EP3687985A1

EP3687985A1 - Process for producing 5-hydroxymethylfurfural in the presence of an inorganic dehydration catalyst and a chloride source

Info

Publication number: EP3687985A1
Application number: EP18770055.4A
Authority: EP
Inventors: Justine DENIS; Marc Jacquin; Damien Delcroix
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 2017-09-28
Filing date: 2018-09-25
Publication date: 2020-08-05
Also published as: BR112020004961A2; FR3071497B1; US20200299250A1; JP2020535146A; US11084797B2; WO2019063546A1; FR3071497A1; CN111295377A

Abstract

The invention relates to a process for converting a feedstock comprising at least one sugar into 5-hydroxymethylfurfural, wherein said feedstock 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.

Description

PROCESS FOR THE PRODUCTION OF 5-HYDROXYMETHYLFURFURAL IN THE PRESENCE OF AN INORGANIC DEHYDRATION CATALYST AND A SOURCE OF

CHLORIDE

TECHNICAL FIELD OF THE INVENTION The invention relates to a process for converting sugars and in particular 5-hydroxymethylfurfural hexoses in the presence of inorganic dehydration catalysts and a chloride source in the presence of at least one aprotic polar solvent. .

Prior art

5-hydroxymethylfurfural (5-HMF) is a compound derived from biomass that can be valorized in many fields, particularly as a precursor of active ingredients in pharmacy, agrochemicals or specialty chemicals. His interest in recent years is in its use as a precursor of furanedicarboxylic acid (FDCA) which is used as a substitute for terephthalic acid as a monomer for the production of polyester fibers or convenience plastics. The production of 5-HMF by dehydration of hexoses has been known for many years and has been the subject of a large number of research projects. On the one hand, the dehydration of glucose or fructose to 5-HMF is described in the presence of aprotic polar solvent, for example dimethylsulfoxide DMSO or N-methyl-pyrrolidone NMP, in the presence of heterogeneous acidic catalyst, that is, that is, supported catalysts insoluble in the reaction medium such as sulphonic silicas described by Bao et al., Catal. Common. 2008, 9, 1383, with performance corresponding to 5-HMF yields of about 70%. On the other hand, the dehydration of glucose or fructose to 5-HMF is described, for example in US Patent Application Nos. 2014/0235881, US 2014/0357878 and US 2015/0045576 in the presence of protic polar solvent, by US Pat. water or ethanol, in the presence of heterogeneous or homogeneous acidic catalysts, that is to say for the latter that they are soluble in the reaction medium, with formation of by-products of the carboxylic acid family esters and ethers such as levulinic acid and its esters, formic acid and its esters and alkoxylated derivatives of 5-HMF such as 5-ethoxymethylfurfural. Obtaining these products is detrimental to performance, and require additional expensive separation and purification steps that reduce the economic viability of the process. There is therefore a need for the development of new processes for the selective transformation of sugars into 5-HMF which makes it possible to obtain better yields by limiting the formation of undesired by-products. Surprisingly, the applicant has demonstrated that the contacting of sugars with one or more inorganic dehydration catalysts and one or more sources of chloride in the presence of at least one aprotic polar solvent significantly increases the yields of 5-HMF by limiting the formation of undesired by-products compared to inorganic dehydration catalysts used without a chloride source.

The invention therefore relates to a process for producing 5-hydroxymethylfurfural from sugars using an inorganic dehydration catalyst in combination with a source of chloride in the presence of at least one aprotic polar solvent.

OBJECT OF THE INVENTION An object of the present invention is therefore to provide a new process for transforming a feedstock comprising at least one 5-hydroxymethylfurfural sugar, wherein said feedstock is brought into contact with one or more inorganic acid catalysts and one or more sources of chloride 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. An advantage of the present invention is to provide a process for converting sugars into 5-hydroxymethylfurfural (5-HMF) to increase the yield of 5-HMF and to limit the formation of undesired by-products such as products of the family of carboxylic acids, esters, ethers and humins. Humines are secondary products of condensation in acidic medium such as polyfurans. Definitions and Abbreviations

It is specified that, throughout this description, the expression "understood between ... and ..." should be understood as including the boundaries quoted.

