Inorganic nanoparticle deposited catalyst for hydrogenation and manufacturing method of the same, and hydrogenation for biomass derived hydrocarbon compounds

Patent metadata

Field	Value
Publication number	US-9421527-B2
Application number	US-201414513529-A
Country	US
Kind code	B2
Filing date	Oct 14, 2014
Priority date	Feb 13, 2014
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

A hydrogenation catalyst and a method of hydrogenating a hydrocarbon compound as a substrate using the same are provided. The hydrogenation catalyst includes inorganic nanoparticles and a nitrogen-doped reduced graphene oxide support for supporting the inorganic nanoparticles, and the hydrocarbon compound is derived from a biomass and contains a functional group. Therefore, the hydrogenation catalyst which exhibits a high conversion rate and high selectivity, is stable, and can be easily separated after a hydrogenation reaction, and whose catalytic activities are not significantly altered even when recovered and repeatedly recycled can be provided. The method of hydrogenating a hydrocarbon compound in which hydrogen can be directly produced in a reactor using formic acid as a hydrogen source without supplying additional hydrogen gas and simultaneously be used under normal pressure can also be provided.

First claim

What is claimed is:

1. A hydrogenation catalyst, comprising:
inorganic nanoparticles; and
a nitrogen-doped reduced graphene oxide support for supporting the inorganic nanoparticles;
wherein the inorganic nanoparticles comprise silver nanoparticles, palladium nanoparticles, and Fe 3 O 4 nanoparticles.

2. The hydrogenation catalyst of claim 1 , wherein the inorganic nanoparticles have an average particle size of 3 to 10 nm.

3. The hydrogenation catalyst of claim 1 , wherein the hydrogenation catalyst comprises the inorganic nanoparticle at 1 to 5 atomic %.

4. A method of manufacturing a hydrogenation catalyst, comprising:
obtaining a nitrogen-doped reduced graphene oxide by reacting a nitrogen-containing compound with a colloidal suspension of graphene oxide;
obtaining a dispersion of the nitrogen-doped reduced graphene oxide by dispersing the nitrogen-doped reduced graphene oxide in water;
dispersing the dispersion of the nitrogen-doped reduced graphene oxide by adding an aqueous solution of an inorganic nanoparticle precursor to the dispersion of the nitrogen-doped reduced graphene oxide, wherein the inorganic nanoparticle precursor comprises salts of silver, palladium and iron; and
adding a reducing agent to perform a reaction.

5. The method of claim 4 , wherein the inorganic nanoparticle precursor is selected from the group consisting of a chloride, a sulfate, a nitrate, a carbonate of the inorganic nanoparticle, and a mixture thereof.

6. The method of claim 4 , wherein the reducing agent is selected from the group consisting of hydrazine, hydrazine hydrate, a borohydride, sodium borohydride, and a mixture thereof.

7. A method of hydrogenating a biomass-derived hydrocarbon compound, comprising:
a hydrogenation operation of allowing a hydrocarbon compound as a substrate to react with the catalyst of claim 1 in the presence of a hydrogen source,
wherein the hydrocarbon compound is derived from a biomass and contains a functional group.

8. The method of claim 7 , wherein the hydrogen source is formic acid.

9. The method of claim 7 , wherein the hydrogenation operation is performed without supplying hydrogen gas from the outside of a reactor.

10. The method of claim 7 , wherein the hydrogenation operation is performed under reaction conditions of 80 to 130° C. and 6 to 12 hours.

11. The method of claim 7 , wherein the hydrogen source is used at an equivalent content of 1.5 to 3.5 moles, based on the total content of the substrate.

12. The method of claim 7 , wherein the hydrocarbon catalyst is used at a content of 1.8 to 4.0 g per mole of a reaction product, based on the total content of the inorganic nanoparticles included in the catalyst.

13. The method of claim 7 , wherein the substrate is at least one compound selected from the group consisting of an aromatic compound containing a carbonyl group, a hydrocarbon compound containing an alkene group, a hydrocarbon compound containing an alkyne group, and a hydrocarbon compound containing a nitro group.

14. The method of claim 13 , wherein the substrate is vanillin.

15. The method of claim 7 , wherein the catalyst comprises the inorganic nanoparticles having an average particle size of 3 to 10 nm.

16. The method of claim 7 , wherein the catalyst comprises the inorganic nanoparticle at a content of 1 to 5 atomic %.

17. The method of claim 7 , further comprising:
recovering the catalyst after the hydrogenation operation.

18. The method of claim 17 , wherein the recovering of the catalyst is performed using at least one method selected from the group consisting of centrifugation, filtration, and a magnetic method.

Assignees

• Postech Academy-Industry Found

Inventors

• Kim Dong-Pyo
• Singh Ajay K

Classifications

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J2235/15

  X-ray diffraction · CPC title