IP Library Granted Patent US 10,266,474
Granted Patent B2
US 10,266,474 · App. 15/737,141 · Granted Apr 23, 2019

Use of molybdenum and vanadium mixed oxides as catalysts for the oxidation of unsaturated alcohols into unsaturated carboxylic acids

Inventors: Sébastien Paul (Thun Saint Amand, FR); Benjamin Katryniok (Meurchin, FR); Franck Dumeignil (Villeneuve d'Ascq, FR); Marcia Araque Marin (Lille, FR); Toru Murayama (Hokkaido, JP); Wataru Ueda (Tokyo, JP)
Assignees: Centre National De La Recherche Scientifique; Universite Des Sciences et Technologies De Lille 1; Hokkaido University; Ecole Centrale De Lille
C07C51/235B01J23/28B01J23/8877B01J2523/00
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Quick Facts
Patent No.
US 10,266,474
App. No.
15/737,141
Granted
Apr 23, 2019
Kind
B2
Abstract

The present invention relates to the use of molybdenum and vanadium mixed oxides, optionally iron doped, as catalysts for the oxidation of unsaturated alcohols, in particular allyl alcohol, and also to a process for the production of unsaturated carboxylic acids, in particular acrylic acid, in the gas phase, in the presence of such a catalyst.

Claims (22)

1. Process for the production of an unsaturated carboxylic acid from an alcohol in the presence of a catalyst, said process comprising one step of oxidation of an alcohol of following formula (II):

CH 2 ═C(R 1 )—CH 2 —OH  (II)

in which R 1 is a hydrogen atom or a methyl radical, to result in an unsaturated carboxylic acid of following formula (III):

CH 2 ═C(R 1 )—COOH  (III)

in which R 1 has the same meaning as in the above formula (II), said reaction being carried out in the gas phase, the said gas phase comprising at least oxygen, and in the presence of a solid catalyst chosen from the compounds of following formula (I):

Mo a VFe b O c   (I)

wherein:

a, b and c denotes the atomic ratio of Mo, Fe and O respectively;

a varies from 3 to 4 inclusive,

b varies from 0 to 1 inclusive,

c varies from 10 to 15 inclusive,

said compound of formula (I) being in an orthorhombic or trigonal crystalline phase.

2. Process according to claim 1 , wherein R 1 is a hydrogen atom and said process comprises a step of oxidation of allyl alcohol to give acrylic acid.

3. Process according to claim 1 , wherein the solid catalyst is chosen among compounds of formula (I) in which a=3 and b=0 to 0.5 inclusive.

4. Process according to claim 1 , wherein the solid catalyst is chosen among trigonal Mo 3 VO c , orthorhombic Mo 3 VO c and trigonal Mo 3 VFe 0.2 O c , in which c as the same meaning as in the formula (I).

5. Process according to claim 1 , wherein the oxidation reaction is carried out at a temperature varying inclusively from 330 to 370° C.

6. Process according to claim 1 , wherein the oxidation reaction is carried out at a temperature of 350° C.

7. Process according to claim 1 , wherein the oxidation reaction is carried out at a pressure ranging from 1 to 1·10 6 Pa.

8. Process according to claim 1 , wherein within the gas phase, the alcohol of formula (II)/oxygen molar ratio varies from 0.1 to 2.

9. Process according to claim 1 , wherein the oxidation reaction is carried out using a gas phase comprising nitrogen as carrier gas and in which the alcohol of formula (II)/oxygen/nitrogen molar ratio is 1/2.2/11.8.

10. Process according to claim 1 , wherein the oxidation reaction is carried out using a gas phase comprising a mixture of nitrogen and helium as carrier gas and in which the alcohol of formula (II)/oxygen/nitrogen+helium ratio molar ration is 0.7/1.5/8.

11. Process according to claim 1 , wherein the catalyst of formula (I) is supported by a porous solid support.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 22, 2022
From: HOKKAIDO UNIVERSITY
To: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITE DE LILLE; CENTRALE LILLE INSTITUT
Reel/Frame 060853/0825 →
CHANGE OF NAME Recorded Aug 12, 2022
From: ECOLE CENTRALE DE LILLE
To: CENTRALE LILLE INSTITUT
Reel/Frame 060791/0201 →
MERGER Recorded Aug 10, 2022
From: UNIVERSITE DES SCIENCES ET TECHNOLOGIES DE LILLE - LILLE 1
To: UNIVERSITE DE LILLE
Reel/Frame 060765/0589 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 21, 2018
From: PAUL, SÉBASTIEN; KATRYNIOK, BENJAMIN; MARIN, MARCIA ARAQUE; UEDA, WATARU; MURAYAMA, TORU; DUMEIGNIL, FRANCK
To: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITE DES SCIENCES ET TECHNOLOGIES DE LILLE 1; NATIONAL UNIVERSITY CORPORATION HOKKAIDO UNIVERSITY; ECOLE CENTRALE DE LILLE
Reel/Frame 047560/0421 →
Continuity (1)
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