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

Definitions

• the invention relates to a particular process for obtaining a mixture of 5-hydroxymethylfurfural and hexoses by converting mixtures of different sugars or oligomers of different sugars, more specifically mixtures of hexoses, and more particularly mixtures. of fructose and glucose or of mixed oligomers of these two sugars, such as sucrose, in a mixture of sugars and 5-hydroxymethylfurfural (hereinafter referred to as 5-HMF) in the presence of at least one aprotic polar solvent , and in the presence of one or more catalysts.
• 5-HMF 5-hydroxymethylfurfural
• 5-Hydroxymethylfurfural is a compound derived from biomass which can be valued in many fields as a precursor of active ingredients in pharmacy, agrochemistry or specialty chemicals. Its interest in recent years resides in its use as a precursor of 2,5-furan dicarboxylic acid (FDCA) which is used as a substitute for terephthalic acid as a monomer for the production of polyester fibers, convenience plastics or more plasticizers.
• FDCA 2,5-furan dicarboxylic acid
• fructose is the one which makes it possible to achieve the highest yields by reacting at moderate temperatures in the presence of a Bronsted or Lewis acid catalyst, in particular when the reaction solvent is dimethylsulfoxide (DMSO ).
• DMSO dimethylsulfoxide
• the article Bull. Chem. Soc. Japan., 1980, 53, 3705 describes obtaining yields of 5-HMF of 90% after reaction at 80 ° C.
• the cost of hexose fillers can be very variable depending on their local abundance, their ease of extraction and their degree of purification.
• Glucose is relatively abundant, whereas fructose must be obtained by isomerization of glucose, for example by means of enzymatic catalysis (Parker et al, Vol. 5 (5), pp. 71 - 78, December 2010 Biotechnol. Mol. Mol. . Biol. Rev). This isomerization is limited by thermodynamics, a mixture of glucose and fructose is obtained, and the fructose must then be separated from the residual glucose.
• sucrose a very abundant disaccharide, consists of a unit of the fructose type and of a unit of the glucose type.
• fructose It is possible to produce an equimolar mixture of glucose and fructose by hydrolysis (called invert sugar), but again, a separation step would be required to isolate the fructose. Due to the structural similarities of sugars, glucose / fructose separation processes make pure fructose feedstocks more expensive, which limits the attractiveness of processes for converting fructose to 5-HMF.
• fructose Under the most common conditions for the transformation of fructose into 5-HMF at temperatures above 100 ° C), glucose is not or only slightly transformed into 5-HMF, but undergoes decomposition reactions into heavy polymeric species ( humins). Examples of reaction carried out under mild conditions (temperatures below 100 ° C.) show that fructose can nevertheless be transformed with good yields (Chemical Reviews, 2013, 113, 1499-1597). Nevertheless, these reactions are either carried out in aqueous solvent with high concentrations of acid catalyst, which is accompanied by side reactions of rehydration in levulinic and formic acids, or in solvents of the ionic liquid type or deep eutectic solvents, which pose problems well known for their application on an industrial scale.
• the method according to the present invention aims to remedy the drawbacks of the prior art.
• the Applicant has discovered a process for the production of 5-hydroxymethylfurfural (5-HMF) allowing the selective conversion of a fructosidic fraction to 5-HMF in the presence of a non-fructosidic fraction.
• 5-HMF 5-hydroxymethylfurfural
• the non-fructosidic fraction is weakly altered, that is to say weakly converted.
• the differences in physicochemical properties between 5-HMF and the non-fructosidic fraction make it possible to facilitate the separation of these two compounds.
• the process according to the present invention makes it possible to obtain very good yields of 5-HMF and of unconverted non-fructosidic fraction such as glucose.
• Another advantage of the process according to the invention is to facilitate the separation between the 5-HMF and the unconverted non-fructosidic fraction obtained.
• mass concentration of 5-HMF glucose or fructose is meant the ratio between the mass of 5-HMF, glucose or fructose, respectively, and the mass of reaction medium.
• homogeneous catalyst is understood to mean a catalyst which is soluble in the reaction medium.
• heterogeneous catalyst means a catalyst which is insoluble in the reaction medium.
• Bronsted acid is meant a molecule of the Bronsted acid family capable of releasing an H + proton in the reaction medium.
• inorganic catalyst a catalyst in which the function responsible for the catalytic dehydration activity is not linked to a hydrocarbon chain by a covalent bond.
