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

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.

Claims

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) ##STR00005## wherein the groups R.sub.5 to R.sub.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.sub.2SO.sub.3, H.sub.2SO.sub.4, H.sub.3PO.sub.2, H.sub.3PO.sub.4, HNO.sub.2, HNO.sub.3, H.sub.2WO.sub.4, H.sub.4SiW.sub.12O.sub.40, H.sub.3PW.sub.12O.sub.40, (NH.sub.4).sub.6(W.sub.12O.sub.40).xH.sub.2O, H.sub.4SiMo.sub.12O.sub.40, H.sub.3PMo.sub.12O.sub.40, (NH.sub.4).sub.6Mo.sub.7O.sub.24.xH.sub.2O, H.sub.2MoO.sub.4, HReO.sub.4, H.sub.2CrO.sub.4, H.sub.2SnO.sub.3, H.sub.4SiO.sub.4, H.sub.3BO.sub.3, HClO.sub.4, HBF.sub.4, HSbF.sub.5, HPF.sub.6, H.sub.2FO.sub.3P, ClSO.sub.3H, FSO.sub.3H, HN(SO.sub.2F).sub.2 or HIO.sub.3.

6. The process as claimed in claim 4, wherein the homogeneous inorganic Lewis acid(s) are compounds of formula (II) M.sub.oX.sub.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) ##STR00006## wherein R.sub.11 to R.sub.14, which may be identical or different, are independently alkyl groups, aryl groups, phosphazene groups of formula ##STR00007## wherein R.sub.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.sub.2SO.sub.3, H.sub.2SO.sub.4, H.sub.3PO.sub.2, H.sub.3PO.sub.4, HNO.sub.2, HNO.sub.3, H.sub.2WO.sub.4, H.sub.4SiW.sub.12O.sub.40, H.sub.3PW.sub.12O.sub.40, (NH.sub.4).sub.6(W.sub.12O.sub.40).xH.sub.2O, H.sub.4SiMo.sub.12O.sub.40, H.sub.3PMo.sub.12O.sub.40, (NH.sub.4).sub.6Mo.sub.7O.sub.24.xH.sub.2O, H.sub.2MoO.sub.4, HReO.sub.4, H.sub.2CrO.sub.4, H.sub.2SnO.sub.3, H.sub.4SiO.sub.4, H.sub.3BO.sub.3, HClO.sub.4, HBF.sub.4, HSbF.sub.5, HPF.sub.6, H.sub.2FO.sub.3P, ClSO.sub.3H, FSO.sub.3H, HN(SO.sub.2F).sub.2 or HIO.sub.3.

17. The process as claimed in claim 15, wherein the homogeneous inorganic Lewis acid(s) are compounds of formula (II) M.sub.oX.sub.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.

Description

EXAMPLES

(1) The examples below illustrate the invention without limiting the scope thereof.

(2) In the examples below, the glucose and fructose used as feedstock are commercially available and used without further purification.

(3) The aluminum chloride denoted AlCl.sub.3, the lithium chloride denoted LiCl, the potassium chloride denoted KCl, the lithium bromide denoted LiBr, the lithium fluoride denoted LiF, the choline chloride denoted ChCl, the betaine chloride denoted BetC, the tetramethylammonium chloride denoted TMACl, and the dimethyl sulfoxide, noted DMSO, in the examples below are commercially available and used without additional purification.

(4) The dimethyl sulfoxide, denoted DMSO in the examples, used as aprotic polar solvent, is commercially available and used without further purification.

(5) For examples 1 to 8 of conversion of sugars into 5-HMF, the molar yield of 5-HMF is calculated by the ratio between the number of moles of 5-HMF obtained and the number of moles of sugar feedstock used.

(6) The processes of examples from 1 to 10 are carried out at 0.1 MPa.

Example 1

Fructose Conversion Using Aluminum Chloride Alone in DMSO (Not in Accordance with the Invention)

(7) The aluminum chloride (0.045 g, 0.19 mmol) is added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 62%. The yield of unwanted humins is 30%.

Example 2

Fructose Conversion Using Lithium Chloride Alone in DMSO (Not in Accordance with the Invention)

(8) The lithium chloride (0.008 g, 0.19 mmol) is added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 1 bar for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography and by size exclusion chromatography. The molar yield of 5-HMF after 6 h is 0%.

Example 3

Fructose Conversion Using Potassium Chloride Alone in DMSO (Not in Accordance with the Invention)

(9) The potassium chloride (0.014 g, 0.19 mmol) is added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 0%.

Example 4

Fructose Conversion Using Aluminum Chloride and Lithium Chloride in DMSO (In Accordance with the Invention)

(10) The aluminum chloride (0.045 g, 0.19 mmol) and the lithium chloride (0.008 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The feedstock/chloride source weight ratio is 250. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 79%. The yield of unwanted humins is 12%.

