Process for synthesizing 5-hydroxymethylfurfural

Patent metadata

Field	Value
Publication number	US-11261168-B2
Application number	US-201816961184-A
Country	US
Kind code	B2
Filing date	Dec 21, 2018
Priority date	Jan 10, 2018
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

The invention relates to a process for synthesizing 5-hydroxymethylfurfural from a fructose-containing feedstock in the presence of at least one aprotic polar solvent and at least one dehydration catalyst, in which process the maximum instantaneous fructose concentration 5.0 wt %.

First claim

The invention claimed is:

1. A process for the production of 5-hydroxymethylfurfural comprising
bringing at least one fructose-containing saccharide feedstock into contact, in at least one polar aprotic solvent, with at least one dehydration catalyst chosen from homogeneous or heterogeneous and organic or inorganic Brønsted acids and Lewis acids,
said process being carried out at a temperature of between 30° C. and 175° C. and at a pressure of between 0.0001 MPa and 8.0 MPa, wherein the instantaneous fructose concentration is less than or equal to 4.0 wt %.

2. The process of claim 1 , wherein the instantaneous fructose concentration is less than 3.5 wt %.

3. The process of claim 1 , wherein the maintenance of the instantaneous fructose concentration is obtained by the sequential or continuous introduction of the feedstock.

4. The process of claim 3 , wherein the feedstock is introduced in the liquid form in the presence of an additional solvent selected from the group consisting of butan-2-one, acetone, acetic anhydride, N,N,N′, N′-tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone, propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate, γ-valerolactone, water, methanol, ethanol, formic acid and acetic acid.

5. The process of claim 3 , wherein the feedstock is introduced in the liquid form in the presence of an additional solvent corresponding to a fraction or to all of the reaction mixture.

6. The process of claim 1 , wherein the temperature is between 40° C. and 150° C.

7. The process of claim 1 , wherein the saccharide feedstock comprises fructose in monomeric, oligomeric or polymeric form.

8. The process of claim 1 , wherein the feedstock is chosen from fructose, sucrose, kestose, fructans, oligofructans or inulin.

9. The process of claim 1 , wherein the feedstock is introduced in a solvent/feedstock ratio by weight of between 0.1 and 200.

10. The process of claim 1 , wherein the polar aprotic solvent is selected from the group consisting of butan-2-one, acetone, acetic anhydride, N,N,N′,N′-tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone, propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate and γ-valerolactone.

11. The process of claim 1 , wherein the polar aprotic solvent is dimethyl sulfoxide.

12. The process of claim 1 , wherein the homogeneous organic Brønsted acid catalysts are selected from the group consisting of organic acids of formulae R′COOH, R′SO 2 H, R′SO 3 H, (R′SO 2 )NH, (R′O) 2 PO 2 H, R′OH, in which R′ is chosen from the following groups:
alkyls, which are or are not substituted by at least one substituent selected from the group consisting of a hydroxyl, an amine, a nitro, a halogen, a fluorine, and an alkyl halide,
alkenyls, which are or are not substituted by at least one group selected from the group consisting of a hydroxyl, an amine, a nitro, an oxo, a halogen, a fluorine, and an alkyl halide,
aryls, which are or are not substituted by a substituent selected from the group consisting of a hydroxyl, an amine, a nitro, an oxo, a halogen, a fluorine, and an alkyl halide,
heteroaryls, which are or are not substituted by a substituent selected from the group consisting of a hydroxyl, an amine, a nitro, an oxo, a halogen, a fluorine, and an alkyl halide.

13. The process of claim 1 , wherein the homogeneous inorganic Brønsted catalysts are selected from the group consisting of HF, HCl, HBr, HI, H 2 SO 3 , H 2 SO 4 , H 3 PO 2 , H 3 PO 4 , HNO 2 , HNO 3 , H 2 WO 4 , H 4 SiW 12 O 40 , H 3 PW 12 O 40 , (NH 4 ) 6 (W 12 O 40 ).xH 2 O, H 4 SiMo 12 O 40 , H 3 PMo 12 O 40 , (NH 4 ) 6 Mo 7 O 24 .xH 2 O, H 2 MoO 4 , HReO 4 , H 2 CrO 4 , H 2 SnO 3 , H 4 SiO 4 , H 3 BO 3 , HClO 4 , HBF 4 , HSbF 5 , HPF 6 , H 2 FO 3 P, ClSO 3 H, FSO 3 H, HN(SO 2 F) 2 and HIO 3 .

14. The process of claim 1 , wherein the dehydration catalyst(s) are introduced in a solvent/catalyst(s) ratio by weight of between 20 and 10 000, wherein the weight of solvent corresponds to the total weight of solvent employed in the process.

15. The process of claim 1 , wherein at least two dehydration catalysts are employed and wherein at least one of the catalysts is a chlorine-comprising catalyst.

16. The process of claim 12 wherein the alkyls are comprised of between 1 and 15 carbon atoms, the aryls are comprises of between 5 and 15 carbon atoms, and the heteroaryls are comprises of between 4 and 15 carbon atoms.

Assignees

• Ifp Energies Now

Inventors

• Jacquin Marc
• Delcroix Damien

Classifications

• C07D307/48 Primary

  Furfural · CPC title

• C07D307/44 Primary

  Furfuryl alcohol · CPC title