Process for producing 2,5-furandicarboxylic acid from ethers of 5-hydroxymethylfurfural

Patent metadata

Field	Value
Publication number	US-12281090-B2
Application number	US-202017778921-A
Country	US
Kind code	B2
Filing date	Dec 18, 2020
Priority date	Dec 20, 2019
Publication date	Apr 22, 2025
Grant date	Apr 22, 2025

Abstract

A process for producing a carboxylic acid composition including 2,5-furandicarboxylic acid, including the steps: a) oxidizing an oxidizable compound including 5-alkoxymethylfurfural in an oxidation reactor in the presence of a saturated organic acid solvent having from 2 to 6 carbon atoms and a catalyst system comprising cobalt, manganese and bromine using an oxidizing gas at a temperature in the range of 160 to 210° C. to obtain a crude carboxylic acid composition including mono alkyl ester of 2,5-furandicarboxylic acid and solid 2,5-furandicarboxylic acid, b) isolating at least a portion of the solid 2,5-furandicarboxylic acid from the crude carboxylic acid composition in a solid-liquid separation zone to generate a solid cake and a mother liquor, c) determining the amount of manganese and/or cobalt in the cake, and d) increasing the amount of one or more controlling acids in the oxidation reactor.

First claim

The invention claimed is:

1. A process for producing a carboxylic acid composition comprising 2,5-furandicarboxylic acid, comprising the steps:
a) oxidizing an oxidizable compound comprising 5-alkoxymethylfurfural in an oxidation reactor in the presence of a saturated organic acid solvent having from 2 to 6 carbon atoms and a catalyst system comprising cobalt, manganese and bromine using an oxidizing gas at a temperature in the range of 160 to 210° C. to obtain a crude carboxylic acid composition comprising mono alkyl ester of 2,5-furandicarboxylic acid and solid 2,5-furandicarboxylic acid,
b) isolating at least a portion of the solid 2,5-furandicarboxylic acid from the crude carboxylic acid composition in a solid-liquid separation zone to generate a solid cake and a mother liquor,
c) determining the amount of manganese and/or cobalt in the cake, and
d) increasing the amount of one or more controlling acids in the oxidation reactor, if the determined amount of manganese and/or cobalt in the cake exceeds a predefined threshold value,
wherein the one or more controlling acids are selected from the group consisting of hydrobromic acid and mono—or dicarboxylic acids having from 2 to 5 carbon atoms and a pKa of less than 3.2, and
wherein the mother liquor comprises mono alkyl ester of 2,5-furandicarboxylic acid in the range of 0.5 to 7% by weight with respect to the weight of the mother liquor.

2. The process according to claim 1 , wherein the one or more controlling acids are selected from the group consisting of hydrobromic acid, bromoacetic acid, dibromoacetic acid, 5-bromo-2-furoic acid, fumaric acid, acetoxy-acetic acid, maleic acid and furoic acid.

3. The process according to claim 1 , wherein the process of producing a carboxylic acid composition is a continuous process wherein at least 60% by weight, of the mother liquor is routed from the solid-liquid separation zone to the oxidation reactor as recycled mother liquor stream.

4. The process according to claim 1 , wherein the oxidizable compound comprises 5-methoxymethylfurfural, and wherein the crude carboxylic acid composition comprises mono methyl ester of 2,5-furandicarboxylic acid.

5. The process according to claim 1 , wherein the mother liquor comprises mono alkyl ester of 2,5-furandicarboxylic acid in the range of 1.0 to 4% by weight with respect to the weight of the mother liquor.

6. The process according to claim 1 , wherein the mother liquor comprises bromoacetic acid and/or dibromoacetic acid and/or 5-bromo-2-furoic acid.

7. The process according to claim 1 , wherein the predefined threshold value for cobalt in the cake is 200 ppm by weight with respect to the weight of the 2,5-furandicarboxylic acid and/or wherein the predefined threshold value for manganese in the cake is 100 ppm by weight, with respect to the weight of the 2,5-furandicarboxylic acid.

8. The process according to claim 3 , wherein the amount of one or more controlling acids in the oxidation reactor is increased by adding the one or more controlling acids to the oxidation reactor by increasing the portion of the mother liquor which is routed to the oxidation reactor as recycled mother liquor stream.

9. The process according to claim 1 , wherein the weight ratio of cobalt to manganese in the catalyst system is 10 or higher and/or wherein the weight ratio of bromine to the combined weight of cobalt and manganese in the catalyst system is 1 or higher.

10. The process according to claim 1 , wherein the isolating at least a portion of the solid 2,5-furandicarboxylic acid in a solid-liquid separation zone comprises washing the solid 2,5-furandicarboxylic acid with a washing solution comprising acetic acid, and less than 15%; by weight of water.

11. The process according to claim 1 , wherein the solid 2,5-furandicarboxylic acid isolated in step b) is further washed with a second washing solution comprising water in an amount of more than 95% by weight with respect to the weight of the washing solution.

12. The process according to claim 1 , wherein the temperature in step a) is in the range of 170 to 190° C.

13. The process according to claim 1 , wherein the pressure in step a) is in the range of 700 to 2000 kPa, and/or wherein the oxidation reactor comprises one or more continuous stirred tank reactors.

14. The process according to claim 1 , wherein the ratio of the weight ratio of manganese to cobalt in the cake to the weight ratio of manganese to cobalt in the catalyst system is less than 2.5.

15. The process according to claim 1 , wherein the cake comprises 2,5-furandicarboxylic acid in an amount greater than 95% by weight with respect to the weight of the dry cake.

16. The process according to claim 5 , wherein the mother liquor comprises mono methyl ester of 2,5-furandicarboxylic acid in the range of 1.0 to 4% by weight with respect to the weight of the mother liquor.

17. The process according to claim 6 , wherein the mother liquor comprises bromoacetic acid in an amount of 0.5% or more by weight with respect to the weight of the mother liquor, and/or dibromoacetic acid in an amount of 0.1% or more by weight with respect to the weight of the mother liquor, and/or 5-bromo-2-furoic acid in an amount of 0.02% or more by weight with respect to the weight of the mother liquor.

18. The process according to claim 14 , wherein the ratio of the weight ratio of manganese to cobalt in the cake to the weight ratio of manganese to cobalt in the catalyst system is less than 2.

19. The process according to claim 18 , wherein the ratio of the weight ratio of manganese to cobalt in the cake to the weight ratio of manganese to cobalt in the catalyst system is less than 1.5.

20. The process according to claim 15 , wherein the cake comprises mono alkyl ester of 2,5-furandicarboxylic acid in an amount in the range of 0.1 to 3%.

21. The process according to claim 20 , wherein the cake comprises 2,5-furandicarboxylic acid in an amount greater than 98% by weight with respect to the weight of the dry cake and mono alkyl ester of 2,5-furandicarboxylic acid in an amount in the range of 0.15 to 2.3% by weight with respect to the weight of the dry cake.

Assignees

• Furanix Technologies Bv

Inventors

• Baars Hendrikus Jacob
• Blank Jan Hendrik
• Kolstad Jeffrey John
• De Sousa Dias Ana Sofia Vagueiro

Classifications

• C07D307/68 Primary

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