Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters

Patent metadata

Field	Value
Publication number	US-10259797-B2
Application number	US-201615772207-A
Country	US
Kind code	B2
Filing date	Nov 3, 2016
Priority date	Nov 4, 2015
Publication date	Apr 16, 2019
Grant date	Apr 16, 2019

Abstract

Provided herein is a process for preparing a mixture including 5-(hydroxy-methyl)furfural (HMF) and one or more HMF esters of formula (I), the process including the following steps: (A-1) preparing or providing a starting mixture which includes one, two or more carbohydrate compounds and as the solvent or as a co-solvent for the carbohydrate compounds an amount of one or more carboxylic acid esters of formula (II); (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, so that a mixture results that includes 5-(hydroxy-methyl)furfural and/or the one or more HMF esters of formula (I), one or more carboxylic acids of 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 a mixture comprising 5-(hydroxyl-methyl)furfural (HMF) and one or more HMF esters of formula (I),

wherein in each of said HMF esters of formula (I), independently of each other, R1 is
(i) hydrogen or
(ii) a substituted or unsubstituted, branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less,
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 comprising hexose units, and polysaccharides comprising hexose units,
a catalytically effective amount of one, two or more alkali halide catalysts, and as the solvent or as a co-solvent for said carbohydrate compounds an amount of one or more carboxylic acid esters of formula (II)

wherein in each of said carboxylic acid esters of formula (II)
R1 is the same as defined for formula (I) above and
R2 is a substituted or unsubstituted, 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 said one or more HMF esters of formula (I),
one or more carboxylic acids of 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),

wherein the starting mixture prepared or provided in step (A-1) comprises a total amount of carboxylic acid esters of formula (II) of at least 50 wt.-%, based on the total weight of the starting mixture.

2. The process according to claim 1 ,
wherein in the mixture resulting in step (A-2) the total amount of 5-(hydroxyl-methyl)furfural and HMF esters of formula (I) is in the range of from 0.5 to 50 wt.-%, based on the total weight of the mixture resulting in step (A-2), and/or
wherein the 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 the total weight of the starting mixture, and/or has an acid value below 50.

4. The process according to claim 1 , wherein the starting mixture prepared or provided in step (A-1) comprises Bronsted acids, and wherein the total concentration of the Bronsted acids.

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

6. The process according to claim 1 , wherein said one or at least one of said one or 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-Methoxyethanol.

7. 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.

8. The process according to claim 1 , wherein said one or at least one of said one or more 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.

9. The process according to claim 1 , wherein in step (A-2) said starting mixture is subjected to said reaction conditions in a pressurized reactor.

10. The process according to claim 1 , wherein the molar ratio of the 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 comprising hexose units, and polysaccharides comprising hexose units is above 1.

11. The process according claim 1 ,
wherein said starting mixture prepared or provided in step (A-1) comprises water,
wherein the molar ratio of the 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 (i) the total amount of water, and (ii) three times the total amount of hexoses and hexose units is above 1.

12. The process according to claim 1 , wherein the one, two or more catalysts is selected from a sodium halide and a lithium halide.

13. 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) are 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, are obtained in step (A-2), and/or said one or more alcohols R2-OH used in the esterification, or a portion thereof, are obtained in step (A-2).

14. The process according to claim 1 , additionally comprising the step of (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).

15. The process according to claim 1 , wherein a total yield of 5-(Hydroxymethyl)furfural and 5-(acetoxymethyl)furfural is at least 40%.

16. The process according to claim 1 , wherein the starting mixture prepared or provided in step (A-1) doe

Assignees

• Basf Se

Inventors

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

Classifications

• C07D307/50 Primary

  Preparation from natural products · CPC title

• C07D307/46

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