Process for preparing furan-2,5-dicarboxylic acid

Patent metadata

Field	Value
Publication number	US-10428039-B2
Application number	US-201615773411-A
Country	US
Kind code	B2
Filing date	Nov 3, 2016
Priority date	Nov 4, 2015
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

Provided herein is a process for preparing furan-2,5-dicarboxylic acid. The process includes the following steps: (A-1) preparing a starting mixture comprising one, two or more carbohydrate compounds selected from the group consisting of: hexoses, oligosaccharides comprising hexose units, and polysaccharides including hexose units, and as a solvent or as a co-solvent for the carbohydrate compounds an amount of one or more carboxylic acid esters of a formula (II) and (A-2) subjecting the starting mixture to reaction conditions so that at least one of the one, two or more carbohydrate compounds reacts, and a fraction of the amount of one or more carboxylic acid esters of formula (II) is hydrolyzed, resulting in a mixture including 5-(hydroxymethyl)furfural and/or the one or more HMF esters of a formula (I), one or more carboxylic acids of a formula (III) and a remaining fraction of the amount of one or more carboxylic acid esters of formula (II).

First claim

The invention claimed is:

1. A process for preparing furan-2,5-dicarboxylic acid, the process comprising the following steps:
(A-1) preparing or providing a starting mixture comprising:
one, two, or more carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides, and polysaccharides,
and as a solvent or as a co-solvent for said carbohydrate compounds an amount of one or more carboxylic acid esters of a formula (II)

wherein for each of said carboxylic acid esters of formula (II):
R1 is hydrogen or a branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less, and
R2 is a branched or linear or cyclic, aliphatic hydrocarbon radical having a total number of 10 carbon atoms or less,

(A-2) subjecting said starting mixture to reaction conditions such that at least one of said one, two, or more carbohydrate compounds reacts, and a fraction of said amount of one or more carboxylic acid esters of formula (II) is hydrolyzed, such that a mixture results comprising:
5-(hydroxymethyl)furfural and/or one or more HMF esters of formula (I)

wherein for each of said HMF esters of formula (I), independently of each other, R1 is
(i) hydrogen or
(ii) a branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less,
one or more carboxylic acids of a formula (III)

wherein R1 is the same as defined for formula (I) above,
one or more alcohols R2-OH, wherein R2 is the same as defined for formula (II) above, and
a remaining fraction of said amount of one or more carboxylic acid esters of formula (II),

(B-1) subjecting
said mixture resulting in step (A-2) or
a mixture comprising 5-(hydroxymethyl)furfural and/or one or more HMF esters of formula (I) obtained from said mixture resulting in step (A-2) by additional treatment steps

to oxidation conditions such that a product mixture results comprising furan-2,5-dicarboxylic acid and one or more carboxylic acids of formula (III).

2. The process according to claim 1 , wherein for the mixture resulting in step (A-2), a total amount of 5-(hydroxymethyl)furfural and HMF esters of formula (I) is in the range of from 0.5 to 50 wt.-% based on a total weight of the mixture resulting in step (A-2), and/or wherein a total weight of the one, two, or more carbohydrate compounds in the starting mixture prepared or provided in step (A-1) is in the range of from 1 to 70 wt % based on the total weight of the starting mixture.

3. The process according to claim 1 , wherein the starting mixture prepared or provided in step (A-1) comprises fructose and glucose, and/or comprises less than 35 wt % of water based on a total weight of the starting mixture, and/or
has an acid value below 50 and/or
comprises a total amount of carboxylic acid esters of formula (II) of at least 10 wt. %, based on the total weight of the starting mixture.

4. The process according to claim 1 , wherein for the mixture resulting in step (A-2), a molar ratio of the amount of 5-(hydroxymethyl)furfural to a total amount of HMF esters of formula (I) is in the range of from 100 to 0.001, and/or wherein said subjecting said starting mixture to reaction conditions of step (A-2) comprises subjecting said starting mixture to a reaction temperature for at least 10 minutes, the reaction temperature in the range of from 70° C. to 300° C. and/or wherein in step (A-2) the reaction temperature is in the range of from 185° C. to 220° C.

5. The process according to claim 1 , wherein said one or at least one of said more alcohols R2-OH:
(i) has a vapor pressure of at least 0.1 kPa at 25° C., and/or
(ii) is selected from the group consisting of: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hydroxy-2-methylpropan, 2-hydroxy-2-methylpropan, and 2-Methoxy ethanol.

6. The process according to claim 1 , wherein R1 is:
(i) hydrogen or
(ii) a linear or branched, saturated or unsaturated hydrocarbon radical having 15 carbon atoms or less.

7. The process according to claim 1 , wherein said one or at least one of said carboxylic acid esters of formula (II) is selected from the group consisting of methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, and butyl acetate.

8. The process according to claim 1 , wherein a molar ratio of a total amount of said carboxylic acid esters of formula (II) present in the starting mixture prepared or provided in step (A-1) to a total amount of water
(i) present in the starting mixture prepared or provided in step (A-1) and
(ii) produced in step (A-2) by reaction of said carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides, and polysaccharides is above 1.

9. The process according to claim 1 , wherein said starting mixture prepared or provided in step (A-1) comprises water, wherein the molar ratio of a total amount of said carboxylic acid esters of formula (II) to water is above 3, and/or wherein said starting mixture prepared or provided in step (A-1) comprises water, wherein in said starting mixture the molar ratio of the total amount of said carboxylic acid esters of formula (II) to the sum of the total amount of water plus three times the total amount of hexoses and hexose units is above 1.

10. The process according to claim 1 , wherein the starting mixture prepared or provided comprises a catalytically effective amount of one, two, or more catalysts being an alkali halide.

11. The process according to claim 1 , wherein said one or more carboxylic acid esters of formula (II)

present in said starting mixture prepared or provided in step (A-1) is prepared in a separate reactor by esterification of
one or more carboxylic acids of formula (III)

with one or more alcohols R2-OH, wherein said one or more carboxylic acids of formula (III) used in the esterification, or a portion thereof, is obtained in step (A-2) and/or said one or more alcohols R2-OH used in the esterification, or a portion thereof, is obtained in step (A-2).

12. The process for preparing furan-2,5-dicarboxylic acid according to claim 1 , wherein said additional treatment steps comprise:
(A-3) separating, by distillation from said mixture resulting in step (A-2):
at least a portion of the one or more alcohols R2-OH, and/or
at least a portion of the remaining fraction of said amount of one or more carboxylic acid esters of formula (II).

13. The process according to claim 1 , wherein at least 90% by weight of the total amount of said one or more carboxylic acids of formula (III)

as obtained in step (A-2) is present in the mixture subjected to oxidation conditions in step (B-1), and/or
wherein between steps (A-2) and (B-1):
(i) there is no solvent change step, or
(ii) no carboxylic acid of formula (III) is removed, and an additional amount of one, two, or more carboxylic acids of formula (III) i

Assignees

• Basf Se

Inventors

• Gordillo Alvaro
• Bohn Martin Alexander
• Schunk Stephan A
• Jevtovikj Ivana
• Backes Rene
• Werhan Holger
• Duefert Svenia
• Dehn Richard
• Piepenbrink Markus

Classifications

• C07D307/68

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

• C07D307/46 Primary

  Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom · CPC title