Processes for producing 2,5-furandicarboxylic acid and derivatives thereof and polymers made therefrom

Patent metadata

Field	Value
Publication number	US-11028063-B2
Application number	US-202016946850-A
Country	US
Kind code	B2
Filing date	Jul 9, 2020
Priority date	Apr 14, 2015
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

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).

First claim

The invention claimed is:

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.

2. 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).

3. 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.

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

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

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

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

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

9. 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.

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

11. The process according to claim 1 , wherein the feed is dehydrated in the further presence of a C 1 -C 5 alcohol.

12. 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.

13. The process according to claim 1 , further comprising esterifying 2,5-furandicarboxylic acid with a C 1 -C 12 aliphatic alcohol or a C 1 -C 12 aliphatic diol, under conditions effective for carrying out the esterification and optionally in the presence of a suitable esterification catalyst.

14. 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 C 2 to C 12 aliphatic diol or a polyol and optionally at least one of a polyalkylene ether glycol (PAEG), a polyfunctional acid or a polyfunctional hydroxyl acid.

15. 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.

Assignees

• Dupont Ind Biosciences Usa Llc
• Archer Daniels Midland Co

Inventors

• Howard Stephen J
• Kreutzer Kristina A
• Rajagopalan Bhuma
• Sacia Eric R
• Sanborn Alexandra
• Smith Brennan

Classifications

• C08L77/10

  Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids · CPC title

• C08G69/32

  from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound · CPC title

• B01J2231/70

  Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues · CPC title

• B01J31/04

  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)} · CPC title

• Y02P20/10

  Process efficiency · CPC title