The term "inorganic acid dehydration catalyst" is understood to mean any catalyst chosen from Bronsted acids and Lewis acids, homogeneous or heterogeneous, capable of inducing dehydration reactions such as those of 5-hydroxymethylfurfural sugars.

By chloride source is meant any compound of general formula Q _y Cl _z in which Q may represent a hydrogen, an alkali or alkaline earth metal chosen from groups 1 and 2 of the periodic table or an organic cation chosen from the family of ammoniums, phosphonium and guanidinium. By inorganic catalyst is meant a catalyst in which the acid function responsible for the catalytic dehydration activity is not bound to a hydrocarbon chain by a covalent bond. The term "homogeneous catalyst" means a catalyst that is soluble in the reaction medium.

Heterogeneous catalyst is understood to mean a catalyst that is insoluble in the reaction medium.

The term "inorganic Bronsted acid catalyst" means a Bronsted acid catalyst containing no carbon atoms.

By inorganic Lewis acid catalyst is meant a Lewis acid catalyst containing an atom of the family of metals or lanthanides.

The term "alkyl group" means a hydrocarbon chain saturated between 1 and 20 carbon atoms, linear or branched, and non-cyclic, cyclic or polycyclic.

By alkenyls is meant a hydrocarbon chain between 1 and 20 atoms, comprising at least one unsaturated, linear or branched, cyclic or non-cyclic.

By aryl group is meant an aromatic group, mono or polycyclic, fused or not, comprising between 5 and 30 carbons.

The term heteroaryl group, an aromatic group comprising between 4 and 30 carbon atoms and at least within at least one aromatic ring, a heteroatom selected from oxygen, sulfur, nitrogen.

The term "alkyl halide" means an alkyl substituted with at least one halogen atom chosen from fluorine, chlorine, bromine or iodine.

Anionic halide is an anionic species of a halogen atom chosen from fluorine, chlorine, bromine or iodine.

Aprotic solvent is understood to mean a molecule acting as a solvent and all of whose hydrogens are borne by carbon atoms.

By polar solvent is meant a molecule acting as a solvent whose dipole moment μ expressed in Debye has a numerical value greater than or equal to 2.00 measured at 25 ° C.

The term "aprotic polar solvent" is therefore intended to mean a molecule acting as a solvent in which all the hydrogens are borne by carbon atoms and whose dipole moment μ expressed in Debye has a numerical value greater than or equal to 2.00 measured at 25 °. C. Brief description of the invention

Advantageously, the process according to the invention is a process for transforming a feedstock comprising at least one 5-hydroxymethylfurfural sugar, said feedstock is brought into contact with at least one inorganic dehydration catalyst and at least one source of chloride of general formula (III) QyClz in the presence of at least one aprotic polar solvent, at a temperature between 30 ° C and 200 ° C and a pressure of between 0.1 and 10 MPa, wherein

Q is selected from hydrogen, an alkali metal or alkaline earth metal selected from groups 1 and 2 of the periodic table or an organic cation selected from the family of ammonium, phosphonium, guanidinium.

y is between 1 and 10,

z is between 1 and 10.

Detailed description of the invention

In the sense of the present invention, the various embodiments presented can be used alone or in combination with each other, without limitation of combination.

Load

The filler treated in the process according to the invention is a filler comprising at least one sugar, preferably chosen from oligosaccharides and monosaccharides, alone or as a mixture.

Monosaccharide means the compounds corresponding to the general formula (la) C ₆ (H ₂ O) ₆ or C ₆ H ₁₂ 0 ₆ . Preferably, the monosaccharides are chosen from glucose, mannose and fructose, taken alone or as a mixture.

By oligosaccharide, is meant

compounds having the formula (Ib) C _6nH _{1 0} n ₊ 2O 5 _{n + 1} in which n is an integer between 1 and 10, the monosaccharide units making up said oligosaccharide being identical or different, and

compounds having the formula (Ie) in which m and p are independently integers between 1 and 10, the monosaccharide units making up said oligosaccharide being identical or different.

