claim 1, wherein when injected at a coal-fired power plant combusting low rank coal will result in emissions of mercury of less than 4.0 lbs/Tbtu at composition injection rates (in lbs/MMacf) of at least approximately 50% less as compared to Comparative Sample D under comparable operating conditions.

14. The multi-functional composition of matter recited in claim 1, wherein when injected in a beta test at a coal-fired power plant combusting low rank coal and when the mercury emission rate (lb Hg/Tbtu) is plotted as a function of the composition injection rate (lbs matter/MMacf), the slope of the trendline with the highest R² value at 4.0 lbs Hg/Tbtu will be more negative than about −

8.

15. The multi-functional composition of matter recited in claim 1, wherein the minerals are native to a feedstock for the manufacture of the multi-functional composition of matter.

16. The multi-functional composition of matter recited in claim 1, wherein the minerals are selected from the group consisting of calcium-containing minerals, potassium-containing minerals, iron-containing minerals, silicon-containing minerals, silicate-containing minerals, sodium-containing minerals, tin-containing minerals, zinc-containing minerals, magnesium-containing minerals, alumino-silicate containing minerals, and combinations thereof.

17. The multi-functional composition of matter recited in claim 1, wherein the minerals comprise oxide minerals.

18. The multi-functional composition of matter recited in claim 1, wherein the minerals comprise at least 1 wt. % iron-containing minerals.

19. The multi-functional composition of matter recited in claim 1, wherein the multi-functional composition of matter comprises at least about 3 wt. % and not greater than about 8 wt. % aqueous-based solubilizing medium.

20. The multi-functional composition of matter recited in claim 1, wherein the multi-functional composition of matter has a median particle size of not greater than about 12 micron.

21. The multi-functional composition of matter recited claim 1, wherein the multi-functional composition of matter has a median particle size of at least about 5 micron.

22. The multi-functional composition of matter recited in claim 1, wherein the multi-functional composition of matter has a Hardgrove Grindability Index of at least about 90.

23. The multi-functional composition of matter recited in claim 1, wherein the multi-functional composition of matter has a Hardgrove Grindability Index of at least about 100.

24. The multi-functional composition of matter as recited claim 1, wherein the multi-functional composition of matter has a mercury particle density of at least about 0.5 g/cc and not greater than about 0.9 g/cc.

25. The multi-functional composition of matter as recited claim 1, wherein the multi-functional composition of matter has an envelope particle density of at least about 0.3 g/mL and not greater than about 1.5 g/mL.

26. The multi-functional composition of matter recited in claim 1, wherein the multi-functional composition of matter has an envelope particle density of at least about 0.5 g/cc and not greater than about 1.0 g/cc.

27. The multi-functional composition of matter recited in claim 1, wherein the sum of micropore volume plus mesopore volume of the multi-functional composition of matter is at least about 0.25 cc/g.

28. The multi-functional composition of matter recited in claim 1, wherein:

the mesopore volume of the multi-functional composition of matter is at least about 0.10 cc/g and is not greater than about 0.15 cc/g;

the micropore volume of the multi-functional composition of matter is at least about 0.10 cc/g and is not greater than about 0.15 cc/g; and

the ratio of micropore volume to mesopore volume is greater than about 0.9 and less than about 1.5.

29. The multi-functional composition of matter recited in claim 1, wherein the pH of the multi-functional composition of matter is greater than about 8 and is less than about 12.

30. The multi-functional composition of matter recited in claim 1, wherein when the multi-functional composition of matter is analyzed by Scanning Electron Microscopy and Energy Dispersive Spectrometry at a magnification of 12,000 times over at least a 20 micron by 10 micron image area, the pixels attributed to the halogen exhibit a mean width of at least about 0.05 micron and not greater than about 2 micron, wherein the overall pixel area attributed to the halogen represents at least about 10% of the overall image area.

31. The multi-functional composition of matter recited in claim 1, wherein when the composition of matter is analyzed by Scanning Electron Microscopy and Energy Dispersive Spectrometry at a magnification of 12,000 times over at least a 20 micron by 15 micron image area, the pixels attributed to the halogen appear in at least 20% of the pixel area in any 10 micron by 10 micron scanning area.

32. The multi-functional composition of matter recited in claim 1, wherein when the halogen is in the form of a halide salt.

33. The multi-functional composition of matter recited in claim 1, wherein when the halogen is in the form of a bromide salt.

2. A composition of matter that when injected in a beta test at a coal-fired power plant combusting high rank coal will result in emissions of mercury of less than 1.2 lbs/Tbtu at composition injection rates (in lbs/MMacf) of at least approximately 30% less as compared to Comparative Sample C under comparable operating conditions.

3. A composition of matter that when injected in a beta test at a coal-fired power plant combusting high rank coal will result in emissions of mercury of less than 1.2 lbs/Tbtu at composition injection rates (in lbs/MMacf) of at least approximately 60% less as compared to Comparative Sample C under comparable operating conditions.

4. A composition of matter that when injected in a beta test at a coal-fired power plant combusting high rank coal and when the mercury emission rate (lb Hg/Tbtu) is plotted as a function of the composition injection rate (lbs/MMacf), the slope of the trendline with the highest R² value at 1.2 lbs Hg/Tbtu will be more negative than about −

0.6.

5. A composition of matter that when injected in a beta test at a coal-fired power plant combusting high rank coal and when the mercury emission rate (lb Hg/Tbtu) is plotted as a function of the composition injection rate (lbs/MMacf), the slope of the trendline with the highest R² value at 1.2 lbs Hg/Tbtu will be more negative than about −

1.5.

6. A composition of matter that when injected at a coal-fired power plant combusting low rank coal will result in emissions of mercury of less than 4.0 lbs/Tbtu at composition injection rates (in lbs/MMacf) of at least approximately 50% less as compared to Comparative Sample D under comparable operating conditions.

7. A composition of matter that when injected in a beta test at a coal-fired power plant combusting low rank coal and when the mercury emission rate (lb Hg/Tbtu) is plotted as a function of the composition injection rate (lbs/MMacf), the slope of the trendline with the highest R² value at 4.0 lbs Hg/Tbtu will be more negative than about −

8.