Core-shell particles with catalytic activity

Patent metadata

Field	Value
Publication number	US-10005069-B2
Application number	US-201615188517-A
Country	US
Kind code	B2
Filing date	Jun 21, 2016
Priority date	Dec 4, 2012
Publication date	Jun 26, 2018
Grant date	Jun 26, 2018

Abstract

The present invention pertains to novel core-shell particles comprising a core of alumina and a shell of cobalt oxide, characterized in that they are spherical with a number average diameter, as measured by TEM, of between 10 and 30 nm. This invention also pertains to the method for preparing these core-shell particles and to their uses in the manufacture of a catalyst.

First claim

The invention claimed is:

1. A method for the preparation of spherical core-shell particles, comprising the following successive steps:
(a) mixing a cobalt salt with (i) ammonium carbonate, bicarbonate or carbamate and (ii) ammonium hydroxide in water, so as to obtain an aqueous solution comprising a cobalt amine complex;
(b) heating said aqueous solution to a temperature comprised between 40 and 90° C., either before, while or after adding under agitation particles of alumina having a substantially spherical shape and a number average diameter of less than 30 nm as measured by TEM, so as to disintegrate alumina aggregates into primary particles and precipitate cobalt carbonate onto the surface of the alumina primary particles and to obtain core-shell particles having a core of alumina and a shell of cobalt carbonate; and
(c) converting cobalt carbonate in the shell of said core-shell particles into cobalt oxide, wherein the core-shell particles obtained are spherical with a number average diameter, as measured by TEM, of between 10 and 30 nm and a number average thickness of the cobalt oxide shell, as measured by TEM, is comprised between 1 and 5 nm.

2. The method according to claim 1 , wherein the temperature in step (b) is comprised between 50 and 70° C.

3. The method according to claim 1 , wherein the cobalt salt represents from 0.5 to 10 wt. % of the solution in step (a).

4. A core-shell particle obtainable according to the method of claim 1 , comprising a core of alumina and a shell of cobalt oxide, wherein said core-shell particles are spherical with a number average diameter, as measured by TEM, of between 10 and 30 nm and the number average thickness of the cobalt oxide shell, as measured by TEM, is between 1 and 5 nm.

5. A method for manufacturing an activated catalyst, said method comprising the steps of:
mixing the core-shell nanoparticles obtainable according to the method of claim 1 , comprising a core of alumina and a shell of cobalt oxide, with nanometric particles of a carrier material having a number average diameter as measured by TEM of below 100 nm and water so as to obtain a slurry,
homogenizing and drying said slurry to obtain a porous catalyst and optionally shaping said catalyst,
reducing said catalyst in order to at least partially convert cobalt oxide into elemental cobalt.

6. The method according to claim 1 wherein the core-shell particles obtained at step (b) are recovered and dried before the step (c) of conversion.

7. A catalyst comprising core-shell particles as defined in claim 4 , embedded in a carrier comprising nanometric particles of a carrier material having a number average diameter as measured by TEM of below 100 nm, wherein the carrier material is selected from the group consisting of alumina, silica, titania, activated carbon, silicon carbide and their mixtures.

Assignees

• Total Raffinage Chimie
• Total Raffinage Marketing

Inventors

• Calderone Vincenzo Roberto
• Shiju Nirappurackal Raveendran
• Rothenberg Gad
• Curulla-Ferre Daniel

Classifications

• C10G2/332

  of the iron-group · CPC title

• B01J37/18

  with gases containing free hydrogen · CPC title

• B01J37/035

  Precipitation on carriers · CPC title

• B01J23/75 Primary

  Cobalt · CPC title

• B01J21/04

  Alumina · CPC title