Carbon-based, precious metal-transition metal composite catalyst and preparation method therefor

Patent metadata

Field	Value
Publication number	US-11969711-B2
Application number	US-201917417377-A
Country	US
Kind code	B2
Filing date	Dec 10, 2019
Priority date	Dec 31, 2018
Publication date	Apr 30, 2024
Grant date	Apr 30, 2024

Abstract

The present invention relates to a carbon-based precious metal-transition metal composite catalyst and a preparation method therefor, and more particularly, to a catalyst synthesis method in which, when preparing a high-content precious metal-transition metal composite catalyst, a catalyst having uniform particles and composition can be prepared, and cyclohexane dimethanol (CHDM) is efficiently produced by the hydrogenation reaction of cyclohexane dicarboxylic acid (CHDA) in an aqueous solution. Provided is a method for preparing a carbon-based precious metal-transition metal composite catalyst, wherein, in the carbon-based precious metal-transition metal composite catalyst, the precious metal is included in an amount of 10-20 parts by weight, and the transition metal is included in an amount of 10-20 parts by weight based on 100 parts by weight of the composite catalyst, and thus a total amount of the precious metal-transition metal is 20-40 parts by weight based on 100 parts by weight of the composite catalyst.

First claim

The invention claimed is:

1. A carbon-based precious metal-transition metal composite catalyst comprising 10-20 parts by weight of the precious metal and 10-20 parts by weight of the transition metal based on 100 parts by weight of the composite catalyst, wherein a total amount of the precious metal-transition metal is 20-40 parts by weight based on 100 parts by weight of the composite catalyst, wherein the precious metal-transition metal forms a homogeneous mixed phase.

2. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the precious metal includes one or more selected from the group consisting of palladium (Pd), rhodium (Rh), ruthenium (Ru), and platinum (Pt).

3. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the transition metal includes one or more selected from the group consisting of tin (Sn), iron (Fe), rhenium (Re), and gallium (Ga).

4. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the precious metal-transition metal is an active metal having a metal crystallite size of 1-20 nm.

5. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the precious metal and the transition metal are supported on a support in a range of 0.5-3 moles of the transition metal with respect to 1 mole of the precious metal.

6. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein an average particle size (d 50 ) of the precious metal-transition metal composite catalyst is 3-50 μm.

7. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the carbon includes one or more selected from the group consisting of activated carbon, carbon black, graphite, graphene, ordered mesoporous carbon (OMC), and carbon nanotubes.

8. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the carbon has a specific surface area of 100-1,500 m 2 /g and a pore volume of 0.1-1.5 ml/g.

9. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the carbon has ordered mesopores of 2-25 nm.

10. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the carbon support is pretreated with an aqueous nitric acid (HNO 3 ) solution, and includes 1-50 parts by weight of nitric acid based on 100 parts by weight of the total aqueous nitric acid (HNO 3 ) solution.

11. The carbon-based precious metal-transition metal composite catalyst of claim 1 , wherein the composite catalyst is used in a hydrogenation reaction.

12. The carbon-based precious metal-transition metal composite catalyst of claim 11 , wherein the hydrogenation reaction reduces a dicarboxylic acid group to a dialcohol group.

13. The carbon-based precious metal-transition metal composite catalyst of claim 11 , wherein the hydrogenation reaction reduces a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group to an alcohol functional group.

14. The carbon-based precious metal-transition metal composite catalyst of claim 13 , wherein the carboxylic acid functional group includes one or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isopthalic acid, cyclohexane dicarboxylic acid, and terephthalic acid.

15. A method for preparing a carbon-based precious metal-transition metal composite catalyst, the method comprising the steps of:
(a) preparing a support dispersion in which a carbon support is dispersed in a solvent;
(b) adding a precious metal-transition metal precursor aqueous solution and a precipitant to the support dispersion, supporting a metal oxide or a metal hydrate on the carbon support, and performing precipitating thereon; and
(c) reducing and passivating the precipitate,
wherein the precious metal-transition metal forms a homogeneous mixed phase.

16. The method of claim 15 , wherein the precious metal-transition metal composite catalyst includes 10-20 parts by weight of the precious metal and 10-20 parts by weight of the transition metal based on 100 parts by weight of the composite catalyst, and a total amount of the precious metal-transition metal is 20-40 parts by weight based on 100 parts by weight of the composite catalyst.

17. The method of claim 15 , wherein the precious metal in the step (b) includes one or more selected from the group consisting of palladium (Pd), rhodium (Rh), ruthenium (Ru), and platinum (Pt).

18. The method of claim 15 , wherein the transition metal in the step (b) includes one or more selected from the group consisting of tin (Sn), iron (Fe), rhenium (Re), and gallium (Ga).

19. The method of claim 15 , wherein the precipitating in step (b) uses an alkaline solution precipitant, and the precipitant includes one or more selected from the group consisting of hydroxide (OH − ), carbonate (CO 3 2- ), and urea.

20. The method of claim 15 , wherein a pH is 3-7 when a precipitate is produced in the precipitating in the step (b).

21. The method of claim 15 , wherein the reducing in the step (c) is performed in a range of 300-600° C. in a hydrogen atmosphere.

Assignees

• Hanwha Solutions Corp

Inventors

• Kim Jeong Kwon
• Yook Sun Woo
• Jeon Bong Sik
• Myeong Wan Jae

Classifications

• B01J35/647

  2-50 nm · CPC title

• B01J35/638

  more than 1.0 ml/g · CPC title

• B01J35/635

  0.5-1.0 ml/g · CPC title

• B01J35/633

  less than 0.5 ml/g · CPC title

• B01J35/618

  more than 1000 m2/g · CPC title