WO2016207365A1 - Procédé pour la production en continu de 5-hydroxyméthylfurfural (hmf) dans un système de réacteur - Google Patents

Procédé pour la production en continu de 5-hydroxyméthylfurfural (hmf) dans un système de réacteur Download PDF

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WO2016207365A1
WO2016207365A1 PCT/EP2016/064693 EP2016064693W WO2016207365A1 WO 2016207365 A1 WO2016207365 A1 WO 2016207365A1 EP 2016064693 W EP2016064693 W EP 2016064693W WO 2016207365 A1 WO2016207365 A1 WO 2016207365A1
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hmf
mixture
group
organic salts
hydroxymethylfurfural
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PCT/EP2016/064693
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German (de)
English (en)
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Benoit BLANK
Johannes David HOECKER
Sunghee Son
Alois Kindler
Markus Piepenbrink
René BACKES
Carmen FELDNER
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

Definitions

  • the present invention relates to a process for the continuous production of 5-hydroxymethylfurfural (hereinafter referred to as HMF, compound of formula (I))
  • Adjusting reaction conditions in a mixture G comprising one, two or more educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, one, two or more organic salts with a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa, selected from the group of organic salts with an imidazolium or phosphonium cation,
  • HMF is usually prepared by acid-catalyzed dehydration of hexoses such as glucose or fructose.
  • Typical product mixtures are pH-acidic solutions, which in addition to HMF usually contain unreacted starting materials and / or by-products.
  • ionic liquids (hereinafter also referred to only as "IL") (an ionic liquid in the context of the present invention is one or two organic salts with a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013, 25 hPa) as solvent in the HMF synthesis is particularly advantageous, since high yields of HMF are usually obtained in these solvents Since the dehydration of fructose is usually catalysed by Brönsted acids, it is advantageous to ensure that the Anion of the acid used and the anion of the IL to agree to an additional (and undesirable) to change the composition of the product mixture (by entry of the anion of the acid used) to avoid, especially if the acid (s) used a Have boiling point, which is at least a pressure value in the range of 0, 1 to 500 mbar lower than the boiling point of the 5-Hyd roxymethylfurfurals at the same pressure value.
  • IL ionic liquid in the context of the present invention is one or two organic salts with
  • ionic liquids ionic liquids
  • ionic liquids are typically expensive, so it is desirable to achieve a relatively high mass ratio of fructose (or other reactant compounds) used to IL without lowering HMF selectivity to an undesirable level
  • EP 2 813 494 A1 discloses "a process for the preparation of 5-hydroxymethylfurfural (HMF)" (title), preferably an embodiment of a corresponding process "in which the intermediate mixture or parts to be transferred to the second reactor (fraction) thereof or upon entry into the second reactor are subjected to the conditions of distillationtinct whereby HMF is separated "(see section [0061]). It was a primary object of the present invention to provide an improved process for the continuous production of 5-hydroxymethylfurfural in a reactor assembly which largely satisfies the above-mentioned claims.
  • the object is achieved by an inventive method for the continuous production of 5-hydroxymethylfurfural (HMF) in a reactor arrangement, with the following step:
  • a mixture G comprising one, two or more educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, one, two or more organic salts with a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013,25 hPa selected from the group of organic salts with an imidazolium or phosphonium cation, - water,
  • HMF 5-hydroxymethylfurfural
  • the concentration of the HMF in the reaction mixture is preferably increased at least temporarily (but preferably throughout the reaction period), ie the reaction for forming the HMF predominates at least temporarily (but preferably throughout the entire reaction) Reaction time) in comparison with optionally competing reactions of the HMF to secondary products.
  • a "reactor arrangement" in the context of the present invention collectively designates a single reactor or a number of reactors arranged in parallel and / or in series Particularly preferred is a method according to the invention (as described above, preferably as defined above as preferred), wherein the reactor arrangement consists of a
  • a preferred reactor arrangement is a combination of (i) a stirred tank reactor and a tubular reactor, or (ii) a tubular reactor and a reactor, and / or a plurality of reactors Stirred tank reactor, which are each arranged one after the other (serial arrangement).