Example 5

Fructose Conversion Using Aluminum Chloride and Potassium Chloride in DMSO (In Accordance with the Invention)

(11) The aluminum chloride (0.045 g, 0.19 mmol) and the potassium chloride (0.014 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The feedstock/chloride source weight ratio is 140. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 75%. The yield of unwanted humins is 15%.

Example 6

Fructose Conversion Using Aluminum Chloride and Choline Chloride in DMSO (In Accordance with the Invention)

(12) The aluminum chloride (0.045 g, 0.19 mmol) and the choline chloride (0.027 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The feedstock/chloride source weight ratio is 74. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 78%. The yield of unwanted humins is 12%.

Example 7

Fructose Conversion Using Aluminum Chloride and Betaine Chloride in DMSO (In Accordance with the Invention)

(13) The aluminum chloride (0.045 g, 0.19 mmol) and the choline chloride (0.029 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The feedstock/chloride source weight ratio is 69. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 80%. The yield of unwanted humins is 10%.

Example 8

Fructose Conversion Using Aluminum Chloride and Tetramethylammonium Chloride in DMSO (In Accordance with the Invention)

(14) The aluminum chloride (0.045 g, 0.19 mmol) and the tetramethylammonium chloride (0.021 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The feedstock/chloride source weight ratio is 95. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 80%. The yield of unwanted humins is 10%.

Example 9

Fructose Conversion Using Aluminum Chloride and Lithium Bromide in DMSO (Not in Accordance with the Invention)

(15) The aluminum chloride (0.045 g, 0.19 mmol) and the lithium chloride (0.016 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The feedstock/bromide source weight ratio is 125. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 63%. The yield of unwanted humins is 32%.

Example 10

Fructose Conversion Using Aluminum Chloride and Lithium Fluoride in DMSO (Not in Accordance with the Invention)

(16) The aluminum chloride (0.045 g, 0.19 mmol) and the lithium fluoride (0.005 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20 g). The feedstock/catalyst weight ratio is 111. The feedstock/fluoride source weight ratio is 400. The solvent/feedstock weight ratio is 10. The reaction medium is then stirred at 70° C. at 0.1 MPa for 6 h. The conversion of fructose into 5-HMF is monitored by regularly taking samples of an aliquot of solution which is instantly cooled to 0° C., redissolved in water and checked by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 0%.

(17) TABLE-US-00001 TABLE 1 5-HMF Unwanted Dehydration Chloride yield products Example Feedstock catalyst source (%) yield (%) 1 Fructose AlCl.sub.3 — 63 Humins (not in 26 accordance with the invention) 2 Fructose — LiCl  0 — (not in accordance with the invention) 3 Fructose — KCl  0 — (not in accordance with the invention) 4 Fructose AlCl.sub.3 LiCI 77 Humins (in 12 accordance with the invention) 5 Fructose AlCl.sub.3 KCI 74 Humins (in 15 accordance with the invention) 6 Fructose AlCl.sub.3 ChCl 78 Humins (in 12 accordance with the invention) 7 Fructose AlCl.sub.3 BetCl 81 Humins (in 10 accordance with the invention) 8 Fructose AlCl.sub.3 TMACl 79 Humins (in 10 accordance with the invention) 9 Fructose AlC1.sub.3 LiBr 61 Humins (in 32 accordance with the invention) 10 Fructose AlC1.sub.3 LiF  0 — (in accordance with the invention)

(18) The 5-HMF yield obtained by means of the process according to the invention is higher in the case of the combination of an inorganic dehydration catalyst such as AlCl.sub.3 and a chloride source such as LiCl, KCl, ChCl, BetCl or TMACl in an aprotic polar solvent compared to the dehydration catalyst alone or the chloride source alone.

(19) The formation of unwanted products such as humins is lower in the case of the association of an inorganic dehydration catalyst such as AlCl.sub.3 and a chloride source such as LiCl, KCl, ChCl, BetCl or TMACl in an aprotic polar solvent according to the invention compared to the dehydration catalyst alone.

(20) The 5-HMF yield is higher in the case of the combination of an inorganic dehydration catalyst such as AlCl.sub.3 and a chloride source such as LiCl, KCl, ChCl, BetCl or TMACl in an aprotic polar solvent according to the invention compared to the combination of a dehydration catalyst in combination with a bromide source LiBr or a fluoride source LiF.

(21) It therefore unexpectedly appears that it is clearly advantageous to use dehydration catalysts in combination with a chloride source in an aprotic polar solvent according to the invention for the conversion of sugars into 5-HMF.