Perovskite oxides for thermochemical conversion of carbon dioxide

Patent metadata

Field	Value
Publication number	US-10946362-B1
Application number	US-201815903196-A
Country	US
Kind code	B1
Filing date	Feb 23, 2018
Priority date	Feb 24, 2017
Publication date	Mar 16, 2021
Grant date	Mar 16, 2021

Abstract

Perovskite oxides and catalysts containing the perovskite oxides are provided for the thermochemical conversion of carbon dioxide to carbon monoxide. The perovskite oxides can exhibit large carbon monoxide production rates and/or low carbon monoxide production onset temperatures as compared to existing materials. Reactors are provided containing the perovskite oxides and catalysts, as well as methods of use thereof for the thermochemical conversion of carbon dioxide to carbon monoxide.

First claim

We claim:

1. A perovskite oxide having a composition according to the formula A 1 x A 2 (1-x) B 1 O 3 , the formula A 1 B 1 y B 2 (1-y) O 3 , or the formula A 1 B 1 y B 2 z B 3 (1-y-z) O 3 ;
wherein x is about 0.2 to 0.8;
wherein y is about 0.2 to 0.8;
wherein z is about 0.2 to 0.8;
wherein A 1 and A 2 are independently selected from the group consisting of La, Sr, Ca, and Ba, provided that A 1 and A 2 are not the same;
wherein B 1 , B 2 , and B 3 are independently transition metals, provided that B 1 , B 2 , and B 3 are not the same.

2. The perovskite oxide according to claim 1 , wherein B 1 , B 2 , and B 3 are independently selected from the group consisting of Al, Fe, Mn, Cr, and Co.

3. The perovskite oxide according claim 2 , wherein the perovskite oxide has a composition according to the formula A 1 x A 2 (1-x) B 1 O 3 , wherein A 1 is La.

4. The perovskite oxide according to claim 2 , wherein the perovskite oxide has a composition according to the formula A 1 B 1 y B 2 (1-y) O 3 , wherein A 1 is La.

5. The perovskite oxide according to claim 2 , wherein the perovskite oxide has a composition according to the formula AB 1 y B 2 z B 3 (1-y-z) O 3 , wherein A 1 is La.

6. The perovskite oxide according to claim 2 , wherein x is about 0.3 to 0.7.

7. The perovskite oxide according to claim 6 , wherein y is about 0.4 to 0.6.

8. The perovskite according to claim 1 , wherein the perovskite oxide is selected from the group consisting of La 0.6 Ca 0.4 MnO 3 , LaCo 0.33 Fe 0.33 Mn 0.33 O 3 , LaCo 0.5 Fe 0.25 Mn 0.25 O 3 , LaCo 0.25 Fe 0.5 Mn 0.25 O 3 , and LaCo 0.25 Fe 0.25 Mn 0.5 O 3 .

9. The perovskite oxide according claim 1 , wherein the perovskite oxide has a composition according to the formula A 1 x A 2 (1-x) B 1 O 3 , wherein A 1 is La, A 2 is Sr, Ba, or Ca, and B 1 is Fe.

10. A catalyst comprising a perovskite oxide according to claim 1 , wherein the perovskite oxide has been packed into at least one structure for packing a chemical reactor, wherein the structure is selected from the group consisting of beads, pellets, and fluidized bed powders.

11. The catalyst according to claim 10 , wherein the perovskite oxide is supported on a surface of the substrate.

12. The catalyst according to claim 11 , wherein the substrate comprises a monolith having the perovskite oxide deposited on at least a surface of the monolith.

13. The catalyst according to claim 12 , wherein the monolith comprises platinum, a cordierite, a mullite, and silicon carbide.

14. The catalyst according to claim 13 , wherein the monolith has a Brunauer, Emmet, and Teller (BET) specific surface area of about 5 m 2 /g to about 100 m 2 /g.

15. A method of converting carbon dioxide to carbon monoxide, the method comprising contacting a perovskite according to claim 1 with hydrogen gas at a first elevated temperature to produce an oxygen-deficient perovskite oxide, and
contacting the oxygen-deficient perovskite oxide with the carbon dioxide at a second elevated temperature to produce the carbon monoxide.

16. The method according to claim 15 , wherein the first elevated temperature is about 350° C. to 600° C.

17. The method according to claim 16 , wherein the second elevated temperature is about 400° C. to about 800° C.

18. The method according to claim 17 , wherein the second elevated temperature is about 440° C. to about 550° C.

19. The method according to claim 18 , wherein the carbon monoxide is produced at a rate of about 140 μmoles g −1 min −1 to 275 μmoles g −1 min −1 based upon the mass of the perovskite oxide.

20. The method according to claim 15 , wherein the carbon monoxide is produced at a rate of about 140 μmoles g −1 min −1 to 275 μmoles g −1 min −1 based upon the mass of the perovskite oxide.

21. A perovskite oxide having a composition according to the formula A 1 x A 2 (1-x) B 1 y B 2 (1-y) O 3 ;
wherein x is about 0.2 to 0.8;
wherein y is about 0.2 to 0.8;
wherein A 1 and A 2 are independently selected from the group consisting of La, Sr, Ca, and Ba, provided that A 1 and A 2 are not the same;
wherein B 1 and B 2 are independently transition metals, provided that B 1 and B 2 are not the same; and
wherein B 1 and B 2 are not Co.

22. The perovskite oxide according to claim 21 , wherein A 1 is La, and A 2 is Ba or Ca.

23. The perovskite oxide according to claim 22 , wherein B 1 and B 2 are independently selected from the group consisting of Al, Fe, Mn, and Cr.

24. The perovskite according to claim 21 , wherein the perovskite oxide is selected from the group consisting of La 0.6 Ca 0.4 Fe 0.4 Mn 0.6 O 3 , La 0.6 Ca 0.4 Al 0.4 Mn 0.6 O 3 , La 0.6 Ba 0.4 Fe 0.6 Al 0.4 O 3 , La 0.6 Ca 0.4 Cr 0.4 Mn 0.6 O 3 , La 0.6 Ca 0.4 Cr 0.6 Al 0.4 O 3 , La 0.6 Ca 0.4 Cr 0.6 Fe 0.4 O 3 , La 0.6 Ba 0.4 Mn 0.6 Fe 0.4 O 3 , La 0.6 Ba 0.4 MnO 3 , La 0.6 Ba 0.4 Mn 0.6 Cr 0.4 O 3 , La 0.6 Ba 0.4 Cr 0.8 Co 0.2 O 3 , La 0.6 Ca 0.4 Cr 0.8 Co 0.2 O 3 , and La 0.6 Ba 0.4 Cr 0.6 Fe 0.4 O 3 .

Assignees

• Kuhn John N
• Maiti Debtanu
• Daza Yolanda A
• Hare Bryan J
• Ramos Adela E
• Bhethanabotla Venkat R
• Univ South Florida

Inventors

• Kuhn John N
• Maiti Debtanu
• Daza Yolanda A
• Hare Bryan J
• Ramos Adela E
• Bhethanabotla Venkat R

Classifications

• C01B32/40

  Carbon monoxide · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01P2002/34

  perovskite-type (ABO3) · CPC title

• C01F17/34

  Aluminates, e.g. YAlO3 or Y3-xGdxAl5O12 · CPC title

• C01F17/32

  oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO · CPC title