Methods and compositions for microwave catalytic ammonia synthesis

Patent metadata

Field	Value
Publication number	US-10974969-B2
Application number	US-201816127843-A
Country	US
Kind code	B2
Filing date	Sep 11, 2018
Priority date	Sep 11, 2018
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

In one aspect, the disclosure relates to relates to heterogeneous catalysts useful for the synthesis of ammonia under microwave irradiation, processes for preparing the disclosed heterogeneous catalysts, and processes for synthesizing ammonia using the heterogeneous catalysts with microwave irradiation. In various aspects, the disclosed heterogeneous catalysts comprise: a metal selected from Group 7, Group 8, Group 9, Group 10, Group 11, or combinations thereof; a metal oxide support; and optionally a promoter material. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

First claim

What is claimed is:

1. A process for the synthesis of ammonia, comprising:
providing a reaction chamber with a heterogeneous catalyst;
wherein the heterogeneous catalyst comprises a metal selected from Group 7, Group 8, Group 9, Group 10, Group 11, or combinations thereof; wherein the metal is present in an amount from about 0.1 wt % to about 20 wt % based on the total weight of the heterogeneous catalyst; and a metal oxide support;
wherein the reaction chamber has a pressure of about 1 atm to about 20 atm;

conveying a flow of a reactant gas mixture into the reaction chamber via an entry port;
wherein the reactant gas mixture comprises nitrogen and hydrogen;

contacting the reactant gas mixture and the heterogeneous catalyst;
heating the heterogeneous catalyst using microwave energy, thereby providing a product gas mixture; and
wherein the product gas mixture comprises ammonia;

conveying the product gas mixture from the reaction chamber via an exit port.

2. The process of claim 1 , wherein the metal is selected from ruthenium, rhodium, palladium, osmium, iridium, platinum, iron, cobalt, manganese, or combinations thereof.

3. The process of claim 1 , wherein the metal is ruthenium; and wherein the ruthenium is present as ruthenium (0), ruthenium (II), ruthenium (Ill), ruthenium (IV), or combinations thereof.

4. The process of claim 1 , wherein the metal is present in an amount from about 0.5 wt % to about 10 wt %.

5. The process of claim 1 , wherein the metal oxide support comprises MgO, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , or combinations thereof.

6. The process of claim 1 , the heterogeneous catalyst further comprising a promoter material in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the heterogeneous catalyst; wherein the promoter material comprises a Group I compound, a Group II compound, a lanthanide compound, or combinations thereof; and wherein when a combination of promoter materials is present, each is present in an amount independent of any other promoter material.

7. The process of claim 5 , wherein the promoter material is present in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the heterogeneous catalyst; wherein the promoter material comprises an oxide of K, Ce, Ba, or combinations thereof.

8. The process of claim 1 , wherein the heterogeneous catalyst has an average particle size (d) of about 0.5 nm to about 30 nm.

9. The process of claim 1 , wherein the reactant gas mixture comprises about 15 vol % to about 25 vol % of nitrogen; and about 45 vol % to about 75 vol % of hydrogen; provided that the vol % ratio of nitrogen to hydrogen is about 1 to about 5 and the total vol % of all gases in the reactant gas mixture is equal to about 100 vol %.

10. The process of claim 1 , wherein the vol % ratio of hydrogen to nitrogen is about 2 to about 5.

11. The process of claim 10 , wherein the vol % ratio of hydrogen to nitrogen is about 2.5 to about 3.5.

12. The process of claim 1 , wherein the heating the reaction chamber is using microwave energy having at a frequency of about 1 MHz to about 50 GHz.

13. The process of claim 1 , wherein the product gas mixture has an ammonia concentration of about 10 ppm to about 30 vol %.

14. The process of claim 1 , wherein the process yields ammonia at about 0.001 g NH3 /(g catalyst ·hour) to about 2.0 g NH3 (g catalyst ·hour).

15. The process of claim 1 , further comprising reducing the heterogeneous catalyst prior providing the reaction chamber with the heterogeneous catalyst.

16. The process of claim 15 , wherein the reducing the heterogeneous catalyst comprises conveying a flow of a first reducing gas comprising H 2 such that the first reducing gas comprising H 2 contacts the heterogeneous catalyst; and heating the heterogeneous catalyst at a first catalyst reducing temperature from about 100° C. to about 1,000° C. for first catalyst reducing period of time sufficient to reduce at least 80 wt % of the ruthenium to ruthenium (0).

17. The process of claim 15 , wherein the first catalyst reducing period of time is about 1 min to about 12 hours.

18. The process of claim 1 , further comprising reducing the heterogeneous catalyst in the reaction chamber prior to conveying the flow of the reactant gas mixture into the reaction chamber.

19. The process of claim 18 , wherein the reducing the heterogeneous catalyst comprises conveying a flow of a second reducing gas comprising H 2 such that the second reducing gas comprising H 2 contacts the heterogeneous catalyst; and heating the heterogeneous catalyst using microwave energy at a second catalyst reducing temperature from about 100° C. to about 1,000° C. for second catalyst reducing period of time sufficient to reduce at least 80 wt % of the ruthenium to ruthenium (0).

20. A process for the synthesis of ammonia, comprising:
providing a reaction chamber with a heterogeneous catalyst;
wherein the heterogeneous catalyst comprises:
(a) a metal selected from Group 7, Group 8, Group 9, Group 10, Group 11, or combinations thereof; wherein the metal is present in an amount from about 0.1 wt % to about 20 wt % based on the total weight of the heterogeneous catalyst; and a metal oxide support; and
(b) a promoter comprising an oxide of K, an oxide of Ba and an oxide of Ce;

wherein each promoter material is present independently in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the heterogeneous catalyst;
wherein the reaction chamber has a pressure of about 2 torr to about 20 atm;

conveying a flow of a reactant gas mixture into the reaction chamber via an entry port;
wherein the reactant gas mixture comprises nitrogen and hydrogen;

contacting the reactant gas mixture and the heterogeneous catalyst;
heating the heterogeneous catalyst using microwave energy, thereby providing a product gas mixture; and
wherein the product gas mixture comprises ammonia;

conveying the product gas mixture from the reaction chamber via an exit port.

Assignees

• Univ West Virginia
• Battelle Memorial Institute
• Univ Florida State Res Found
• Us Energy

Inventors

• Hu Jianli
• Shekhawat Dushyant
• Wildfire Christina
• Dagle Robert A
• Tian Hanjing
• Stiegman Albert
• Spencer Michael
• Abdelsayed Victor
• Bearden Mark D

Classifications

• B01J35/45

  Nanoparticles · CPC title

• B01J2219/1227

  Reactors comprising tubes with open ends · CPC title

• B01J23/462

  Ruthenium · CPC title

• B01J8/0221

  in a cylindrical shaped bed (B01J8/0214 takes precedence) · CPC title

• B01J19/126

  Microwaves · CPC title