The oligosaccharides are preferably chosen from oligomers of hexoses or pentoses and hexoses, preferably from hexose oligomers. They can be obtained by hydrolysis partial polysaccharides from renewable resources such as starch, inulin, cellulose or hemicellulose, possibly from lignocellulosic biomass. The steam explosion of lignocellulosic biomass is a process of partial hydrolysis of cellulose and hemicellulose contained in lignocellulosic biomass producing a flux of oligo- and monosaccharides. The oligosaccharides are preferably chosen from sucrose, lactose, maltose, isomaltose, inulobiose, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose and oligosaccharides resulting from the hydrolysis of said oligosaccharides. polysaccharides derived from the hydrolysis of starch, inulin, cellulose or hemicellulose, alone or as a mixture.

Preferably, the filler is chosen from sucrose, fructose and glucose, taken alone or as a mixture. Very preferably, said filler is chosen from fructose and glucose, taken alone or as a mixture.

Dehydration catalysts

According to the invention, said filler is brought into contact in the process with at least one inorganic dehydration catalyst chosen from homogeneous Bronsted inorganic acids and homogeneous or heterogeneous Lewis inorganic acids, capable of catalyzing the dehydration of the filler. in 5-hydroxymethylfurfural.

Preferably, the inorganic dehydration catalyst is chosen from the following homogeneous Bronsted inorganic acids: HF, HCl, HBr, H1, 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 0 ₂₄ .xH ₂ O, H ₂ MoO ₄ , HRe0 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 F0 ₃ P, CISO ₃ H, FSO ₃ H, HN (SO ₂ F) ₂ and HI0 ₃ . Preferably, the inorganic Bronsted acids are chosen from the following list: H ₂ SO ₄ , H ₃ PO ₄ , HNO ₃ .

Preferably, the inorganic dehydration catalyst is chosen from homogeneous Lewis inorganic acids having the general formula (II) M ₀ X _P , solvated or unsolated, in which

M is an atom chosen from among the atoms of groups 3 to 16, preferably 6 to 13, of the periodic classification, including lanthanides, and preferably from B, Al, Fe, Zn, Sn, Cr, Ce Er, and preferred among Al, Sn, Cr,

o is an integer between 1 and 10, preferably between 1 and 5, and preferably between 1 and 2,

p is an integer between 1 and 10, preferably between 1 and 5, and preferably between 1 and 3, and X is an anion chosen from hydroxides, halides, nitrates, carboxylates, halocarboxylates, acetylacetonates, alkoxides, phenolates, substituted or unsubstituted, sulphates, alkyl sul binders, phosphates, alkyl phosphates, halosulfonates, alkylsulphonates, perhaloalkylsulphonates, bis (perhaloalkylsulphonyl) amides, arenesulphonates, which may or may not be substituted by halogen or haloalkyl groups, more preferably X is chosen from halides, sulphates, alkylsulphonates and perhaloalkylsulphonates, which may or may not be substituted by halogen or haloalkyl groups, said anions X being identical or different in the case where o is greater than 1. Very preferably, the inorganic acids of homogeneous Lewis are selected from BF _3, AlCl _3, Al (OTf) _3, FeCl _3, ZnCl _2, SnCl _2, CRCI _3, this ₃ and Erci _3. Most preferably, the homogeneous Lewis inorganic acid is AICI ₃ .

The heterogeneous Lewis inorganic acids are chosen from single or mixed oxides of the compounds chosen from among silicon, aluminum, zirconium, titanium, niobium and tungsten, doped or not by an element chosen from tin, tungsten and hafnium and among the phosphates of metals, said metals being selected from niobium, zirconium, tantalum, tin and titanium. In a preferred manner, the heterogeneous Lewis acids are chosen from zirconium oxides, titanium oxides, mixed oxides of aluminum and tin-doped silicon, such as Sn-β zeolite or Sn-MCM-mesostructured silica. 41, phosphates of tin and titanium. Chloride sources

According to the invention, in combination with the inorganic dehydration catalyst or catalysts defined above, said feedstock is brought into contact in the process according to the invention with one or more sources of chloride of general formula (III) Q _y Cl _z in which

y is between 1 and 10, preferably between 1 and 5 and preferably between 1 and 2;

z is between 1 and 10, preferably between 1 and 5 and preferably between 1 and 2;

Preferably Q is a cation selected from H, Li, Na, K, Rb, Cs, Fr, Mg, Ca, Sr, Ba, preferably from H, Li, Na, K, Cs, Mg, Ca, Ba, and most preferably from Li, Na, K, Mg, Ca.

