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    • 专利摘要:
    The invention relates to a method for producing 5-hydroxymethylfurfural from a feedstock containing fructose in the presence of at least one aprotic polar solvent and at least one dehydration catalyst, wherein the instant fructose concentration is less than or equal to 5.0% wt.
    公开号:FR3076554A1
    申请号:FR1850210
    申请日:2018-01-10
    公开日:2019-07-12
    发明作者:Marc Jacquin；Damien Delcroix
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    Technical Field of the Invention The invention relates to a particular process for transforming sugars, more specifically hexoses and more specifically fructose, into 5-hydroxymethylfurfural (hereinafter designated by the abbreviation 5-HMF) in the presence of minus an aprotic polar solvent, and in the presence of one or more catalysts.
    Prior art
    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 chemistry. Its interest lies in recent years 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.
    The production of 5-HMF by dehydration of hexoses has been known for many years and has been the subject of a significant number of research works.
    Mention may be made in particular of the work which has focused on the dehydration of sugars in aprotic polar solvents. More particularly still, mention may be made of the work which has focused on the dehydration of sugars in dimethylsulfoxide (DMSO): the selectivity of transformation of sugars into 5-HMF is particularly good there, and it is possible to work on total conversion of sugars. (absence of parasitic reaction of rehydration of 5-HMF to formic acid and levulinic acid). However, it is well known that the distillation of 5-HMF solutions in DMSO is problematic. Thus, separation techniques other than distillation must be considered, such as that described in patent FR 2669635. In this patent, a process is described for the liquid-liquid extraction of the 5-HMF contained in DMSO, by addition of water and an organic solvent such as dichloromethane or diethyl ether for example. The cost of this separation is inversely proportional to the concentration of 5-HMF in DMSO (reduction in the water and solvent flow rates required, reduction in the number of stages of the liquid-liquid extractor required for example). It is therefore advantageous to be able to produce, from sugar, the most concentrated possible solution of 5-HMF in DMSO.
    When the protocols described in the literature are reproduced at higher initial concentrations of sugars, a notable loss of selectivity is recorded with in particular the formation of non-recoverable and non-recyclable secondary products such as humines. For example, in RSC Adv. 2014, 4, 13434. Xu et al. describe the dehydration of fructose in DMSO in the presence of HCl at 5% by weight of fructose in DMSO and at 30% by weight of fructose in DMSO. By thus increasing the concentration of the fructose load in DMSO, the molar yield of 5-HMF drops from 88% to 69%. However, the high cost of the envisaged charges from saccharifying biomass does not allow the slightest loss of selectivity. In addition, the presence of secondary products such as humines complicates the process for extracting 5-HMF as described in patent FR 2,669,635 (partial precipitation of humines by adding water, requiring a filtration step). This greatly limits the attractiveness of this synthesis and extraction pathway for 5-HMF, in particular with a view to industrializing the process. The invention then aims to remedy the drawbacks of the prior art. It aims in particular to improve the production of 5-HMF in DMSO, and more particularly to produce with a high degree of selectivity a very concentrated solution of 5-HMF in DMSO, while having a high productivity. A subsidiary aim of the invention is to facilitate the extraction of 5-HMF from said solution due to its high concentration. Definitions and Abbreviations
    The expression instantaneous fructose concentration is understood to mean the concentration of monomeric fructose measured at all times in the reaction mixture and corresponding to the mass ratio between the mass of monomeric fructose present in the reaction medium and the mass of reaction solvent at this same instant of the reaction.
    By selectivity is meant the ratio between the number of moles of 5-HMF produced and the number of converted moles of fructose contained in the feed introduced into the process.
    By productivity is meant the number of moles of 5-HMF produced per hour and per mass of reaction solvent, expressed in mol / (h * kg).
    The term “final concentration of 5-HMF” is understood to mean the ratio between the mass of 5-HMF and the mass of reaction solvent.
    The term “homogeneous catalyst” is understood to mean a catalyst soluble in the reaction medium.
    By heterogeneous catalyst is meant a catalyst insoluble in the reaction medium.
    By Bronsted acid is meant a molecule from the family of Bransted acids which can release an H + proton in the reaction medium.
    The term inorganic catalyst is understood to mean a catalyst in which the function responsible for the catalytic dehydration activity is not linked to a hydrocarbon chain by a covalent bond.
    The term inorganic Bransted acid catalyst is understood to mean a Bransted acid catalyst which does not contain carbon atoms and which can release an H + proton in the reaction medium.
    The term “inorganic Lewis acid catalyst” is understood to mean a Lewis acid catalyst containing an atom from the family of metals or lanthanides.