  • reaction conditions in a mixture G comprises in particular the reaction parameters (a) reaction temperature, (b) pressure, (c) concentration and quantitative ratios of the substances / compounds present (starting materials, products, catalysts, solvents), in each case based on the mixture G.
  • a "process for the continuous production of 5-hydroxymethylfurfural (HMF)" in the context of the present invention is when a continuous or semi-continuous process is carried out in its entirety so that continuously (ie, for example, regardless of the discontinuous design individual steps of a semi-continuous process) HMF is formed.
  • the period of preparation of HMF is at least 10 times the average residence time of said organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa in the reactor arrangement in a process according to the invention for the continuous preparation of 5-hydroxymethylfurfural (HMF) (as described above, preferably as previously defined as preferred) in a reactor assembly for an uninterrupted period of at least 8 hours, preferably at least 24 hours, producing HMF in the reactor assembly.
  • HMF 5-hydroxymethylfurfural
  • the process according to the invention defines that an amount of one educt compound or at least one of the two or more educt compounds converts to 5-hydroxymethylfurfural (HMF) in the mixture G, the mixture G 5-hydroxymethylfurfural (HMF) already having a concentration in the range of 15% by weight to 35% by weight, based on the total mass of the mixture G.
  • HMF 5-hydroxymethylfurfural
  • HMF 5-hydroxymethylfurfural
  • the selectivity is at least 50%, more preferably at least 70%.
  • the process according to the invention offers various advantages, since it allows recycling of the ionic liquids together with residual amounts of HMF in the production process.
  • Our own investigations have shown that the conversion to HMF at already present comparatively high HMF concentrations (at least 15% by weight, based on a corresponding total mixture) is only possible in combination with the specific ILs mentioned above in the text. Only these ILs stabilize the comparatively high amount of HMF in such a way that degradation and side reactions can be largely avoided. This has the consequence that the mixture that results after the conversion to HMF, not nearly all HMF must be removed by means of separation operations. A common way of separation is a distillation. However, our own investigations have shown that distillation usually always leads to thermal loading of the HMF.
  • the process according to the invention before the step of adjusting the reaction conditions in the mixture G comprises the additional step:
  • One or more acids (as a catalyst (s) for the reaction of the reactant compound or at least one of the two or more reactant compounds to 5-hydroxymethylfurfural (HMF)) selected from the group consisting of homogeneous acids and heterogeneous acids, preferably the Anion or the anions of the one or more acids is identical or are each identical to the anion of or one, two or more organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa, - preferably added to the mixture G of one or more acids (as catalysts) for the reaction of the one educt compound or at least one of the two or more educt compounds to 5-hydroxymethylfurfural (HMF)) selected from the group consisting of sulfuric acid, phosphoric acid , Methanesulfonic acid and p-toluenesulfonic acid, preferably the one or at least one of the plurality of acids is methanesul
  • the mixture G comprises as further substance one or more acids selected from the group consisting of homogeneous acids and heterogeneous acids, wherein preferably the anion or the anions of the one or more acids is identical or in each case identical with the anion of or one, two or more organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa.
  • the mixture G comprises one or more acids selected from the group consisting of sulfuric acid, phosphoric acid, methanesulfonic acid and p-toluenesulfonic acid, more preferably, the one or at least one of the plurality of acids is methanesulfonic acid.
  • the anion or the anions of the one or more acids are identical or are each identical to the anion of the or the one, two or more organic salts with a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa.
  • the mixture G is a solids-free mixture, which preferably comprises a single liquid phase.
  • the total amount of (i) is water and (ii) compounds having a boiling temperature which is at least a pressure in the range of 0, 1 to 500 mbar lower than the boiling point of 5-hydroxymethylfurfural at the same pressure value in the mixture G. at most 10% by weight, based on the total mass of the mixture G.