In the case where Q is an organic cation chosen from the family of ammoniums, the source of chloride is chosen from the compounds corresponding to the general formula (Nia) (Nia):

wherein R ₄ to R ₄ , which are identical or different, are independently selected from

Alkyl groups comprising from 1 to 20 carbons, optionally substituted with at least one group chosen from the following list: aldehyde -C (O) H, ketone -C (O) R ", carboxylic acid -COOH, ester -COOR" , hydroxymethyl -CH ₂ OH, ether -CH ₂ O R ", halogenated -CH ₂ X with X = Cl, Br, I

Aryl groups comprising from 5 to 20 carbons, optionally substituted with at least one group chosen from the following list: aldehyde -C (O) H, ketone -C (O) R ", carboxylic acid -COOH, ester -COOR" , hydroxymethyl -CH ₂ OH, ether -CH ₂ O R ", halogenated -CH ₂ X with X = Cl, Br, I.

In which R "is an alkyl group comprising from 1 to 15 carbon atoms, preferably from 1 to 10 and preferably from 1 to 6.

Preferably, the groups R 1 to R ₄ , which are identical or different, preferably linear, are chosen independently from among the alkyl groups preferably comprising between 1 and 15 carbon atoms, preferably between 1 and 10, preferably between 1 and 10. 8, preferably between 1 and 6, and preferably from 1 to 4 carbon atoms.

Preferably, said groups R 1 to R ₄ are chosen from alkyls substituted with at least one group chosen from -OH, and -COOH.

Preferably, the groups R 1 to R ₄ are independently selected from n-butyl, methyl, n-octyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, -CH ₂ COOH, -CH _{2 groups.} CH ₂ COOH and CH ₂ CH ₂ CH ₂ COOH, preferably from methyl, hydroxyethyl and -CH ₂ CH ₂ COOH groups.

Very preferably, the ammoniums are chosen from trioctylmethylammonium chloride ([(CH ₃ (CH ₂ ) ₇ ) ₃ (CH ₃ ) N ⁺ Cr]), choline chloride ([((CH ₃ ) ₃ NCH ₂ CH ₂ OH) ⁺ CI ^" ]), betaine chloride ([((CH ₃ ) ₃ NCH ₂ COOH) ⁺ CI ^" ]), and tetramethylammonium chloride ([(CH ₃ ) ₄ N ⁺ Cl ^" ]).

In the case where Q is an organic cation chosen from the family of guanidinium chlorides, the source of chloride is chosen from the compounds corresponding to the general formula (IIIb)

(lllb) in which the groups R ₅ to R ₁₀ , which are identical or different, are chosen independently from hydrogen, alkyl and aryl groups.

Preferably, the groups R ₅ to R ₁₀ , which are identical or different, are chosen from hydrogen, the alkyl groups, preferably linear, comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms and from preferred way of 1 to 6 carbon atoms.

Very preferably, the groups R ₅ to R ₁₀ , which are identical or different, are chosen independently from hydrogen, methyl, ethyl, propyl or butyl groups.

Preferably, the groups R ₅ to R ₁₀ , which are identical or different, are chosen from aryl groups comprising between 5 and 20 carbon atoms.

Preferably, in the case where Q is an organic cation chosen from the family of guanidiniums, the source of chloride is guanidinium chloride and hexamethylguanidinium chloride.

