Process for the preparation of 2,5-furan-dicarboxylic acid

Patent metadata

Field	Value
Publication number	US-9643945-B2
Application number	US-201414781993-A
Country	US
Kind code	B2
Filing date	Apr 4, 2014
Priority date	Apr 5, 2013
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

2,5-Furandicarboxylic acid and methyl acetate are prepared in a continuous process by introducing a 5-methoxymethylfurfural-containing feedstock, an oxygen-containing gas, an oxidation catalyst and an acetic acid-containing solvent into a reactor; allowing 5-methoxymethylfurfural to react with oxygen and acetic acid in the presence of the oxidation catalyst to yield 2,5-furandicarboxylic acid as main product and methyl acetate; withdrawing 2,5-furandicarboxylic acid-containing product from the reactor and recovering 2,5-furandicarboxylic acid product; and withdrawing a vaporous stream containing methyl acetate from the reactor.

First claim

The invention claimed is:

1. A continuous process for the preparation of 2,5-furan-dicarboxylic acid and methyl acetate, comprising:
introducing a 5-methoxymethyl furfural-containing feedstock, an oxygen-containing gas, an oxidation catalyst and an acetic acid-containing solvent into a reactor;
allowing 5-methoxymethyl furfural to react with oxygen and acetic acid in the presence of the oxidation catalyst to yield 2,5-furan-dicarboxylic acid as main product and methyl acetate;
withdrawing 2,5-furan-dicarboxylic acid-containing product from the reactor and recovering 2,5-furan-dicarboxylic acid product; and
withdrawing a vaporous stream containing methyl acetate from the reactor.

2. The process according to claim 1 , wherein the feedstock comprises from 2 to 50% by weight of 5-methoxymethyl furfural, based on the weight of the feedstock, catalyst and solvent.

3. The process according to claim 1 , wherein the feedstock, in addition to 5-methoxymethyl furfural, comprises up to 20% by weight 5-hydroxymethyl furfural, based on the weight of the feedstock.

4. The process according to claim 1 , wherein the feedstock consists of 50 to 100% by weight of 5-methoxymethyl furfural.

5. The process according to claim 4 , wherein the feedstock consists from 90 to 100% by weight of 5-methoxymethyl furfural.

6. The process according to claim 1 , wherein the oxygen-containing gas being introduced into the reactor comprises from 6 to 22% by volume oxygen, based on the volume of the oxygen-containing gas.

7. The process according to claim 1 , wherein the oxidation catalyst comprises at least one metal selected from the group consisting of cobalt and manganese.

8. The process according to claim 7 , wherein the oxidation catalyst comprises cobalt and manganese.

9. The process according to claim 8 , wherein the oxidation catalyst comprises both cobalt and manganese in an atomic ratio ranging from 1:1 to 100:1.

10. The process according to claim 8 , wherein the catalyst further comprises a source of bromide.

11. The process according to claim 10 , wherein the source of bromide is hydrobromic acid.

12. The process according to claim 8 , wherein the oxidation catalyst further comprises an additional metal selected from the group consisting of zirconium, cerium, nickel, molybdenum, hafnium, zinc, chromium, ruthenium, iron and mixtures thereof.

13. The process according to claim 1 , wherein the concentration of the oxidation catalyst in the reactor is such that it comprises from 500 to 6000 ppm by weight of cobalt and from 20 to 6000 ppm by weight of manganese, based on the weight of the feedstock, solvent and oxidation catalyst.

14. The process according to claim 1 , wherein the acetic acid-containing solvent comprises from 1 to 15% by weight water, based on the solvent.

15. The process according to claim 14 , wherein the acetic acid-containing solvent comprises from 2 to 6% by weight water, based on the solvent.

16. The process according to claim 1 , which is carried out in a plurality of reactors in series.

17. The process according to claim 16 , wherein the plurality of reactors comprises reactors that are continuous stirred tank reactors.

18. The process according to claim 16 , wherein the average contact time in each reactor of the plurality of reactors ranges from 5 minutes to 2 hours.

19. The process according to claim 16 , wherein the number of reactors ranges from two to five.

20. The process according to claim 16 , wherein the 5-methoxymethyl furfural-containing feedstock is introduced into the first reactor and at least part of the 2,5-furan-dicarboxylic acid-containing product that is withdrawn from any reactor is used as feedstock for the subsequent reactor, the 2,5-furan-dicarboxylic acid-containing product that is withdrawn from the last reactor being recovered.

21. The process according to claim 20 , wherein the 2,5-furandicarboxylic acid that is withdrawn from the last reactor of a plurality of reactors is subjected to purification.

22. The process according to claim 21 , wherein the purification entails one or more crystallization steps.

23. The process according to claim 21 , wherein the purification comprises one or more washing steps.

24. The process according to claim 1 , wherein the reactor is a continuous stirred tank reactor.

25. The process according to claim 1 , wherein the vaporous stream containing methylacetate that is withdrawn from a reactor is cooled so that part thereof is condensed, and part of the condensate is recycled to the reactor.

26. The process according to claim 25 , wherein the part of the vaporous stream that is not condensed is at least partly subjected to methyl acetate recovery.

27. The process according to claim 25 , wherein the part of the condensate that is not recycled is subjected to methyl acetate recovery.

28. The process according to claim 1 , wherein the 2,5-furandicarboxylic acid that is withdrawn from the reactor is subjected to purification.

29. The process according to claim 28 , wherein the purification entails one or more crystallization steps.

30. The process according to claim 28 , wherein the purification comprises one or more washing steps.

31. The process according to claim 30 , wherein the washing steps comprise the treatment with a washing liquid selected from water, acetic acid and mixtures thereof.

32. The process according to claim 31 , wherein the washing liquid is subjected to separation of water, the remainder being at least partly recycled to a reactor.

33. The process according to claim 1 , wherein the 5-methoxymethyl furfural is allowed to react with oxygen and acetic acid in the presence of the oxidation catalyst at a temperature of 125 to 180° C. and a pressure of 3 to 15 bar.

34. The process according to claim 1 , wherein the average contact time in the reactor ranges from 5 minutes to 2 hours.

Assignees

• Furanix Technologies Bv

Inventors

• Mazoyer Etienne
• De Sousa Dias Ana Sofia Vagueiro
• Mckay Benjamin
• Baars Hendrikus Jacob
• Vreeken Victor Peter Charles
• Gruter Gerardus Johannes Maria
• Sikkenga David Lee

Classifications

• C07D307/68 Primary

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title