  • Our own investigations have shown that a total amount of (i) and (ii) of (significantly) greater than 10% by weight regularly leads to an undesired precipitation of water-insoluble impurities (eg water-insoluble humins), in particular if the water content in the total amount of (i) and (ii) is at least 50% by weight, based on the total amount of (i) and (ii).
  • the total amount of (i) and (ii) is at most 5% by weight, based on the total mass of the mixture G.
  • the one, two or more educt compounds comprise one, two or more than two compounds selected from the group consisting of fructose, glucose, oligosaccharides comprising fructose units, oligosaccharides comprising glucose units, polysaccharides comprising fructose units and polysaccharides comprising glucose units, preferably one, two or more than two compounds selected from the group consisting of fructose, oligosaccharides comprising fructose units and polysaccharides comprising fructose units.
  • a process according to the invention is preferred (as described above, preferably as defined above as preferred) wherein the mixture G is directly preparable by (i) respectively preparing or providing (a) one, two or more organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa selected from the group of organic salts with an imidazolium or phosphonium cation and (b) one, two or more educt compounds selected from the group consisting of hexoses, Oligosaccharides comprising hexose units, and polysaccharides comprising hexose units and (c) water and (d) 5-hydroxymethylfurfural (HMF) in a concentration in the range of 15% by weight to 35% by weight, based on the Total mass of the mixture G and (ii) mixing the components (a), (b), (c) and (d).
  • HMF 5-hydroxymethylfurfural
  • the mixture G is preparable by (i) respectively preparing or providing (a) one, two or more organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa selected from the group the organic salts having an imidazolium or phosphonium cation and (b) one, two or more reactant compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units and (ii) reacting an amount of the one Reactant compound or at least one of the two or more starting compounds to 5-hydroxymethylfurfural (HMF), so that the mixture G results, comprising one, two or more educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose Units, one, two or more organic salts with a
  • HMF 5-hydroxymethylfurfural
  • a fructose syrup preferably from a fructose syrup.
  • Such syrups include water.
  • Particularly preferred syrups are fructose syrups whose fructose content is at least 85% by weight, preferably at least 90% by weight, more preferably at least 94% by weight, based in each case on the total mass of the anhydrous syrup.
  • Typical other ingredients of such syrups are comparatively small amounts of other monosaccharides (e.g., glucose, mannose, idose, galactose), hexose oligosaccharides (e.g., maltose), hexose polysaccharides, inorganic salts.
  • monosaccharides e.g., glucose, mannose, idose, galactose
  • hexose oligosaccharides e.g., maltose
  • hexose polysaccharides e.g., inorganic salts.
  • the mixture G defined according to the process according to the invention comprises water. This water comes, inter alia, from the dehydration of the educt compounds. In addition, additional water can be introduced into the mixture G by the educt compounds used (see what was said about syrups above).
  • Particularly preferred is a process according to the invention (as described above, preferably as defined above as preferred), wherein the one or at least one of two or more of said organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa is selected from the group of organic salts having an imidazolium or phosphonium cation and an anion selected from the group consisting of methylsulfonate and tosylate.
  • ⁇ is preferably selected from the group of organic salts having a dialkylimidazolium cation or tetraalkylphosphonium cation, more preferably selected from the group of organic salts with a dialkylimidazolium cation or tetraalkylphosphonium cation and an anion selected from the group consisting of methylsulfonate and tosylate.
