Process for the production of the mixture 2,4 furandicarboxylic acid (FDCA) and 2,5 furandicarboxylic acid via disproportionation reaction

Patent metadata

Field	Value
Publication number	US-9284290-B2
Application number	US-201114368676-A
Country	US
Kind code	B2
Filing date	Dec 29, 2011
Priority date	Dec 29, 2011
Publication date	Mar 15, 2016
Grant date	Mar 15, 2016

Abstract

The present invention refers to a process for production of a mixture including 2,4-furandicarboxylic acid (2,4-FDCA) and 2,5 furandicarboxylic acid (2,5-FDCA) through the disproportionation route, using as base compounds oxidation products of furfural. This invention also relates to a process for production of 2,4-FDCA as a result of a disproportionation route and the use of 2,4-FDCA as a monomer or comonomer to synthesize esters or any compounds which can generate macromolecules, such as polyesters.

First claim

What is claimed is:

1. A process for producing a mixture of 2,4-FDCA and 2,5-FDCA by a disproportionation route comprising the following steps:
a) oxidizing furfural compounds in the presence of catalysts and alkaline solution in order to obtain biobased furoic acid salts, wherein the catalysts are selected from the group consisting of Au/TiO 2 , Au/C, Au/ZnO, Au/Fe 2 O 3 or other Au catalysts;
b) heating the furoic acid salts under stirring in the presence of a metal based catalyst to prepare a reaction mixture and cooling the reaction mixture until room temperature;
c) collecting furan from the reaction mixture obtained in item (b) in order to obtain the mixture of 2,4-FDCA and 2,5-FDCA;
d) optionally, filtering off black insoluble material of the reaction mixture obtained in item (c) and acidifying the reaction mixture in order to collect 2,5-FDCA; and
e) optionally, subjecting the mixture obtained in item 1 (c), to an extraction or other separation method in order to purify 2,4-FDCA.

2. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 1 wherein an amount of pressure of oxygen used in step 1 (a) comprises from 10 5 to 5×10 5 Pa.

3. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 1 wherein the alkaline solution used in step 1 (a) is chosen from NaOH, KOH, LiOH, K 2 CO 3 or other alkaline solution.

4. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 1 wherein the oxidation of step 1 (a) is performed at a temperature of 0 to 50° C. for 1-5 hours.

5. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 1 wherein the furoic acid salts obtained in step 1 (a) comprise potassium, sodium, lithium or cesium.

6. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 1 wherein the furoic acid salts are heated in step 1 (b) at a temperature of 220° to 280° C. for 1 to 5.5 hours.

7. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 1 wherein the metal based catalyst used in step 1 (b) comprises transition metal salts, alkaline earth metal salts, or combinations thereof.

8. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 7 wherein the metal based catalyst used in step 1 (b) is chosen from FeCl 2 or CdI 2 or Zn(OTf) 2 or ZnCl 2 or ZnI 2 or mixtures thereof.

9. A process for producing 2,4-FDCA and 2,5-FDCA by disproportionation route according to claim 1 wherein the reaction mixture is acidified in step 1 (d) with HCl until the reaction mixture has a pH of 1-3.

Assignees

• Van Haveren Jacco
• Thiyagarajan Shanmugam
• Teruo Morita Augusto
• Braskem Sa

Inventors

• Van Haveren Jacco
• Thiyagarajan Shanmugam
• Teruo Morita Augusto

Classifications

• C07D307/68 Primary

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

• C08G63/181

  Acids containing aromatic rings · CPC title