Ceramic materials for gas separation and oxygen storage

Patent metadata

Field	Value
Publication number	US-9764985-B2
Application number	US-201514657263-A
Country	US
Kind code	B2
Filing date	Mar 13, 2015
Priority date	Oct 28, 2010
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

A manganese oxide contains M1, optionally M2, Mn and O. M1 is selected from the group consisting of In, Sc, Y, Dy, Ho, Er, Tm, Yb and Lu. M2 is different from M1, and M2 is selected from the group consisting of Bi, In, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. These ceramic materials are hexagonal in structure, and provide superior materials for gas separation and oxygen storage.

First claim

What is claimed is:

1. A method of preparing oxygen, comprising:
separating oxygen from a mixture of gases containing the oxygen, by conducting the oxygen through a manganese oxide, or absorbing and releasing the oxygen from the manganese oxide,
wherein the manganese oxide comprises M1, optionally M2, Mn and O, and
wherein
M1 is selected from the group consisting of In, Sc, Y, Dy, Ho, Er, Tm, Yb and Lu,
M2 is different from M1, and M2 is selected from the group consisting of Bi, In, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, Mn and O are present in an atomic ratio of 1:z, and z is at least 3.15, and

the separating is carried out at a temperature of at most 400° C.

2. The method of claim 1 , wherein z is at least 3.2.

3. The method of claim 1 , wherein z is 3.15 to 3.4.

4. The method of claim 1 , wherein M1 and M2 are present in an atomic ratio of x:1−x, and x =0.1 to 1.

5. The method of claim 4 , wherein x =0.3 to 1.

6. The method of claim 1 , wherein M1 is selected from the group consisting of Y and Ho.

7. The method of claim 1 , wherein M1 is Y and M2 is selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy.

8. The method of claim 1 , wherein M1 is Y and M2 is Dy.

9. The method of claim 5 , wherein M1 and Mn are present in an atomic ratio of 1 :y, and 0 <y ≦10.

10. The method of claim 1 , wherein the separating is carried out at a temperature of at most 300° C.

11. The method of claim 1 , wherein the separating is carried out at a temperature of at most 250° C.

12. The method of claim 1 wherein the formal oxidation state of Mn is between 3 and 4.

13. The method of claim 12 , wherein the formal oxidation state of Mn is 3.3 to 3. 8.

14. The method of claim 1 , wherein the method is thermal swing absorption or ceramic autothermal recovery.

15. The method of claim 1 , wherein z is 3.15 to 3.4,
M1 and M2 are present in an atomic ratio of x:1−x, and x =0.3 to 1, and
M1 and Mn are present in an atomic ratio of 1:y, and 0<y≦10.

16. A method of generating electricity, comprising:
(1) preparing oxygen by the method of claims 1 , and
(2) burning a carbon-containing fuel with the oxygen, in a generator or power plant.

17. A method of preparing oxygen, comprising separating oxygen from a mixture of gases containing the oxygen, by conducting the oxygen through a manganese oxide, or absorbing and releasing the oxygen from the manganese oxide,
wherein the manganese oxide comprises M1, M2, Mn and O, and
wherein:
M1 is selected from the group consisting of In, Sc, Y, Dy, Ho, Er, Tm, Yb and Lu,
M2 is different from M1, and M2 is selected from the group consisting of Bi, In, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu,
M1 and M2 are present in an atomic ratio of x:1−x, and x =0.1 to 0.9,
Mn and O are present in an atomic ratio of 1:z, and z >3, and

the separating is carried out at a temperature of at most 400° C.

18. The method of claim 17 , wherein z is at least 3.15.

19. The method of claim 18 , wherein z is at least 3.25.

20. The method of claim 18 , wherein z is 3.15 to 3.4.

21. The method of claim 17 , wherein x =0.3 to 0.9.

22. The method of claim 17 , wherein M2 is selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy.

23. The method of claim 17 , wherein M1 is Y and M2 is Tb.

24. The method of claim 17 , wherein z is 3.15 to 3.4,
x=0.3 to 0.9, and
M1 and Mn are present in an atomic ratio of 1:y, and 0<y≦10.

25. A method of generating electricity, comprising:
(1) preparing oxygen by the method of claims 17 , and
(2) burning a carbon-containing fuel with the oxygen, in a generator or power plant.

26. A method of preparing oxygen, comprising:
separating oxygen from a mixture of gases containing the oxygen, by conducting the oxygen through an oxygen conducting membrane,
wherein the oxygen conducting membrane comprises
(1) a rare earth manganese oxide, and
(2) a support material,

the membrane has first and second opposing surfaces,
the membrane is not permeable to nitrogen gas,
the rare earth manganese oxide forms a contiguous structure exposed on both the first and second opposing surfaces, and
the rare earth manganese oxide has an average temperature of maximum oxygen absorption upon heating and cooling, T maxA , of at most 400° C., and a temperature of maximum oxygen desorption, T maxD , of at most 400° C.

27. The method of claim 26 , wherein the support material comprises at least one member selected from the group consisting of an organic polymer, a silicone rubber, and glass.

28. The method of claim 26 , wherein the support material is electrically conductive, and forms a contiguous structure exposed on both the first and second opposing surfaces.

29. The method of claim 28 , wherein the support material comprises at least one member selected from the group consisting of graphite, carbon black, aluminum, copper, iron, nickel, steel, zinc, tin, lead and alloys thereof.

30. The method of claim 26 , wherein the average temperature of maximum oxygen absorption upon heating and cooling, T maxA , is at most 300° C.

31. The method of claim 26 , wherein the temperature of maximum oxygen desorption, T maxD , is at most 300° C.

32. The method of claim 26 , wherein the support material decomposes when exposed to air at a temperature of 500° C., or has a glass transition temperature or a melting point of at most 500° C.

33. The method of claim 26 , wherein the manganese oxide comprises Mn and O in an atomic ratio of 1:z, and z is 3.15 to 3.4.

34. A method of generating electricity, comprising:
(1) preparing oxygen by the method of claims 26 , and
(2) burning a carbon-containing fuel with the oxygen, in a generator or power plant.

Assignees

• Dabrowski Bogdan
• Remsen Steven
• Univ Northern Illinois Board Of Trustees

Inventors

• Dabrowski Bogdan
• Remsen Steven

Classifications

• C04B2235/6565

  Cooling rate · CPC title

• C01P2002/88

  by thermal analysis data, e.g. TGA, DTA, DSC · CPC title

• Y02P20/129

  Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines · CPC title

• B01D71/024

  Oxides · CPC title

• C04B2235/658

  Atmosphere during thermal treatment · CPC title