  • methylsulfonate (methylsulfonate is also referred to as methanesulfonate and mesylate) is a compound of formula (II)
  • the anion "tosylate” is a compound of the formula (III)
  • Preferred organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa are thus combinations of:
  • Preferred dialkylimidazolium cations are selected from the group consisting of 1, 3-dimethylimidazolium, 1, 3-diethylimidazolium, 1, 3-di (1-propyl) -imidazolium, 1, 3-di (2-propyl) -imidazolium, 1 , 3-di (1-allyl) -imidazolium, 1, 3-di (1-butyl) -imidazolium, 1, 3-di (1-octyl) -imidazolium, 1, 3-di (1-dodecyl) -imidazolium , 1,3-di (1-tetradecyl) -imidazolium, 1,3-di (1-hexadecyl) -imidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- ( 1-butyl) -3-ethylimidazolium
  • dialkylimidazolium cations are selected from the group consisting of 1, 3-dimethylimidazolium, 1, 3-diethylimidazolium, 1-ethyl-3-methylimidazolium and 1- (1-butyl) -3-methylimidazolium.
  • Preferred tetraalkylphosphonium cations are selected from the group consisting of tetraalkylphosphonium cations of the formula (II)
  • R1, R2, R3 and R4 are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, n-hexyl, n-octyl, Dodecyl, tetradecyl, hexadecyl and allyl.
  • Particularly preferred tetraalkylphosphonium cations are selected from the group consisting of trihexyl (tetradecyl) phosphoniunr), tributyl (octyl) phosphoniunr), tributyl (tetradecyl) phosphoniunr), tetrabutylphosphonium, tributyl (ethyl) phosphoniunr), triisobutyl (methyl) phosphoniunr) and tributyl (methyl) phosphoniunr).
  • mixtures of the aforementioned preferred tetraalkylphosphonium cations are preferred.
  • a particularly preferred ionic liquid (organic salt) is ⁇ , ⁇ '- ethylmethylimidazolium methyl sulfonate (or 1-ethyl-3-methylimidazolium methyl sulfonate called - EMIM OMs).
  • this particularly preferred IL has a largely excellent thermal stability up to at least 200 ° C. In addition, no decomposition was regularly observed in aqueous solutions. In addition, this particularly preferred IL usually does not react with the educt compounds, in particular with fructose (cf., for example, Clough et al., Lonic Liquids: Not Always Innocent Solvents for Cellulose, Green Chemistry, 17, 231 (2015)).
  • the mixture G contains one, two or more organic salts with a melting point ⁇ 180 ° C. and a boiling point> 200 ° C. at 1013.25 hPa, selected from the group of organic salts having an imidazolium or phosphonium cation, wherein the total amount of chloride ions in the mixture G is less than 0.1% by weight, more preferably the mixture G comprises no chloride ions.
  • the mixture G comprises an amount of at most 0, 1 wt .-%, preferably no alkylated cations of such organic salts, which are fully alkylated at a temperature of 25 ° C, but with a heat treatment of 24 Hours and a temperature of 200 ° C, especially in the presence of
  • educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, (ii) HMF,
  • the mixture G comprises no organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa, which are selected from the group of organic salts with an ammonium, piperidinium or pyridinium cation.
  • the mixture G comprises no choline chloride, more preferably no choline cation.
  • reaction temperature is in the range of 100 to 160 ° C, preferably in the range of 120 to 140 ° C at the set reaction conditions.
  • the abovementioned reaction temperatures relate to the abovementioned reaction conditions in the process according to the invention, in which an amount of one educt compound or at least one of the two or more educt compounds reacts to give 5-hydroxymethylfurfural (HMF).
  • HMF 5-hydroxymethylfurfural
  • a method according to the invention is preferred (as described above, preferably as defined above as preferred), wherein when adjusting the reaction conditions, a reaction pressure in the range of 20 to 500 mbar is set, preferably a reaction pressure in the range of 50 to 300 mbar, respectively particularly preferably in a stirred tank reactor of a reactor arrangement comprising the method according to the invention.
  • the abovementioned reaction pressures relate to the abovementioned reaction conditions in the process according to the invention, in which an amount of one educt compound or at least one of the two or more educt compounds reacts to give 5-hydroxymethylfurfural (HMF).
  • HMF 5-hydroxymethylfurfural
  • the abovementioned reaction temperatures are present in combination with the reaction pressures mentioned.
