Process for the synthesis of 5-hydroxymethylfurfural from saccharides

Patent metadata

Field	Value
Publication number	US-9409877-B2
Application number	US-201414889526-A
Country	US
Kind code	B2
Filing date	May 9, 2014
Priority date	May 9, 2013
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

This invention relates to a process for the synthesis of 5-hydroxymethylfurfural (HMF) from saccharides. In particular this invention relates to a process for the dehydration of monosaccharides having 6 carbon atoms (hexoses), disaccharides, oligosaccharides, and polysaccharides to yield highly pure 5-hydroxymethylfurfural (HMF) in high yield.

First claim

The invention claimed is:

1. A process for preparing 5-hydroxymethylfurfural comprising the steps of:
A) heating at a temperature from 60° C. to 120° C. for a time from 10 minutes to 12 hours a reaction mixture consisting of:
a) a quaternary ammonium salt R 3 R′N + X − wherein:
R, which is the same or different, is a C 1 -C 4 alkyl group;
R′ is a C 1 -C 15 alkyl group;
X − is an anion selected from chloride, bromide, iodide, fluoride, and hydroxide;

b) at least one catalyst selected from:
b-i) titanium (IV) oxide supported on silica having a surface area from 150 m 2 /g to 900 m 2 /g, calcined at a temperature from 150° C. to 900° C.;
b-ii) phosphotungstic acid, H 3 [P(W 3 O 10 ) 4 ], supported on silica having a surface area from 150 m 2 /g to 900 m 2 /g, calcined at a temperature of from 150° C. to 900° C.;
b-iii) zirconium phosphate Zr(HPO 4 ) 2 ; and
b-iv) titanium phosphate Ti(HPO 4 ) 2 ;

c) water in a quantity from 1% by weight to 50% by weight with respect to the quaternary ammonium salt;
d) a saccharide selected from a monosaccharide having 6 carbon atoms, and a disaccharide, oligosaccharide, and polysaccharide formed from a monosaccharide unit having 6 carbon atoms;

B) adding to the reaction mixture an organic solvent or a mixture of organic solvents in which the quaternary ammonium salt and the catalyst are highly insoluble and 5-hydroxymethylfurfural is soluble, at a temperature from 15° C. to the boiling point of the organic solvent or of the mixture of organic solvents, obtaining the quaternary ammonium salt and the catalyst as solid phase, and the organic solvent or mixture of organic solvents and 5-hydroxymethylfurfural as liquid phase;
C) removing the solid phase from the liquid phase of step B);
D) separating off the organic solvent or mixture of organic solvents from the 5-hydroxymethylfurfural by distillation.

2. The process according to claim 1 , wherein B) and C) are repeated one or more times.

3. The process according to claim 1 , wherein the saccharide in D) is selected from fructose, glucose, saccharose, oligofructose, inulin and mixtures thereof.

4. The process according to claim 1 , wherein X − is chloride or bromide.

5. The process according to claim 1 , wherein the quaternary ammonium salt is selected from tetramethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, and tetrabutylammonium bromide.

6. The process according to claim 1 , wherein the catalyst is titanium (IV) oxide, supported on silica having a surface area from 150 m 2 /g to 900 m 2 /g calcined at a temperature from 150° C. to 900° C.

7. The process according to claim 6 , wherein the catalyst titanium (IV) oxide is supported on silica having a surface area from 150 m 2 /g to 500 m 2 /g calcined at a temperature from 200° C. to 600° C.

8. The process according to claim 6 , wherein the catalyst has a surface area from 100 m 2 /g to 350 m 2 /g.

9. The process according to claim 1 , wherein the catalyst is phosphotungstic acid, H 3 [P(W 3 O 10 ) 4 ], supported on silica having a surface area from 150 m 2 /g to 900 m 2 /g calcined at a temperature from 150° C. and 900° C.

10. The process according to claim 9 , wherein the catalyst H 3 [P(W 3 O 10 ) 4 ] is supported on silica having a surface area from 150 m 2 /g and 500 m 2 /g calcined at a temperature from 200° C. to 600° C.

11. The process according to claim 9 , wherein the catalyst has a surface area from 100 m 2 /g to 350 m 2 /g.

12. The process according to claim 1 wherein the catalyst is zirconium phosphate Zr(HPO 4 ) 2 .

13. The process according to claim 1 , wherein the catalyst is titanium phosphate Ti(HPO 4 ) 2 .

14. The process according to claim 1 , wherein the saccharide is selected from monosaccharides and/or disaccharides and the quantity of water in step A) is from 5% by weight to 15% by weight with respect to the quaternary ammonium salt.

15. The process according to claim 1 , wherein the organic solvent of step B) is selected from ethyl acetate, butyl acetate, isopropyl acetate, 2-butanone, 4-methyl-2-pentanone, tetrahydrofuran, chloroform and mixtures thereof.

16. The process according to claim 1 , wherein the time of step A) is from 15 minutes to 10 hours.

17. The process according to claim 1 , wherein the time of step A) is from 20 minutes to 8 hours.

18. The process according to claim 1 wherein the saccharide is selected from monosaccharides and/or disaccharides and the time of step A) is from 10 minutes to 2 hours.

19. The process according to claim 1 , wherein the saccharide is selected from oligosaccharides and/or polysaccharides and the time of step A) is from 1 hour to 6 hours.

20. The process according to claim 1 , wherein the ratio by weight between the saccharide and the active phase of the catalysts in step A) is from 500:1 to 1:1.

Assignees

• Novamont Spa

Inventors

• Capuzzi Luigi
• Digioia Francesca
• Carotenuto Giuseppina

Classifications

• B01J27/188 Primary

  with chromium, molybdenum, tungsten or polonium · CPC title

• C07D307/50

  Preparation from natural products · CPC title

• C07D307/46 Primary

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

• B01J35/615

  100-500 m2/g · CPC title