FR2663933A1 - New process for the preparation of 5-hydroxymethylfurfural from saccharides - Google Patents

New process for the preparation of 5-hydroxymethylfurfural from saccharides Download PDF

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FR2663933A1
FR2663933A1 FR9008065A FR9008065A FR2663933A1 FR 2663933 A1 FR2663933 A1 FR 2663933A1 FR 9008065 A FR9008065 A FR 9008065A FR 9008065 A FR9008065 A FR 9008065A FR 2663933 A1 FR2663933 A1 FR 2663933A1
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hmf
saccharide
salt
acid
fructose
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FR2663933B1 (en
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Neyret Claire
Cottier Louis
Nigay Henri
Descotes Gerard
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Beghin Say SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/126—Microwaves
    • 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
    • C07D307/50—Preparation from natural products

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Saccharide Compounds (AREA)

Abstract

Process for the preparation of pure 5-hydroxymethylfurfural (HMF) by thermal degradation of a saccharide in substantially anhydrous medium or in aqueous medium, in the presence of an acid catalyst, characterised in that the said acid catalyst is composed of a mixture of a first salt of an inorganic or organic acid with a second salt of an inorganic or organic acid of stronger acidity.

Description

NOUVEAU PROCEDE DE PREPARATION DU 5-HYDROXYMETHYLFURFURAL
A PARTIR DE SACCHARIDES
La présente invention concerne un nouveau procédé de préparation du 5-hydroxyméthylfurfural (HMF) à partir de saccharides, en particulier d'hexoses ou de leurs précurseurs, et plus particulièrement la synthèse de HMF de pureté élevée.NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL
FROM SACCHARIDES
The present invention relates to a new process for the preparation of 5-hydroxymethylfurfural (HMF) from saccharides, in particular hexoses or their precursors, and more particularly the synthesis of HMF of high purity.

De nombreux procédés de synthèse du HMF à partir d'hexoses ont été décrits dans la littérature. La synthèse du HMF en milieu aqueux, par thermolyse entre 100 et 1800C d'hexoses avec des acides organiques ou minéraux a été décrite par W. R. HAWORTH et al., J. Many methods for synthesizing HMF from hexoses have been described in the literature. The synthesis of HMF in aqueous medium, by thermolysis between 100 and 1800C of hexoses with organic or mineral acids has been described by W. R. HAWORTH et al., J.

Chem. Soc., 1944, 35, 667 ainsi que dans le DE-A-3601281. Le HMF brut obtenu, avec des rendements de 15 à 33 %, doit être séparé des nombreuses humines formées, par exemple par extraction avec un solvant organique ou bien en utilisant la technique de chromatographie échangeuse dotions. Ce dernier procédé, qui évite l'emploi de solvants organiques, requiert cependant un appareillage lourd. De plus, la formation importante d'humines nécessite plusieurs purifications successives avant d'obtenir le HMF recherché pur.Chem. Soc., 1944, 35, 667 as well as in DE-A-3601281. The crude HMF obtained, with yields of 15 to 33%, must be separated from the numerous humines formed, for example by extraction with an organic solvent or else by using the dotation exchange chromatography technique. The latter process, which avoids the use of organic solvents, however requires heavy equipment. In addition, the significant formation of humines requires several successive purifications before obtaining the desired pure HMF.

L'emploi de milieux de synthèse biphasiques, avec des solvants tels le polyéthylène glycol, le diméthylsulfoxyde ou le 1,4-dioxane permet d'augmenter la sélectivité de transformation des saccharides en HMF. Cependant les proportions importantes de solvant nécessaires rendent les procédés utilisant de tels milieux peu intéressants industriellement. The use of two-phase synthesis media with solvents such as polyethylene glycol, dimethylsulfoxide or 1,4-dioxane makes it possible to increase the selectivity of transformation of saccharides into HMF. However, the large proportions of solvent necessary make the processes using such media of little interest industrially.

