IP Library Granted Patent US 9,873,107
Granted Patent B2
US 9,873,107 · App. 15/126,801 · Granted Jan 23, 2018

Process for the production of a carbon supported catalyst

Inventors: Andreas Hass (Mannheim, DE); Ekkehard Schwab (Neustadt, DE); Franz Weber (Eppelheim, DE); Nicole Becker (Böhl-Iggelheim, DE)
Assignee: BASF SE
B01J21/18B01J23/6484B01J35/0013B01J35/1019B01J35/1023B01J37/0045B01J37/0221B01J37/035B01J37/08
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Quick Facts
Patent No.
US 9,873,107
App. No.
15/126,801
Granted
Jan 23, 2018
Kind
B2
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.

Claims (28)

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.

Assignments (2)
NUNC PRO TUNC ASSIGNMENT Recorded Dec 16, 2024
From: BASF SE
To: BASF CATALYSTS GERMANY GMBH
Reel/Frame 069598/0586 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 19, 2016
From: HAAS, ANDREAS; SCHWAB, EKKEHARD; WEBER, FRANZ; BECKER, NICOLE
To: BASF SE
Reel/Frame 039778/0264 →
Priority Claims (1)
EP 14160516 · Mar 18, 2014 · regional
Continuity (1)
Related Publication 20170100706A1 · Apr 13, 2017