FR2664273A1 - New process for the preparation of 5-hydroxymethylfurfural from saccharides - Google Patents
New process for the preparation of 5-hydroxymethylfurfural from saccharides Download PDFInfo
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- FR2664273A1 FR2664273A1 FR9011479A FR9011479A FR2664273A1 FR 2664273 A1 FR2664273 A1 FR 2664273A1 FR 9011479 A FR9011479 A FR 9011479A FR 9011479 A FR9011479 A FR 9011479A FR 2664273 A1 FR2664273 A1 FR 2664273A1
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- Prior art keywords
- hmf
- saccharide
- hydroxymethylfurfural
- preparation
- steam
- Prior art date
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 17
- 150000001720 carbohydrates Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- 239000002609 medium Substances 0.000 claims abstract description 5
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 239000003377 acid catalyst Substances 0.000 claims abstract description 3
- 239000011541 reaction mixture Substances 0.000 claims abstract description 3
- 229930091371 Fructose Natural products 0.000 claims description 7
- 239000005715 Fructose Substances 0.000 claims description 7
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 150000002402 hexoses Chemical class 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 229920001202 Inulin Polymers 0.000 claims description 2
- 235000021433 fructose syrup Nutrition 0.000 claims description 2
- 229930182479 fructoside Natural products 0.000 claims description 2
- 150000008132 fructosides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 2
- 229940029339 inulin Drugs 0.000 claims description 2
- 238000001256 steam distillation Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
NOUVEAU PROCEDE DE PREPARATION DU 5-HYDROXYMETHYLFIJRFURAL
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-HYDROXYMETHYLFIJRFURAL
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 180 C d'hexoses avec des acides organiques ou minéraux a été décrite par W. N. 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 180 C of hexoses with organic or mineral acids has been described by W. N. 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 d'ions. 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 using the ion 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, dimethyl sulfoxide 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 dtun 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, 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 100 C, les condensats obtenus étant concentrés sous pression réduite. 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, characterized in that the HMF is separated from the reaction medium during its formation by entrainment with superheated steam above 100 C, the condensates obtained being concentrated under reduced pressure.
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.
La dégradation thermique dudit saccharide est par exemple effectuée par chauffage, en présence d'un catalyseur acide, à une température comprise entre environ 100 et 180 C, de préférence entre 120 et 150 C, pendant une durée d'environ 5 à 60 mn, de préférence 10 à 40 mn. The thermal degradation of said saccharide is for example carried out by heating, in the presence of an acid catalyst, at a temperature of between approximately 100 and 180 ° C., preferably between 120 and 150 ° C., for a period of approximately 5 to 60 min, preferably 10 to 40 min.
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.
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 of 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
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 1
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 pâle. 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, apres 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 2
La solution aqueuse extraite avec l'acétate d'éthyle selon l'Exemple 1 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 2
The aqueous solution extracted with ethyl acetate according to Example 1 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). Yield in HMF taking into account the recycling of the catalysts: 20% from 20 g of fructose, 2.8 g of pure HMF are obtained).
Exemple 3
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 1300C, puis la vapeur surchauffée à 160 C 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 3
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 1700C in 17 min, then the superheated steam at 160 C 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%.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9011479A FR2664273B1 (en) | 1990-06-27 | 1990-09-18 | NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9008065A FR2663933B1 (en) | 1990-06-27 | 1990-06-27 | NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES. |
| FR9011479A FR2664273B1 (en) | 1990-06-27 | 1990-09-18 | NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2664273A1 true FR2664273A1 (en) | 1992-01-10 |
| FR2664273B1 FR2664273B1 (en) | 1994-04-29 |
Family
ID=26228106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR9011479A Expired - Fee Related FR2664273B1 (en) | 1990-06-27 | 1990-09-18 | NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES. |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2664273B1 (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2741344A1 (en) * | 1995-11-20 | 1997-05-23 | Agrichimie Sa | Selective production of hydroxymethyl-furfural |
| 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 |
| US7317116B2 (en) | 2004-12-10 | 2008-01-08 | Archer-Daniels-Midland-Company | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| EP1958944A1 (en) | 2007-02-16 | 2008-08-20 | Evonik Degussa GmbH | Method for producing enantiomer 5-hydroxymethylfurfural with 5-acyloxymethylfurfural as intermediate |
| DE102008009933A1 (en) | 2008-02-18 | 2009-08-20 | Friedrich-Schiller-Universität Jena | Preparing 5-hydroxymethylfurfural, useful e.g. to manufacture pharmaceutical products such as fungicides, comprises thermally reacting carbohydrates in ionic liquid and discharging formed 5-hydroxymethylfurfural using extracting agent |
| WO2010144873A1 (en) | 2009-06-13 | 2010-12-16 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US7880049B2 (en) | 2006-06-06 | 2011-02-01 | Wisconsin Alumni Research Foundation | Production of liquid alkanes in the jet fuel range (C8-C15) from biomass-derived carbohydrates |
| US8324376B2 (en) | 2008-06-17 | 2012-12-04 | Wisconsin Alumni Research Foundation | Chemical transformation of lignocellulosic biomass into fuels and chemicals |
| CN103012335A (en) * | 2012-11-30 | 2013-04-03 | 中国科学院广州能源研究所 | Method for co-producing furfural and 5-hydroxymethylfurfural by using lignocellulose-containing biomass |
| 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 |
| US8669397B2 (en) | 2009-06-13 | 2014-03-11 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US8669393B2 (en) | 2010-03-05 | 2014-03-11 | Rennovia, Inc. | Adipic acid compositions |
| US8722878B2 (en) | 2009-07-01 | 2014-05-13 | Wisconsin Alumni Research Foundation | Biomass hydrolysis |
| US8785683B2 (en) | 2009-06-13 | 2014-07-22 | Rennovia, Inc. | Production of glutaric acid and derivatives from carbohydrate-containing materials |
| EP2813494A1 (en) | 2013-06-12 | 2014-12-17 | Basf Se | Method for the preparation of 5-hydroxymethylfurfural (HMF) |
| US9162998B2 (en) | 2011-12-13 | 2015-10-20 | 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) |
| EP2802570A4 (en) * | 2012-01-10 | 2016-01-06 | Archer Daniels Midland Co | PROCESS FOR THE PREPARATION OF HMF AND HMF DERIVATIVES FROM SUGARS, WITH RECOVERY OF NON-REAGENT SUGARS, SUITABLE FOR DIRECT ETHANOL FERMENTATION |
| US9586920B2 (en) | 2014-12-02 | 2017-03-07 | Rennovia Inc. | Process for production of hexanetriol from 5-hydroxymethylfurfural |
| US9611241B2 (en) | 2014-01-27 | 2017-04-04 | Rennovia Inc. | Conversion of fructose-containing feedstocks to HMF-containing product |
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| US10208006B2 (en) | 2016-01-13 | 2019-02-19 | Stora Enso Oyj | Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof |
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| US2917520A (en) * | 1957-09-11 | 1959-12-15 | Arthur C Cope | Production and recovery of furans |
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| FR1176945A (en) * | 1957-03-12 | 1959-04-17 | Continuous process and equipment for the production of furfuraldehyde | |
| US2917520A (en) * | 1957-09-11 | 1959-12-15 | Arthur C Cope | Production and recovery of furans |
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| FR2664273B1 (en) | 1994-04-29 |
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