Process for the production of a carbon supported catalyst

Patent metadata

Field	Value
Publication number	US-9873107-B2
Application number	US-201515126801-A
Country	US
Kind code	B2
Filing date	Mar 17, 2015
Priority date	Mar 18, 2014
Publication date	Jan 23, 2018
Grant date	Jan 23, 2018

Abstract

A process for the production of a carbon supported catalyst, which comprises the following steps:
(a) precipitation of at least one metal oxide onto a surface of a carbon-comprising support by preparing an initial mixture, comprising the carbon-comprising support, at least one metal oxide precursor and an organic solvent, and spray-drying of the initial mixture to obtain an intermediate product, (b) loading of noble-metal-comprising particles onto the surface of the intermediate product in a liquid medium by deposition, precipitation and/or reduction of a noble-metal-comprising precursor with a reducing agent, (c) heat treatment of the catalyst precursor resulting from step (b) at a temperature higher than 400° C.

First claim

The invention claimed is:

1. A process for the production of a carbon supported catalyst, which comprises the following steps:
(a) precipitation of at least one metal oxide onto a surface of a carbon-comprising support by preparing an initial mixture, comprising the carbon-comprising support, at least one metal oxide precursor and an organic solvent, and spray-drying of the initial mixture to obtain an intermediate product,
(b) loading of noble-metal-comprising particles onto the surface of the intermediate product in a liquid medium by deposition, precipitation and/or reduction of a noble-metal-comprising precursor with a reducing agent,
(c) heat treating the catalyst precursor resulting from step (b) at a temperature higher than 400° C.,

wherein the spray-drying is carried out with a drying gas at a temperature between 60° C. and 300° C.

2. The process according to claim 1 , wherein the at least one metal oxide precursor comprises niobium, titanium, tantalum, molybdenum, vanadium, tungsten, cerium, zirconium, tin, silicon, or mixtures thereof and the metal oxide precursor is an alcoholate or a halide.

3. The process according to claim 1 , wherein the metal oxide precursor is an alcoholate selected from the group consisting of ethanolate, n-propanolate, iso-propanolate, n-butanolate, iso-butanolate and tert-butanolate, or the metal oxide precursor is a chloride.

4. The process according to claim 1 , wherein the organic solvent is an alcohol, a carboxylate ester, acetone or tetrahydrofuran.

5. The process according to claim 1 , wherein the initial mixture comprises less than 2% by weight of water.

6. The process according to claim 1 , wherein the initial mixture comprises up to 20% by weight of water.

7. The process according to claim 1 , wherein the carbon-comprising support has a BET surface area of at least 500m 2 /g.

8. The process according to claim 1 , wherein the carbon-comprising support comprises carbon black, graphene, graphite, activated carbon or carbon nanotubes.

9. The process according to claim 1 , wherein the loaded noble-metal-comprising particles comprise platinum and optionally cobalt, nickel, chromium, copper, palladium, gold, ruthenium, scandium, yttrium, lanthanium, niobium or titanium.

10. A carbon supported catalyst produced according to claim 9 , wherein the carbon supported catalyst comprises between 2% by weight and 25% by weight of niobium oxide, a mass ratio of niobium comprised in the carbon supported catalyst and platinum comprised in the carbon supported catalyst is between 0.05 and 0.5, and at least 90% by number of platinum comprising particles comprised in the carbon supported catalyst have a diameter smaller than 20 nm.

11. The process according to claim 1 , wherein the spray-drying is operated with a residence time of less than 3 minutes.

12. The process according to claim 1 , wherein the heat treatment in step (c) is carried out in a reducing atmosphere.

13. The process according to claim 12 , wherein the reducing atmosphere comprises up to 5% by volume of hydrogen.

14. The process according to claim 1 , wherein a molar ratio of metal comprised in the at least one metal oxide precursor and carbon comprised in the carbon-comprising support in the initial mixture is between 0.00005 and 0.01, a carbon content in the initial mixture is between 1% and 30% by weight and a molar ratio of metal, originating from the at least one metal oxide precursor and comprised in the intermediate product, and the noble-metal-comprising particles comprise platinum and the platinum comprised in the liquid medium is between 0.05 and 0.8.

15. A process for the production of a carbon supported catalyst, which comprises the following steps:
(a) precipitation of at least one metal oxide onto a surface of a carbon-comprising support by preparing an initial mixture, comprising the carbon-comprising support, at least one metal oxide precursor and an organic solvent, and spray-drying of the initial mixture to obtain an intermediate product,
(a) loading of noble-metal-comprising particles onto the surface of the intermediate product in a liquid medium by deposition, precipitation and/or reduction of a noble-metal-comprising precursor with a reducing agent,
(b) heat treating the catalyst precursor resulting from step (b) at a temperature higher than 400° C.

wherein the spray-drying is carried out in a countercurrent mode.

16. A process for the production of a carbon supported catalyst, which comprises the following steps:
(c) precipitation of at least one metal oxide onto a surface of a carbon-comprising support by preparing an initial mixture, comprising the carbon-comprising support, at least one metal oxide precursor and an organic solvent, and spray-drying of the initial mixture to obtain an intermediate product,
(d) loading of noble-metal-comprising particles onto the surface of the intermediate product in a liquid medium by deposition, precipitation and/or reduction of a noble-metal-comprising precursor with a reducing agent,
(e) heat treating the catalyst precursor resulting from step (b) at a temperature higher than 400° C.,

wherein the spray-drying is carried out with an inert drying gas.

Assignees

• Basf Se

Inventors

• Hass Andreas
• Schwab Ekkehard
• Weber Franz
• Becker Nicole

Classifications

• B01J21/18 Primary

  Carbon · CPC title

• B01J23/6484

  Niobium · CPC title

• B01J37/0045

  Drying a slurry, e.g. spray drying · CPC title

• B01J37/0221

  of particles · CPC title

• B01J23/6522

  Chromium · CPC title