# US 11,028,063 B2 · Processes for producing 2,5-furandicarboxylic acid and derivatives thereof and polymers made therefrom

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- Number: US 11,028,063 B2
- Document ID: US11028063B2
- Status: Granted
- Kind: B2
- Application number: 16/946,850
- Filed: 2020-07-09
- Published: 2020-10-29
- Granted: 2021-06-08
- Earliest claimed: 2015-04-14
- Assignees: Dupont Industrial Biosciences USA, LLC; Archer Daniels Midland Company
- Applicants: Dupont Industrial Biosciences USA, LLC; Archer Daniels Midland Company
- Inventors: Stephen J. Howard; Kristina A. Kreutzer; Bhuma Rajagopalan; Eric R. Sacia; Alexandra Sanborn; Brennan Smith
- Web page: https://patentgrep.com/patent/US11028063B2

## CPC

- C07D 307/40: Radicals substituted by oxygen atoms
- C07D 307/68: Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof}
- B01J 23/10: of rare earths
- B01J 23/6562: {Manganese}
- B01J 23/75: Cobalt
- B01J 31/04: containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)}
- C07B 33/00: Oxidation in general
- C07B 63/00: Purification; Separation (separation of optically-active compounds C07B57/00); Stabilisation; Use of additives
- C08G 63/181: Acids containing aromatic rings
- C08G 63/672: Dicarboxylic acids and dihydroxy compounds
- C08G 63/78: Preparation processes
- C08G 63/80: Solid-state polycondensation
- C08G 69/28: Preparatory processes
- C08G 69/32: from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
- C08L 77/10: Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
- B01J 2231/70: Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- Y02P 20/10: Process efficiency
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

An integrated process is useful for producing 2,5-furandicarboxylic acid (FDCA) and/or a derivative thereof from a six-carbon sugar-containing feed. The process includes a) dehydrating a feed containing a six-carbon sugar unit, in the presence of a bromine source and of a solvent, to generate an oxidation feed that contains at least one of 5-hydroxymethylfurfural (HMF) and/or a derivative or derivatives of HMF in the solvent, together with at least one bromine containing species; b) contacting the oxidation feed from step (a) with a metal catalyst and with an oxygen source under oxidation conditions to produce an oxidation product mixture of at least FDCA and/or a derivative thereof, the solvent, and a residual catalyst; c) purifying and separating the mixture obtained in step (b) to obtain FDCA and/or a derivative thereof and the solvent; and d) recycling at least a portion of the solvent obtained in step (c) to step (a).

## Claims

### Claim 1

An integrated process for producing 2,5-furandicarboxylic acid and/or a derivative thereof from a six-carbon sugar-containing feed, comprising:
a) dehydrating a feed comprising a six-carbon sugar unit, in the presence of a bromine source and of a solvent, at an elevated temperature and for a time sufficient to generate an oxidation feed comprised of at least one of 5-hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural in the solvent, together with at least one bromine containing species;
b) removing water from the oxidation feed from step a);
c) contacting the oxidation feed from step b) with a homogeneous metal catalyst based on Co and Mn and with an oxygen source at an elevated temperature for a time sufficient to produce an oxidation product mixture comprising 2,5-furandicarboxylic acid (FDCA) and/or a derivative thereof, the solvent, and a residual catalyst;
d) purifying and separating the mixture obtained in step c) to obtain FDCA and/or a derivative thereof and the solvent;
e) recycling at least a portion of the solvent obtained in step d) to step a); and
f) providing more or less of the at least one bromine containing species used in step a) in step c), together with optionally other bromine containing species,
wherein each optionally present derivative is at least one selected from the group consisting of diacid, diether, diester, ether-acid, ether-ester, ester-acid, ester-aldehyde, ether-aldehyde, ether-acetal, ester-acetal, acetal-acid, alcohol-acid, alcohol-ester, alcohol-acetal, diol, diacetal, and aldehyde-acetal.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the step of providing more or less of the at least one bromine containing species used in step a) in step c) together with optionally other bromine containing species, comprises adding to or removing bromine containing species from the oxidation feed prior to step c).

### Claim 3 (depends on 1)

The process according to claim 1, wherein the bromine containing species in the oxidation feed comprise one or more of an inorganic bromide and organic bromide.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the metal catalyst comprises one or more transition metals.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the metal catalyst comprises cobalt (II) acetate tetrahydrate, and manganese (II) acetate tetrahydrate.

### Claim 6 (depends on 1)

The process according to claim 1, wherein the metal catalyst further comprises Zr.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the metal catalyst further comprises Ce.

### Claim 8 (depends on 1)

The process according to claim 1, wherein the bromine source in step a) comprises hydrogen bromide.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the feed to the dehydration step comprises one or more of starch, amylose, galactose, cellulose, hemicellulose, inulin, fructan, glucose, fructose, sucrose, maltose, cellobiose, lactose, and sugar oligomers.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the solvent comprises acetic acid or a mixture of acetic acid and water.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the feed is dehydrated in the further presence of a C1-C5 alcohol.

### Claim 12 (depends on 1)

The process according to claim 1, wherein the oxidation step is performed at a temperature of from about 120 to about 250 degrees Celsius and at an oxygen partial pressure of from about 0.02 to about 100 bar.

### Claim 13 (depends on 1)

The process according to claim 1, further comprising esterifying 2,5-furandicarboxylic acid with a C1-C12 aliphatic alcohol or a C1-C12 aliphatic diol, under conditions effective for carrying out the esterification and optionally in the presence of a suitable esterification catalyst.

### Claim 14 (depends on 1)

The process according to claim 1, further comprising preparing a polyester by transesterification of at least one ester of 2,5-furandicarboxylic acid with a C2 to C12 aliphatic diol or a polyol and optionally at least one of a polyalkylene ether glycol (PAEG), a polyfunctional acid or a polyfunctional hydroxyl acid.

### Claim 15 (depends on 2)

The process according to claim 2, wherein the bromine containing species in the oxidation feed comprise one or more of an inorganic bromide and organic bromide.