    The term “aprotic solvent” is understood to mean a molecule acting as a solvent and in which all the hydrogens are carried by carbon atoms.
    The term “polar solvent” is understood to mean a molecule playing the role of 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 understood to mean a molecule acting as a solvent in which all the hydrogens are carried by carbon atoms and in which the dipole moment μ expressed in Debye has a numerical value greater than or equal to 2.00 measured at 25 °. vs.
    We denote by% wt, a mass percentage (by weight).
    OBJECT OF THE INVENTION The invention relates to a process for the production of 5-hydroxymethylfurfural (5-HMF) comprising bringing a saccharide filler containing fructose into contact with an aprotic polar solvent with at least one dehydration catalyst chosen from Bransted acids and Lewis acids, homogeneous or heterogeneous, organic or inorganic, said process being carried out at a temperature between 30 and 175 ° C and at a pressure between 0.0001 MPa and 8.0 MPa, in which the instantaneous fructose concentration is less than or equal to 5.0% by weight.
    Advantageously, the combination of the various parameters of the process according to the invention, in particular the control of the instantaneous fructose concentration, makes it possible to obtain 5-HMF with very good yield and excellent selectivity and is accompanied by an improvement in productivity.
    Detailed description of the invention
    Charge
    The saccharide filler containing fructose used in the process according to the invention comprises fructose or any saccharide filler containing fructose either in the form of free fructose, or in the form of saccharide fructoside monomeric, oligomeric or polymeric unit capable of releasing fructose by a hydrolysis step. Preferably, the filler treated in the process is fructose.
    Advantageously, the saccharide filler containing fructose comprises fructose in monomeric, oligomeric or polymeric form.
    By load containing free fructose, we mean for example fructose, pure fructose syrups, or 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 understood to mean 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.
    The term "sugar filler containing fructose in monomeric, oligomeric or polymeric fructoside form" denotes oligosaccharides and polysaccharides in which at least one monosaccharide unit is fructose. For example, fillers such as sucrose, kestose, fructans, oligofructans, inulin are designated.
    Advantageously, the saccharide fillers are capable of releasing monomeric fructose by osidic hydrolysis, said fructose produced being able to be transformed into 5-HMF.
    The term “oligosaccharide” denotes more particularly a carbohydrate having the crude formula (CemHwm + sOsrri + iXCsnHsn + gO ^ + i) where m and n are integers whose sum is between 2 and 6. The monosaccharide units making up said oligosaccharide are identical or not, and at least one unit of formula (C6mHiom + 205m + i) is fructose. By extension, the term “polysaccharide” denotes a carbohydrate having the crude formula (Ο6πΗ10π + 2θ5π. ^ (Ο5πΗ8π + 2θ4π + ι) where m and n are integers whose sum is greater than or equal to 7.
    Advantageously, in the case where the feed does not only contain fructose but also glucose, the method according to the invention can make it possible to produce a mixture of 5-HMF and glucose. For example, in the case where the filler is sucrose, the method according to the invention can make it possible to produce an equimolar mixture of 5-HMF and glucose. Similarly, in the case where the filler is a High-Fructose-Corn-Syrup syrup, the method 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 filler is introduced into the process in a solvent / filler mass ratio of between 0.1 and 200.0, preferably between 0.3 and 100.0 and more preferably between 1.0 and 50.0.
    solvents
    The process according to the invention is carried out in the presence of at least one polar aprotic solvent. The aprotic polar solvent is advantageously chosen from butan-2-one, acetone, acetic anhydride, Λ /, Λ /, Λ / ', Λ /' - tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone , propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, N, N-dimethylformamide, / V, / / - dimethylacetamide, sulfolane, / V-methylpyrrolidone, dimethylsulfoxide, propylene carbonate and γ- valerolactone. Preferably, the aprotic polar solvent is chosen from acetone, hexamethylphosphoramide, Λ /, / V-dimethylformamide, sulfolane, / V-methylpyrrolidone, dimethylsulfoxide, propylene carbonate and γ-valerolactone. Preferably, the aprotic polar solvent is dimethylsulfoxide (DMSO).
    Dehydration catalyst
    According to the invention, the process is carried out in the presence of at least one dehydration catalyst chosen from Bransted acids and Lewis acids, homogeneous or heterogeneous, organic or inorganic, capable of catalyzing the dehydration of fructose to 5 -hydroxyméthylfurfural.
    In one embodiment, at least one dehydration catalyst is chosen from homogeneous or heterogeneous organic Bransted acids, capable of catalyzing the dehydration of fructose to 5-hydroxymethylfurfural.
