Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof

Patent metadata

Field	Value
Publication number	US-10442780-B2
Application number	US-201916264188-A
Country	US
Kind code	B2
Filing date	Jan 31, 2019
Priority date	Jan 13, 2016
Publication date	Oct 15, 2019
Grant date	Oct 15, 2019

Abstract

The present disclosure provides processes for the production of 2-5-furandicarboxylic acid (FDCA) and intermediates thereof by the chemocatalytic conversion of a furanic oxidation substrate. The present disclosure further provides processes for preparing derivatives of FDCA and FDCA-based polymers. In addition, the present disclosure provides crystalline preparations of FDCA, as well as processes for making the same.

First claim

We claim:

1. A process for producing a first 2,5-furandicarboxylic acid (FDCA) pathway product from a first furanic oxidation substrate, the process comprising:
(a) contacting an oxidation feedstock comprising a first furanic oxidation substrate and a first oxidation solvent with oxygen in the presence of a first heterogeneous oxidation catalyst under conditions sufficient to form a reaction mixture for oxidizing the first furanic oxidation substrate to a first FDCA pathway product, and producing the first FDCA pathway product;
wherein the first oxidation solvent is a multi-component solvent comprising water and a water-miscible aprotic organic solvent;
wherein no base is added to the reaction mixture during (first) contacting step (a); and
wherein the first heterogeneous oxidation catalyst comprises a first solid support and a first noble metal.

2. The process of claim 1 , wherein the first noble metal is selected from the group consisting of platinum, gold, and combinations thereof.

3. The process of claim 1 , wherein the water-miscible aprotic organic solvent is selected from the group consisting of tetrahydrofuran, a glyme, dioxane, a dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone (“NMP”), methyl ethyl ketone (“MEK”), and gamma-valerolactone;
and, if the water-miscible aprotic organic solvent is a glyme, then the glyme is selected from the group consisting of a monoglyme (1,2-dimethoxyethane), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, and a polyglyme.

4. The process of claim 3 , wherein the water-miscible aprotic organic solvent is a glyme.

5. The process of claim 4 , wherein the water-miscible aprotic organic solvent is 1,2-dimethoxyethane (“DME”).

6. The process of claim 4 , wherein the water-miscible aprotic organic solvent is diglyme.

7. The process of claim 3 , wherein the water-miscible aprotic organic solvent is dioxane.

8. The process of claim 3 , wherein the water-miscible aprotic organic solvent is NMP.

9. The process of claim 3 , wherein the water-miscible aprotic organic solvent is MEK.

10. The process of claim 1 , wherein the weight percent ratio of the water-miscible aprotic organic solvent:water is in the range of from or any number in between 70:30 to 20:80.

11. The process of claim 10 , wherein the weight percent ratio of the water-miscible aprotic organic solvent:water is in the range of from or any number in between 60:40 to 40:60.

12. The process of claim 1 , wherein the first oxidation feedstock comprises the first furanic oxidation substrate at a concentration of at least 5% by weight.

13. The process of claim 1 , wherein the first heterogeneous oxidation catalyst comprises the first noble metal at a loading in the range of from or any number in between 0.3% to 5% by weight of the first heterogeneous oxidation catalyst.

14. The process of claim 1 , wherein the first solid support comprises a material selected from the group consisting of a metal oxide, a carbonaceous material, a polymer, a metal silicate, a metal carbide, and any combination of two or more thereof.

15. The process of claim 1 , wherein the first solid support comprises a plurality of pores and a specific surface area in the range of from or any number in between 20 m 2 /g to 500 m 2 /g.

16. The process of claim 15 , wherein the first solid support comprises a specific surface area in the range of from or any number in between 25 m 2 /g to 350 m 2 /g.

17. The process of claim 15 , wherein the first solid support comprises a specific surface area in the range of from or any number in between 20 m 2 /g to 50 m 2 /g.

18. The process of claim 17 , wherein the first solid support comprises a specific surface area in the range of from or any number in between 20 m 2 /g to 40 m 2 /g.

19. The process of claim 16 , wherein the first solid support comprises a pore volume wherein at least 50% of the pore volume is from pores having a pore diameter in the range of from or any number in between 5 nm to 100 nm.

20. The process of claim 1 , wherein oxygen is present at a molar ratio of oxygen:the first furanic oxidation substrate in the range of from or any number in between 2:1 to 10:1.

21. The process of claim 1 , wherein (first) contacting step (a) is carried out at a temperature in the range of from or any number in between 50° C. to 200° C.

22. The process of claim 1 , wherein the first FDCA pathway product is produced at a yield of at least 80%.

23. The process of claim 1 , wherein the first FDCA pathway product is FDCA.

24. The process of claim 1 , further comprising a second oxidation step, wherein the second oxidation step comprises:
(b) contacting a second oxidation feedstock comprising a second furanic oxidation substrate and a second oxidation solvent with oxygen in the presence of a second heterogeneous oxidation catalyst under conditions sufficient to form a second reaction mixture for oxidizing the second furanic oxidation substrate to produce a second FDCA pathway product, and producing the second FDCA pathway product;
wherein the first FDCA pathway product is an FDCA pathway intermediate compound, either alone or together with FDCA;
wherein the second furanic oxidation substrate is the first FDCA pathway product;
wherein the second reaction mixture is substantially free of added base; and
wherein the second heterogeneous oxidation catalyst comprises a second solid support and a second noble metal, that may be the same or different from the first noble metal.

25. The process of claim 24 , wherein the second noble metal is selected from the group consisting of platinum, gold, and a combination thereof.

26. The process of claim 24 , wherein the second solid support comprises a plurality of pores and a specific surface area in the range of from or any number in between 20 m 2 /g to 500 m 2 /g.

27. The process of claim 1 , further comprising:
(a°) prior to (first) contacting step (a), contacting a carbohydrate feedstock comprising a sugar and a dehydration solvent with a dehydration catalyst under conditions sufficient to form a dehydration reaction mixture for dehydrating the sugar to produce the first furanic oxidation substrate, wherein the first furanic oxidation substrate is present in a dehydration product solution that comprises the first furanic oxidation substrate and the dehydration solvent.

28. The process of claim 27 , wherein the dehydration catalyst is an acid catalyst.

29. The process of claim 28 , wherein the acid catalyst is an acid selected from the group consisting of HBr, H 2 SO 4 , HNO 3 , HCl, HI, H 3 PO 4 , triflic acid, methansulfonic acid, benzenesulfonic acid, and p-toluene sulfonic acid.

30. The process of claim 29 , wherein when the acid catalyst is not HBr, the dehydration reaction mixture further comprises a bromide salt.

31. The process of claim 27 , wherein the dehydration solvent comprises N-methyl-pyrrolidone (NMP).

32. The process of claim 27 , wherein the sugar is fructose and the first furanic oxidation substrate is HMF.

33. The process of claim 27 , wherein the (pior) contacting step)(a°) is carried out at a temperature of less than 110° C.

Assignees

• Stora Enso Oyj

Inventors

• Sokolovskii Valery
• Murphy Vincent J
• Boussie Thomas R
• Diamond Gary M
• Dias Eric L
• Zhu Guang
• Longmire James M
• Herrmann Stanley
• Torssell Staffan
• Lavrenko Mayya

Classifications

• B01J8/02 Primary

  with stationary particles, e.g. in fixed beds · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07D307/68 Primary

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

• B01J2208/00893

  Feeding means for the reactants · CPC title

• B01J23/52

  Gold · CPC title