  • the total amount of water in the mixture G is already reduced by evaporation, preferably it is Total water content in a range of 0, 1 to 5.0 wt .-%, based on the total mass of the mixture G.
  • a process according to the invention is preferred (as described above, preferably as defined above as preferred), wherein (depending on the operating mode) the reaction conditions are adjusted
  • HMF 5-hydroxymethylfurfural
  • HMF (further) HMF in a mixture which already contains a comparatively high concentration of HMF
  • dimers of HMF and (mostly mixture-soluble) humins are formed in many cases.
  • Humins in the context of the present invention are oligomers and polymers of the HMF and their blends with other oligomers and polymers. The formation of such humins is favored, since there is already a comparatively high concentration of HMF.
  • the risk of the formation of humins can be reduced by selecting suitable ILs, so that when using the ILs defined according to the method according to the invention, an acceptable conversion to HMF also takes place even at an HMF concentration of up to and including 35% by weight. Although under these conditions, formation of unwanted humins is observed, the extent of humin formation is still acceptable in most cases. Therefore, it is preferable in some cases to design the method according to the invention such that the mixture G has lower HMF maximum concentrations than 35% by weight. includes. According to their own investigations, this regularly leads to the formation of less humins.
  • a process according to the invention (as described above, preferably as defined above as preferred), the process being carried out such that no reaction of educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose Units in a mixture comprising more than 37% by weight of 5-hydroxymethylfurfural (HMF), preferably more than 33% by weight, more preferably more than 32% by weight.
  • HMF 5-hydroxymethylfurfural
  • the process according to the invention (as described above, preferably as defined above as preferred) is a process for the continuous preparation of 5-hydroxymethylfurfural (HMF) in a reactor arrangement.
  • the result is an HMF-containing mixture as the final product or intermediate.
  • the valuable product HMF must usually be separated by one or more separation steps from other constituents in the resulting HMF-containing mixture.
  • the process according to the invention after the step of adjusting the reaction conditions in the mixture G comprises one or more than one further step, preferably one, more than one or all steps selected from the group of steps consisting of partial neutralization with a Bronsted Base, water separation, separation of volatile compounds and HMF separation.
  • Highly volatile compounds are compounds having a boiling temperature which is lower than the boiling point of 5-hydroxymethylfurfuraldehyde (HMF) at the same pressure value at at least one pressure value in the range from 0.1 to 500 mbar.
  • a process according to the invention wherein 5-hydroxymethylfurfural (HMF) prepared in the process is removed by distillation, preferably by short-path distillation.
  • the short path distillation is carried out at a pressure in the range of 0.001 to 1 mbar and a temperature in the range of 50 to 250 ° C.
  • the (preferred) short path distillation is fed with a mixture comprising water in an amount of not more than 0.5% by weight.
  • the total water content before the short path distillation is preferably reduced to not more than 0.5% by weight by further distillation at a pressure in the range from 1 to 200 mbar and a temperature in the range from 80 to 180 ° C.
  • reaction conditions in the mixture G are controlled or regulated depending on the concentration of one or more substances selected from the group consisting of (i) educt compounds, (ii) 5-hydroxymethylfurfural (HMF) and (iii) humins in one place within the reactor, preferably in the mixture G and / or at the reactor outlet.
  • substances selected from the group consisting of (i) educt compounds, (ii) 5-hydroxymethylfurfural (HMF) and (iii) humins in one place within the reactor, preferably in the mixture G and / or at the reactor outlet.
  • the amount of one, two or more reactant compounds introduced into the reactor per unit time selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units is preferably determined by means of flow measurement and / or scale-controlled metering.
  • the person skilled in this conventional measuring devices are known.
  • the composition of starting mixtures comprising one, two or more educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units we refer to the statements below.
  • Ways of determining the average residence time in the reactor arrangement are also known to the person skilled in the art.
  • the skilled person is usually familiar with the volume of the reactor or reactors used (preferably reactors selected from the group consisting of tubular reactors and stirred tank reactors).