In the case where Q is an organic cation chosen from the family of phosphoniums, the source of chloride is chosen from the compounds corresponding to the general formula (IIIc)

(lllc) ^H 13 wherein R to R ₁₄ , which are identical or different, are chosen independently from alkyl groups, aryl groups and phosphazenic groups of general formula (Nid)

wherein ₁₅ is an alkyl group comprising 1 to 10 carbon atoms, preferably 1 to 5, and q an integer of 0 to 10. Preferably, R ₁₄ to R ₁₄ , which may be identical or different, are chosen from alkyl groups, preferably linear, comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms and preferably from 1 to 6 carbon atoms. carbon,

Preferably, the groups R to R ₁₄ , which are identical or different, are chosen from

"A phosphazene group characterized by R ₁₅ = methyl and q = 1,

A methyl, ethyl, n-propyl or n-butyl group.

Preferably, in the case where Q is an organic cation chosen from the family of phosphoniums, the source of chloride is tetraethylphosphonium chloride and tetra (n-butyl) phosphonium chloride. Advantageously, the use of a chloride source in a conversion process according to the invention makes it possible to limit the formation of undesired by-products such as products of the family of carboxylic acids, esters, ethers and humines.

Process of transformation

According to the invention, the process for transforming the feedstock comprising at least one sugar is carried out in a reaction chamber in the presence of at least one solvent, said solvent being an aprotic polar solvent or a mixture of aprotic polar solvents, at a temperature between 30 ° C and 200 ° C, and at a pressure between 0.1 MPa and 10 MPa.

The process may be carried out in a reaction vessel comprising at least one aprotic polar solvent and wherein said feedstock is placed in the presence of one or more dehydration catalysts and one or more sources of chloride.

According to the invention, the process operates in the presence of at least one solvent, said solvent being an aprotic polar solvent or a mixture of aprotic polar solvents.

The aprotic polar solvents are advantageously chosen from all aprotic polar solvents whose dipole moment expressed in Debye (D) is greater than or equal to 2.00. Preferably, the polar aprotic solvents are chosen from pyridine (2,37), butan-2-one (5,22), acetone (2,86), acetic anhydride (2,82), Α, β-tetramethylurea (3.48), benzonitrile (4.05), acetonitrile (3.45), methyl ethyl ketone (2.76), propionitrile (3.57), hexamethylphosphoramide (5.55), nitrobenzene (4.02), nitromethane (3.57), N, N-dimethylformamide (3.87), M / V-dimethylacetamide (3.72), sulfolane (4.80), N-methylpyrrolidone (4.09), dimethylsulfoxide (3.90), propylene carbonate (4.94) and γ-valerolactone (4.71) alone or in admixture. Preferably, the aprotic polar solvents are advantageously chosen from acetone, N, N-dimethylformamide, N, N-dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethylsulfoxide, propylene carbonate and γ-dimethylformamide. valerolactone alone or as a mixture.

Preferably, the aprotic polar solvents are advantageously chosen from N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and γ-valerolactone, alone or as a mixture.

Preferably, said process according to the invention operates at a temperature between 40 ° C and 175 ° C, preferably between 50 and 120 ° C, preferably between 60 and 100 ° C and very preferably between 65 and 90 ° C ° C, and at a pressure between 0.1 MPa and 8 MPa and preferably between 0.1 and 5 MPa.

Generally the method can be operated according to different embodiments. Thus, the process can advantageously be implemented batchwise or continuously. It can be carried out in a closed reaction chamber or in a semi-open reactor.

The inorganic dehydration catalyst or catalysts are introduced into the reaction chamber in an amount corresponding to a mass ratio filler / catalyst (s) of between 1 and 1000, preferably between 1 and 500, preferably between 1 and 200. preferably between 1 and 150.

The source (s) of chloride are introduced into the reaction chamber in an amount corresponding to a mass ratio filler / source (s) chloride between 1 and 1000, preferably between 1 and 800, preferably between 1 and 500, preferably between 1 and 400. The feedstock is introduced into the process in an amount corresponding to a mass ratio solvent / load of between 0.1 and 200, preferably between 0.3 and 100 and even more preferably between 1 and 50.

If a continuous process is chosen, the hourly mass velocity (mass flow rate / mass of catalyst (s)) is between 0.01 and 10 h, preferably between 0.02 and 5 h ^-1 , preferably between 0 , 03 and 2 hrs ^"1 .