On connait également un procédé de synthèse du HMF ne nécessitant aucun solvant par dégradation de fructose en présence de sels d'ammonium (C. Fayet et al, Carbohydr. Res., 1983, 122, 59). Toutefois les proportions élevées nécessaires de ces sels, ainsi que leur coût et leur toxicité, limitent leur utilisation. There is also known a process for the synthesis of HMF requiring no solvent by degradation of fructose in the presence of ammonium salts (C. Fayet et al, Carbohydr. Res., 1983, 122, 59). However, the high proportions necessary for these salts, as well as their cost and their toxicity, limit their use.

Il existe donc un besoin industriel de disposer d'un procédé de préparation de HMF pur, simple, économique et ne conduisant pas à des problèmes liés à la toxicité des produits utilisés. There is therefore an industrial need to have a process for preparing pure HMF, simple, economical and not leading to problems linked to the toxicity of the products used.

La présente invention répond à un tel objet et fournit un procédé de préparation de 5-hydroxyméthylfurfural (HMF) pur par dégradation thermique d'un saccharide en milieu sensiblement anhydre ou en milieu aqueux, en présence d'un catalyseur acide, caractérisé en ce que ledit catalyseur acide est composé d'un mélange d'un premier sel d'acide minéral ou organique avec un second sel d'acide minéral ou organique d'acidité plus forte. The present invention fulfills such an object and provides a process for the preparation of pure 5-hydroxymethylfurfural (HMF) by thermal degradation of a saccharide in a substantially anhydrous medium or in an aqueous medium, in the presence of an acid catalyst, characterized in that said acid catalyst is composed of a mixture of a first mineral or organic acid salt with a second mineral or organic acid salt of higher acidity.

Ledit premier sel est par exemple choisi parmi les mono- et polyphosphates, les métaphosphates et les monocitrates de sodium, potassium ou calcium et ledit second sel est par exemple un sulfate acide, tel le sulfate acide de potassium. Said first salt is for example chosen from mono- and polyphosphates, metaphosphates and monocitrates of sodium, potassium or calcium and said second salt is for example an acid sulfate, such as potassium acid sulfate.

Le rapport molaire dudit premier sel d'acide et dudit second sel d'acide est compris dans l'intervalle d'environ 0,3 à 1 de préférence de 0,7 à 0,9. The molar ratio of said first acid salt and said second acid salt is in the range of about 0.3 to 1, preferably 0.7 to 0.9.

Le rapport molaire de chacun desdits sels dudit catalyseur acide audit saccharide de départ est compris dans l'intervalle d'environ 0,15 à 1, de préférence, de 0,6 à 0,8. The molar ratio of each of said salts of said acid catalyst to said starting saccharide is in the range of about 0.15 to 1, preferably 0.6 to 0.8.

Ledit saccharide de départ est choisi parmi les hexoses et leurs précurseurs tels fructosides courants comme le fructose et les sirops de fructose, le saccharose, l'inuline, etc. Said starting saccharide is chosen from hexoses and their precursors such as common fructosides such as fructose and fructose syrups, sucrose, inulin, etc.

Selon un mode de réalisation de l'invention, ladite dégradation thermique dudit saccharide est effectué par chauffage à une température comprise entre environ 100 et 1800C, de préférence entre 120 et 1500C, pendant une durée d'environ 5 à 60 mn, de préférence 10 à 40 mn. According to one embodiment of the invention, said thermal degradation of said saccharide is carried out by heating to a temperature of between approximately 100 and 1800C, preferably between 120 and 1500C, for a period of approximately 5 to 60 min, preferably 10 40 mins.

Le HMF formé peut être obtenu par extraction avec un solvant organique tel l'acétate d'éthyle du milieu réactionnel dilué avec de 11 eau.  The HMF formed can be obtained by extraction with an organic solvent such as ethyl acetate from the reaction medium diluted with water.

Selon un autre mode de réalisation avantageux, la présente invention fournit un procédé de préparation de HMF pur par dégradation thermique d'un saccharide en milieu sensiblement anhydre ou aqueux caractérisé par le fait que le HMF est séparé du milieu réactionnel au cours de sa formation par entraînement à la vapeur surchauffée au-dessus de 1000C, les condensats obtenus étant concentrés sous pression réduite. According to another advantageous embodiment, the present invention provides a process for the preparation of pure HMF by thermal degradation of a saccharide in a substantially anhydrous or aqueous medium, characterized in that the HMF is separated from the reaction medium during its formation by entrainment in superheated steam above 1000C, the condensates obtained being concentrated under reduced pressure.