    Preferably, the homogeneous organic Bransted acid catalysts are chosen from organic acids of general formulas R'COOH, R'SO2H, R'SO3H, (R'SO2) NH, (R'O) 2PO2H, R'OH, in which R ′ is chosen from alkyl groups, 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, a amine, nitro, 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 the 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, halogen, preferably fluorine and halogenu alkyl, heteroaryls comprising between 4 and 15 carbon atoms and preferably between 4 and 12 carbon atoms, substituted or not by a substituent chosen from a hydroxyl, an acid, an amine, a nitro, an oxo, a halogen, preferably fluorine and an alkyl halide.
    When the Bransted organic acid catalysts are chosen from organic acids of general formulas R’-COOH, R ’can also be hydrogen.
    Preferably, the organic Bransted 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'-binaphtyl-2, 2'-diyl hydrogenophosphate. Very preferably, the homogeneous organic Bransted acid catalyst is chosen from methanesulfonic acid (CH3SO3H) and trifluoromethanesulfonic acid (CF3SO3H).
    The heterogeneous organic Bransted acid catalysts are chosen from ion exchange resins, in particular from sulphonic acid resins based on a sulphonated styrene-divinylbenzene copolymer or a sulphonated tetrafluoroethylene copolymer (such as for example following commercial resins: Amberlyst ® 15, 16, 35 or 36; Dowex® 50 WX2, WX4 or WX8, Nation ® PFSA NR-40 or NR-50, Aquivion ® PFSA PW 66, 87 or 98), coals functionalized with sulfonic and / or carboxylic groups, silicas functionalized by sulfonic and / or carboxylic groups. Preferably, the heterogeneous organic Bransted acid catalyst is chosen from sulfonic acid resins.
    In one embodiment, at least one dehydration catalyst is chosen from homogeneous inorganic Bransted acids and homogeneous or heterogeneous inorganic Lewis acids, capable of catalyzing the dehydration of fructose to 5-hydroxymethylfurfural.
    Preferably, the homogeneous inorganic Bransted catalysts are chosen from HF, HCl, HBr, Hl, H2SO3, H2SO4, H3PO2, H3PO4, HNO2, HNO3, H2WO4, H4SiW12O40, H3PW12O40, (NH4) 6 (W1204o), xH20, H40 Η3ΡΜθι204ο, (NH4) 3Mo7O24.xH2O, H2MoO4, HReO4, H2CrO4, H2SnO3, H4SiO4, H3BO3, HCIO4, HBF4, HSbF5, HPF6, H2FO3P, CISO3H, FSO3H, HN (SO2F). Preferably, the inorganic Bransted acids are chosen from HCl, HBr, Hl, H2SO4, H3PO4, HNO3. Most preferably, the inorganic acid from Bransted is HCl.
    Preferably, the inorganic dehydration catalyst is chosen from homogeneous inorganic Lewis acids corresponding to the general formula (II) MOXP, solvated or not, in which M is an atom chosen from lithium, atoms from groups 3 to 16, preferably 6 to 13, of the periodic table, lanthanides included, and preferably among Li, B, Al, Fe, Zn, Sn, Cr, Ce, Er, and preferably among Li, 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 halides, alkylsulfonates, perhaloalkylsulfonates, bis (perhaloalkylsulfonyl) amides, preferably X is chosen from halides chosen from Cl ", Br" and Γ, alkylsulfonates, perhaloalkylsulfonates , said anions X can be identical or different in the case where o is greater than 1.
    Very preferably, the homogeneous inorganic Lewis acids are chosen from LiCI, BF3, AICI3, FeCI3, ZnCI2, SnCI2, CrCI3, CeCI3 and ErCI3. Very preferably, the homogeneous inorganic Lewis acid is chosen from LiCI, AI (OTf) 3 and AICI3.
    The heterogeneous inorganic Lewis acids are chosen from simple or mixed oxides of the compounds chosen from silicon, aluminum, zirconium, titanium, niobium, tungsten, doped or not with an element chosen from tin, tungsten and hafnium and among the phosphates of metals, said metals being chosen from niobium, zirconium, tantalum, tin and titanium. Preferably, the heterogeneous Lewis acids are chosen from zirconium oxides, titanium oxides, mixed oxides of aluminum and silicon doped with tin such as the Sn-β zeolite or the mesostructured silica Sn-MCM- 41, tin and titanium phosphates.
    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 2,000, preferably between 100 and 1,000, in which the mass of solvent corresponds to the total mass of solvent used in the process.
