Preparation of 5-hydroxymethylfurfural (HMF) from saccharide solutions in the presence of a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short)

Patent metadata

Field	Value
Publication number	US-9162998-B2
Application number	US-201213712056-A
Country	US
Kind code	B2
Filing date	Dec 12, 2012
Priority date	Dec 13, 2011
Publication date	Oct 20, 2015
Grant date	Oct 20, 2015

Abstract

A process for preparing 5-hydroxymethylfurfural (HMF), which comprises
a) feeding solutions (hereinafter called starting solution) comprising
one or more saccharides and an organic solvent having a boiling point greater than 200° C. (at standard pressure) (called high boiler for short) and water,
 and a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short) to a reaction vessel, b) effecting a conversion of hexose to HMF in the reaction vessel in the presence of water vapor with simultaneous distillative removal of the HMF and c) obtaining, as the distillate, an aqueous, HMF-comprising solution (hereinafter called distillate).

First claim

The invention claimed is:

1. A process for preparing 5-hydroxymethylfurfural (HMF), which comprises
a) feeding a starting solution comprising
at least one hexose and
a high boiler comprising an organic solvent having a boiling point greater than 200° C. (at standard pressure) and
water,

 and low boiler comprising a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure) to a reaction vessel,
b) converting hexose to HMF in the reaction vessel in the presence of the low boiler with simultaneous distillative removal of the HMF and
c) obtaining, as a distillate, an aqueous, HMF-comprising solution.

2. The process according to claim 1 , wherein the at least one hexose is fructose, glucose or mixtures of fructose and glucose.

3. The process according to claim 1 , wherein the high boiler is a polyether or an ionic liquid.

4. The process according to claim 3 , wherein the ionic liquid comprises imidazolium chlorides or imidazolium methanesulfonates.

5. The process according to claim 1 , wherein the starting solution is prepared by the following steps:
A1) the at least one hexose and water are present in a reaction vessel,
A2) a further reaction vessel is initially charged with the high boiler and preferably a catalyst,
A3) immediately prior to process step b), the components are mixed, optionally in a mixing chamber,
the solutions of steps A1 and A2 being preheated to a temperature between 150 and 200° C. in the two reaction vessels separated from one another prior to the mixing.

6. The process according to claim 1 , wherein the low boiler is water vapor, methanol or 2-butanol.

7. The process according to claim 1 , wherein the starting solution comprises the high boiler in amounts of 5 to 90% by weight.

8. The process according to claim 1 , wherein the starting solution comprises a metal chloride or metal nitrate of the formula MXn where M is a metal, X is chlorine or nitrate and n is an integer from 1 to 4.

9. The process according to claim 1 , wherein the conversion to HMF is effected in the presence of an acid soluble in the starting solution.

10. The process according to claim 1 , wherein the conversion to HMF is effected at a temperature from 100° C. to 250° C.

11. The process according to claim 1 , wherein the conversion to HMF is effected at a pressure of 10 to 200 mbar.

12. The process according to claim 1 , which is performed continuously, the starting solution and the low boiler being supplied continuously to the evaporator and the product solution being removed continuously.

13. The process according to claim 1 , wherein the reaction vessel is a thin-film evaporator or a stripping column.

14. The process according to claim 1 , wherein the low boiler is supplied in countercurrent to the starting solution.

15. The process according to claim 1 , wherein more than 60% of the HMF obtained is present in the distillate.

16. The process according to claim 1 , wherein the distillate is used for preparation of 2,5-furandicarboxylic acid or 2,5-bis(hydroxymethyl)furan.

17. The process according to claim 1 , wherein the ionic liquid comprises 1-ethyl-3-methylimidazolium chloride (EMIM Cl), 1-butyl-3-methylimidazolium chloride (BMIM Cl), 1-ethyl-3-methylimidazolium methanesulfonate (EMIM CH3SO3) or 1-butyl-3-methylimidazolium methanesulfonate (BEMIM CH3SO3) or mixtures thereof.

18. The process according to claim 1 , wherein at least 60% of the at least one saccharide hexose is converted to I-IMF in the process.

19. The process according to claim 1 , wherein the ratio of the amount of low boiler supplied to the amount of the starting solution supplied is from 0.2:1 to 4:1.

20. The process according to claim 1 , wherein in step b) the starting solution is contacted with the low boiler under reduced pressure.

21. The process according to claim 1 , further comprising:
d) discharging the low boiler and the volatile constituents of the starting solution via a separator at the top of the evaporator; and
e) condensing the low boiler and the volatile constituents to from the distillate.

22. The process according to claim 1 comprising as step b) converting hexose to HMF in the reaction vessel in the presence of water vapor with simultaneous distillative removal of the HMF.

Assignees

• Basf Se

Inventors

• Backes René
• Blank Benoit
• Kindler Alois
• Feldner Carmen

Classifications

• C07D307/46 Primary

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

• Y02P20/10

  Process efficiency · CPC title