Process for making esters of 2,5-furandicarboxylic acid

Patent metadata

Field	Value
Publication number	US-11078174-B2
Application number	US-201816622713-A
Country	US
Kind code	B2
Filing date	Jun 20, 2018
Priority date	Jun 22, 2017
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

Abstract

A process is provided for making esters of FDCA, in which an aqueous feed comprising glucaric acid is first reacted with a high boiling first alcohol in the presence of an acid catalyst and with removing water during the reaction, to form a first product mixture comprising a first ester of FDCA and the high boiling first alcohol, then unreacted high boiling first alcohol is removed from the first product mixture. The first ester of FDCA and the high boiling first alcohol is then transesterified with a lower boiling second alcohol selected from the group consisting of methanol, ethanol, isopropanol and n-propanol, to form a second product mixture comprising a second ester of FDCA with the lower boiling second alcohol, and the second ester of FDCA with the lower boiling second alcohol is recovered.

First claim

What is claimed is:

1. A process for making esters of 2,5-furandicarboxylic acid, comprising:
reacting an aqueous feed comprising glucaric acid with a high boiling first alcohol in the presence of an acid catalyst and with removing water during the reaction, to form a first product mixture comprising a first ester of 2,5-furandicarboxylic acid and the high boiling first alcohol;
removing unreacted high boiling first alcohol from the first product mixture;
combining the first ester of 2,5-furandicarboxylic acid and the high boiling first alcohol with a lower boiling second alcohol selected from the group consisting of methanol, ethanol, isopropanol and n-propanol;
transesterifying the first ester with the lower boiling second alcohol to form a second product mixture comprising a second ester of 2,5-furandicarboxylic acid with the lower boiling second alcohol; and
recovering the second ester of 2,5-furandicarboxylic acid with the lower boiling second alcohol.

2. The process of claim 1 , wherein 2,3- and/or 2,5-isomers of the first diester
are present in the first product mixture and further comprising recovering at least a portion or portions of either or both of these isomers prior to the transesterification step.

3. The process of claim 2 , wherein at least a portion of the 2,3-isomer is preferentially isolated from the first product mixture by distillation, solid-liquid extraction or chromatography.

4. The process of claim 1 , wherein 2,3- and/or 2,5-isomers of the second diester are present in the second product mixture and further comprising separating the second product mixture into a first fraction enriched in the 2,3-isomer and a second fraction enriched in the 2,5-isomer by one or more of distillation, solid-liquid extraction, fractional crystallization and chromatography.

5. The process of any one of claims 1 - 4 , wherein the high boiling first alcohol is
selected from the C 4 to C 11 linear alcohols and C 4 to C 11 branched alcohols.

6. The process of claim 5 , wherein the high boiling first alcohol is selected from 2-ethyl-1-hexyl alcohol, isobutyl alcohol, 2-propylheptyl alcohol, isononyl alcohol, isodecyl alcohol, isooctyl alcohol, isoamyl alcohol, isohexyl alcohol, fusel oil and mixtures of any of these.

7. The process of claim 1 , further comprising removing impurities
from the recovered second ester by one or more of distillation, crystallization, chromatography, absorption, adsorption and hydrotreating to reduce unsaturation.

8. The process of claim 7 , further comprising adding an antioxidant or oxygen
scavenger to the recovered second ester.

9. The process of claim 8 , further comprising storing or transporting the recovered second ester in or under a reduced oxygen environment.

10. The process of claim 1 , wherein water is continuously removed from the
reaction to form the first ester.

11. The process of claim 1 , wherein either or both of the formation of the first
ester and the transesterification of the first ester with the lower boiling second alcohol take place in a reduced oxygen environment.

12. The process of claim 1 , further comprising recovering and recycling at least
a portion of high boiling first alcohol to the step of reacting the aqueous feed with high boiling first alcohol to form the first ester.

Assignees

• Archer Daniels Midland Co

Inventors

• Anklam Pam
• Hoffman William Chris
• Howard Stephen J
• Sanborn Alexandra
• Schultz Mitchell
• Soper John G

Classifications

• B01D15/1821

  Simulated moving beds · CPC title

• B01D15/364

  Amphoteric or zwitterionic ion-exchanger · CPC title

• C07D307/68 Primary

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

• B01J43/00

  Amphoteric ion-exchange, i.e. using ion-exchangers having cationic and anionic groups; Use of material as amphoteric ion-exchangers; Treatment of material for improving their amphoteric ion-exchange properties (ion-exchange chromatography processes B01D15/36) · CPC title

• B01D2215/023

  Operations & Transport · mapped topic