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

Patent metadata

Field	Value
Publication number	US-2021060534-A1
Application number	US-201816958493-A
Country	US
Kind code	A1
Filing date	Dec 27, 2018
Priority date	Dec 29, 2017
Publication date	Mar 4, 2021
Grant date	—

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

1 . A carbon-based noble metal-transition metal catalyst enabling selective conversion, which is a hydrogenation catalyst using porous carbon as a carrier, 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.

2 . The carbon-based noble metal-transition metal catalyst of claim 1 , wherein the carbon includes at least one selected from the group consisting of activated carbon, carbon black, graphite, graphene, ordered mesoporous carbon (OMC), and carbon nanotubes.

3 . The carbon-based noble metal-transition metal catalyst of claim 1 , wherein the active metal includes:
one or more noble metals selected from the group consisting of palladium (Pd), rhodium (Rh), ruthenium (Ru), and platinum (Pt); and one or more transition metals selected from the group consisting of tin (Sn), iron (Fe), rhenium (Re), and gallium (Ga).

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

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

6 . The carbon-based noble metal-transition metal catalyst of claim 5 , 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.

7 . The carbon-based noble metal-transition metal 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.

8 . The carbon-based noble metal-transition metal 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.

9 . A use of a hydrogenation catalyst for hydrogenating a carboxylic acid group to an alcohol group by using the catalyst according to claim 1 .

10 . A method for producing a carbon-based noble metal-transition metal 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 once or more times.

11 . The method of claim 10 , wherein the pre-treatment process is performed in a temperature range of 50° C. to 150° C.

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

13 . The method of claim 10 , wherein the pre-treatment process is performed before the active metal is supported.

14 . A hydrogenation method for hydrogenating a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group to an alcohol functional group by using the catalyst according to claim 1 .

15 . The hydrogenation method of claim 14 , 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.

16 . The hydrogenation method of claim 14 , 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, adipic acid, sebacic acid, cyclohexane carboxylic acid, and benzoic acid.

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

18 . The hydrogenation method of claim 14 , wherein ketones having the ketone functional group include acetone, butanone, pentanone, hexanone, cyclohexanone, and acetophenone.

Assignees

• Hanwha Solutions Corp

Inventors

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

Classifications

• B01J37/0207

  Pretreatment of the support · CPC title

• B01J35/54

  Bars or plates · 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