• inorganic Bronsted acid catalyst is meant a Bronsted acid catalyst not containing carbon atoms and capable of releasing an H + proton in the reaction medium.
• inorganic Lewis acid catalyst is meant a Lewis acid catalyst containing an atom from the family of metals or lanthanides.
• aprotic solvent a molecule playing the role of solvent and all of the hydrogens of which are carried by carbon atoms.
• polar solvent is understood to mean a molecule acting as a solvent, the dipole moment m of which expressed in Debye has a numerical value greater than or equal to 2.00 measured at 25 ° C.
• aprotic polar solvent therefore means a molecule acting as a solvent in which all the hydrogens are carried by carbon atoms and whose dipole moment m expressed in Debye has a numerical value greater than or equal to 2.00 measured at 25 ° vs.
• wt% denotes a mass percentage (by weight).
• the term “weakly converted” is understood to mean a non-fructosidic fraction which is converted in a proportion of less than 20%, preferably less than 16%, preferably comprised between 0 and 15%, preferably between 0.1 and 12.0%, so between 0.5 and 10.0%, very preferably between 0.5 and 5.0%.
• the invention relates to a process for the production of 5-hydroxymethylfurfural comprising contacting, in a polar aprotic solvent having a boiling point of less than 300 ° C, a feed containing the free fructose taken in admixture with any saccharide species or polysaccharide, or any polysaccharide charge containing one or more non-fructosidic units and one or more fructosidic units, with at least one dehydration catalyst chosen from homogeneous or heterogeneous, organic or inorganic Bronsted acids, said process being carried out at a temperature between 50 and 90 ° C.
• the process according to the present invention makes it possible to obtain very good yields of 5-HMF and of unconverted non-fructosidic fraction such as glucose.
• Another advantage of the process according to the invention is to facilitate the separation between the 5-HMF and the unconverted non-fructosidic fraction obtained.
• the process is carried out at a temperature between 60 and 85 ° C, preferably between 60 and 80 ° C, preferably between 65 and 75 ° C and very preferably at 70 ° C.
• the dehydration catalyst has a pKa in DMSO between 0 and 5.0.
• the aprotic polar solvent has a boiling point of less than 250 ° C, preferably less than 200 ° C.
• the conversion of the fructosidic fraction to 5-HMF is greater than or equal to 70% and the conversion of the non-fructosidic fraction is less than or equal to 20%.
• the charge is introduced into at an initial mass concentration of fructosidic unit greater than 7% by weight, preferably between 8 and 30% by weight relative to the total mass of solvent.
• the filler is introduced in a solvent / filler mass ratio of between 0.1 and 200.
• the filler is chosen from sucrose or a mixture of glucose and fructose.
• the aprotic polar solvent is chosen from butan-2-one, acetone, acetic anhydride, 1a / V, / V, / V ', / V'-tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone, propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, / V, / V-dimethylformamide, / V, / V-dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate and y-valerolactone.
• the aprotic polar solvent is dimethylsulfoxide.
• the homogeneous Bronsted organic acid catalysts are chosen from organic acids of general formulas R'COOH, R'S0 2 H, R'S0 3 H, (R'S0 2 ) NH, (R'0) 2 P0 2 H, R'OH, in which R 'is chosen from the groups
• alkyls preferably comprising between 1 and 15 carbon atoms, substituted or not by at least one substituent chosen from a hydroxyl, an amine, a nitro, a halogen, preferably fluorine and an alkyl halide,
• alkenyls substituted or not by at least one group chosen from a hydroxyl, an amine, a nitro, an oxo, a halogen, preferably fluorine, and an alkyl halide,
• - aryls preferably comprising between 5 and 15 carbon atoms, substituted or not by a substituent chosen from a hydroxyl, an amine, a nitro, an oxo, a halogen, preferably fluorine and an alkyl halide,
• heteroaryls preferably comprising between 4 and 15 carbon atoms, substituted or not by a substituent chosen from a hydroxyl, an amine, a nitro, an oxo, a halogen, preferably fluorine and an alkyl halide.
• homogeneous Bronsted inorganic catalysts are chosen from HF, HCl, H Br, Hl, H 2 S0 3 , H 2 S0 4 , H 3 P0 2 , H 3 P0 4 , HN0 2 , HN0 3 , H 2 W0 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 0, H 2 Mo0 4 , HRe0 4 , H 2 Cr0 4 , H 2 Sn0 3 , H 4 Si0 4 , H 3 B0 3 , HCI0 4 , HBF 4 , HSbF 5 , HPF 6 , H 2 F0 3 P, CIS0 3 H, FSO s H, HN (S0 2 F) 2 and HI0 3 .