  • the average residence time can thus be controlled or regulated via the feeds (for example, in a tubular reactor).
  • the mean residence time is preferably controlled by a level-dependent discharge pump. If the discharge is increased, the volume of the liquid phase in the reactor and thus also the residence time decreases. If the discharge is reduced, the volume of the liquid phase in the reactor and thus also the residence time increases.
  • the reaction conditions in the mixture G can be determined by the skilled person by means of conventional measuring devices, largely even determined continuously.
  • Typical parameters are the reaction temperature in the mixture G, the pressure above the liquid phase of the mixture G and the pH in the mixture G (or alternatively the acid number in mg KOH per g mixture G).
  • Such analyzes allow statements about the concentration or quantitative ratios of present compounds / substances and / or classes of compounds (eg starting material (s), intermediate (s), product (s), catalyst (s), solvent).
  • the reactor arrangement consists of one or more reactors, wherein the or at least one of the plurality of reactors is selected from the group consisting of tubular reactors and stirred tank reactors.
  • a process according to the invention (as described above, preferably as defined above as preferred) is particularly preferred, wherein the reactor arrangement comprises a tubular reactor, wherein at the entrance of the tubular reactor, a starting mixture S is used, from which said mixture G is formed by reaction of educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, wherein the starting mixture S preferably comprises less than 10 wt .-% 5-hydroxymethylfurfural (HMF), based on the total mass of Starting mixture S, preferably less than 5% by weight 5-hydroxymethylfurfural (HMF).
  • HMF 5-hydroxymethylfurfural
  • the reactor arrangement in the process according to the invention comprises a tubular reactor, in many cases no back-mixing occurs. As a result, comparatively accurate concentration profiles can be established in a tubular reactor depending on the reactor length.
  • a reactor arrangement comprising a tubular reactor in which the reaction temperature within the tubular reactor is controlled by means of a temperature gradient.
  • the starting mixture S preferably comprises (a) one, two or more educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units and (b) one, two or more organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa, selected from the group of organic salts with an imidazolium or phosphonium cation.
  • educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units
  • organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa, selected from the group of organic salts with an imidazolium or phosphonium cation.
  • starting mixture S the mass ratio of the respective total amounts of (a) one, two or more educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units and (b) one, two or more organic salts having a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013,25 hPa, selected from the group of organic salts having an imidazolium or phosphonium cation, in a range from 0.4 to 1.7, preferably in a range from 0.4 to 1.1.
  • the process according to the invention (as described above, preferably as defined above as being preferred) can be controlled or regulated particularly advantageously via the starting mixture S.
  • a corresponding control or regulation (or a correspondingly controlled or regulated method according to the invention) is thus preferred.
  • the amount introduced per time of the starting mixture S be increased or decreased (i.e., adjusted) (feed rate), for example, by increasing or decreasing the flow rate in a corresponding flow meter.
  • the mass ratio of the respective total amounts of (a) one, two or more educt compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units and (b) one, two or more organic salts with a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa, selected from the group of organic salts with an imidazolium or phosphonium cation, in the starting mixture S is changed, so that the inventive method (as described above, preferably as defined above as preferred) is controlled or regulated.
  • the total amount of said one, two or more reactant compounds in the starter mixture S is increased or decreased while the total amount of the said one, two or more organic salts remains the same.
  • Such a control or regulation is particularly preferred in the case of a continuous feeding of the starting mixture S into the reactor arrangement, preferably into a tubular reactor or into a stirred tank reactor.
  • the amount of HMF forming in the mixture G is thereby particularly preferably controlled or regulated.
  • a process according to the invention (as described above, preferably as defined above as preferred) is particularly preferred, wherein the reactor arrangement comprises a stirred tank reactor in which the mixture G is present.
  • the reactor arrangement in the process according to the invention comprises a stirred tank (also referred to as stirred tank reactor), in many cases a complete backmixing occurs.
