IP Library Granted Patent US 11,925,921
Granted Patent B2
US 11,925,921 · App. 16/994,296 · Granted Mar 12, 2024

Methods of making YSZ supported catalyst, and methods of using the same

Inventors: James Douglas Way (Boulder, CO); Colin A. Wolden (Denver, CO); Zhenyu Zhang (Arvada, CO)
Assignee: COLORADO SCHOOL OF MINES
B01J23/462B01J23/02B01J23/10B01J35/1009B01J37/0201C01C1/0411B01J21/066
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Quick Facts
Patent No.
US 11,925,921
App. No.
16/994,296
Granted
Mar 12, 2024
Kind
B2
Abstract

The present invention relates to catalysts, methods of making catalysts, and methods of using catalysts, where the catalysts include: at least one of a transition metal and a transition metal oxide supported by yttria-stabilized zirconia (YSZ), where the transition metal is promoted by at least one of an alkali metal and an alkaline-earth metal.

Claims (26)

1. A catalyst for synthesizing ammonia, the catalyst comprising:

at least one of a transition metal and a transition metal oxide comprising ruthenium (Ru) supported by yttria-stabilized zirconia (YSZ), wherein the transition metal is promoted by at least one of an alkali metal and an alkaline-earth metal including barium (Ba), and wherein the Ru-supported and Ba-promoted YSZ has an activation energy E a of no more than about 46.2 kJ/mol for synthesis temperatures ranging between 300 degrees Celsius (° C.) and 450° C.

2. The catalyst of claim 1 , wherein the YSZ includes yttrium (Y) and zirconium dioxide (ZrO 2 ), wherein the ZrO 2 is modified by Ba and potassium (K), and wherein the Ru is supported on the Ba-modified and K-modified ZrO 2 .

3. The catalyst of claim 2 , wherein the Ru is alloyed with the Y of the YSZ.

4. The catalyst of claim 1 , wherein the YSZ is a porous YSZ tube, and wherein the porous YSZ tube comprises an outside diameter of 1 centimeter (cm) and a wall thickness of 0.134 cm.

5. The catalyst of claim 4 , wherein the porous YSZ tube comprises 4% yttrium oxide (Y 2 O 3 ) and 96% zirconium dioxide (ZrO 2 ).

6. The catalyst of claim 4 , wherein a Brunauer, Emmett and Teller (BET) surface area of the YSZ is 2.24 square meters per gram (m 2 g −1 ).

7. A method of making a catalyst for synthesizing ammonia, comprising:

providing a support comprising a porous tube yttria-stabilized zirconia (YSZ);

loading at least one of a transition metal and a transition metal oxide comprising ruthenium (Ru) onto the support using wet impregnation; and

loading at least one of an alkali metal and an alkaline-earth metal including Barium (Ba) as a promoter onto the support using wet impregnation, wherein the Ru-supported and Ba-promoted YSZ has an activation energy E a of no more than about 46.2 kJ/mol for synthesis temperatures ranging between 300 degrees Celsius (° C.) and 450° C.

8. The method of claim 7 , wherein multiple promoters comprising the promoter are loaded individually onto the support.

9. The method of claim 7 , wherein the Ru is loaded in a range of about 0.4≤weight percent ≤1.0.

10. The method of claim 7 , wherein the porous tube YSZ comprises about 4% yttrium oxide (Y 2 O 3 ) and about 96% zirconium dioxide (ZrO 2 ).

11. The method of claim 7 , wherein a Brunauer, Emmett and Teller (BET) surface area of the porous tube YSZ is about 2.24 square meters per gram (m 2 g −1 ).

12. A method of producing ammonia, comprising:

providing a catalyst, comprising at least one of a transition metal and a transition metal oxide comprising ruthenium (Ru) supported by yttria-stabilized zirconia (YSZ), wherein the transition metal is promoted by at least one of an alkali metal and an alkaline-earth metal including Cesium (Cs), and wherein the Ru-supported and Cs-promoted YSZ has an activation energy E a of no more than about 65.0 kJ/mol for synthesis temperatures ranging between 300 degrees Celsius (° C.) and 450° C.; and

providing nitrogen and hydrogen to the catalyst to produce the ammonia.

13. The catalyst of claim 1 , wherein the YSZ includes yttrium oxide (Y 2 O 3 ) and zirconium dioxide ZrO 2 .

14. A catalyst for synthesizing ammonia, the catalyst comprising:

at least one of a transition metal and a transition metal oxide comprising ruthenium (Ru) supported by yttria-stabilized zirconia (YSZ), wherein the transition metal is promoted by at least one of an alkali metal and an alkaline-earth metal including cesium (Cs), and wherein the Ru-supported and Cs-promoted YSZ has an activation energy E a of no more than about 65.0 kJ/mol for synthesis temperatures ranging between 300 degrees Celsius (° C.) and 450° C.

15. The catalyst of claim 14 , wherein the YSZ includes yttrium (Y) and zirconium dioxide (ZrO 2 ), wherein the ZrO 2 is modified by Cs and potassium (K), and wherein the Ru is supported on the Cs-modified and K-modified ZrO 2 .

16. The catalyst of claim 15 , wherein the Ru is alloyed with the Y of the YSZ.

17. The catalyst of claim 14 , wherein the YSZ is a porous YSZ tube, and wherein the porous YSZ tube comprises an outside diameter of 1 centimeter (cm) and a wall thickness of 0.134 cm.

18. The catalyst of claim 17 , wherein the porous YSZ tube comprises 4% yttrium oxide (Y 2 O 3 ) and 96% zirconium dioxide (ZrO 2 ).

19. The catalyst of claim 17 , wherein a Brunauer, Emmett and Teller (BET) surface area of the YSZ is 2.24 square meters per gram (m 2 g −1 ).

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 28, 2023
From: WAY, JAMES DOUGLAS; WOLDEN, COLIN A.; ZHANG, ZHENYU
To: COLORADO SCHOOL OF MINES
Reel/Frame 064094/0055 →
CONFIRMATORY LICENSE Recorded Dec 7, 2020
From: COLORADO SCHOOL OF MINES
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 054560/0772 →
Continuity (2)
Provisional Application 62886770 · Aug 14, 2019
Related Publication 20210046456A1 · Feb 18, 2021