At the end of the reaction, the dehydration catalyst and the chloride source can be easily recovered by precipitation, distillation, extraction or washing.

The products obtained and their method of analysis

The product obtained selectively by the conversion process according to the invention is 5-hydroxymethylfurfural (5-HMF). At the end of the reaction carried out in the process according to the invention, the reaction medium is analyzed by gas phase chromatography (GC) to determine the content of 5-HMF in the presence of an internal standard and by ion chromatography for determine the conversion of the load in the presence of an external standard and to quantify unwanted products such as levulinic acid and formic acid. The humins are quantified by difference in carbon balance with the carbon initially introduced.

EXAMPLES

The examples below illustrate the invention without limiting its scope.

In the examples below, glucose and fructose used as feed are commercial and used without further purification.

Aluminum chloride noted AICI ₃ , lithium chloride noted LiCI, potassium chloride noted KCI, lithium bromide noted LiBr, lithium fluoride noted LiF, choline chloride noted ChCI, betaine chloride noted BetC, chloride tetramethylammonium TMACI, and dimethylsulfoxide, noted DMSO in the examples below are commercial and used without further purification. Dimethylsulfoxide, denoted DMSO in the examples, used as aprotic polar solvent, is commercial and used without further purification.

For Examples 1-8 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 filler engaged. The methods of Examples 1 to 10 are implemented at 0.1 MPa.

EXAMPLE 1 Transformation of Fructose Using Aluminum Chloride Alone in DMSO (Non-Conforming)

Aluminum chloride (0.045 g, 0.19 mmol) is added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 70 ° C. at 0.1 MPa for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 62%. The yield of unwanted humines is 30%. EXAMPLE 2 Transformation of Fructose Using Lithium Chloride Alone in the

DMSO (non-compliant)

Lithium chloride (0.008 g, 0.19 mmol) is added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 70 ° C. at 1 bar for 6 hours. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantaneously cooled to 0 ° C, redissolved in water and monitored by gas chromatography, ion chromatography and size exclusion chromatography. . The molar yield of 5-HMF after 6 h is 0%. Example 3 Transformation of Fructose Using Potassium Chloride Alone in DMSO (Non-Conforming)

Potassium chloride (0.014 g, 0.19 mmol) is added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 70 ° C. at 0.1 MPa for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 0%.

Example 4 Transformation of Fructose Using Aluminum Chloride and Lithium Chloride in DMSO (Compliant)

Aluminum chloride (0.045 g, 0.19 mmol) and lithium chloride (0.008 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The weight ratio charge / source of chloride is 250. The mass ratio solvent / charge is 10. The reaction medium is then stirred at 70 ° C at 0.1 MPa for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 hours is 79%. The yield of unwanted humines is 12%.

Example 5 Transformation of Fructose Using Aluminum Chloride and Potassium Chloride in DMSO (Compliant)

Aluminum chloride (0.045 g, 0.19 mmol) and potassium chloride (0.014 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The mass load / source ratio of chloride is 140. The ratio The solvent / filler mass is 10. The reaction medium is then stirred at 70 ° C. at 0.1 MPa for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 hours is 75%. The yield of unwanted humines is 15%.

Example 6 Transformation of Fructose Using Aluminum Chloride and Choline Chloride in DMSO (Compliant)

Aluminum chloride (0.045 g, 0.19 mmol) and choline chloride (0.027 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The mass load / source ratio of chloride is 74. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 70 ° C. at 0.1 MPa for 6 hours. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 hours is 78%. The yield of unwanted humines is 12%.

EXAMPLE 7 Transformation of Fructose Using Aluminum Chloride and Betaine Chloride in DMSO (Compliant)

Aluminum chloride (0.045 g, 0.19 mmol) and choline chloride (0.029 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The weight ratio charge / source of chloride is 69. The weight ratio solvent / charge is 10. The reaction medium is then stirred at 70 ° C at 0.1 MPa for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 hours is 80%. The yield of unwanted humines is 10%.