    In a particular embodiment, the method is implemented with at least two dehydration catalysts in which at least one of the two catalysts is a chlorinated catalyst. Preferably, said chlorinated catalyst is chosen from HCl, LiCI, AICI3i FeCI3, ZnCI2, SnCI2, CrCI3, CeCI3 and ErCI3.
    Implementation of the process
    Preferably, said process is carried out at a temperature between 30 and 175 ° C, preferably between 40 and 150 ° C, preferably between 45 and 130 ° C, preferably 50 and 100 ° C, very preferred between 60 and 90 ° C and at a pressure between 0.0001 and 8.0 MPa, preferably between 0.001 and 5.0 MPa, and preferably between 0.01 and 3.0 MPa.
    According to the invention, the process is characterized in that the instantaneous fructose concentration in the reaction mixture is less than or equal to 5.0% by weight. Preferably the instantaneous concentration is between 0.001 and 5.0% by weight, preferably between 0.001 and 4.0% by weight, preferably between 0.001 and 3.0% by weight, preferably between 0.001 and 2.0% wt, very preferably between 0.001 and 1.0 wt%.
    Maintaining the instantaneous fructose concentration can be obtained by any means known to those skilled in the art. Preferably, the maintenance of the instantaneous fructose concentration is controlled by measuring the instantaneous fructose concentration during the implementation of the method according to the invention. Said measurement can be carried out by any method known to a person skilled in the art, and preferably by high performance liquid chromatography (HPLC).
    Maintaining the instantaneous concentration in accordance with the invention is obtained by controlling the amount of fructose in the reaction medium. Said control can be obtained by the use of an oligosaccharide or polysaccharide charge which limits said instantaneous concentration as a function of the rate of hydrolysis of the oligosaccharide or polysaccharide into monosaccharides. Said control can also be obtained by adapting the feed feed in the reaction mixture as a function of the instantaneous fructose concentration measured.
    Advantageously, controlling the instantaneous fructose concentration makes it possible to obtain excellent selectivity for 5-HMF.
    Said supply to the reaction mixture can be carried out according to several methods of introducing said charge.
    In a first embodiment, the charge is introduced into the reaction mixture in solid form, using a suitable device making it possible to control the charge rate. Without limitation, this device can be a worm or a pneumatic system for transporting solid particles. Without limitation, this embodiment is preferred for an oligosaccharide or polysaccharide type filler. The possibility of introducing a filler in solid form corresponding to sucrose, kestose or inulin from which fructose is gradually released by hydrolysis is a possibility. Said introduction can be carried out in one or more times, sequentially or else continuously, in order to maintain an instantaneous fructose concentration less than or equal to 5.0% by weight.
    In a second embodiment, the charge 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 charge . The choice of additional solvent to dissolve the charge is then essential to obtain a high final concentration of 5-HMF. This embodiment is particularly well suited to a filler of the monosaccharide or even oligosaccharide type, which can be dissolved in the additional solvent at high concentrations.
    Preferably, the gradual introduction of a charge corresponding to a fructose syrup or a fructose and glucose syrup (of the High-Fructose-Corn-Syrup type according to the English name) via a pump is Implementation. Said introduction can be carried out in one or more times, sequentially or else continuously, as long as the instantaneous fructose concentration is maintained less than or equal to 5.0% by weight.
    Additional solvent
    In a second particular embodiment, the method also comprises the use of at least one additional solvent chosen from aprotic or practical polar solvents. Preferably, said additional solvent is chosen from butan-2-one, acetone, acetic anhydride, Ν, Ν, Ν ', Ν'-tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone, propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, / V, / V-dimethylforrnarnide, N, N-dimethylacetamide, suifolane, / V-methylpyrrolidone, dimethylsulfoxide, propylene carbonate, γ-valerolactone, water , methanol, ethanol, formic acid and acetic acid.
    Preferably, the additional solvent chosen from aprotic or practical polar solvents is acetone, hexamethylphosphoramide, / V, / V-dimethylforrnamide, suifolane, / V-methylpyrrolidone, dimethylsulfoxide, propylene carbonate, γ- valerolactone water, methanol and ethanol, preferably from / V, / V-dimethylformamide, suifolane, / V-methylpyrrolidone, dimethyl sulfoxide, water and methanol, and very preferably from additional solvent is chosen from water and dimethylsulfoxide.
    In this second embodiment, the final concentration of 5-HMF cannot exceed the limit of solubility of the sugar in the additional solvent, affected by the molar mass ratio between fructose and 5-HMF, and affected by the dilution of the charge by mass of aprotic polar solvent.
