Method for synthesizing an alkenoic acid

Patent metadata

Field	Value
Publication number	US-10077227-B2
Application number	US-201615541925-A
Country	US
Kind code	B2
Filing date	Apr 15, 2016
Priority date	Apr 15, 2015
Publication date	Sep 18, 2018
Grant date	Sep 18, 2018

Abstract

There is provided a method for synthesizing an alkenoic acid, in particular acrylic acid comprising the step of oxidizing an alkenyl alcohol in the presence of a metal oxide catalyst to form the alkenoic acid. The invention further provides a step of deoxydehydrating a polyol, including glycerol to obtain said alkenyl alcohol including an allyl alcohol.

First claim

The invention claimed is:

1. A method for synthesizing an alkenoic acid comprising the step of oxidizing an alkenyl alcohol in the presence of a metal oxide catalyst to form said alkenoic acid, wherein said metal oxide catalyst has the formula Mo x V y W m O d
wherein
x is 8;
y is 2;
m is 1; and
d is calculated based on the formula 3x+2y+3m.

2. The method of claim 1 , further comprising, before said oxidizing step, the step of deoxydehydrating a polyol to obtain said alkenyl alcohol.

3. The method of claim 2 , wherein said polyol is a triol, tetraol, pentanol or hexanol.

4. The method of claim 3 , wherein said polyol is selected from the group consisting of glycerol, 2-methyl-1,2,3-propanetriol, 1,2,3-butanetriol, 2-methyl-1,2,3-butanetriol, 2-methyl-1,2,3,4-butanetetraol, 1,2,3-pentanetriol, 1,2,3-hexanetriol, xylitol, sorbitol, arabinitol, ribitol, mannitol, galactitol, iditol, erythritol, threitol and mixtures thereof.

5. The method of claim 1 , wherein said alkenyl alcohol is a 2-alkenyl alcohol.

6. The method of claim 5 , wherein said 2-alkenyl alcohol is selected from the group consisting of allyl alcohol, 2-buten-1-ol, 2-hexen-1-ol, 2-penten-1,4,5-triol, 2,4-hexadien-1,6-diol, 2-hexene-1,4,5,6-tetraol, 2-methyl-2-butenol, 2-butene-1,4-diol, 2-methyl-2-butene-1,4-diol, methallyl alcohol, and 2-chloroallyl alcohol.

7. The method of claim 1 , wherein said alkenoic acid is a linear or branched monocarboxylic or dicarboxylic acid having three to six carbon atoms.

8. The method of claim 7 , wherein said alkenoic acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, 4-hydroxy-2-butenoic acid, 2-hydroxy-3-pentendioic acid, 4,5-dihydroxy-2-pentenoic acid, 2,5-dihydroxy-3-pentenoic acid, crotonic acid, citraconic acid, mesaconic acid, angelic acid, tiglic acid, 4,5,6-trihydroxy-2-hexenoic acid, 2,3,5-trihydroxy-4-hexenoic acid and 4,5-dihydroxy-2-hexenedionic acid.

9. The method of claim 1 , wherein the metal oxide catalyst is provided on a support.

10. The method of claim 1 , wherein the amount of metal oxide catalyst used in the oxidizing step is in the range of 10 mg to 500 mg.

11. The method of claim 1 , wherein the oxidizing step is undertaken at a temperature above 300° C.

12. The method of claim 1 , wherein the oxidizing step is undertaken at an oxygen content of about 5 vol % to about 20 vol %.

13. The method of claim 2 , wherein the deoxydehydrating step is undertaken in the presence of a carboxylic acid.

14. The method of claim 2 , wherein the deoxydehydrating step is undertaken at a temperature in the range of about 200° C. to about 280° C.

15. The method of claim 2 , wherein the deoxydehydrating step is undertaken in an inert gas atmosphere or in air.

16. The method of claim 13 , wherein the carboxylic acid is present at a molar ratio in the range of about 1:1 to about 3.0:1 (carboxylic acid:polyol).

17. A method for synthesizing an alkenoic acid from a polyol comprising the steps of:
(a) deoxydehydrating the polyol in the presence of a carboxylic acid to form an alkenyl alcohol; and
(b) oxidizing the alkenyl alcohol in the presence of a metal oxide catalyst to form the alkenoic acid, wherein said metal oxide catalyst has the formula Mo x V y W m O d
wherein
x is 8;
y is 2;
m is 1; and
d is calculated based on the formula 3x+2y+3m.

Assignees

• Agency Science Tech & Res

Inventors

• Zhang Yugen
• Li Xiukai

Classifications

• B01J37/0009

  Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst · CPC title

• B01J2523/68

  Molybdenum · CPC title

• C07C51/25 Primary

  of unsaturated compounds containing no six-membered aromatic ring · CPC title

• B01J23/28

  Molybdenum · CPC title

• B01J23/22

  Vanadium · CPC title