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

Patent metadata

Field	Value
Publication number	US-2024254097-A1
Application number	US-202318391421-A
Country	US
Kind code	A1
Filing date	Dec 20, 2023
Priority date	Jan 13, 2016
Publication date	Aug 1, 2024
Grant date	—

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

1 . (canceled)

2 . A process for producing 2,5-furandicarboxylic acid (FDCA) from a first furanic oxidation substrate, the process comprising:
providing a crude oxidation substrate comprising a first furanic oxidation substrate, a first oxidation solvent and one or more additional components; separating the one or more additional components from the crude oxidation substrate to form a first oxidation feedstock comprising the first furanic oxidation substrate and the first oxidation solvent; and (a) contacting the first oxidation feedstock 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 FDCA, and producing FDCA; 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; and (b) converting the FDCA to an ester of FDCA; wherein the conversion step comprises contacting the FDCA with a branched or unbranched, C 1 -C 20 alcohol in the presence of an acid catalyst at a temperature in the range of from 50° C. to 150° C.

3 . The process of claim 2 , wherein the alcohol is a methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, 2-methylpropan-1-ol, 2-methyl-2-propanol, n-butyl, as well as any combination thereof.

4 . The process of claim 2 , wherein the alcohol is a diol or polyol.

5 . The process of claim 4 , wherein the alcohol is ethanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, a hexanediol, hexanetriol, bis(hydroxymethyl)benzene, 1,8-octanediol, 4-octene-1,8-diol, 1,9-nonanediol, 2-nonene-1,4-diol, 7-nonene-1,5-diol, 7-nonene-1,5-diol, 1,10-decanediol, or 1,12-dodecanediol, as well as any combination thereof.

6 . The process of claim 2 , wherein the acid catalyst is HCl, or H 2 SO 4 .

7 . The process of claim 3 , wherein the alcohol is methanol and the methyl ester or dimethyl ester of FDCA is produced.

8 . The process of claim 3 , wherein the alcohol is ethanol and the ethyl ester or diethyl ester of FDCA is produced.

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

10 . The process of claim 2 , 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.

11 . The process of claim 2 , 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.

12 . The process of claim 2 , 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 2 , 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 2 , 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 2 , wherein the first solid support comprises a plurality of pores.

16 . The process of claim 2 , 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 30 m 2 /g.

17 . The process of claim 2 , 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.

18 . The process of claim 2 , 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.

19 . The process of claim 2 , wherein the first oxidation feedstock has a pH of about 3-6.

20 . The process of claim 2 , wherein the FDCA is produced at a yield of at least 80%.

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

• B01J2208/00893

  Feeding means for the reactants · CPC title

• B01J8/02 Primary

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

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• B01J35/64

  Pore diameter · CPC title

• B01J35/63

  Pore volume · CPC title