Example 8 Transformation of Fructose Using Aluminum Chloride and Tetramethylammonium Chloride in DMSO (Compliant)

Aluminum chloride (0.045 g, 0.19 mmol) and tetramethylammonium chloride (0.021 g, 0.19 mmol) are added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The mass charge / source ratio of chloride is 95. The weight ratio solvent / charge is 10. The reaction medium is then stirred at 70 ° C. at 0.1 MPa for 6 hours. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and controlled by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 hours is 80%. The yield of unwanted humines is 10%.

EXAMPLE 9 Transformation of Fructose Using Aluminum Chloride and Lithium Bromide in DMSO (Non-Conforming) Aluminum Chloride (0.045 g, 0.19 mmol) and Lithium Chloride (0.016 g) 19 mmol) are added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The feed / source weight ratio of bromide is 125. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 70 ° C. at 0.1 MPa for 6 hours. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 hours is 63%. The yield of unwanted humines is 32%.

EXAMPLE 10 Transformation of Fructose Using Aluminum Chloride and Lithium Fluoride in DMSO (Non-Conforming) Aluminum Chloride (0.045 g, 0.19 mmol) and Lithium Fluoride (0.005 g. 19 mmol) are added to a solution of fructose (2.0 g, 1 1, 10 mmol) in DMSO (20 g). The mass ratio filler / catalyst is 1 1 1. The load / source weight ratio of fluoride is 400. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 70 ° C. at 0.1 MPa for 6 hours. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and monitored by gas chromatography, and by ion chromatography. The molar yield of 5-HMF after 6 h is 0%.

Example Catalyst Feed of Source of Yield 5- Yield of HMF Chloride Dehydration Products (%) unwanted (%)

1

Fructose AICI ₃ - 63 Humins 26

(improper)

2

Fructose - LiCl 0 -

(improper)

3

Fructose - KCI 0 -

(improper)

4

Fructose AlC LiCI 77 Humids 12

(Compliant)

5

Fructose AlC KCI 74 Humids 15

(Compliant)

6

Fructose AlCb ChCI 78 Humids 12

(Compliant)

7

Fructose AlCb BetCI 81 Humids 10

(Compliant)

8

Fructose AICI3 TMACI 79 Humids 10

(Compliant)

9

Fructose AICI3 LiBr 61 Humins 32

(Compliant)

10

Fructose AICI3 LiF 0 -

(Compliant)

Table 1 The yield of 5-HMF obtained by the process according to the invention is greater in the case of the combination of an inorganic dehydration catalyst such as AlCl ₃ and a chloride source such as LiCl, KCl, ChCl, BetCl. or TMACI in an aprotic polar solvent compared to the dehydration catalyst alone or at the chloride source alone. The formation of unwanted products such as humins is inferior in the case of the combination of an inorganic dehydration catalyst such as AlCl ₃ and a chloride source such as LiCl, KCl, ChCl, BetCl or TMACI in a polar aprotic solvent according to the invention compared to the dehydration catalyst alone.

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

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

Claims

A method of transforming a feed comprising at least one 5-hydroxymethylfurfural sugar, said feedstock is contacted with at least one inorganic dehydration catalyst and at least one source of chloride of the general formula (III) Q _y Cl _z in the presence at least one aprotic polar solvent, at a temperature between 30 ° C and 200 ° C and a pressure of between 0.1 and 10 MPa,

in which

y is between 1 and 10,

z is between 1 and 10.

The process of claim 1 wherein the filler is selected from oligosaccharides and monosaccharides, alone or in admixture.

A process according to any one of the preceding claims wherein the filler is selected from sucrose, lactose, maltose, isomaltose, inulobiose, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose and oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, taken alone or as a mixture.

A process as claimed in any one of the preceding claims wherein the dehydration catalyst (s) are independently selected from homogeneous or heterogeneous inorganic Bronsted acids and Lewis inorganic acids.

Process according to the preceding claim wherein the inorganic Bronsted acid or acids are chosen from HF, HCl, HBr, Hl, H ₂ SO ₃ , H ₂ SO ₄ , H ₃ PO ₂ , H ₃ PO ₄ , HNO ₂ and 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 0 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 F0 ₃ P, CISO ₃ H, FSO ₃ H, HN (S0 ₂ F) ₂ and HI0 ₃ .

