Catalyst composite for conversion of methane gas and method for converting methane gas using the same

Patent metadata

Field	Value
Publication number	US-11077429-B2
Application number	US-201816233686-A
Country	US
Kind code	B2
Filing date	Dec 27, 2018
Priority date	Dec 29, 2017
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

Abstract

The present disclosure relates to a catalyst composite for conversion of methane gas, which includes Co3O4 nanoplates and ZrO2 nanoparticles adsorbed to the surface of the Co3O4 nanoplates, and is used for converting methane gas into alcohols, and a method for conversion of methane gas using the same. When using the catalyst composite, it is possible to convert methane gas into alcohols with high efficiency under a mild condition of room temperature and ambient pressure.

First claim

What is claimed is:

1. An electrochemical catalyst for conversion of methane gas, which comprises:
a conductive substrate selected from graphite paper, graphene, carbon black, copper, nickel and alumina;
a catalyst composite layer for conversion of methane gas, formed on the conductive substrate; and
optionally, a cover layer for protecting the catalyst composite layer for conversion of methane gas,
wherein the catalyst composite layer comprises a support and ZrO 2 nanoparticles adsorbed to the surface of the support, wherein the support has a structure of Co 3 O 4 nanoplates or NiCo 2 O 4 nanowires, and the catalyst composite is used for converting methane gas into alcohols.

2. The electrochemical catalyst for conversion of methane gas according to claim 1 , wherein when the support is Co 3 O 4 nanoplates, the elemental ratio of Co to Zr in the catalyst composite may be 0.2:1-6.5:1, and
when the support is NiCo 2 O 4 nanowires, the elemental ratio of Zr:Ni:Co in the composite may be 0.1-2.5:2-3:5.

3. The electrochemical catalyst for conversion of methane gas according to claim 1 , which is coated with graphene.

4. The electrochemical catalyst for conversion of methane gas according to claim 3 , wherein the ZrO 2 nanoparticles have an average particle diameter of 10 nm-1 μm, and the Co 3 O 4 nanoplates have an average particle diameter of 1 μm -10 μm.

5. The electrochemical catalyst for conversion of methane gas according to claim 1 , wherein the ZrO 2 nanoparticles have a spherical shape, rod-like shape, hollow shape, or an ellipsoidal solid shape.

6. The electrochemical catalyst for conversion of methane gas according to claim 1 , wherein the adsorption is physical adsorption.

7. A method for preparing an electrochemical catalyst for conversion of methane gas as claimed in claim 1 , comprising the steps of:
(a) introducing ZrOCl 2 hydrate, Co(NO 3 ) 2 hydrate and hydroxide to water and dissolving them therein to obtain an aqueous precursor solution;
(b) heating the aqueous precursor solution to 150-250° C. to precipitate ZrO 2 /Co 3 O 4 composite powder;
(c) carrying out centrifugal separation of the product of step (b) to obtain ZrO 2 /Co 3 O 4 powder; and
(d) washing and drying the ZrO 2 /Co 3 O 4 powder of step (c) and carrying out heat treatment at 400-600° C. to obtain a ZrO 2 /Co 3 O 4 catalyst composite.

8. The method for preparing a catalyst composite for conversion of methane gas according to claim 7 , wherein the hydroxide is any one selected from Na(OH), K(OH), Ca(OH) 2 and Sr(OH) 2.

9. The method for preparing a catalyst composite for conversion of methane gas according to claim 7 , wherein the ZrOCl 2 hydrate and Co(NO 3 ) 2 hydrate are mixed at a molar compositional ratio of 1:1-1:6.

10. A method for conversion of methane gas, comprising: carrying out electrochemical oxidation of methane gas at a graphite electrode surface-coated with the ZrO 2 /Co 3 O 4 electrochemical catalyst as defined in claim 1 to convert methane gas into alcohols.

11. The method for conversion of methane gas according to claim 10 , wherein the coating is carried out by adding a dispersion of the ZrO 2 /Co 3 O 4 catalyst composite in water to a graphite electrode, followed by drying.

12. The method for conversion of methane gas according to claim 10 , wherein the electrode surface-coated with the ZrO 2 /Co 3 O 4 catalyst composite is further coated with a protective layer on the catalyst composite layer.

13. The method for conversion of methane gas according to claim 10 , which further comprises a step of removing oxygen through bubbling of methane in a carbonate electrolyte before the electrochemical oxidation.

14. The method for conversion of methane gas according to claim 10 , wherein the final product obtained by the electrochemical oxidation comprises at least one selected from 1-propanol, 2-propanol, methanol, formaldehyde, ethanol, acetaldehyde and acetone.

15. The method for conversion of methane gas according to claim 14 , wherein 1-propanol and 2-propanol are produced from acetaldehyde.

16. The method for conversion of methane gas according to claim 15 , wherein 1-propanol and 2-propanol are produced through nucleophilic addition and free radical addition.

17. The method for conversion of methane gas according to claim 10 , wherein the electrochemical oxidation is carried out at room temperature under ambient pressure, or under pressure to increase the solubility of methane.

Assignees

• Univ Yonsei Iacf

Inventors

• Park Jong Hyeok
• Kim Jiwon
• Ma Ming

Classifications

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J35/23

  in a colloidal state · CPC title

• B01J35/50

  characterised by their shape or configuration · CPC title

• B01J35/54

  Bars or plates · CPC title

• B01J35/51

  Spheres · CPC title