Ladite vapeur surchauffée est à une température dans l'intervalle d'environ 130 à 180 C.  Said superheated steam is at a temperature in the range of about 130 to 180 C.

La concentration des condensats résultants sous pression réduite permet d'obtenir directement le HMF pur, sous forme cristallisée.  The concentration of the resulting condensates under reduced pressure makes it possible to directly obtain pure HMF, in crystallized form.

Le mélange réactionnel aqueux obtenu après extraction à la vapeur du HMF peut être réutilisé directement pour la synthèse de ce composé. The aqueous reaction mixture obtained after steam extraction of the HMF can be reused directly for the synthesis of this compound.

On peut également régénérer certains des sels minéraux du catalyseur en fin de réaction. La faible solubilité des sels minéraux dans l'eau permet par exemple de séparer ces sels des polysaccharides sous-produits par simple filtration du résidu aqueux en fin de réaction. It is also possible to regenerate some of the mineral salts of the catalyst at the end of the reaction. The low solubility of mineral salts in water makes it possible, for example, to separate these salts from the by-product polysaccharides by simple filtration of the aqueous residue at the end of the reaction.

Selon un autre mode de réalisation de la présente invention, le mélange réactionnel de départ contenant ledit saccharide et ledit catalyseur est chauffé par irradiation par microondes. According to another embodiment of the present invention, the starting reaction mixture containing said saccharide and said catalyst is heated by microwave irradiation.

Le HMF est alors obtenu sous forme cristallisé après neutralisation de la solution aqueuse résultante par un sel de calcium ou de magnésium, extraction par solvant organique, tel l'acétate d'éthyle, et concentration. The HMF is then obtained in crystallized form after neutralization of the resulting aqueous solution with a calcium or magnesium salt, extraction with organic solvent, such as ethyl acetate, and concentration.

Le procédé de l'invention permet l'obtention de HMF de grande pureté de façon simple et économique, sans utilisation de solvants toxiques, avec des rendements pouvant atteindre 33 % par rapport au saccharide de départ. The process of the invention makes it possible to obtain high purity HMFs in a simple and economical manner, without the use of toxic solvents, with yields up to 33% relative to the starting saccharide.

Les Exemples suivants illustrent l'invention sans la limiter. The following Examples illustrate the invention without limiting it.

Exemple 1
A partir de 1 kg (5,55 mole) de fructose dans 100 ml d'eau, de 585 g (3,75 moles) de monophosphate de sodium dihydraté et de 575 g (4,22 moles) de sulfate acide de potassium, on obtient après 15 mn à 1300C et arrêt par 750 ml d'eau, une solution aqueuse de i400 ml, contenant 235 g de HMF d'après les analyses H.P.L.C. et U.V.Example 1
From 1 kg (5.55 mole) of fructose in 100 ml of water, 585 g (3.75 moles) of sodium monophosphate dihydrate and 575 g (4.22 moles) of potassium acid sulfate, after 15 min at 1300 ° C. and stopping with 750 ml of water, an i400 ml aqueous solution containing 235 g of HMF is obtained according to HPLC and UV analyzes

Rendement brut en HMF = 33 %. 30 ml de cette solution sont dilués avec 70 ml d'eau puis filtrés sur verre fritté. L'extraction avec de l'acétate d'éthyle (50 ml) de 40 ml de cette nouvelle solution donne après séchage et évaporation 1,68 g de HMF. La solution aqueuse de 1400 ml contient ainsi 197 g de HMF, soit un rendement après extraction par un solvant organique de 28 %.Gross HMF yield = 33%. 30 ml of this solution are diluted with 70 ml of water and then filtered through a sintered glass. The extraction with ethyl acetate (50 ml) of 40 ml of this new solution gives, after drying and evaporation, 1.68 g of HMF. The 1400 ml aqueous solution thus contains 197 g of HMF, ie a yield after extraction with an organic solvent of 28%.

