Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
  • C07D307/48—Furfural

Definitions

• 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. .
• 5-hydroxymethylfurfural is a compound derived from biomass that can be efficiently 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.
• FDCA furanedicarboxylic acid
• 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.
• 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%.
• aprotic polar solvent for example dimethylsulfoxide DMSO or N-methyl-pyrrolidone NMP
• 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
• the dehydration of glucose or fructose to 5-HMF is described, for example in US Patent Application Nos.
• 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.
• 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
• 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.
• chloride source 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.
• 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.
• 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.
• inorganic Bronsted acid catalyst means a Bronsted acid catalyst containing no carbon atoms.
• inorganic Lewis acid catalyst is meant a Lewis acid catalyst containing an atom of the family of metals or lanthanides.
• alkyl group means a hydrocarbon chain saturated between 1 and 20 carbon atoms, linear or branched, and non-cyclic, cyclic or polycyclic.
• alkenyls is meant a hydrocarbon chain between 1 and 20 atoms, comprising at least one unsaturated, linear or branched, cyclic or non-cyclic.
• aryl group is meant an aromatic group, mono or polycyclic, fused or not, comprising between 5 and 30 carbons.
• 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.
• 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.
• polar solvent By polar solvent is meant a molecule acting as a solvent whose dipole moment ⁇ expressed in Debye has a numerical value greater than or equal to 2.00 measured at 25 ° C.
• 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 ⁇ expressed in Debye has a numerical value greater than or equal to 2.00 measured at 25 °. C. Brief description of the invention
• 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.
• 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 .
• the monosaccharides are chosen from glucose, mannose and fructose, taken alone or as a mixture.
• oligosaccharide is meant
• 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.
• the filler is chosen from sucrose, fructose and glucose, taken alone or as a mixture.
• said filler is chosen from fructose and glucose, taken alone or as a mixture.
• 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.
• 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.
• 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 3
• 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 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.
• 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.
• the heterogeneous Lewis acids are chosen from zirconium oxides, titanium oxides, mixed oxides of aluminum and tin-doped silicon, such as Sn- ⁇ zeolite or Sn-MCM-mesostructured silica. 41, phosphates of tin and titanium. Chloride sources
• said feedstock in combination with the inorganic dehydration catalyst or catalysts defined above, 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
• 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, 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;
• 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.
• the source of chloride is chosen from the compounds corresponding to the general formula (Nia) (Nia):
• R 4 to R 4 which are identical or different, are independently selected from
• R is an alkyl group comprising from 1 to 15 carbon atoms, preferably from 1 to 10 and preferably from 1 to 6.
• 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.
• said groups R 1 to R 4 are chosen from alkyls substituted with at least one group chosen from -OH, and -COOH.
• 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.
• 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 " ]).
• 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 " ]
• tetramethylammonium chloride [(CH 3 ) 4 N + Cl " ]
• 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.
• the groups R 5 to R 10 which are identical or different, are chosen independently from hydrogen, methyl, ethyl, propyl or butyl groups.
• the groups R 5 to R 10 which are identical or different, are chosen from aryl groups comprising between 5 and 20 carbon atoms.
• the source of chloride is guanidinium chloride and hexamethylguanidinium chloride.
• 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,
• the groups R to R 14 which are identical or different, are chosen from
• a methyl, ethyl, n-propyl or n-butyl group A methyl, ethyl, n-propyl or n-butyl group.
• the source of chloride is tetraethylphosphonium chloride and tetra (n-butyl) phosphonium chloride.
• 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.
• 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.
• solvent being an aprotic polar solvent or a mixture of aprotic polar solvents
• 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.
• 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.
• the polar aprotic solvents are chosen from pyridine (2,37), butan-2-one (5,22), acetone (2,86), acetic anhydride (2,82), ⁇ , ⁇ -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 ⁇ -vale
• the aprotic polar solvents are advantageously chosen from acetone, N, N-dimethylformamide, N, N-dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethylsulfoxide, propylene carbonate and ⁇ -dimethylformamide. valerolactone alone or as a mixture.
• the aprotic polar solvents are advantageously chosen from N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and ⁇ -valerolactone, alone or as a mixture.
• 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.
• the method can be operated according to different embodiments.
• 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.
• 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 .
• the dehydration catalyst and the chloride source can be easily recovered by precipitation, distillation, extraction or washing.
• the product obtained selectively by the conversion process according to the invention is 5-hydroxymethylfurfural (5-HMF).
• 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.
• GC gas phase chromatography
• 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.
• 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.
• 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.
• 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%.
• 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%.
• 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%.
• 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%.
• 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%.
• 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%.
• 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%.
• 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%.
• 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.
• a chloride source such as LiCl, KCl, ChCl, BetCl. or TMACI in an aprotic polar solvent 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.
• an inorganic dehydration catalyst such as AlCl 3
• a source of chloride such as LiCl, KCl, ChCl, BetCl or TMACI

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