    In a third embodiment, the additional solvent used corresponds to all or to a fraction of the reaction mixture. In this case, the additional solvent therefore contains at least the polar aprotic solvent, at least one dehydration catalyst used in the process, and optionally at least a fraction of unconverted filler 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.
    In a continuous implementation of the process according to the invention, the hourly mass speed (mass charge flow rate / mass of catalysts) is between 0.01 h "1 and 5.0 h" 1 and preferably between 0, 02 hrs 1 and 2.0 hrs 1.
    Whatever the implementation of the process, the water contained in the reaction mixture is preferably removed, by any method known to those skilled in the art, preferably continuously, in order to maintain a water content. less than 30.0% by weight relative to the total mass of solvent, preferably less than 20.0% by weight, preferably less than 15.0% by weight, and very preferably less than 10.0% by weight.
    Advantageously, the implementation of the process for producing 5-HMF, in particular by controlling the instantaneous concentration, makes it possible to obtain good conversion of the committed fructose, as well as excellent selectivity in favor of 5-HMF and to improve productivity in 5-HMF.
    Thus, the selectivity, yield and productivity obtained by implementing the method according to the invention make it possible, for example, to reach final mass concentrations of 5-HMF greater than 3.5% by weight. The process according to the invention advantageously makes it possible to reach final mass concentrations of 5-HMF greater than 5.0% by weight, preferably greater than 10% by weight, and very preferably greater than 15% by weight.
    The products obtained and their mode of analysis
    The product obtained selectively by the transformation process according to the invention is 5-hydroxymethylfurfural (5-HMF). At the end of the reaction implemented 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 liquid chromatography for determine the conversion of the load in the presence of an external standard and to quantify the unwanted products such as levulinic acid, formic acid and any co-product containing sugars. The humines are quantified by difference in carbon balance with the carbon initially introduced.
    EXAMPLES
    In the examples below, the fructose used as filler is commercial and used without further purification. Hydrochloric acid is used in the form of a 1.0 M (mol / L) concentrated commercial solution in diethyl ether. Methanesulfonic acid, noted AMS in the examples, is commercially available and used without further purification.
    Dimethyl sulfoxide, denoted DMSO in the examples, used as aprotic polar solvent, is commercially available and used without further purification.
    In the examples below, the rate of conversion of fructose to 5-HMF is total. The announced 5-HMF selectivity can therefore be compared to the yield of the transformation process.
    Example 1 (non-compliant) Conversion of fructose into 5-HMF in the presence of hydrochloric acid with ÎFructoseln = 9.0% wt Hydrochloric acid (1.0 M in Et2O) (200 μΙ equivalent to 0.007 g, 0, 19 mmol) is added to a solution of fructose (2.0 g, 11.10 mmol) in DMSO (20.0 g). The initial fructose concentration is 9.0% by weight. The solvent / catalyst mass ratio is 2857. The reaction medium is stirred at 70 ° C. for 12 h. The conversion of fructose to 5-HMF is followed by regular samples of an aliquot of solution which is instantly cooled to 0 ° C, dissolved in water and checked by liquid chromatography. The selectivity for 5-HMF after 12 h is 90.0%. The mass concentration of 5-HMF in DMSO at the end of the reaction is 5.7% by weight. The yield of unwanted humines is 5.0%. The associated productivity is 41.6 mmol / kg / h.
    Example 2 (non-compliant) Conversion of fructose into 5-HMF in the presence of hydrochloric acid with ÎFructoseln = 30.0% wt Hydrochloric acid (1.0 M in Et2O) (200 μΙ equivalent to 0.007 g, 0, 19 mmol) is added to a solution of fructose (8.6 g, 47.73 mmol) in DMSO (20.0 g). The initial fructose concentration is 30.0% wt. The solvent / catalyst mass ratio is 2857. The reaction medium is stirred at 70 ° C. for 24 h. The conversion of fructose to 5-HMF is obtained by taking an aliquot of solution at the end of the test which is instantly cooled to 0 ° C, dissolved in water and checked by liquid chromatography. The selectivity for 5-HMF after 24 h is 70.0%. The mass concentration of 5-HMF in DMSO at the end of the reaction is 14.7% by weight. The yield of unwanted humines is 25.0%. The associated productivity is 69.6 mmol / kg / h.
