Carbon-based noble metal-transition metal catalyst enabling high selective conversion and production method therefor

Patent metadata

Field	Value
Publication number	US-11517880-B2
Application number	US-201816958493-A
Country	US
Kind code	B2
Filing date	Dec 27, 2018
Priority date	Dec 29, 2017
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

Provided are a carbon-based noble metal-transition metal composite catalyst enabling high selective conversion of a carboxylic acid functional group into an alcohol functional group by pre-treating a carbon carrier including a predetermined ratio or more of mesopores, and a production method therefor.

First claim

The invention claimed is:

1. A carbon-based catalyst enabling selective conversion, which is a hydrogenation catalyst comprising porous carbon as a carrier and an active metal supported on the carbon, wherein
the carbon is 50% or more in a volume ratio of mesopores having a pore size of 2 nm to 50 nm among the total pores, and an amount of an active metal is in a range of 1 part by weight to 20 parts by weight based on 100 parts by weight of the carrier, and
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,
wherein the active metal comprises:
one or more noble metals selected from the group consisting of palladium (Pd), rhodium (Rh), ruthenium (Ru), and platinum (Pt); and
one or more metals selected from the group consisting of tin (Sn), iron (Fe), rhenium (Re), and gallium (Ga).

2. The carbon-based catalyst of claim 1 , wherein the noble metal is ruthenium, and the metal is tin.

3. The carbon-based catalyst of claim 1 , wherein the carbon carrier is pre-treated with an aqueous nitric acid (HNO 3 ) solution.

4. The carbon-based catalyst of claim 3 , wherein the aqueous nitric acid (HNO 3 ) solution includes 1 part by weight to 50 parts by weight of nitric acid based on 100 parts by weight of the solution.

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

6. The carbon-based catalyst of claim 1 , wherein the carbon has a three-dimensional rod-shaped or three-dimensional tubular pore structure having ordered mesopores of 2 nm to 25 nm.

7. A hydrogenation method comprising hydrogenating a carboxylic acid group to an alcohol group in the presence of the catalyst according to claim 1 .

8. A method for producing the carbon-based catalyst enabling high selective conversion according to claim 1 , wherein the carbon carrier is pre-treated with an aqueous nitric acid (HNO 3 ) solution including 1 part by weight to 50 parts by weight of nitric acid one or more times.

9. The method of claim 8 , wherein the pre-treatment process is performed in a temperature range of 50° C. to 150° C.

10. The method of claim 8 , wherein the pre-treatment process is performed for 1 hour to 10 hours.

11. The method of claim 8 , wherein the pre-treatment process is performed before the active metal is supported.

12. A hydrogenation method comprising hydrogenating a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group to an alcohol functional group in the presence of the catalyst according to claim 1 .

13. The hydrogenation method of claim 12 , wherein the carboxylic acid includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isopthalic acid, terephthalic acid, formic acid, acetic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearylic acid, oleic acid, maleic acid, cyclohexane carboxylic acid, and benzoic acid.

14. The hydrogenation method of claim 12 , wherein aldehydes having the aldehyde functional group include formaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, valeraldehyde, 2-methylbutylaldehyde, 3-methylbutylaldehyde, 2,2-dimethylpropionaldehyde, caproaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutylaldehyde, 2,2-dimethylbutylaldehyde, 3,3-dimethylbutylaldehyde, caprylaldehyde, caprinealdehyde, and glutalaldehyde.

15. The hydrogenation method of claim 12 , wherein ketones having the ketone functional group include acetone, butanone, pentanone, hexanone, cyclohexanone, and acetophenone.

16. A hydrogenation method comprising hydrogenating a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group to an alcohol functional group in the presence of a hydrogenation catalyst comprising porous carbon as a carrier and an active metal supported on the carbon,
wherein a hydrogenation reaction pressure is 2 MPa to 15 MPa, a reaction temperature is 140° C. to 280° C., and a reaction time is 0.5 hours to 10 hours, and
the carbon is 50% or more in a volume ratio of mesopores having a pore size of 2 nm to 50 nm among the total pores, and an amount of an active metal is in a range of 1 part by weight to 20 parts by weight based on 100 parts by weight of the carrier.

Assignees

• Hanwha Solutions Corp

Inventors

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

Classifications

• B01J23/626 Primary

  with tin · CPC title

• B01J23/8906

  Iron and noble metals · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• B01J37/0207

  Pretreatment of the support · CPC title

• C07C29/149

  with hydrogen or hydrogen-containing gases · CPC title