  • a reaction vessel comprising a reactor arrangement, wherein the water contained in the mixture G in the stirred tank is already largely separated by means of vacuum.
  • the reactor assembly preferably comprising a stirred tank reactor, in which the mixture G is present, also the starting mixture S is fed.
  • a mass ratio in the starting mixture S (both for process configurations according to the invention comprising a tubular reactor and for process configurations according to the invention comprising a stirred tank reactor) in the range of 0.4 kg (a) one, two or more educt compounds selected from the group consisting of hexoses, Oligosaccharides comprising hexose units, and polysaccharides comprising hexose units per 1 kg (b) one, two or more organic salts with a melting point ⁇ 180 ° C and a boiling point> 200 ° C at 1013.25 hPa, selected from Group of organic salts with an imidazolium or phosphonium cation to 1, 5 kg (a) per 1 kg (b) presented.
  • a mass ratio in the starting mixture S in the range of 0.4 kg fructose per 1 kg (b) to 1, 5 kg of fructose per 1 kg (b) presented, preferably a mass ratio in the range of 0.4 kg fructose per 1 kg (b) to 1, 2 kg of fructose per 1 kg (b).
  • the dehydration was carried out in a 2L jacketed glass reactor with disc stirrer, flow breakers and thermostat, and a distillate transfer with snake cooler and connection for a vacuum pump.
  • the starting compound used was fructose syrup which was fed via a pump to the reactor at a constant metering rate.
  • the ionic liquid used was a salt of the formula (III) (EMIM OMs).
  • a first partial step the ionic liquid EMIM OMs (Basionics ST 35) was initially charged in the reactor and then a catalytic amount of methanesulfonic acid (1 mol%, based on the total amount of fructose used) was added to the ionic liquid. It resulted in a first sub-mixture. Subsequently, this first part mixture was heated to 150 ° C. at 100 mbar.
  • an aqueous fructose solution (about 67% in water) was continuously fed to the reactor at a constant metering rate of about 9 g / min via a pump, with the introduced water evaporating.
  • Example 2 a total of five individual experiments (2 (a) to 2 (e)) were carried out. Each individual test was carried out in a 250 mL double-jacket glass reactor with disk stirrer, flow breakers and thermostat, as well as a distillate transition with a snake cooler and connection for a vacuum pump.
  • the ionic liquids (a) and (b) and (d) and (e) were added with a Brönsted acid whose anion is identical to the anion of the respective ionic liquid. In each case, only enough of the corresponding acid was added so that the acid number of the respectively resulting partial mixtures was 6 ⁇ 0.5 mg KOH / g of ionic liquid.
  • the acid number was determined using a Metrohm 848 Titrino Plus Titrometer. For this purpose, 0, 1 to 0.2 g of a corresponding sample against
  • Weight percentages in the above table refer to the total mass of the product mixture.
  • conversion of fructose [%] and Yield HMF [%] in the table above, the statements made in relation to example 1 apply accordingly.
  • the continuous production of HMF in a stirred tank was carried out in a continuously operated thermostated glass reactor with disk stirrers and flow breakers, wherein the stirred tank with (i) two separate feeds (for the streams to be supplied), (ii) a reflux condenser with vacuum port for distilling off Water and (iii) an overflow for a discharge of the liquid phase (product mixture) is equipped.
  • the weight of the liquid phase (Mixture G) in the reactor was 187 g; It is thus possible to calculate the residence time of the liquid phase in the reactor (and thus also the one, two or more organic salts used).
  • the reaction temperature corresponds to the temperature of the liquid phase in the stirred tank reactor. Experimental parameters were first determined and recorded after a steady state condition was reached.
  • the stirred tank was also operated during steady state with the following parameters:
  • Feed 1 aqueous fructose syrup (about 67% in water) with a feed rate of 53.4 g / h,
  • Feed 2 EMIM OMs (Basionics ST 35) with additionally 0.35% by weight of methanesulfonic acid (based on the total amount of EMIM OMs and methanesulfonic acid in feed 2 (ie based on the total amount of feed 2) with a feed rate of 56, 1 g / h,
  • the continuous production of HMF in a tubular reactor was carried out in a glass ring-filled continuous jacketed tubular reactor (12 mm diameter, 140 cm long filled with 5 mm diameter glass rings as a bed to reduce the volume) with external thermostat.