    Example 3 (compliant) Conversion of fructose into 5-HMF in the presence of hydrochloric acid with fFructoselinst maintained less than or equal to 1.0% by weight Hydrochloric acid (1.0 M in Et2O) (200 μΙ equivalent to 0.007 g, 0.19 mmol) is added to 5.0 g of DMSO, which constitutes the initial reaction medium. The initial fructose concentration is 0% wt in this medium. The reaction medium is thermostatically controlled at 70 ° C. A syringe containing a 12.0% wt fructose solution in 15.0g of DMSO is added to the initial reaction medium at a rate of 4.0 ml / h for 4 hours. The total solvent / catalyst mass ratio is 2857. At the end of the addition, the reaction medium is maintained at 70 ° C. for an additional 1 hour The instantaneous concentration of fructose in the reaction mixture during the reaction is checked by liquid chromatography and is less than or equal to 1.0% wt. The yield of 5-HMF is obtained by sampling an aliquot of solution at the end of the test which is instantly cooled to 0 ° C., dissolved in water and checked by liquid chromatography. The selectivity for 5-HMF after 5 h is 99.5%. The final concentration of 5-HMF in DMSO at the end of the reaction is 6.7% by weight. The yield of unwanted humines is 0.5%. The associated productivity is 113.4 mmol / kg / h.
    Example 4 (compliant) Conversion of fructose into 5-HMF in the presence of hydrochloric acid with ÎFructoselnst maintained less than or equal to 1.0% wd Hydrochloric acid (1.0 M in Et2O) (670 μΙ equivalent to 0.023 g, 0.64 mmol) is added to 10.0 g of DMSO, which constitutes the initial reaction medium. The initial fructose concentration is 0% wt in this medium. The reaction medium is thermostatically controlled at 70 ° C. A syringe containing a solution of fructose at 32.0% w / w in 140.0 g of DMSO is added to the initial reaction medium at a rate of 8.0 ml / h for 16 hours. The total solvent / catalyst mass ratio is 6521. At the end of the addition, the reaction medium is maintained at 70 ° C. for 2 additional hours. The instantaneous fructose concentration in the reaction mixture during the reaction is checked by liquid chromatography and is less than or equal to 1.0% by weight. The yield of 5-HMF is obtained by taking an aliquot of solution at the end of the test which is instantly cooled to 0 ° C., dissolved in water and checked by liquid chromatography. The selectivity for 5-HMF after 18 h is 99.0%. The mass concentration of 5-HMF in DMSO at the end of the reaction is 21.0% by weight. The yield of unwanted humines is 1.0%. The associated productivity is 134.1 mmol / kg / h.
    Example 5 (non-compliant) Conversion of fructose into 5-HMF in the presence of methanesulfonic acid with ÎFructoseln = 9.0% wt. Methanesulfonic acid (0.018 g, 0.19 mmol) is added to a solution of fructose (2 , 0 g, 11.10 mmol) in DMSO (20.0 g). The initial fructose concentration is 9.0% by weight. The solvent / catalyst mass ratio is 1111. The reaction medium is stirred at 70 ° C for 12 h. The conversion of fructose to 5-HMF is followed by regular samples of an aliquot of solution which is instantly cooled to 0 ° C, dissolved in water and checked by liquid chromatography. The selectivity for 5-HMF after 12 h is 74.0%. The final concentration of 5-HMF in DMSO at the end of the reaction is 4.7% by weight. The yield of unwanted humines is 10.0%. The associated productivity is 34.2 mmol / kg / h.
    Example 6 (compliant) Conversion of fructose to 5-HMF in the presence of methanesulfonic acid with Î ± structosehmaintene less than or equal to 1.0% wt. Methanesulfonic acid (0.018 g, 0.19 mmol) is added to 5.0 g of DMSO, which constitutes the initial reaction medium. The initial fructose concentration is 0% wt in this medium. The reaction medium is thermostatically controlled at 70 ° C. A syringe now containing a 12.0% wt fructose solution in 15.0 g of DMSO is added to the initial reaction medium at a rate of 4.0 ml / h for 4 hours. The total solvent / catalyst mass ratio is 1111. At the end of the addition, the reaction medium is maintained at 70 ° C. for an additional 1 hour. The instantaneous fructose concentration in the reaction mixture during the reaction is checked by liquid chromatography and is less than or equal to 1.0% by weight. The yield of 5-HMF is obtained by taking an aliquot of solution at the end of the test which is instantly cooled to 0 ° C., dissolved in water and checked by liquid chromatography. The selectivity for 5-HMF after 5 h is 88.0%. The final concentration of 5-HMF in DMSO at the end of the reaction is 5.6% by weight. The yield of unwanted humines is 3.0%. The associated productivity is 100.3 mmol / kg / h.
    The selectivity for 5-HMF is greater in the case of maintaining the instantaneous fructose concentration of less than 5.0% by weight and in particular in the examples less than 1.0% by weight.
