Process for controlling the emission of flue gases

• US 9,114,360 B2
• Filed: 01/31/2013
• Issued: 08/25/2015
• Est. Priority Date: 02/01/2012
• Status: Active Grant

• Current Assignee: Yissum Research Development Company of the Hebrew University of Jerusalem Ltd. (Hebrew University of Jerusalem)
• Original Assignee: Yissum Research Development Company of the Hebrew University of Jerusalem Ltd. (Hebrew University of Jerusalem)
• Inventors: Sasson, Yoel, Sachs, Tatyana, Dvash, Effi, Barnea, Zach
• Primary Examiner(s): VANOY, TIMOTHY C
• Application Number:
  US14/374,412
• Publication Number:
  US 20140369916A1
• Time in Patent Office: 936 Days
• US Class Current: 1/1
• CPC Class Codes: B01D 2251/108 Halogens or halogen compounds
• CPC Class Codes: B01D 2252/202 Alcohols or their derivatives
• CPC Class Codes: B01D 2252/205 Other organic compounds not covered by B01D2252/00 - B01D2252/20494
• CPC Class Codes: B01D 2252/30 Ionic liquids and zwitter-ions
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/60 Heavy metals or heavy metal compounds
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/1425 Regeneration of liquid absorbents
• CPC Class Codes: B01D 53/1481 Removing sulfur dioxide or sulfur trioxide
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• CPC Class Codes: B01D 53/507 by treating the gases with other liquids
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury

Abstract

Provided is a process for controlling heavy metal (e.g., mercury) emission in SO₂-containing flue gas, comprising passing a stream of the flue gas (2) through a wet scrubber (1) where it is brought into contact with a liquid absorbent (8) comprising an ionic liquid, an oxidizer (11) and polar protic organic solvent, wherein the amount of said organic solvent is adjusted such that the SO₂ absorption is minimized while operating said wet scrubber at a temperature lower than the normal working temperature that would be used in the absence of said solvent. The process may be preceded by an initial stage where a fluoride-containing liquid is used for reducing the amount of sulfur dioxide in the flue gas stream; the sulfur dioxide can be subsequently desorbed from the fluoride-containing liquid upon the addition of a polar solvent.

Claims

1. A process for controlling heavy metal emission in SO2-containing flue gas, comprising passing a stream of the flue gas through a wet scrubber where it is brought into contact with a liquid absorbent comprising an ionic liquid, an oxidizer and polar protic organic solvent, wherein the amount of said organic solvent is adjusted such that the SO₂ absorption is minimized while operating said wet scrubber at a working temperature lower than the normal working temperature that would be used in the absence of said solvent.

2. A process according to claim 1, wherein the liquid absorbent comprises bromide ionic liquid, with the weight ratio between the polar protic organic solvent and said ionic liquid being at least 1:

20 and wherein the working temperature is from 100 to 135°

C.

3. A process according to claim 1, wherein the liquid absorbent comprises chloride ionic liquid, with the weight ratio between the polar protic organic solvent and said ionic liquid being at least 1:

10 and wherein the working temperature is from 100 to 170°

C.

4. A process according to claim 1, wherein the ionic liquid comprises 1-butyl-3-methylimidazolium bromide or 1-butyl-3-methylimidazolium chloride, respectively, and the oxidizer is iodine.

5. A process according to claim 4, wherein the ionic liquid further comprises at least one additional 1-butyl-3-methylimidazolium salt selected from the group consisting the BF₄⁻

and PF₆⁻

salts.

6. A process according to claim 1, wherein the polar protic organic solvent comprises a diprotic acid.

7. A process according to claim 6, wherein the diprotic acid has the formula HOOC(CH₂)_nCOOH, wherein n is an integer of not less than 3.

8. A process according to claim 7, wherein the acid is adipic acid and/or pimelic acid.

9. A process according to claim 1, wherein the heavy metal is mercury.

10. A process according to claim 1, wherein the SO₂-containing flue gas stream is treated before it is passed through the wet scrubber for removal of heavy metals, said treatment comprises contacting said SO₂-containing flue gas with a fluoride-containing liquid absorbent comprising one or more fluoride salts, whereby SO₂ molecules are captured by said fluoride-containing liquid absorbent and separated from the gaseous stream such that a treated flue gas stream having reduced SO₂ content is obtained, adding a polar solvent to said fluoride-containing liquid absorbent to remove the sulfur dioxide captured, regenerating and recycling the fluoride-containing liquid absorbent and directing the treated flue gas stream having reduced SO₂ content to the wet scrubber in which the removal of the heavy metal is accomplished.

11. The process of claim 10, wherein the fluoride-containing liquid absorbent comprises one or more fluoride ionic liquids.

12. The process of claim 10, wherein the fluoride-containing liquid absorbent is a mixture of halide ionic liquids, said mixture comprises, in addition to the fluoride ionic liquid, also at least one chloride, bromide or iodide ionic liquids which are miscible with the fluoride ionic liquid.

13. The process of claim 10, wherein the solvent added to the fluoride-containing liquid absorbent is a polar protic solvent.

14. The process of claim 13, wherein the polar protic solvent is selected from the group consisting of C1-C5 alkanols.

15. The process of claim 10, wherein the treatment comprises the absorption of the sulfur dioxide at a temperature from 100°

C. to 160°

C.

16. The process of claim 15, wherein the absorption temperature is from 110 to 140°

C.

17. A process for removing sulfur dioxide from gaseous mixtures, comprising contacting said gaseous mixture with a liquid absorbent comprising one or more fluoride salts, adding a polar solvent to said absorbent to remove the sulfur dioxide from said absorbent and regenerating the absorbent.

18. The process of claim 17, wherein the absorbent comprises one or more fluoride ionic liquids.

19. The process of claim 18, wherein the absorbent is a mixture of halide ionic liquids, said mixture comprising at least one chloride, bromide or iodide ionic liquids which are miscible with the fluoride ionic liquid(s).

20. The process of claim 17, wherein the solvent added to the absorbent is a polar protic solvent.

21. The process of claim 20, wherein the polar protic solvent is selected from the group consisting of C1-C5 alkanols.

22. The process of claim 17, wherein the absorption of the sulfur dioxide by the absorbent is carried out at a temperature ranging from 100°

C. to 160°

C.

23. The process of claim 22, wherein the temperature is from 110 to 140°

C.

24. A process for controlling metal emission in SO₂-containing flue gas, comprising passing a stream of the flue gas through a wet scrubber where it is brought into contact with a liquid absorbent comprising a ionic liquid and an oxidizer, wherein the molar ratio between the oxidizer and the ionic liquid is not less than 1:

2, and wherein the absorption temperature is from 20°

C. to 35°

C.

25. A process for controlling heavy metal emission in SO₂-containing flue gas, comprising passing a stream of the flue gas through a wet scrubber where it is brought into contact with a liquid absorbent comprising an ionic liquid and an oxidizer, wherein at least one organic acid is present in the liquid absorbent.