• the homogeneous Bronsted organic acid catalysts are chosen from formic acid, acetic acid, trifluoroacetic acid, lactic acid, levulinic acid, 2,5-furan dicarboxylic acid, methanesulfinic acid, methanesulfonic acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) amine, benzoic acid, paratoluenesulfonic acid, 4-biphenylsulfonic acid, diphenylphosphate, and 1, 1 '-binaphthyl-2 , 2'-diyl hydrogenphosphate.
• the dehydration catalyst (s) are introduced in a solvent / catalyst (s) mass ratio of between 20 and 10,000, in which the mass of solvent corresponds to the total mass of solvent used in the process.
• the saccharide filler used in the method according to the invention comprises either a filler containing free fructose mixed with any saccharide or polysaccharide species, or any polysaccharide filler containing one or more non-fructosidic units and one or more fructosidic units which can release fructose by one or more hydrolysis steps.
• the feed treated in the process is sucrose or a mixture of glucose and fructose.
• the saccharide filler containing fructose comprises fructose in monomeric, oligomeric or polymeric form.
• filler containing free (or monomeric) fructose taken as a mixture with any saccharide species is meant for example syrups of the High-Fructose-Corn-Syrup type containing fructose and glucose in different proportions (glucose / fructose in mass ratios or molars 58/42, 45/55, 10/90 for example).
• syrup is meant a solution of sugar in water having a concentration of at least 30% by weight, preferably at least 50% by weight, preferably at least 70% by weight.
• polysaccharide filler containing one or more non-fructosidic units and one or more fructosidic units capable of releasing fructose by one or more hydrolysis steps denotes the oligosaccharides and the polysaccharides in which at least one monosaccharide unit is fructose.
• fillers such as sucrose, kestose, fructans, oligofructans and inulin are denoted.
• the polysaccharide fillers listed above are capable of releasing monomeric fructose by hydrolysis, said fructose product being able to be converted into 5-HMF in the process according to the invention.
• oligosaccharide denotes more particularly a carbohydrate having the crude formula (C 6m Hio m + 2 0 5m + i ) (C 5n H 8n + 2 0 4n + i ) where m and n are integers whose sum is between 2 and 6.
• the monosaccharide units making up said oligosaccharide may or may not be identical, and at least one unit of formula (C 6m Hio m + 2 0 5m + i ) is fructose.
• polysaccharide denotes a carbohydrate having the crude formula (C 6m Hio m + 2 0 5m + i ) (C 5n H 8n + 2 0 4n + i ) where m and n are integers whose sum is greater than or equal to 7.
• the feed contains a mixture of fructosidic and glucosidic units so that the process according to the invention allows a mixture of 5-HMF and glucose to be obtained.
• the process according to the invention can make it possible to produce an equimolar mixture of 5-HMF and glucose.
• the filler is a High-Fructose-Corn-Syrup syrup
• the process according to the invention makes it possible to produce a mixture of 5-HMF and glucose, the stoichiometry of which depends on the composition of the High- Starting Fructose-Corn-Syrup.
• the feed is advantageously introduced into the process in a solvent / feed mass ratio of between 0.1 and 200.0, preferably between 0.3 and 100.0 and even more preferably between 1.0 and 50.0.
• the process according to the invention is carried out in the presence of at least one aprotic polar solvent having a boiling point lower than 300 ° C, preferably lower than 250 ° C, preferably lower than 200 ° C.
• the polar aprotic solvent is advantageously chosen from butan-2-one, acetone, acetic anhydride, 1a / V, / V, / V ', / V'-tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone , propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, / V, / V-dimethylformamide, / V, / V-dimethylacetamide, sulfolane, / V-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate and y - valerolactone.
• the aprotic polar solvent is chosen from acetone, hexamethylphosphoramide, / V, / V-dimethylformamide, sulfolane, / V-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate and g-valerolactone.
• the aprotic polar solvent is dimethylsulfoxide (DMSO).
• the process is carried out in the presence of at least one dehydration catalyst chosen from homogeneous or heterogeneous, organic or inorganic Bronsted acids, capable of catalyzing the dehydration of fructose to 5-hydroxymethylfurfural.
