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

An integrated process for producing from a six-carbon sugar-containing feed 2,5-furandicarboxylic acid and/or a derivative thereof, and optionally co-producing at least one of furan-2,5-dimethanol, (tetrahydrofuran-2,5-diyl) dimethanol, a derivative of furan-2,5-dimethanol, and a derivative of (tetrahydrofuran-2,5-diyl) dimethanol, comprising:

• a) dehydrating a feed comprising a six-carbon sugar unit in the presence of a solvent, at an elevated temperature and for a time sufficient to provide a dehydration product including at least one of 5-hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural in the solvent;
• b) hydrogenating at least a portion of the at least one of hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural to form reduced derivatives therefrom, by combining at least a portion of the dehydration product with hydrogen;
• and
• c) oxidizing a portion of the dehydration product not hydrogenated, if any, and optionally including oxidizing at least a portion of the reduced derivatives from step b), by combination with an oxygen source in the presence of a metal catalyst at an elevated temperature and for a time sufficient to produce a mixture comprising an oxidation product 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;
• and
• e) recycling at least a portion of the solvent obtained in step d) to step a);
• wherein either or both of steps a) and b) are carried out in the presence of a bromine source so that a bromine-containing species, a reduced bromine-containing species or both are included in the dehydration product and/or the reduced derivatives fed to the oxidation step, and
• 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.

An integrated process for producing from a six-carbon sugar-containing feed 2,5-furandicarboxylic acid and/or a derivative thereof, and optionally co-producing at least one of:

• furan-2,5-dimethanol, (tetrahydrofuran-2,5-diyl) dimethanol, a derivative of furan-2,5-dimethanol, a derivative of (tetrahydrofuran-2,5-diyl) dimethanol, a monoether of any of furan-2,5-dimethanol, (tetrahydrofuran-2,5-diyl) dimethanol, a derivative of furan-2,5-dimethanol, and a derivative of (tetrahydrofuran-2,5-diyl) dimethanol, and a diether of any of furan-2,5-dimethanol, (tetrahydrofuran-2,5-diyl) dimethanol, a derivative of furan-2,5-dimethanol, and a derivative of (tetrahydrofuran-2,5-diyl) dimethanol, comprising the steps of:
• a) dehydrating a feed comprising a six-carbon sugar unit in the presence of a solvent, at an elevated temperature and for a time sufficient to provide a dehydration product including at least one of 5-hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural in the solvent;
• b) hydrogenating at least a portion of the at least one of hydroxymethylfurfural and/or a derivative or derivatives of 5-hydroxymethylfurfural to form reduced derivatives therefrom, by combining at least a portion of the dehydration product with hydrogen;
• c) etherifying at least a portion of the reduced derivatives formed in step b), by combining the same with an alcohol to form an ether derivative from a reduced derivative of 5-hydroxymethylfurfural formed in step b);
• and
• d) oxidizing a portion of the dehydration product not hydrogenated in step b), if any, and optionally including oxidizing at least a portion of the reduced derivatives from step b), at least some of the ether derivatives produced by step c) or both reduced derivatives from step b) and ether derivatives from step c), by combination with an oxygen source in the presence of a metal catalyst at an elevated temperature and for a time sufficient to produce a mixture comprising an oxidation product comprising 2,5-furandicarboxylic acid (FDCA) and/or a derivative thereof, the solvent and a residual catalyst;
• e) purifying and separating the mixture obtained in step d) to obtain FDCA and/or a derivative thereof and the solvent;
• and
• f) recycling at least a portion of the solvent obtained in step e) to step a), and
• 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.