Absorption and oxidation of NO in ionic liquids

Patent metadata

Field	Value
Publication number	US-9289719-B2
Application number	US-201214361642-A
Country	US
Kind code	B2
Filing date	Nov 29, 2012
Priority date	Nov 29, 2011
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

The present invention concerns the absorption and in situ oxidation of nitric oxide (NO) in the presence of water and oxygen in ionic liquid compositions at ambient temperature.

First claim

The invention claimed is:

1. A method for capturing nitric oxide (NO) from gasses containing more than one gaseous compound, comprising:
a. absorbing said NO in a liquid ionic composition in the presence of oxygen and water, and
b. reacting the absorbed NO with oxygen and water to form nitric acid which accumulates in the liquid ionic composition, wherein said liquid ionic composition comprises one or more ionic compounds.

2. The method according to claim 1 wherein the liquid ionic composition comprises one or more organic cations selected from:

wherein
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 can be, independently, hydrogen, alkyl, halogenated alkyl, aminoalkyl, hydroxyalkyl, alkoxyalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl;
the positively charged P, N and S atoms may individually be part of heterocyclic or heteroaromatic structures by:
fusing two of R 19 R 20 , R 21 , and R 22 to form a cyclic phosphonium ion, or
fusing two of R 6 R 7 , R 8 , and R 9 to form a cyclic ammonium ion, or
fusing two of R 11 , and R 12 , or R 13 and R 14 , or R 15 and R 10 to form a cyclic guanidinium ion, or
fusing two of R 16 , R 17 and R 18 to form a cyclic sulfonium ion, and

one or more anions selected from C 1 -C 6 alkanoates, arylcarboxylates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, C 1 -C 6 perfluoroalkylsulfonates, C 1 -C 6 perfluoroalkanoates, C 1 -C 6 perfluoroalkylsulfonimides, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate and halides.

3. The method according to claim 1 wherein the liquid ionic composition comprises a cation having the following structure:

wherein R 1 and R 2 are individually selected from C 1 -C 8 alkyl groups or aryl groups, and wherein R 3 , R 4 and R 5 are individually selected from hydrogens, C 1 -C 6 alkyl groups or aryl groups or wherein R 3 and R 4 together with the imidazolium group may form a 4- to 6-membered saturated, unsaturated or aromatic ring, which may further contain up to three hetero atoms selected from oxygen, nitrogen and phosphorus.

4. The method according to claim 1 wherein said ionic composition comprises one or more ionic compounds selected from 1-ethyl-3-methylimidazolium ([EMIM] + ) acetate, 1-butyl-3-methylimidazolium ([BMIM] + ) acetate, 1-ethyl-3-methylimidazolium ([EMIM] + ) triflate, 1-butyl-3-methylimidazolium ([BMIM] + ) triflate, 1-ethyl-3-methylimidazolium ([EMIM] + ) nitrate, 1-butyl-3-methylimidazolium ([BMIM] + ) nitrate, 1-butyl-2,3-dimethylimidazolium ([BDMIM] + ) nitrate, choline chloride, choline acetate and 1,1,3,3-tetramethylguanidinium chloride.

5. The method according to claim 1 , wherein the liquid ionic composition further comprises one or more cations selected from Li + , Na + and K + .

6. The method according to claim 1 , wherein the liquid ionic composition further comprises a non-ionic solvent.

7. The method according to claim 1 , wherein the liquid ionic composition is absorbed in a porous carrier and used in the form of a supported ionic liquid phase (SILP) material.

8. The method according to claim 7 wherein the porous carrier material is selected from SiO 2 , Al 2 O 3 , TiO 2 , CeO 2 , ZrO 2 , or carbon, or a combination thereof.

9. The method according to claim 7 wherein the porous carrier material is anatase TiO 2 .

10. A method according to claim 8 , wherein the porous carrier material is anatase TiO 2 .

11. A method according to claim 8 , wherein the porous carrier material is calcined SiO 2 .

12. The method according to claim 1 , wherein the nitric acid is desorbed from said liquid ionic composition by increasing the temperature and increasing the flow rate.

13. The method of claim 1 , wherein said gasses are flue gases.

14. The method of claim 1 , which further comprises:
c. removing the formed nitric acid from the liquid ionic composition solution by increasing the temperature and/or decreasing the pressure.

15. The method according to claim 1 , wherein the liquid ionic composition comprises one or more organic cations selected from:

wherein
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 can be, independently, hydrogen, alkyl, halogenated alkyl, aminoalkyl, hydroxyalkyl, alkoxyalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl;
the positively charged P, N and S atoms may individually be part of heterocyclic or heteroaromatic structures by:
fusing two of R 19 R 20 ,R 21 and R 22 to form a cyclic phosphonium ion, or
fusing two of R 6 , R 7 , R 8 , and R 9 to form a cyclic ammonium ion, or
fusing two of R 11 and R 12 , or R 13 and R 14 , or R 15 and R 10 to form a cyclic guanidinium ion, or
fusing two of R 16 , R 17 and R 18 to form a cyclic sulfonium ion.

16. The method according to claim 1 , wherein the liquid ionic composition comprises one or more anions selected from C 1 -C 6 alkanoates, arylcarboxylates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, C 1 -C 6 perfluoroalkylsulfonates, C 1 -C 6 perfluoroalkanoates, C 1 -C 6 perfluoroalkylsulfonimides, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate and halides.

17. The method of claim 1 , wherein the liquid ionic composition comprises one or more anions selected from nitrate and chloride.

18. A method of producing nitric acid (HNO 3 ) from nitric oxide (NO), comprising absorbing said nitric oxide in a liquid ionic composition in the presence of oxygen and water, wherein said nitric oxide is converted into nitric acid.

19. A method for the preparation of an anhydrous nitric acid solution of nitric acid (HNO 3 ) in a liquid ionic composition, comprising absorbing NO and/or NO 2 in said liquid ionic composition followed by conversion to HNO 3 .

Assignees

• Univ Danmarks Tekniske

Inventors

• Riisager Anders
• Kunov-Kruse Andreas J
• Mossin Susanne L
• Fehrmann Rasmus

Classifications

• B01D53/1493

  Selection of liquid materials for use as absorbents · CPC title

• B01D2252/30

  Ionic liquids and zwitter-ions · CPC title

• B01D53/1456 Primary

  Removing acid components · CPC title

• B01D2257/404

  Nitrogen oxides other than dinitrogen oxide · CPC title

• B01D2251/102

  Oxygen · CPC title