Noble metal-transition metal complex catalyst supported on carbon-coated silica-alumina support, and preparation method therefor

Patent metadata

Field	Value
Publication number	US-11912653-B2
Application number	US-201816958430-A
Country	US
Kind code	B2
Filing date	Dec 26, 2018
Priority date	Dec 29, 2017
Publication date	Feb 27, 2024
Grant date	Feb 27, 2024

Abstract

Provided are a noble metal-transition metal complex catalyst supported on a carbon-coated silica-alumina support and a preparation method therefor, the catalyst being capable of obtaining a fast reaction rate and catalyst stability, as compared to a conventional catalyst, when cyclohexane dimethanol (CHDM) production is carried out by a cyclohexane dicarboxylic acid (CHDA) hydrogenation reaction in an aqueous solution by using a carbon-coated supported catalyst.

First claim

The invention claimed is:

1. A noble metal-transition metal complex catalyst supported on a carbon-coated silica-alumina carrier, wherein
40 parts by weight to 95 parts by weight of alumina (Al 2 O 3 ) and 5 parts by weight to 60 parts by weight of silica (SiO 2 ) are included based on 100 parts by weight of the carbon-coated silica-alumina carrier; and
2 parts by weight to 20 parts by weight of the noble metal and the transition metal are included based on 100 parts by weight of the carbon-coated silica-alumina carrier,
wherein the noble metal includes one or more selected from the group consisting of palladium (Pd), rhodium (Rh), ruthenium (Ru), and platinum (Pt),
the transition metal includes one or more selected from the group consisting of tin (Sn), iron (Fe), rhenium (Re), and gallium (Ga), and
an amount of the transition metal is in a range of 1 part by weight to 10 parts by weight based on 100 parts by weight of the carbon-coated silica-alumina carrier.

2. The noble metal-transition metal complex catalyst of claim 1 , wherein an amount of the noble metal is in a range of 1 part by weight to 10 parts by weight based on 100 parts by weight of the carbon-coated silica-alumina carrier.

3. The noble metal-transition metal complex catalyst of claim 1 , wherein a noble metal precursor and a transition metal precursor are supported on the carbon-coated silica-alumina carrier at the same molar ratio before being reduced with hydrogen.

4. The noble metal-transition metal complex catalyst of claim 1 , wherein the carbon is coated on the surface of the silica-alumina through a carbonization process.

5. A hydrogenation method comprising hydrogenating a dicarboxylic acid group in the presence of the catalyst according to claim 1 .

6. The hydrogenation method of claim 5 , wherein the dicarboxylic acid is one selected from the group consisting of an oxalic acid, a malonic acid, a succinic acid, a glutaric acid, an adipic acid, a pimelic acid, a suberic acid, an azelaic acid, a sebacic acid, a malic acid, an aspartic acid, a glutamic acid, a phthalic acid, an isopthalic acid, a terephthalic acid, and a cyclohexane dicarboxylic acid.

7. A method for preparing the noble metal-transition metal complex catalyst supported on a carbon-coated silica-alumina carrier of claim 1 , the method comprising:
(a) preparing a complex by dissolving a boric acid in an aqueous carbon precursor solution and supporting the resultant mixture on silica-alumina (SiO 2 —Al 2 O 3 );
(b) carbonizing the complex;
(c) supporting a noble metal-transition metal on a carbon-coated silica-alumina (SiO 2 —Al 2 O 3 ) carrier; and
(d) reducing a noble metal-transition metal oxide supported on the silica-alumina (SiO 2 —Al 2 O 3 ) carrier with hydrogen.

8. The method of claim 7 , wherein, in the step (a), the carbon precursor and the boric acid are added at a weight ratio of 1:0.005 to 1:0.1.

9. The method of claim 7 , wherein, in the step (a), the complex is prepared by being supported on the carrier by incipient-wetness impregnation.

10. The method of claim 7 , wherein, in the step (b), the carbonization process is performed in a temperature range of 300° C. to 700° C. in a nitrogen atmosphere.

11. The method of claim 7 , wherein, in the step (c), the noble metal and the transition metal are supported in 2 parts by weight to 20 parts by weight based on 100 parts by weight of the carbon-coated silica-alumina carrier.

12. The method of claim 7 , wherein, in the step (d), the reduction process is performed in a temperature range of 400° C. to 600° C.

Assignees

• Hanwha Solutions Corp

Inventors

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

Classifications

• C07C31/276 Primary

  with a six-membered ring · CPC title

• B01J21/12

  Silica and alumina · CPC title

• B01J21/18

  Carbon · CPC title

• B01J23/626 Primary

  with tin · CPC title

• B01J37/0205

  in several steps · CPC title