• dehydration catalyst chosen from homogeneous or heterogeneous, organic or inorganic Bronsted acids, capable of catalyzing the dehydration of fructose to 5-hydroxymethylfurfural.
• At least one dehydration catalyst is chosen from homogeneous or heterogeneous organic Bronsted acids, capable of catalyzing the dehydration of fructose to 5-hydroxymethylfurfural.
• the homogeneous or heterogeneous Bronsted organic acids have a pKa in DMSO of between 0 and 5.0, preferably between 0.5 and 4.0 and more preferably between 1.0 and 3.0.
• Said pKa are as defined in the article by F. G. Bordwell et al. (J. Am. Chem. Soc., 1991, 113, 8398-8401).
• the homogeneous Bronsted organic acid catalysts are chosen from organic acids of general formulas R'COOH, R'S0 2 H, R'S0 3 H, (R'S0 2 ) NH, (R'0) 2 P0 2 H, R'OH, in which R 'is chosen from the groups
• alkyls preferably comprising between 1 and 15 carbon atoms, preferably between 1 and 10, and preferably between 1 and 6, substituted or not by at least one substituent chosen from a hydroxyl, an amine, a nitro, a halogen, preferably fluorine and an alkyl halide,
• alkenyls substituted or not by at least one group chosen from a hydroxyl, an amine, a nitro, an oxo, a halogen, preferably fluorine, and an alkyl halide,
• - aryls comprising between 5 and 15 carbon atoms and preferably between 6 and 12 carbon atoms, substituted or not by a substituent chosen from a hydroxyl, an amine, a nitro, an oxo, a halogen, preferably fluorine and a alkyl halide,
• the Bronsted organic acids are chosen from formic acid, acetic acid, trifluoroacetic acid, lactic acid, levulinic acid, 2,5-furan dicarboxylic acid, acid methanesulfinic, methanesulfonic acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) amine, benzoic acid, paratoluenesulfonic acid, 4-biphenylsulfonic acid, diphenylphosphate, and 1, 1 - binaphthyl-2,2 '-diyl hydrogenphosphate.
• the homogeneous Brcnsted organic acid catalyst is chosen from methanesulfonic acid (CH 3 S0 3 H) and trifluoromethanesulfonic acid (CF 3 S0 3 H).
• the heterogeneous Brcnsted organic acid catalysts are chosen from ion exchange resins, in particular from sulfonic acid resins based on a copolymer preferably of sulfonated styrene-divinylbenzene or of a sulfonated tetrafluoroethylene copolymer (such as, for example, following commercial resins: Amberlyst ® 15, 16, 35 or 36; Dowex® 50 WX2, WX4 or WX8, Nafion ® PFSA NR-40 or NR-50, Aquivion ® PFSA PW 66, 87 or 98), carbons functionalized by sulphonic and / or carboxylic groups, silicas functionalized by sulphonic and / or carboxylic groups.
• the heterogeneous Bronsted organic acid catalyst is chosen from sulfonic acid resins.
• At least one dehydration catalyst is chosen from homogeneous Bronsted inorganic acids capable of catalyzing the dehydration of fructose to 5-hydroxymethylfurfural.
• the homogeneous Bronsted inorganic catalysts are chosen from HF, HCl, H Br, Hl, H 2 S0 3 , H 2 S0 4 , H 3 P0 2 , H 3 P0 4 , HN0 2 , HN0 3 , H 2 W0 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 0, H 2 MO0 4 , HRe0 4 , H 2 Cr0 4 , H 2 Sn0 3 , H 4 Si0 4 , H 3 B0 3 , HCI0 4 , HBF 4 , HSbF 5 , HPF 6 , H 2 F0 3 P, CIS0 3 H, FSO s H, HN (S0 2 F) 2 and HI0 3 .
• the inorganic acids of Bronsted are chosen from HCl, HBr, Hl, H 2 S0 4 , H 3 P0 4 , HN0 3 .
• Bronsted's inorganic acid is HCl.
• the dehydration catalyst (s) are introduced into the reaction mixture in a solvent / catalyst (s) mass ratio of between 20 and 10,000, preferably between 40 and 2000, preferably between 100 and 1000, in which the mass of solvent corresponds to the total mass of solvent used in the process.
