Mercury removal from gaseous process streams

• US 6,475,451 B1
• Filed: 08/23/2000
• Issued: 11/05/2002
• Est. Priority Date: 08/23/2000
• Status: Expired due to Term

• Current Assignee: Gas Technology Institute (GTI Energy)
• Original Assignee: Gas Technology Institute (GTI Energy)
• Inventors: Leppin, Dennis, Palla, Nagaraju
• Primary Examiner(s): Silverman, Stanley S.
• Assistant Examiner(s): Vanoy, Timothy C.
• Application Number:
  US09/644,361
• Time in Patent Office: 804 Days
• Field of Search: 423/210, 481/273, 481/275
• US Class Current: 423/210
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: C10L 3/10 Working-up natural gas or synthetic natural gas

Abstract

A process for removing mercury from a gaseous process stream. The process involves contacting a mercury-containing gaseous process stream with a regenerable mercury scavenger solution to form a treated stream having a reduced mercury content as compared to the mercury-containing gaseous process stream and a used scavenger solution having an increased mercury content. The regenerable mercury scavenger solution contains an oxidizing agent such as nitric acid, a complexing agent such as oxygen-containing agents and/or thiol and a solvent, for example, a mixture of methanol and water.

Claims

1. A process for removing mercury from a gaseous process stream, said process comprising:

contacting a first mercury-containing gaseous process stream with a regenerable mercury scavenger solution to form a treated stream having a reduced mercury content and a used scavenger solution having an increased mercury content, the regenerable mercury scavenger solution comprising;

a) nitric acid effective to oxidize mercury contained within the first mercury-containing gaseous process stream to form mercury cations,

b) a complexing agent suitable for forming a soluble mercury compound when contacting the mercury cations, and

c) a solvent effective to dissolve the soluble mercury compound.

2. The process of claim 1 additionally comprising:

regenerating the used scavenger solution.

3. The process of claim 2 wherein the used scavenger solution is regenerated continuously.

4. The process of claim 2 wherein the used scavenger solution is regenerated in a batch fashion.

5. The process of claim 1 wherein the solvent is stable at temperatures up to about 300°

F.

6. The process of claim 5 wherein the solvent has a vapor pressure of less than about 0.01 mm Hg at 20°

C.

7. The process of claim 6 wherein the solvent comprises an aqueous solution of potassium carbonate.

8. The process of claim 6 wherein the solvent comprises at least one member selected from the group consisting of 1,2,3,4 tetrahydronaphthalene, N,N dimethylaniline, diphenyl ether, dibenzyl ether, terphenyls, diphenylethanes, alkylated polycyclic aromatics and mixtures thereof.

9. The process of claim 1 wherein the first mercury-containing gaseous process stream is a flue gas resulting from coal combustion.

10. The process of claim 1 wherein the nitric acid is approximately 0.1 N.

11. The process of claim 1 wherein the complexing agent is selected from the group consisting of oxygen-containing compounds, sulfur-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds and mixtures thereof.

12. The process of claim 1 wherein the complexing agent is selected from the group consisting of a thiol, a dithiocarbamic acid, a thiocarbamic acid, a thiocarbazone, a cryptate and mixtures thereof.

13. The process of claim 1 wherein the solvent comprises a mixture of methanol and water.

14. The process of claim 1 wherein the solvent has a freezing point below −

40°

F.

15. A process for removing mercury from a flue gas process stream, said process comprising:

contacting a mercury-containing flue gas process stream with a regenerable mercury scavenger solution to form a treated stream having a reduced mercury content and a used scavenger solution having an increased mercury content, the regenerable mercury scavenger solution comprising;

a) nitric acid effective to oxidize mercury contained within the mercury-containing flue gas process stream to form mercury cations,

b) a complexing agent suitable for forming a soluble mercury compound when contacting the mercury cations, and

c) a solvent effective to dissolve the soluble mercury compound and regenerating the used scavenger solution.

16. The process of claim 15 wherein the solvent is stable at temperatures up to about 300°

F. and has a vapor pressure of less than about 0.01 mm Hg at 20°

C.

17. The process of claim 15 wherein the mercury-containing flue gas process stream is a flue gas resulting from coal combustion.

18. The process of claim 15 wherein the nitric acid is approximately 0.1 N.

19. The process of claim 15 wherein the complexing agent is selected from the group consisting of oxygen-containing compounds, sulfur-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds and mixtures thereof.

20. The process of claim 15 wherein the complexing agent is selected from the group consisting of a thiol, a dithiocarbamic acid, a thiocarbamic acid, a thiocarbazone, a cryptate and mixtures thereof.

21. The process of claim 15 wherein the solvent comprises an aqueous solution of potassium carbonate.

22. The process of claim 15 wherein the solvent comprises at least one member selected from the group consisting of 1,2,3,4 tetrahydronaphthalene, N,N dimethylaniline, diphenyl ether, dibenzyl ether, terphenyls, diphenylethanes, alkylated polycyclic aromatics and mixtures thereof.

23. A process for removing mercury from a natural gas stream, said process comprising:

contacting a mercury-containing natural gas feed stream with a regenerable mercury scavenger solution to form a treated stream having a reduced mercury content and a used scavenger solution having an increased mercury content, the regenerable mercury scavenger solution comprising;

a) nitric acid effective to oxidize mercury contained within the natural gas feed stream to form mercury cations,

b) a complexing agent suitable for forming a soluble mercury compound when contacting the mercury cations, and

c) a solvent effective to dissolve the soluble mercury compound and regenerating the used scavenger solution.

24. The process of claim 23 wherein the nitric acid is approximately 0.1 N.

25. The process of claim 23 wherein the complexing agent is selected from the group consisting of oxygen-containing compounds, sulfur-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds and mixtures thereof.

26. The process of claim 23 wherein the complexing agent is selected from the group consisting of a thiol, a dithiocarbamic acid, a thiocarbamic acid, a thiocarbazone, a cryptate and mixtures thereof.

27. The process of claim 23 wherein the solvent comprises at least one member selected from the group consisting of a mixture of methanol and water, an aqueous solution of potassium carbonate, 1,2,3,4 tetrahydronaphthalene, N,N dimethylaniline, diphenyl ether, dibenzyl ether, terphenyls, diphenylethanes, alkylated polycyclic aromatics and mixtures thereof.