Method for producing 5-hydroxymethylfurfural in the presence of a Lewis acid catalyst and/or a heterogeneous base catalyst and a homogeneous organic Brønsted acid catalyst in the presence of at least one aprotic polar solvent

Patent metadata

Field	Value
Publication number	US-10526302-B2
Application number	US-201615772592-A
Country	US
Kind code	B2
Filing date	Oct 17, 2016
Priority date	Nov 2, 2015
Publication date	Jan 7, 2020
Grant date	Jan 7, 2020

Abstract

The invention relates to a process for the production of 5-hydroxymethylfurfural from a feedstock comprising at least one sugar using a combination of at least one catalyst selected from the homogeneous Lewis acids, the heterogeneous Lewis acids and the heterogeneous bases and at least one homogeneous Brønsted acid catalyst selected from the families of the thioureas, the sulphonic acids and the phosphorus-containing organic compounds, alone or in a mixture, in the presence of at least one aprotic polar solvent, at a temperature comprised between 30° C. and 300° C., and at a pressure comprised between 0.1 MPa and 10 MPa.

First claim

The invention claimed is:

1. A process for preparing 5-hydroxymethylfurfural from a feedstock comprising at least one sugar, said process comprising reacting the feedstock in the presence of
at least one homogeneous Lewis acid, which is a compound of formula M m X n , which is optionally solvated, in which M is an atom of groups 3 to 16 of the periodic table, including lanthanides, m is an integer of 1 to 10, n is an integer of 1 to 10 and X is an anion, which is a hydroxide, halide, nitrate, carboxylate, halocarboxylate, acetylacetonate, alcoholate, phenolate, which is optionally substituted, sulphate, alkylsulphate, phosphate, alkylphosphate, halosulphonate, alkylsulphonate, per-haloalkylsulphonate, bis(per-haloalkylsulphonyl)amide, or arenesulphonate, which is optionally substituted by one or more halogen or haloalkyl groups, and wherein said anions X is identical or different in the case where n is greater than 1,
and
at least one homogeneous Brønsted acid catalyst, which is:
a phosphorus-containing organic compound of the following formula:

in which
X is OH, SH, SeH or NHR 3 ,
R 3 is aryl, aryl sulphonyl or trifluoromethanesulphonyl,
Y is oxygen, sulphur or selenium atom,
Z 1 and Z 2 are identical or different, and are either an oxygen atom or NR 4 ,
R 4 is trifluoromethanesulphonyl, p-toluenesulphonyl or 2-naphthalenesulphonyl,
R 1 and R 2 are, each independently, alkyl, which is optionally substituted, and is linear, branched or cyclic, or aryl, which is optionally substituted, and is optionally fused;
or
a thiourea of the following formula:

in which
R 5 and R 6 are, each independently, an aromatic group optionally including one or more heteroatoms, or an alkyl group including at least one heteroatom, and is linear, branched or cyclic, and which R 5 and R 6 groups are optionally substituted;
or
a sulphonic acid of the following formula:

in which R 7 is
a halogen,
an alkyl, which is linear, branched or cyclic, and contains 1 to 20 carbon atoms, and is optionally substituted with at least one substituent selected from the group consisting of:
an oxo group,
halogens and,
aryl groups, which are optionally fused, and are optionally substituted with one or more halogen groups and/or one or more linear, branched or cyclic alkyl groups containing 1 to 20 carbon atoms,

an aryl group containing 6 to 14 carbon atoms, which is optionally substituted with at least one substituent selected from the group consisting of:
one or more alkyl groups, which is linear, branched or cyclic, and which contains 1 to 20 carbon atoms, and which is optionally substituted with at least one halogenated group or at least one nitro group,
one or more halogenated groups and
a nitro group;

in the presence of at least one aprotic polar solvent,
at a temperature of 30° C. to 300° C., and at a pressure of 0.1 MPa to 10 MPa.

2. The process according to claim 1 , in which said homogeneous Lewis acid of formula M m X n , is not solvated.

3. The process according to claim 1 , in which said sugar is selected from polysaccharides, oligosaccharides and monosaccharides, alone or in a mixture.

4. The process according to claim 3 , in which said polysaccharides are selected from starch, inulin, lignocellosic biomass, cellulose and hemicellulose, alone or in a mixture.

5. The process according to claim 3 , in which the monosaccharides are selected from glucose, mannose and fructose, alone or in a mixture.

6. The process according to claim 3 , in which the oligosaccharides are selected from saccharose, lactose, maltose, isomaltose, inulobiose, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose and oligosaccharides originating from hydrolysis of polysaccharides originating from the hydrolysis of inulin, cellulose or hemicellulose, alone or in a mixture.

7. The process according to claim 1 , in which said homogeneous Brønsted acid catalyst is a phosphorus-containing organic compound of formula:

8. The process according to claim 1 , in which said homogeneous Brønsted acid catalyst is a thiourea of formula:

9. The process according to claim 1 , in which said homogeneous Brønsted acid catalyst is a sulphonic acid of formula:

10. The process according to claim 1 , which is in the presence of DMSO.

11. The process according to claim 10 , in which said homogeneous Lewis acid catalyst is aluminium triflate and said homogeneous Brønsted acid catalyst is selected from methanesulphonic acid, the phosphorus-containing compound 2 of formula:

and the thiourea compound 1 of formula:

12. The process according to claim 1 , in which the aprotic polar solvent has a dipole moment expressed in Debye (D) of greater than 2.00.

13. The process according to claim 1 , in which the aprotic polar solvent is selected from pyridine, 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, sulpholane, N-methylpyrrolidone, dimethylsulphoxide and propylene carbonate alone or in a mixture.

14. The process according to claim 13 , in which the aprotic polar solvent is acetone, N,N-dimethylformamide, N,N-dimethylacetamide, sulpholane, N-methylpyrrolidone, dimethylsulphoxide, propylene carbonate or γ-valerolactone, alone or in a mixture.

15. The process according to claim 1 , in which the temperature is 50° C. to 200° C., and the pressure is 0.1 MPa to 8 MPa.

16. The process according to claim 1 , in which the feedstock is introduced at a solvent/feedstock mass ratio of 0.1 to 200.

17. The process according to claim 1 , in which the homogeneous sulphonic acid is introduced at a feedstock/organic catalyst(s) mass ratio of 1 to 1000.

18. The process according to claim 1 , wherein the homogeneous Lewis acid is of formula M m X n , solvated or not, in which M is an atom of groups 6 to 13 of the periodic table, including lanthanides, m is an integer of 1 to 5, n is an integer of 1 to 5 and X is an anion selected from the group consisting of halides, sulphates, alkylsulphonates, and per-haloalkylsulphonates, which is substituted or not by one or more halogen or haloalkyl groups, said anions X being able to be identical or different in the case where n is greater than 1.

19. The process according to claim 1 , wherein the homogeneous Lewis acid is BF 3 , AlCl 3 , Al(OTf) 3 , FeCl 3 , ZnCl 2 , SnCl 2 , CrCl 3 , CeCl 3 or ErCl 3 .

20. The process according to claim 1 , for preparing 5-hydroxymethylfurfural from a feedst

Assignees

• Ifp Energies Now

Inventors

• Souleymanou Myriam
• Jacquin Marc
• Delcroix Damien

Classifications

• C07D307/50 Primary

  Preparation from natural products · CPC title

• C07D307/48 Primary

  Furfural · CPC title