Exemple 2
Un mélange contenant 10 g (0,055 mole) de fructose, 4,5 g (0,04 mole) de monophosphate de sodium et 5,7 g (0,041 mole) de sulfate acide de potassium est porté à 1300C en 10 mn, puis la vapeur surchauffée à 1450C est introduite dans le milieu pendant 60 mn. Example 2
A mixture containing 10 g (0.055 mole) of fructose, 4.5 g (0.04 mole) of sodium monophosphate and 5.7 g (0.041 mole) of potassium acid sulfate is brought to 1300C in 10 min, then the steam superheated to 1450C is introduced into the medium for 60 min.

Après arrêt de la réaction, les condensats récupérés (300 ml) sont concentrés sous pression réduite pour donner 1,33 g de HMF, solide jaune pale. After stopping the reaction, the condensates recovered (300 ml) are concentrated under reduced pressure to give 1.33 g of HMF, a pale yellow solid.

Le résidu de polysaccharides et de sels minéraux, après dilution avec 100 ml d'eau, est extrait avec de l'acétate d'éthyle pour donner 0,49 g de HMF. The residue of polysaccharides and mineral salts, after dilution with 100 ml of water, is extracted with ethyl acetate to give 0.49 g of HMF.

Rendement global obtenu en HMF pur : 26 %. Overall yield obtained in pure HMF: 26%.

Rendement de l'extraction par entraînement à la vapeur : 73 %. Efficiency of extraction by steam entrainment: 73%.

Exemple 3
La solution aqueuse extraite avec l'acétate d'éthyle selon l'Exemple 2 est concentrée sous pression réduite, puis portée à 1200C avec 10 g de fructose pendant 20 mn, reprise par de l'eau, et extraite avec l'acétate d'éthyle pour donner 0,98 g de HMF.Example 3
The aqueous solution extracted with ethyl acetate according to Example 2 is concentrated under reduced pressure, then brought to 1200C with 10 g of fructose for 20 min, taken up in water, and extracted with acetate. ethyl to give 0.98 g of HMF.

Rendement en HMF pur : 14 %. Yield in pure HMF: 14%.

Rendement en HMF en tenant compte du recyclage des catalyseurs : 20 % à partir de 20 g de fructose, on obtient 2,8 g de HMF pur). HMF yield taking into account the recycling of the catalysts: 20% from 20 g of fructose, 2.8 g of pure HMF are obtained).

Exemple 4
Un mélange contenant 15 g (0,044 mole) de saccharose, 3,6 g (0,03 mole) de monophosphate de sodium, 4,5 g (0,03 mole) de sulfate acide de potassium est porté à 1300C en 15 mn, repris par 100 ml d'eau, filtré et extrait avec l'acétate d'éthyle pour donner 1,3 g de HMF.Example 4
A mixture containing 15 g (0.044 mole) of sucrose, 3.6 g (0.03 mole) of sodium monophosphate, 4.5 g (0.03 mole) of potassium acid sulfate is brought to 1300C in 15 min, taken up in 100 ml of water, filtered and extracted with ethyl acetate to give 1.3 g of HMF.

Rendement en HMF par rapport au fructose : 24 % et par rapport au saccharose : 12 %. HMF yield compared to fructose: 24% and compared to sucrose: 12%.

Exemple 5
Un mélange contenant 15 g (0,044 mole) de saccharose, 3,4 g (0,029 mole) de monophosphate de sodium et 4,5 g (0,033 mole) de sulfate acide de potassium est porté en 17 mn à 130 C, puis la vapeur surchauffée à 1600C est introduite dans le milieu pendant 60 mn. Après arrêt de la réaction, les condensats récupérés (300 ml) sont concentrés sous pression réduite pour donner 0,85 g de HMF, solide jaune.Example 5
A mixture containing 15 g (0.044 mole) of sucrose, 3.4 g (0.029 mole) of sodium monophosphate and 4.5 g (0.033 mole) of potassium acid sulfate is brought to 17 ° C. in 17 min, then the steam superheated to 1600C is introduced into the medium for 60 min. After stopping the reaction, the condensates recovered (300 ml) are concentrated under reduced pressure to give 0.85 g of HMF, a yellow solid.

Le résidu non entraîné à la vapeur est repris par 100 ml d'eau, extrait à l'acétate d'éthyle pour donner 0,48 g de HMF. The residue not entrained in the vapor is taken up in 100 ml of water, extracted with ethyl acetate to give 0.48 g of HMF.

