Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

Definitions

• 5-HMF is a compound of interest derived from biomass that can be used in many fields, particularly in pharmacy, agrochemicals or specialty chemicals.
• the production of 5-HMF by dehydration of sugars has been known for many years and has been the subject of a large number of research works. There are many dehydration conditions, examples of which include the following methods:
• - 5-HMF can be obtained in an aqueous medium, generally in the presence of an acid catalyst.
• This acid catalyst makes it possible to dehydrate the C6 sugar (in particular fructose) into 5-HMF, but also catalyzes the rehydration of 5-HMF into formic acid and levulinic acid, which is highly detrimental to the yield.
• 5-HMF can also be obtained in a non-aqueous protic polar medium, with solvents such as methanol, ethanol or acetic acid, and in the presence of an acid catalyst. Under these conditions, 5-HMF is obtained as a mixture with an ether or ester derivative of 5-HMF depending on the reaction medium used. The formation of these secondary products is due to the reaction of 5-HMF with the reaction solvent in an acid medium.
• WO 2007/104514 describes the synthesis of 5-HMF by dehydration of sugar using methanol or ethanol as solvent in the presence of an acid catalyst.
• the presence of said catalyst also catalyzes the reaction of etherification of 5-HMF by alcohol to give a mixture of 5-HMF and its form of methyl or ethyl ether depending on the alcohol used as solvent.
• - 5-HMF can also be produced in an aprotic polar medium with or without an acid catalyst.
• DMSO dimethyl sulfoxide
• humines are formed during the production of 5-HMF (van Dam, HE; Kieboom, APG; van Bekkum, H. (1986) The Conversion of Fructose and Glucose in Acidic Media: Formation of Hydroxymethylfurfural. In: Starch-Starke, vol. 38, no. 3, p. 95-101).
• a known method for isolating 5-HMF from DMSO is liquid-liquid extraction, followed by crystallization of the extract, as described in patent FR 2669635.
• the applicant has already proposed an improvement to the method described in patent FR 2669635, which was the subject of patent FR 1758605.
• This improvement is based on the modification of the extraction step, in particular by adding a backwashing step to the water, and by recycling the water from backwash at the optional filtration step.
• This improvement makes it possible to increase the purity of 5-HMF without loss of yield of the product of interest, and to carry out the crystallization step of 5-HMF under more favorable conditions.
• the applicant has discovered a process making it possible to recover 5-HMF not in crystallized form but in aqueous solution, which opens up new possibilities for the valorization of 5-HMF in various applications, or for subsequent transformations which could not be performed neither in DMSO nor in the extraction solvent. Furthermore, the process according to the invention thus makes it possible to recover 5-HMF in aqueous solution, while limiting the costs of operability, water discharges and therefore the environmental impact of said process.
• An object of the present invention relates to a process for the production of an aqueous solution of 5-HMF.
• the invention relates more particularly to a method for producing an aqueous solution of 5-hydroxymethylfurfural (5-HMF), said method comprising the following steps:
• step c) of backwashing with an aqueous solvent so as to produce the intermediate aqueous counter-extract and an organic raffinate which comprises 5-HMF and an organic solvent
• step e) of hydrodistillation implemented by distillation of the concentrated organic extract from step d) in the presence of water, to produce an aqueous solution of 5-HMF and a stream comprising organic solvent,
• step f) of treatment of the water-DMSO mixtures produced within the process making it possible to produce an aqueous effluent, which can be used in whole or in part in step c) of backwashing, and/or in the step e).
• the various embodiments presented can be used alone or in combination with each other, without limitation of combination.
• the various ranges of parameters for a given step such as the pressure ranges and the temperature ranges can be used alone or in combination.
• a preferred range of pressure values can be combined with a more preferred range of temperature values.
• charge 1 comprising 5-HMF and dimethoxysulphoxide (DMSO) introduced in stage a) according to the invention can be obtained during a stage of dehydration of sugars into 5-HMF, very advantageously located upstream of step a) according to the invention, by bringing a sugar feed comprising one or more sugars into contact with DMSO and an acid dehydration catalyst so as to produce an effluent containing at least 5-HMF and DMSO and advantageously corresponding to charge 1 of the process according to the invention introduced in step a) of mixing.