• Said method is carried out at a temperature between 50 and 90 ° C, preferably between 60 and 85 ° C, preferably between 60 and 80 ° C, preferably between 65 and 75 ° C, very preferably at 70 ° C and preferably at a pressure between 0.0001 and 8.0 MPa, preferably between 0.001 and 5.0 MPa, and more preferably between 0.01 and 3.0 MPa.
• the implementation of the process according to the invention at temperatures below 90 ° C makes it possible to selectively transform the fructosidic fraction of the load while retaining the non-fructosidic fraction (for example glucosidic) not or weakly. converted.
• the method makes it possible to achieve conversions of the fructosidic fraction to 5-HMF greater than or equal to 70%, preferably greater than or equal to 75%, more preferably greater than or equal to 80%.
• Said conversions of the fructosidic fraction is accompanied by a conversion of the non-fructosidic fraction less than or equal to 20%, preferably less than or equal to 16%, preferably between 0 and 15%, preferably between 0.1 and 12.0%, between 0.5 and 10.0%, very preferably between 0.5 and 5.0%.
• the method is carried out for a period of between 15 and 300 minutes (min), preferably between 20 and 260 min, preferably between 30 and 240 min, preferably between 30 and 200 min, preferably between 35 and 150 min and very preferably between 45 and 120 min.
• the feeding of the saccharide feed into the reaction mixture can be carried out according to several methods of introducing said feed.
• the feedstock is introduced into the process in at an initial mass concentration of fructosidic unit greater than 7% by weight, preferably between 8 and 30% by weight (wt) relative to the total mass of solvent, preferably between 9 and 26% by weight, preferably between 12 and 22% by weight.
• the feed is introduced into the reaction mixture in solid form, optionally using a suitable device making it possible to control the feed rate.
• this device can be an endless screw or a pneumatic system for transporting solid particles.
• this embodiment is preferred for a filler of oligosaccharide or polysaccharide type.
• the feed is introduced in liquid form into the reaction medium in solution in a solvent, called additional solvent, using a pump making it possible to control the rate of introduction of the solution containing the feed.
• a solvent called additional solvent
• This embodiment is particularly well suited to a feed of monosaccharide, or even oligosaccharide type, which can be dissolved in the additional solvent at high concentrations.
• the gradual introduction of a load corresponding to a fructose and glucose syrup (of the High-Fructose-Corn-Syrup type according to the English name) by means of a pump is implemented. Said introduction can be carried out on one or more occasions, sequentially or even continuously.
• the method also comprises the use of at least one additional solvent selected from aprotic or practical polar solvents.
• Said additional solvent can in particular allow the solubilization of the feed before it is brought into contact with the aprotic polar solvent and the dehydration catalyst according to the invention.
• said additional solvent is chosen from butan-2-one, acetone, acetic anhydride, 1a / V, / V, / V ', / V'-tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone. , propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, N, N- dimethylformamide, / V, / V-dimethylacetamide, sulfolane, / V-methylpyrrolidone, dimethylsulfoxide, propylene carbonate, g-valerolactone , water, methanol, ethanol, formic acid and acetic acid.
• the additional solvent chosen from aprotic or practical polar solvents is acetone, hexamethylphosphoramide, / V, / V-dimethylformamide, sulfolane, / V-methylpyrrolidone, dimethylsulfoxide, propylene carbonate, g- valerolactone water, methanol and ethanol, preferably from / V, / V-dimethylformamide, sulfolane, / V-methylpyrrolidone, dimethylsulfoxide, water and methanol, and very preferably additional solvent is chosen from water and dimethylsulfoxide.
• the additional solvent used corresponds to all or a fraction of the reaction mixture.
• the additional solvent therefore contains at least the aprotic polar solvent, at least one dehydration catalyst used in the process, and optionally at least one unconverted feed fraction of the 5-HMF produced.
• This embodiment advantageously makes it possible to gradually increase the amount of 5-HMF without increasing the volume of additional solvent.
• This embodiment of the 5-HMF production process is carried out batchwise.
• the hourly mass speed (mass feed rate / mass of catalysts) is between 0.01 h 1 and 5.0 h 1 and preferably between 0.02 h 1 and 2.0 h 1 .
• the water contained in the reaction mixture is preferably removed, by any methods known to those skilled in the art, preferably continuously, in order to maintain a water content. less than 30.0% wt relative to the total mass of solvent, preferably less than 20.0% wt, more preferably less than 15.0% wt, and very preferably less than 10.0% wt.