Rendement en HMF pur par rapport au fructose : 24 %, par rapport au saccharose : 12 %. Yield in pure HMF relative to fructose: 24%, relative to sucrose: 12%.

Rendement de l'extraction à la vapeur : 64 %.  Steam extraction yield: 64%.

Exemple 6
Un mélange contenant 20 g (0,011 mole) de fructose, 9,1 g (0,076 mole) de monophosphate de sodium, 11,5 g (ost84 mole) de sulfate acide de potassium dans 10 ml d'eau, est soumis à une irradiation microondes de fréquence 2450 MHz, avec 77 % de la puissance totale de 500 W, soit des impulsions de 23 secondes toutes les 30 secondes.Example 6
A mixture containing 20 g (0.011 mole) of fructose, 9.1 g (0.076 mole) of sodium monophosphate, 11.5 g (ost84 mole) of potassium acid sulfate in 10 ml of water is subjected to irradiation 2450 MHz frequency microwaves, with 77% of the total power of 500 W, i.e. pulses of 23 seconds every 30 seconds.

Après un temps total de 186 secondes et arrêt de la réaction par traitement avec 200 ml d'eau, on obtient une solution aqueuse contenant 4,6 g de HMF. After a total time of 186 seconds and stopping the reaction by treatment with 200 ml of water, an aqueous solution containing 4.6 g of HMF is obtained.

Rendement brut : 33 %. Gross yield: 33%.

Exemple 7
Un mélange contenant 20 g (0,058 mole) de saccharose, 4,7 g (0,040 mole) de monophosphate de sodium, 6 g (0,044 mole) de sulfate acide de potassium dans 10 ml d'eau est soumis à la même irradiation que dans l'Exemple 6, dans les mêmes conditions.Example 7
A mixture containing 20 g (0.058 mole) of sucrose, 4.7 g (0.040 mole) of sodium monophosphate, 6 g (0.044 mole) of potassium acid sulfate in 10 ml of water is subjected to the same irradiation as in Example 6, under the same conditions.

Après un temps total de 145 secondes, et arrêt par 200 ml d'eau, on obtient une solution aqueuse contenant 2,51 g de HMF d'après les analyses U.V. et H.P.L.C. After a total time of 145 seconds, and stopping with 200 ml of water, an aqueous solution containing 2.51 g of HMF is obtained according to the U.V. and H.P.L.C. analyzes.

Rendement brut par rapport au fructose : 34 %, et par rapport au saccharose : 17 %. Crude yield compared to fructose: 34%, and compared to sucrose: 17%.

La solution est neutralisée à pH = 5 par du carbonate de calcium, filtrée et extraite à l'acétate d'éthyle, pour donner le produit pur (2,06 g). The solution is neutralized to pH = 5 with calcium carbonate, filtered and extracted with ethyl acetate, to give the pure product (2.06 g).

Rendement en HMF après purification par rapport au fructose 28 a, et par rapport au saccharose : 14 %.  Yield in HMF after purification with respect to fructose 28 a, and with respect to sucrose: 14%.

Claims (9)