Process according to any one of the preceding claims, in which the homogeneous Lewis inorganic acid (s) is (are) chosen from compounds of the general formula (II) M ₀ X _P , solvated or unsolvated, in which M is an atom chosen from among the atoms of groups 3 to 16, preferably 6 to 13, of the periodic table, including lanthanides,

o is an integer between 1 and 10,,

p is an integer from 1 to 10, and

X is an anion chosen from hydroxides, halides, nitrates, carboxylates, halocarboxylates, acetylacetonates, alcoholates, phenolates, substituted or unsubstituted, sulphates, alkyl sulphates, phosphates, alkyl phosphates, halosulfonates, alkylsulfonates, perhaloalkylsulfonates, bis (perhaloalkylsulfonyl) amides, arenesulphonates, substituted or unsubstituted by halogen or haloalkyl groups,

Process according to any one of the preceding claims, in which the source of chloride of general formula (III) Q _y Cl _z is chosen from compounds in which Q is chosen from a hydrogen, an alkaline or alkaline-earth metal chosen from Li, Na, K, Rb, Cs, Fr, Mg, Ca, Sr, Ba.

Process according to any one of the preceding claims, in which the source of chloride is chosen from compounds corresponding to the general formula (Nia)

(Nia):

wherein Ρ to R ₄ , identical or different, are independently selected from

Alkyl groups comprising between 1 and 20 carbon atoms, optionally substituted with at least one group chosen from the following list: aldehyde -C (O) H, ketone -C (O) R ", carboxylic acid -COOH, ester - COOR ", hydroxymethyl -CH ₂ OH, ether -CH ₂ OR", halogenated -CH ₂ X,

Aryl groups comprising between 5 and 20 carbon atoms optionally substituted with at least one group chosen from the following list: aldehyde -C (O) H, ketone -C (O) R ", carboxylic acid -COOH, ester -COO R ", hydroxymethyl -CH ₂ OH, ether -CH ₂ O R", halogenated -CH ₂ X,

or

R "is an alkyl group comprising from 1 to 15 carbon atoms, and

X is selected from Cl, Br, I.

9. Process according to any one of the preceding claims, in which the source of chloride is chosen from the compounds corresponding to the general formula (IIIb)

(lllb):

in which the groups R ₅ to R ₁₀ , which are identical or different, are chosen independently from among the alkyl groups comprising between 1 and 20 carbon atoms, and aryls comprising between 5 and 20 carbon atoms.

Process according to any one of the preceding claims, in which the source of chloride is chosen from the compounds corresponding to the general formula (IIIc)

(IIIc)

wherein R ₁₄ to R ₁₄ , which are identical or different, are independently selected from

• the alkyl groups,

• aryl groups,

Phosphazenes groups of general formula is an alkyl group comprising from 1 to 10 carbon atoms, and an integer from 0 to 10.

Process according to any one of the preceding claims wherein the aprotic polar solvent or solvents are chosen from all aprotic polar solvents whose dipole moment expressed in Debye (D) is greater than or equal to 2.00.

12. Method according to the preceding claim in at least one aprotic polar solvent, alone or in admixture is selected from pyridine, butan-2-one, acetone, acetic anhydride, Λ /, Λ /, Λ / Tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone, propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, N, N-dimethylformamide, N, N-dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethylsulfoxide, propylene carbonate and γ-valerolactone.

13. Process according to any one of the preceding claims, in which the feedstock is introduced into the process in an amount corresponding to a solvent / charge mass ratio of between 0.1 and 200.

14. Process according to any one of the preceding claims, in which the dehydration catalyst or catalysts are introduced into the reaction chamber in an amount corresponding to a mass ratio of filler / catalyst (s) of between 1 and 1000.

15. Process according to any one of the preceding claims, in which the source or sources of chloride are introduced into the reaction chamber in an amount corresponding to a mass ratio of filler / source (s) of chloride of between 1 and 1000. .