Process for producing 5-hydroxymethylfurfural in the presence of an inorganic dehydration and a chloride source

Patent metadata

Field	Value
Publication number	US-11084797-B2
Application number	US-201816651381-A
Country	US
Kind code	B2
Filing date	Sep 25, 2018
Priority date	Sep 28, 2017
Publication date	Aug 10, 2021
Grant date	Aug 10, 2021

Abstract

The invention relates to a process for converting a feedstock comprising at least one sugar into 5-hydroxymethylfurfural, wherein said feed is brought into contact with one or more inorganic dehydration catalysts and one or more chloride sources in the presence of at least one aprotic polar solvent alone or as a mixture, at a temperature of between 30° C. and 200° C., and at a pressure of between 0.1 MPa and 10 MPa.

First claim

The invention claimed is:

1. A process for converting a feedstock comprising at least one sugar into 5-hydroxymethylfurfural, wherein said feedstock is brought into contact with at least one inorganic dehydration catalyst and at least one chloride source of formula (IIIb)

wherein the groups R 5 to R 10 , which may be identical or different, are independently alkyl groups with 1 to 20 carbon atoms, or aryl groups with 5 to 20 carbon atoms,
in the presence of at least one aprotic polar solvent, at a temperature of 30° C. to 200° C. and a pressure of 0.1 to 10 MPa.

2. The process as claimed in claim 1 , wherein the feedstock comprises oligosaccharides or monosaccharides, alone or as a mixture.

3. The process as claimed in claim 1 , wherein the feedstock is sucrose, lactose, maltose, isomaltose, inulobiose, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose or oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, alone or as a mixture.

4. The process as claimed in claim 1 , wherein the dehydration catalyst(s) are independently homogeneous inorganic Brønsted acids or homogeneous or heterogeneous inorganic Lewis acids.

5. The process as claimed in claim 4 , wherein the inorganic Brønsted acid(s) are 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 or HIO 3 .

6. The process as claimed in claim 4 , wherein the homogeneous inorganic Lewis acid(s) are compounds of formula (II) M o X p , which are optionally solvated, wherein
M is an atom from groups 3 to 16 of the periodic table, lanthanides included,
o is an integer 1 to 10,
p is an integer 1 to 10, and
X is an optionally substituted hydroxide, halide, nitrate, carboxylate, halocarboxylate, acetylacetonate, alkoxide, or phenolate anion, or a sulfate, alkyl sulfate, phosphate, alkyl phosphate, halosulfonate, alkyl sulfonate, perhaloalkyl sulfonate, bis(perhaloalkylsulfonyl)amide, or arenesulfonate, which are optionally substituted with halogen or haloalkyl groups.

7. A process for converting a feedstock comprising at least one sugar into 5-hydroxymethylfurfural, wherein said feedstock is brought into contact with at least one inorganic dehydration catalyst and at least one chloride source of formula (IIIc)

wherein R 11 to R 14 , which may be identical or different, are independently
alkyl groups,
aryl groups,
phosphazene groups of formula

wherein R 15 is an alkyl group with 1 to 10 carbon atoms, and
q an integer 0 to 10,
in the presence of at least one aprotic polar solvent, at a temperature of 30° C. to 200° C. and a pressure of 0.1 to 10 MPa.

8. The process as claimed in claim 1 , wherein the aprotic polar solvent(s) are aprotic polar solvents of which the dipole moment expressed in Debye (D) is greater than or equal to 2.00.

9. The process as claimed in claim 1 , wherein at least one aprotic polar solvent, alone or as a mixture, is 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, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate or γ-valerolactone.

10. The process as claimed in claim 1 , wherein the feedstock is introduced into the process in an amount corresponding to a solvent/feedstock weight ratio of 0.1 to 200.

11. The process as claimed in claim 1 , wherein the dehydration catalyst(s) are introduced into the reaction chamber in an amount corresponding to a feedstock/catalyst(s) weight ratio of 1 to 1000.

12. The process as claimed in claim 1 , wherein the chloride source(s) are introduced into the reaction chamber in an amount corresponding to a feedstock/chloride source(s) weight ratio of 1 to 1000.

13. The process as claimed in claim 7 , wherein the feedstock comprises oligosaccharides or monosaccharides, alone or as a mixture.

14. The process as claimed in claim 7 , wherein the feedstock is sucrose, lactose, maltose, isomaltose, inulobiose, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose or oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, alone or as a mixture.

15. The process as claimed in claim 7 , wherein the dehydration catalyst(s) are independently homogeneous inorganic Brønsted acids or homogeneous or heterogeneous inorganic Lewis acids.

16. The process as claimed in claim 15 , wherein the inorganic Brønsted acid(s) are HF, HCl, H Br, 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 or HIO 3 .

17. The process as claimed in claim 15 , wherein the homogeneous inorganic Lewis acid(s) are compounds of formula (II) M o X p , which is optionally solvated, wherein
M is an atom from groups 3 to 16 of the periodic table, lanthanides included,
o is an integer 1 to 10,
p is an integer 1 to 10, and
X is an optionally substituted hydroxide, halide, nitrate, carboxylate, halocarboxylate, acetylacetonate, alkoxide, or phenolate anion, or a sulfate, alkyl sulfate, phosphate, alkyl phosphate, halosulfonate, alkyl sulfonate, perhaloalkyl sulfonate, bis(perhaloalkylsulfonyl)amide, or arenesulfonate, which are optionally substituted with halogen or haloalkyl groups.

18. The process according to claim 7 , wherein the aprotic polar solvent(s) are aprotic polar solvents of which the dipole moment expressed in Debye (D) is greater than or equal to 2.00.

19. The process as claimed in claim 7 , wherein the dehydration catalyst(s) are introduced into the reaction chamber in an amount corresponding to a feedstock/catalyst(s) weight ratio of 1 to 1000.

20. The process as claimed in claim 7 , wherein the chloride source(s) are introduced into the reaction chamber in an amount corresponding to a feedstock/chloride source(s) weight ratio of 1 to 1000.

Assignees

• Ifp Energies Now

Inventors

• Denis Justine
• Jacquin Marc
• Delcroix Damien

Classifications

• C07D307/46 Primary

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

• C07D307/48 Primary

  Furfural · CPC title