Method for preparing acrolein from glycerol or glycerine

Patent metadata

Field	Value
Publication number	US-9447009-B2
Application number	US-201314010724-A
Country	US
Kind code	B2
Filing date	Aug 27, 2013
Priority date	Dec 16, 2008
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

A method of preparing acrolein from glycerol or glycerine is disclosed. The method includes dehydrating glycerol or glycerine in the presence of a catalyst consisting of at least (a) a mixed oxide of zirconium and at least one metal, said metal being selected from niobium, tantalum and vanadium, or (b) a zirconium oxide and at least one metal oxide, the metal being selected from niobium, tantalum and vanadium, or (c) a silicon oxide and a mixed oxide of zirconium and at least one metal, the metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon, or (d) a titanium oxide and a mixed oxide of zirconium and at least one metal, said metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon.

First claim

The invention claimed is:

1. A method for preparing acrolein from glycerol or glycerine, where dehydration of the glycerol or glycerine is achieved in the presence of a catalyst based on zirconium oxide, the catalyst comprising:
(a) a mixed oxide of zirconium and of at least one metal M, said metal being selected from niobium, tantalum and vanadium, or
(b) a zirconium oxide and at least one metal M oxide, said metal being selected from niobium, tantalum and vanadium, or
(c) a silicon oxide, a mixed oxide of zirconium and of at least two metals M, said metals being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, and vanadium, or
(d) a titanium oxide, a mixed oxide of zirconium and of at least one metal M, said metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon, and
wherein all of said oxides are obtained by calcination.

2. The method according to claim 1 , wherein at least one of the oxides of said catalyst (a), (b), (c) and (d) is supported.

3. The method according to claim 1 , wherein the glycerol is in aqueous solution at a concentration of at least 1% by weight.

4. The method according to claim 3 , wherein the glycerol concentration of the aqueous solution varies from 10 to 50% by weight.

5. The method according to claim 1 , wherein the catalyst is regenerated.

6. The method according to claim 1 , wherein the dehydration reaction is conducted in a gas phase.

7. The method according to claim 6 , wherein the dehydration reaction is conducted in a reactor with a fixed bed, a fluidized bed, or a circulating fluidized bed.

8. The method according to claim 1 , wherein the dehydration reaction is conducted in a liquid phase.

9. The method according to claim 1 , wherein the catalyst comprises a silicon dioxide and a mixed oxide of zirconium and at least tungsten.

10. A method of preparing acrolein from glycerol or glycerine comprising
dehydration of glycerol or glycerin in the presence of a catalyst based on zirconium oxide,
wherein the catalyst comprises a mixed oxide of zirconium and niobium, and
wherein the dehydration step comprises contacting a stream consisting of glycerol, water, and nitrogen with the catalyst.

11. The method according to claim 1 , wherein calcination is carried out at a temperature of 600-650° C.

12. The method according to claim 1 , wherein the catalyst comprises at least
(a) a mixed oxide of zirconium and of at least niobium and
(b) a zirconium oxide and at least one metal M oxide, said metal being selected from the group consisting of niobium, tantalum, and vanadium.

13. The method according to claim 1 , wherein the (Zr/sum of the elements Si, Ti and Nb) molar ratio varies from 0.5 to 200.

14. The method according to claim 13 , wherein said molar ratio varies from 1 to 100.

Assignees

• Adisseo France Sas
• Centre Nat Rech Scient
• Adisseo France Sas

Inventors

• Belliere-Baca Virginie
• Loridant Stephane
• Millet Jean-Marc
• Lauriol-Garbey Pascaline

Classifications

• C07C319/18

  by addition of thiols to unsaturated compounds · CPC title

• C07C45/66 Primary

  by dehydration · CPC title

• B01J23/92

  of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 · CPC title

• C07C45/52 Primary

  by dehydration and rearrangement involving two hydroxy groups in the same molecule · CPC title

• B01J38/12

  Treating with free oxygen-containing gas · CPC title