  • a starting mixture S was fed via the inlet (bottom-up mode) of the tubular reactor at the bottom of the tubular reactor.
  • a mixture G is present.
  • the product HMF-containing mixture G was expanded and collected via a 3.5 bar transfer valve into a cooled receiver.
  • the mass of the liquid phase in the reactor was 1 10 g; Thus, it is possible to calculate the residence time of the liquid phase (and thus also of the one, two or more organic salts used) in the reactor.
  • the measurement of the temperature took place within the tube at two measuring points, in each case at a distance of 5 cm to the tube inlet and to the tube outlet.
  • the temperature of the external thermostat was chosen to reach the following "internal reactor temperature" (liquid phase temperature at the outlet of the reactor) of 130 ° C.
  • the temperature at the inlet of the reactor was 125 ° C.
  • the tubular reactor was also operated during steady state with the following parameters:
  • Containing feed 36.9% by weight of fructose, 3% by weight of water, 59.9% by weight of EMIM OMs (Basionics ST 35), 0.18% by weight of methanesulfonic acid (percent by weight refers to the total amount of the inflow)
  • Discharge comprising: about 1.5% by weight of saccharides, 18.4% by weight of HMF, 0.2% by weight of di-HMF, 0.08% by weight of furfural,> 3% by weight water
  • test duration was 120 min; This resulted in the respective product mixtures (a) and (b).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Furan Compounds (AREA)

Abstract

L'invention concerne un procédé pour la production en continu de 5-hydroxyméthylfurfural (désigné dans ce qui suit par HMF, composé de formule (I)) dans un système de réacteur, comportant l'étape suivante consistant à : adapter des conditions réactionnelles dans un mélange G comprenant - un, deux composants de départ ou plus, choisis dans le groupe constitué d'hexoses, d'oligosaccharides comprenant des motifs hexose et de polysaccharides comprenant des motifs hexose, - un, deux sels organiques ou plus ayant un point de fusion < 180 °C et un point d'ébullition > 200 °C à 1013,25 hPa, choisis dans le groupe constitué des sels organiques ayant un cation imidazolium ou phosphonium, - du 5-hydroxyméthylfurfural (HMF) selon une concentration dans la plage allant de 15 % en poids à 35 % en poids rapportée à la masse totale du mélange G, - d'autres substances facultatives, de sorte que, dans les conditions réactionnelles fixées, une certaine quantité de composants de départ ou au moins d'un, de deux composants de départ ou plus est/sont transformé(e)(s) en 5-hydroxyméthylfurfural (HMF).
PCT/EP2016/064693 2015-06-24 2016-06-24 Procédé pour la production en continu de 5-hydroxyméthylfurfural (hmf) dans un système de réacteur WO2016207365A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10259797B2 (en) 2015-11-04 2019-04-16 Basf Se Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters
US10385033B2 (en) 2015-07-22 2019-08-20 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10428039B2 (en) 2015-11-04 2019-10-01 Basf Se Process for preparing furan-2,5-dicarboxylic acid

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2813494A1 (fr) * 2013-06-12 2014-12-17 Basf Se Procédé de fabrication de 5-hydroxyméthylfurfural (HMF)

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2813494A1 (fr) * 2013-06-12 2014-12-17 Basf Se Procédé de fabrication de 5-hydroxyméthylfurfural (HMF)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10385033B2 (en) 2015-07-22 2019-08-20 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10259797B2 (en) 2015-11-04 2019-04-16 Basf Se Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters
US10428039B2 (en) 2015-11-04 2019-10-01 Basf Se Process for preparing furan-2,5-dicarboxylic acid

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