Supported metal catalyst and method of synthesizing ammonia using the same

Patent metadata

Field	Value
Publication number	US-10173202-B2
Application number	US-201515121702-A
Country	US
Kind code	B2
Filing date	Feb 12, 2015
Priority date	Feb 27, 2014
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

A catalyst is provided which is used for continuously synthesizing ammonia using a gas containing hydrogen and nitrogen as a raw material, wherein a transition metal which exhibits catalytic activity is supported by a support, and the support is a two-dimensional electride or a precursor thereof. The two-dimensional electride or the precursor thereof is a metal nitride represented by MxNyHz (M represents one or two or more of Group II metals selected from the group consisting of Mg, Ca, Sr and Ba, and x, y and z are in ranges of 1≤x≤11, 1≤y≤8, and 0≤z≤4 respectively, in which x is an integer, and y and z are not limited to an integer) or M 3 N 2 (M is the same as above), or a metal carbide selected from the group consisting of Y 2 C, Sc 2 C, Gd 2 C, Tb 2 C, Dy 2 C, Ho 2 C and Er 2 C. These catalysts are used for continuously reacting nitrogen with hydrogen, which are raw materials, on the catalyst, wherein the reaction is performed in an ammonia synthesis reaction system under the preferable conditions of a reaction temperature which is equal to or higher than 100° C. and equal to or lower than 600° C., and a reaction pressure which is equal to or higher than 10 kPa and lower than 20 MPa.

First claim

The invention claimed is:

1. A supported metal catalyst, comprising:
a transition metal which exhibits catalytic activity,
wherein the transition metal is supported by a support, and
the support is a two-dimensional electride or a precursor thereof,
wherein the two-dimensional electride or a precursor thereof is a metal nitride represented by MxNyHz or a hydride thereof,
wherein
M represents one or two or more of Group II metals selected from the group consisting of Mg, Ca, Sr and Ba, and
x, y and z are in ranges of 1≤x≤11, 1≤y≤8, and 0≤z≤4 respectively, in which x is an integer, and y and z are not limited to an integer.

2. The supported metal catalyst according to claim 1 , wherein the supported metal catalyst is a catalyst suitable for synthesizing ammonia.

3. The supported metal catalyst according to claim 1 , wherein the supported metal catalyst is a catalyst suitable for synthesizing ammonia, wherein a gas comprising hydrogen and nitrogen is used as a raw material.

4. The supported metal catalyst according to claim 2 , wherein the ammonia is synthesized continuously.

5. The supported metal catalyst according to claim 1 , wherein the two-dimensional electride or a precursor thereof is a metal nitride represented by M 3 N 2 .

6. The supported metal catalyst according to claim 1 , wherein the two-dimensional electride or a precursor thereof is at least one of Ca 3 N 2 and Mg 3 N 2 .

7. The supported metal catalyst according to claim 1 , wherein the two-dimensional electride or a precursor thereof is a Ca—N—H-based compound.

8. The supported metal catalyst according to claim 1 , wherein the transition metal is at least one selected from the group consisting of Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh and Ir.

9. The supported metal catalyst according to claim 1 , wherein the transition metal is at least one selected from the group consisting of Ru, Co and Fe.

10. The supported metal catalyst according to claim 1 , wherein an amount of the transition metal is in a range of 0.01 to 30 wt % with respect to that of the support.

11. A method of synthesizing ammonia, comprising: preparing (a) the supported metal catalyst of claim 1 , and (b) gas comprising hydrogen and the nitrogen, which is used as a raw material; and reacting the nitrogen with the hydrogen on the catalyst in an ammonia synthesis reaction device, in which the supported metal catalyst is provided, to synthesize ammonia.

12. The method of synthesizing ammonia according to claim 11 , wherein the reaction of the nitrogen and the hydrogen is performed at a reaction temperature which is equal to or higher than 100° C. and equal to or lower than 600° C.

13. The method of synthesizing ammonia according to claim 11 , wherein the reaction of the nitrogen and the hydrogen is performed at a reaction pressure which is equal to or higher than 10 kPa and lower than 20 MPa.

14. A supported metal catalyst, comprising:
a transition metal which exhibits catalytic activity,
wherein the transition metal is supported by a support, and
the support is a two-dimensional electride or a precursor thereof,
wherein
the two-dimensional electride or a precursor thereof is selected from (a) to (c):
(a) at least one compound selected from the group consisting of Ca 2 N, Sr 2 N, Ba 2 N, Ca 2 NH, CaNH, Ca(NH 2 ) 2 , Y 2 C, Sc 2 C, Gd 2 C, Tb 2 C, Dy 2 C, Ho 2 C and Er 2 C;
(b) at least one compound selected from the group consisting of Ca 2 N, Sr 2 N and Ba 2 N, wherein a part of Ca of Ca 2 N, Sr of Sr 2 N, and Ba of Ba 2 N is substituted with at least one or more of alkaline metal elements selected from the group consisting of Li, Na. K, Rb and Cs; and
(c) a metal carbide selected from the group consisting of Y 2 C, Sc 2 C, Gd 2 C, Tb 2 C, Dy 2 C, Ho 2 C and Er 2 C, or is a hydride thereof.

15. A method of synthesizing ammonia, comprising: preparing (a) the supported metal catalyst of claim 14 , and (b) gas comprising hydrogen and the nitrogen, which is used as a raw material; and reacting the nitrogen with the hydrogen on the catalyst in an ammonia synthesis reaction device, in which the supported metal catalyst is provided, to synthesize ammonia.

16. The method of synthesizing ammonia according to claim 15 , wherein the reaction of the nitrogen and the hydrogen is performed at a reaction temperature which is equal to or higher than 100° C. and equal to or lower than 600° C.

17. The method of synthesizing ammonia according to claim 15 , wherein the reaction of the nitrogen and the hydrogen is performed at a reaction pressure which is equal to or higher than 10 kPa and lower than 20 MPa.

18. The supported metal catalyst according to claim 14 , wherein the transition metal is at least one selected from the group consisting of Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co,Rh and Ir.

19. The supported metal catalyst according to claim 14 , wherein the transition metal is at least one selected from the group consisting of Ru, Co and Fe.

20. The supported metal catalyst according to claim 14 , wherein an amount of the transition metal is in a range of 0.01 to 30 wt % with respect to that of the support.

Assignees

• Japan Science & Tech Agency
• Tokyo Inst Tech

Inventors

• Hosono Hideo
• Hara Michikazu
• Kitano Masaaki
• Yokoyama Toshiharu
• Inoue Yasunori
• Kambara Shinji

Classifications

• C01C1/0411

  characterised by the catalyst · CPC title

• C01B21/0612

  with alkaline-earth metals, beryllium or magnesium · CPC title

• B01J27/24 Primary

  Nitrogen compounds · CPC title

• B01J27/22

  Carbides · CPC title

• B01J23/462

  Ruthenium · CPC title