• the implementation of the 5-HMF and glucose production process makes it possible to obtain a good conversion of the fructose involved, as well as an excellent selectivity in favor of 5-HMF while limiting the conversion of glucose.
• the product selectively obtained by the transformation process according to the invention is 5-hydroxymethylfurfural (5-HMF) and glucose.
• the reaction medium is analyzed by high performance liquid chromatography (HPLC) to determine the conversion of the fructoside fraction of the feed. and the content of unconverted glucose and 5-HMF produced in the presence of an internal standard to quantify unwanted products (also called side products) such as levulinic acid, formic acid and any co-product containing sugars such as humins.
• the humins are quantified by the difference in carbon balance with the carbon introduced initially.
• glucose, fructose and sucrose used as filler are commercial and used without further purification.
• Hydrochloric acid is used as a commercial solution concentrated to 1.0 M (mol / L) in diethyl ether.
• Methanesulfonic acid, noted AMS in the examples, is commercial and used without further purification.
• DMSO dimethyl sulfoxide
• the mass concentrations of the constituents of the reaction mixtures are determined by high performance liquid chromatography (HPLC). Aliquots of the reaction mixture are taken at regular intervals to assess the composition by HPLC.
• HPLC high performance liquid chromatography
• the conversion rate of sucrose is 100%, the sucrose being converted into a mixture of glucose, fructose and their reaction products. It is understood that one mole of sucrose consists of one mole of glucosidic units and one mole of fructosidic units.
• the fructose conversion rate (Conv FR u) is defined as the ratio of the molar concentration of fructose converted and of the molar concentration in fructosidic units present in the initial charge, expressed in%.
• the glucose yield (Yield Gi _u) is defined as the ratio of the molar concentration of glucose measured in the samples and of the molar concentration of glucosidic units present in the initial charge, expressed in%.
• the yield of 5-HMF Yield of HMF
• Example 1 (compliant) Conversion of a 1: 1 qlucose / fructose mixture into 5-HMF and glucose in the presence of hydrochloric acid at 70 ° C
• Methanesulfonic acid (2.60 mmol) is added to a solution of sucrose (9.0 g, 26.3 mmol) in DMSO (41.0 g). The initial mass concentration of sucrose is
• Example 5 (compliant) Conversion of sucrose to 5-HMF and glucose in the presence of hydrochloric acid at 90 ° C. Hydrochloric acid (1.0 M in Et 2 0) (2.63 mmol) is added to a solution of Sucrose (9.0 g, 26.3 mmol) in DMSO (41.0 g). The initial sucrose mass concentration is 18.0% by weight. The catalyst / sucrose molar ratio is 0.100. The reaction medium is stirred at 90 ° C. for 4 hours. The yields at different reaction times are reported in Table 5.
• Examples 1 to 4 (compliant) carried out at temperatures less than or equal to 80 ° C, the transformation carried out at low temperature makes it possible to obtain good glucose yields (Yield Gi _u> 80%), which is not transformed into unwanted products, while allowing to obtain a conversion of fructose into 5-HMF with yields of up to 77% under the most efficient conditions (Examples 1 and 2).
• glucose is converted less rapidly in the presence of fructosidic units (Examples 1 and 2) than in its absence under the same conditions (Example 7).
• the presence of glucose or glucosidic units does not appreciably affect the yields obtained from fructosidic units or fructose (Examples 1 and 2 vs. Example 8 with fructose alone), on the contrary the presence of glucose or units Glucosidics surprisingly improves fructose conversion after 30, 60 or 120 minutes, as well as the yield of 5-HMF. .
• Example 5 In Example 5 (compliant) carried out at a temperature of 90 ° C, yields of 85% and 75% of glucose and 5-HMF respectively are obtained at the short reaction times, but a longer reaction time leads to degradation. glucose yield without significantly improving the 5-HMF yield.
• Example 6 (non-compliant) carried out at a temperature above 90 ° C, in particular at 100 ° C, the glucose yield does not exceed 50% without the 5-HMF yield being significantly greater than 75-80% .
• Example 7 In Example 7 (non-compliant) carried out at a temperature of 70 ° C., for 240 minutes, only with glucose, the glucose yield is less than 60% without production of 5-HMF.
• Example 8 In Example 8 (non-compliant) carried out at a temperature of 70 ° C. only with fructose, the fructose yield does not exceed 50% after reaction for 30 minutes with an average fructose conversion of 70%.

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