    The final mass concentration of 5-HMF accessible by the process according to the invention is greater in the case of maintaining the instantaneous fructose concentration of less than 5.0% by weight and in particular in the examples less than 1.0% by weight.
    The yield of unwanted products such as humines is lower in the case of maintaining the instantaneous fructose concentration of less than 5.0% by weight and in particular in the examples less than 1.0% by weight.
    The productivity of 5-HMF expressed in mmoles of 5-HMF produced per kg of solvent and per hour (mmol / kg / h) is higher in the case of maintaining the instantaneous fructose concentration of less than 5.0% by weight and in particular in the examples less than 1.0% wt. It therefore unexpectedly appears that it is clearly advantageous to maintain the instantaneous fructose concentration in accordance with the invention in order to achieve very good selectivities, high mass concentrations of 5-HMF, higher productivities and low yields of non- desired for the transformation of sugars into 5-HMF compared to a transformation where the instantaneous fructose concentration is not controlled.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. A process for the production of 5-hydroxymethylfurfural comprising bringing into contact at least one polar aprotic solvent with at least one saccharide filler containing fructose with at least one dehydration catalyst chosen from Bransted acids and Lewis acids, homogeneous or heterogeneous, organic or inorganic, the said process being carried out at a temperature between 30 and 175 ° C and at a pressure between 0.0001 MPa and 8.0 MPa, in which the instantaneous fructose concentration is lower or equal to 5.0% wt.
    [2" id="c-fr-0002]
    2. Method according to claim 1 wherein the instantaneous fructose concentration is between 0.001 and 4.0% by weight.
    [3" id="c-fr-0003]
    3. Method according to any one of the preceding claims wherein the maintenance of the instantaneous fructose concentration is obtained by the sequential or continuous introduction of the charge.
    [4" id="c-fr-0004]
    4. Method according to claim 3 wherein the filler is introduced in liquid form in the presence of an additional solvent chosen from butan-2-one, acetone, acetic anhydride, Λ /, Λ /, Λ / ', Λ /' - tetramethylurea, benzonitrile, acetonitrile, methyl ethyl ketone, propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, NN-dimethylformamide, N, N-dimethylacetamide, sulfolane, W-methylpyrrolidone , dimethylsulfoxide, propylene carbonate, γ-valerolactone, water, methanol, ethanol, formic acid, and acetic acid.
    [5" id="c-fr-0005]
    5. Process according to claim 3, in which the charge is introduced in liquid form in the presence of an additional solvent corresponding to a fraction or all of the reaction mixture.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, in which the temperature is between 40 and 150 Ό.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, in which the saccharide charge comprises fructose in monomeric, oligomeric or polymeric form.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, in which the filler is chosen from fructose, sucrose, kestose, fructans, oligofructanes, inulin.
    [9" id="c-fr-0009]
    9. Method according to any one of the preceding claims, in which the filler is introduced in a solvent / filler mass ratio of between 0.1 and 200.
    [10" id="c-fr-0010]
    10. Method according to any one of the preceding claims, in which the polar aprotic solvent is chosen from butan-2-one, acetone, acetic anhydride, Ν, Ν, Ν ', Ν-tetramethylurea, benzonitrile. , acetonitrile, methyl ethyl ketone, propionitrile, hexamethylphosphoramide, nitrobenzene, nitromethane, Λ /, / V-dimethylformamide, N, N-dimethylacetamide, suifolane, W-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate and γ-valerolactone.
    [11" id="c-fr-0011]
    11. A method according to any one of the preceding claims wherein the aprotic polar solvent is dimethyl sulfoxide.
    [12" id="c-fr-0012]
    12. Method according to any one of the preceding claims, in which the homogeneous organic acid Bronsted catalysts are chosen from organic acids of general formulas R'COOH, R'SO2H, R'SO3H, (R'SO2) NH, (R 'O) 2PO2H, R'OH, in which R' is chosen from alkyl groups, 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 a halide of 'alkyl, • 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 , • heteroaryl , preferably comprising between 4 and 15 carbon atoms, whether or not substituted by a substituent chosen from a hydroxyl, an amine, a nitro, an oxo, a halogen, preferably fluorine and an alkyl halide.