REVENDICATIONS 1. Procédé de préparation de 5-hydroxyméthylfurfural (HMF) pur par dégradation thermique d'un saccharide en milieu sensiblement anhydre ou en milieu aqueux, en présence d'un catalyseur acide, caractérisé en ce que ledit catalyseur acide est composé d'un mélange d'un premier sel d'acide minéral ou organique avec un second sel d'acide minéral ou organique d'acidité plus forte. 1. Process for the preparation of pure 5-hydroxymethylfurfural (HMF) by thermal degradation of a saccharide in a substantially anhydrous medium or in an aqueous medium, in the presence of an acid catalyst, characterized in that said acid catalyst is composed of a mixture a first mineral or organic acid salt with a second mineral or organic acid salt of higher acidity. 2. Procédé selon la revendication 1 dans lequel ledit premier sel est choisi parmi les mono- et polyphosphates, les métaphosphates et les monocitrates de sodium, potassium ou calcium. 2. Method according to claim 1 wherein said first salt is chosen from mono- and polyphosphates, metaphosphates and monocitrates of sodium, potassium or calcium. 3. Procédé selon l'une quelconque des revendications 1 et 2 dans lequel ledit second sel est un sulfate acide, tel le sulfate acide de potassium. 3. Method according to any one of claims 1 and 2 wherein said second salt is an acid sulfate, such as potassium acid sulfate. 4. Procédé selon l'une quelconque des revendications 1 à 3 dans lequel le rapport molaire dudit premier sel d'acide et dudit second sel d'acide est compris dans l'intervalle d'environ 0,3 à 1, de préférence de 0,7 à 0,9. 4. Method according to any one of claims 1 to 3 wherein the molar ratio of said first acid salt and said second acid salt is in the range of about 0.3 to 1, preferably 0 , 7 to 0.9. 5. Procédé selon l'une quelconque des revendications 1 à 4 dans lequel le rapport molaire de chacun desdits sels dudit catalyseur acide audit saccharide de départ est compris dans l'intervalle d'environ 0,15 à 1, de préférence, de 0,6 à 0,8. 5. Method according to any one of claims 1 to 4 wherein the molar ratio of each of said salts of said acid catalyst to said starting saccharide is in the range of about 0.15 to 1, preferably 0, 6 to 0.8. 6. Procédé selon l'une quelconque des revendications 1 à 5 dans lequel ladite dégradation thermique dudit saccharide est effectuée par chauffage du milieu réactionnel de départ à une température comprise entre environ 100 et 180 C, de préférence entre 120 et 1500C, pendant une durée d'environ 5 à 60 mn, de préférence 10 à 40 mn. 6. Method according to any one of claims 1 to 5 wherein said thermal degradation of said saccharide is carried out by heating the starting reaction medium at a temperature between about 100 and 180 C, preferably between 120 and 1500C, for a period about 5 to 60 minutes, preferably 10 to 40 minutes. 7. Procédé selon l'une quelconque des revendications 1 à 5 dans lequel ladite dégradation thermique dudit saccharide est effectuée par irradiation par microondes. 7. Method according to any one of claims 1 to 5 wherein said thermal degradation of said saccharide is carried out by microwave irradiation. 8. Procédé selon l'une quelconque des revendications 1 à 7 dans lequel ledit saccharide de départ est choisi parmi les hexoses et leurs précurseurs. 8. Method according to any one of claims 1 to 7 wherein said starting saccharide is chosen from hexoses and their precursors. 9. Procédé selon la revendication 8 dans lequel ledit saccharide est choisi parmi les fructosides courants tels le o-Fructose et les sirops de fructose, le saccharose et l'inuline.  9. The method of claim 8 wherein said saccharide is selected from common fructosides such as o-Fructose and fructose syrups, sucrose and inulin.
FR9008065A 1990-06-27 1990-06-27 NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES. Expired - Fee Related FR2663933B1 (en)

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FR9011479A FR2664273B1 (en) 1990-06-27 1990-09-18 NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES.

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WO1996017837A1 (en) * 1994-12-07 1996-06-13 Agrichimie Method for making hydroxymethylfurfural from aldohexose
WO2000072956A1 (en) * 1999-05-26 2000-12-07 Personal Chemistry I Uppsala Ab Preparation and use of ionic liquids in microwave-assisted chemical transformations
WO2006063220A3 (en) * 2004-12-10 2007-01-11 Archer Daniels Midland Co Preparation of 2,5-(hydr0xymethyl)furaldehyde (hmf) , derivatives thereof and levulinic acid from fructose as well as preparation of 2 , 5-bis- (hydroxymethyl) furan from 2 , 5- (hydroxymethyl) furaldehyde
WO2007146636A1 (en) 2006-06-06 2007-12-21 Wisconsin Alumni Research Foundation Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor
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WO2013087614A1 (en) 2011-12-13 2013-06-20 Basf Se Preparation of 5-hydroxymethylfurfural (hmf) from saccharide solutions in the presence of a solvent having a boiling point greater than 60°c and less than 200°c (at standard pressure, called low boiler for short)
WO2013109477A1 (en) 2012-01-18 2013-07-25 Rennovia, Inc. Process for production of hexamethylenediamine from 5 - hydroxymethylfurfural
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