Supported catalyst, method for preparing same, secondary structure of carbon nanostructure manufactured using same

Patent metadata

Field	Value
Publication number	US-10384200-B2
Application number	US-201414422613-A
Country	US
Kind code	B2
Filing date	Jul 15, 2014
Priority date	Jul 19, 2013
Publication date	Aug 20, 2019
Grant date	Aug 20, 2019

Abstract

The present invention relates to a supported catalyst having a structure in which a metal catalyst is supported on a core-shell structured support. The support includes core particles and shell particles having a smaller particle diameter than the core particles and coated on the core particles to form a shell layer. Due to this structure, the supported catalyst can be used to produce carbon nanostructures that form a novel secondary structure in which ends of the carbon nanostructures are supported on the supported catalyst and form independent branches and the opposite ends grow and are assembled together. The novel structure is expected to find application in various fields, such as energy materials, functional composites, pharmaceuticals, batteries, and semiconductors, because of its characteristic shape.

First claim

What is claimed is:

1. A core-shell structured supported catalyst comprising:
a support; and
a metal catalyst supported on the support,
wherein the support comprises core particles and shell particles having a smaller particle diameter than the core particles,
wherein the shell particles form a shell layer which is formed on the core particles,
wherein the core particles and the shell particles are each made of at least one material selected from the group consisting of AlO(OH) and gamma-Al 2 O 3 ,
wherein the ratio of the diameter (d 50 ) of the core particles to the diameter (d 50 ) of the shell particles is 1:0.0001-0.1,
wherein the supported catalyst comprises a main catalyst selected from Co, Fe, and mixtures thereof, and the auxiliary catalyst is selected from Mo, V, and mixtures thereof, and
wherein the supported catalyst comprises 15 to 25% by weight of the main catalyst based on the total weight of the supported catalyst.

2. The core-shell structured supported catalyst according to claim 1 , wherein the diameter (d 50 ) of the core particles is from 1 to 100 μm.

3. The core-shell structured supported catalyst according to claim 1 , wherein the diameter (d 50 ) of the shell particles is from 0.01 to 0.9 μm.

4. The core-shell structured supported catalyst according to claim 1 , wherein the support comprises 1 to 50% by weight of the shell particles, based on the total weight of the support.

5. The core-shell structured supported catalyst according to claim 1 , wherein the metal catalyst comprises the main catalyst and the auxiliary catalyst in a molar ratio of 20-1:1.

6. The core-shell structured supported catalyst according to claim 1 , wherein the core particles are gamma-Al 2 O 3 and the shell particles are AlO(OH).

7. The core-shell structured supported catalyst according to claim 1 , wherein the supported catalyst is one for carbon nanostructure production.

8. The core-shell structured supported catalyst according to claim 7 , wherein the carbon nanostructures are carbon nanotubes, carbon nanorods, carbon nanohairs, or carbon nanofibers.

9. A method for preparing the supported catalyst according to claim 1 , comprising
a) mixing core particles with shell particles to prepare a core-shell structured support in which the shell particles are coated on the core particles,
b) preparing a metal catalyst precursor solution,
c) mixing the metal catalyst precursor solution with the core-shell structured support to prepare a supported catalyst precursor in which the metal catalyst precursor is supported on the support, and
d) calcining the supported catalyst precursor,
wherein the core particles and the shell particles are made of gamma-Al 2 O 3 .

10. The method according to claim 9 , wherein, in step d), the supported catalyst precursor is calcined at 400 to 800° C.

11. The method according to claim 9 , further comprising calcining the core-shell structured support before mixing of the metal catalyst precursor solution with the core-shell structured support in step c).

12. The method according to claim 9 , wherein a dispersant, an adhesive, or a mixture thereof is mixed with the core particles and the shell particles in step a).

13. A method for producing carbon nanostructures, comprising supplying a mixed gas of an inert gas, a carbon source gas and a reducing gas to the supported catalyst according to claim 1 to allow the mixed gas to react with the supported catalyst.

14. The method according to claim 13 , wherein the mixed gas is supplied at a flow rate of 60 to 270 sccm and is allowed to react with the supported catalyst at 500 to 800° C.

15. The method according to claim 13 , wherein the mixed gas is allowed to react with the supported catalyst for 30 minutes to 5 hours.

16. A carbon nanostructure aggregate comprising:
the supported catalyst according to claim 1 ; and
carbon nanostructures grown on the supported catalyst,
wherein each of the carbon nanostructures comprises a first end in contact with the supported catalyst and a second end positioned opposite the first end and growing in the lengthwise direction, and
wherein at least a part of the carbon nanostructures form a secondary structure in which the first ends are each independently supported on the supported catalyst and the second ends are assembled in contact with each other,
wherein the core particles and the shell particles are made of gamma-Al 2 O 3 .

17. The carbon nanostructure aggregate according to claim 16 , wherein the carbon nanostructures have a strand diameter of at least 0.5 μm and a length of at least 200 μm.

18. The carbon nanostructure aggregate according to claim 16 , wherein the carbon nanostructure aggregate has an average particle diameter of 50 to 1000 μm.

Assignees

• Lg Chemical Ltd

Inventors

• Kim Sungjin
• Lee Dongchul
• Kang Kyungyeon
• Son Seungyong

Classifications

• B01J37/18

  with gases containing free hydrogen · CPC title

• B01J37/0205

  in several steps · CPC title

• B01J23/745

  Iron · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• C01B32/162

  characterised by catalysts · CPC title