    [13" id="c-fr-0013]
    13. Method according to any one of the preceding claims, in which the homogeneous inorganic Bronsted catalysts are chosen from HF, HCl, HBr, Hl, H2SO3, H2SO4, H3PO2, H3PO4, HNO2, HNO3, H2WO4, H4SîW12O4O, H3PW12O40i (NH4) 6 (W12O40) .xH2O, H4SiMo12O40, H3PMo1204o, (ΝΗ4) 6ΜθγΟ24.χΗ2Ο, H2MoO4, HReO4, H2CrO4, H2SnO3, H4SiO4, H3BO3, HCI04, HBF4, HSbF3 H2FP, HFF2, HP6 HIO3.
    [14" id="c-fr-0014]
    14. Method according to any one of the preceding claims, in which the dehydration catalyst or catalysts are introduced in a solvent / catalyst mass ratio (s) of between 20 and 10,000, in which the mass of solvent corresponds to the total mass of solvent implemented in the process.
    [15" id="c-fr-0015]
    15. Method according to any one of the preceding claims, in which at least two dehydration catalysts are used and in which at least one of the catalysts is a chlorinated catalyst.
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    同族专利:
    公开号 | 公开日
    CN111770916A|2020-10-13|
    US11261168B2|2022-03-01|
    BR112020012936A2|2020-12-01|
    FR3076554B1|2020-09-18|
    WO2019137810A1|2019-07-18|
    JP2021510371A|2021-04-22|
    US20210053930A1|2021-02-25|
    EP3737674A1|2020-11-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4590283A|1983-09-14|1986-05-20|Roquette Freres|Process for manufacturing 5-hydroxymethylfurfural|
    WO2017016924A1|2015-07-24|2017-02-02|IFP Energies Nouvelles|Method for producing 5-furfural in the presence of organic catalysts of the thiourea family|FR3097547A1|2019-06-24|2020-12-25|IFP Energies Nouvelles|5-HYDROXYMETHYLFURFURAL PRODUCTION PROCESS|FR2669635B1|1990-11-22|1994-06-10|Furchim|PROCESS FOR THE MANUFACTURE OF HIGH PURITY HYDROXYMETHYLFURFURAL .|
    FR3043081B1|2015-11-02|2017-12-08|Ifp Energies Now|PROCESS FOR THE PRODUCTION OF 5-HYDROXYMETHYLFURFURAL IN THE PRESENCE OF A LEWIS ACID CATALYST AND / OR A HETEROGENEOUS BASED CATALYST AND A BROMESTED ACIDIC HOMOGENEOUS ORGANIC CATALYST IN THE PRESENCE OF AT LEAST ONE APROTIC POLAR SOLVENT|
    FR3043082B1|2015-11-02|2019-07-26|IFP Energies Nouvelles|PROCESS FOR THE PRODUCTION OF 5-HYDROXYMETHYLFURFURAL IN THE PRESENCE OF HOMOGENEOUS SULFONIC ACID FAMILY CATALYSTS IN THE PRESENCE OF AT LEAST ONE APROTIC POLAR SOLVENT|
    DE102016224073A1|2016-12-02|2018-06-07|Südzucker AG|Improved HMF manufacturing process|FR3109778A1|2020-04-29|2021-11-05|IFP Energies Nouvelles|5-HYDROXYMETHYLFURFURAL OXIDATION PROCESS|
    法律状态:
    2019-01-21| PLFP| Fee payment|Year of fee payment: 2 |
    2019-07-12| PLSC| Publication of the preliminary search report|Effective date: 20190712 |
    2020-01-28| PLFP| Fee payment|Year of fee payment: 3 |
    2021-01-27| PLFP| Fee payment|Year of fee payment: 4 |
    2022-01-26| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1850210A|FR3076554B1|2018-01-10|2018-01-10|5-HYDROXYMETHYLFURFURAL PRODUCTION PROCESS|
    FR1850210|2018-01-10|FR1850210A| FR3076554B1|2018-01-10|2018-01-10|5-HYDROXYMETHYLFURFURAL PRODUCTION PROCESS|
    EP18836825.2A| EP3737674A1|2018-01-10|2018-12-21|Process for synthesizing 5-hydroxymethylfurfural|
    BR112020012936-4A| BR112020012936A2|2018-01-10|2018-12-21|production process of 5-hydroxymethylfurfural|
    PCT/EP2018/086707| WO2019137810A1|2018-01-10|2018-12-21|Process for synthesizing 5-hydroxymethylfurfural|
    US16/961,184| US11261168B2|2018-01-10|2018-12-21|Process for synthesizing 5-hydroxymethylfurfural|
    CN201880086143.5A| CN111770916A|2018-01-10|2018-12-21|Method for synthesizing 5-hydroxymethylfurfural|
    JP2020537741A| JP2021510371A|2018-01-10|2018-12-21|5-Hydroxymethylfurfural synthesis process|
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