Oxidation of 5-hydroxy-2-furanone to maleates

Patent metadata

Field	Value
Publication number	US-11912656-B2
Application number	US-201917414419-A
Country	US
Kind code	B2
Filing date	Dec 20, 2019
Priority date	Dec 21, 2018
Publication date	Feb 27, 2024
Grant date	Feb 27, 2024

Abstract

The invention is directed to a process for preparing maleic acid or a derivative thereof, the process comprising a step b) of oxidizing 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid to maleic acid or a derivative thereof by contacting the 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid with molecular oxygen (O 2 ) in the presence of a catalyst. In a particular embodiment, the step b) is preceded by a step a) of oxidizing a furanic compound according to formula I into the 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid,

wherein R 1 is H, CH 2 OH, CO 2 H or CHO and R 2 is H, OH, C 1 -C 6 alkyl or O(C 1 -C 6 alkyl), or esters, ethers, amides, acid halides, anhydrides, carboximidates, nitriles, and salts of formula I.

First claim

The invention claimed is:

1. A process for preparing maleic acid or a derivative thereof, said process comprising a step b) of oxidizing 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid to maleic acid or a derivative thereof by contacting said 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid with molecular oxygen (O 2 ) in the presence of a catalyst.

2. The process according to claim 1 , wherein said catalyst comprises a transition metal, metal salt, metal oxide or a phosphate.

3. The process according to claim 1 , wherein said catalyst comprises a solid support selected from the group consisting of zirconia, silica, activated carbon, aluminum oxide, zinc oxide, and titanium dioxide.

4. The process according to claim 1 , wherein said 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid is/are liquid or dissolved in a solvent when contacted with said O 2 .

5. The process according to claim 4 , wherein said solvent comprises an organic solvent or an aqueous solvent.

6. The process according to claim 1 , wherein said step b) is carried out under a pressure of at least 5 bar.

7. The process according to claim 1 , wherein said step b) is carried out at a temperature in the range of 20 to 200° C.

8. The process according to claim 1 , wherein said step b) is carried out in a continuous reactor.

9. The process according to claim 1 , wherein said step b) is preceded by a step of providing 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid in an isolated formulation.

10. The process according to claim 1 , wherein the derivative of maleic acid is one or more selected from the group consisting of maleic anhydride, fumaric acid, succinic acid, succinonitrile, putrescine, malic acid, and salts, anhydrides, amide, imides and esters of any of these compounds.

11. The process according to claim 1 , wherein said step b) of oxidizing said 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid to maleic acid or a derivative thereof is preceded by a step a) of oxidizing a furanic compound according to formula I into said 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid,

wherein R 1 is H, CH 2 OH, CO 2 H or CHO and R 2 is H, OH, C 1 -C 6 alkyl or O(C 1 -C 6 alkyl), esters, ethers, amides, acid halides, anhydrides, carboximidates, nitriles, and salts of formula I.

12. The process according to claim 11 , wherein said step a) comprises electrochemically oxidizing the furanic compound in an aqueous electrolyte solution.

13. The process according to claim 12 , wherein said step a) and said step b) are carried out in said aqueous electrolyte solution.

14. The process according to claim 12 , wherein said step a) is followed by an intermediate extraction step of extracting said 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid with an organic solvent and wherein said step b) is carried out in said organic solvent.

15. The process according to claim 11 , wherein said step a) comprises electrochemically oxidizing the furanic compound in an aqueous electrolyte solution comprising an acid.

16. The process according to claim 11 , wherein said step a) comprises electrochemically oxidizing the furanic compound in an aqueous electrolyte solution comprising a mineral acid.

17. The process according to claim 11 , wherein said step a) comprises electrochemically oxidizing the furanic compound in an aqueous electrolyte solution comprising a mineral acid selected from the group consisting of hydrochloric acid (HCl), nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), sulfuric acid (H 2 SO 4 ), boric acid (H 3 BO 3 ), hydrofluoric acid (HF), hydrobromic acid (HBr), perchloric acid (HClO 4 ) and hydroiodic acid (HI).

18. The process according to claim 17 , wherein the mineral acid is sulfuric acid.

19. The process according to claim 1 , wherein said process further comprises converting said maleic acid into one or more of its derivatives selected from the groups consisting of maleic anhydride, fumaric acid, succinic acid, succinonitrile, putrescine, malic acid, and salts, anhydrides, amide, imides and esters of any of these compounds.

20. The process according to claim 1 , wherein said catalyst comprises a transition metal, metal salt, metal oxide or a phosphate of which the metal is selected from the group consisting of cobalt, manganese, vanadium, molybdenum, copper, silver, gold, palladium, platinum and ruthenium.

21. The process according to claim 1 , wherein said catalyst comprises a transition metal, metal salt, metal oxide or a phosphate of which the metal is gold.

Assignees

• TNO

Inventors

• Crockatt Marc
• Latsuzbaia Roman
• Urbanus Johan
• Goetheer Earl Lawrence Vincent
• Van Heck Richard Antonius

Classifications

• C25B3/07

  Oxygen containing compounds · CPC title

• C25B3/05

  Heterocyclic compounds · CPC title

• C25B11/046

  Alloys · CPC title

• C25B3/23

  Oxidation (halogenation C25B3/27) · CPC title

• C07C51/235 Primary

  of —CHO groups or primary alcohol groups · CPC title