• the process according to the invention can therefore optionally comprise a stage of dehydration of sugars into 5-HMF, located upstream of stage a).
• acid dehydration catalyst means any Br ⁇ nsted acid catalyst chosen from organic or inorganic, homogeneous or heterogeneous Br ⁇ nsted acids, capable of inducing the dehydration of sugars to 5-HMF.
• the acid dehydration catalyst is a Br ⁇ nsted acid having a pKa in DMSO of between 0 and 5.0, preferably between 0.5 and 4.0 and more preferably between 1.0 and 3.0.
• Said pKa are as defined in the article by F. G. Bordwell et al. (J. Am. Chem. Soc., 1991, 113, 8398-8401).
• the acid dehydration catalyst is chosen from HF, HCl, HBr, HI, H 2 SO 3 , H 2 SO 4 , H 3 PO 2 , H 3 PO 4 , HNO 2 , HNO 3 , H 2 WO 4 , H 4 SiW 12 O 40 , H 3 PW 12 O 40 , (NH 4 ) 6 (W 12 O 40 ).
• XH 2 O, H 4 SiMo 12 O 40 , H 3 PMo 12 O 40 (NH 4 ) 6 Mo 7 O 24 .xH 20 , H 2 MoO 4 , HReO 4 , H 2 CrO 4 , H 2 SnO 3 , H 4 SiO 4 , H 3 BO 3 , HCIO 4 , HBF 4 , HSbF 5 , HPF 6 , H 2 FO 3 P, CISO 3 H, FSO 3 H, HN(SO 2 F) 2 , HIO 3 , BF 3 , AICI 3 , AI(OTf) 3 , Fe
• the acid dehydration catalyst is chosen from HCl, H 2 SO 4 , H 3 PO 2 , H 3 PO 4 , HNO 3 , AICI 3 , acetic acid, trifluoroacetic acid, methanesulfinic acid, methanesulfonic acid, trifluoromethanesulfonic acid.
• sugar we mean a sugar containing 6 carbon atoms (hexoses), but this does not exclude the presence in the feed of sugars containing 5 carbon atoms (pentoses), in the form of oligosaccharides and monosaccharides.
• sugar is meant glucose or fructose, alone or in a mixture, sucrose, but also oligosaccharides such as cellobiose, maltose, cellulose or even inulin.
• the sugar filler used can be sugar in solid form, or else an aqueous sugar solution.
• sucrose is generally produced in the form of a solid
• glucose or fructose alone or in a mixture
• aqueous solution for example at 70% weight in sugar.
• the optional dehydration step is carried out at a temperature of between 50 and 150°C, preferably between 60 and 140°C, preferably between 70 and 130°C and in such a way preferably between 80 and 120°C.
• the optional dehydration step is carried out at a pressure of between 1 and 0.001 MPa, preferably between 0.1 and 0.01 MPa.
• the reaction medium is above or below the bubble point of the mixture. Bubble point refers to the pressure and temperature conditions under which the first gas bubbles appear for a liquid.
• the reaction medium is above the bubble point of the mixture, the vapor phase can be withdrawn from the reactor, optionally rectified, and condensed to form the condensates which can be sent to an optional stage f) treatment of the water-DMSO mixtures .
• the acid dehydration catalyst is introduced in the dehydration stage in a molar ratio of the catalyst relative to the sugar charge, denoted Acid/Sugar, expressed in molar percentage (%mol), of between 0.01 and 10 %mol, preferably between 0.05 and 8%mol, preferably between 0.1 and 6%mol, preferably between 0.2 and 5%mol, preferably between 0.3 and 4%mol and so very preferably between 0.5 and 3% mol.
• %mol molar percentage
• the effluent obtained at the end of the optional dehydration step comprises 5-HMF and DMSO.
• the DMSO generally represents between 30 and 95% by weight of the effluent resulting from the dehydration step and treated in step a) of the process according to the invention, preferably between 40 and 90% by weight, preferably between 50 and 90% by weight, preferably between 55 and 85% by weight.
• 5-HMF represents more than 1% by weight of the effluent from the optional dehydration step and treated in step a) of the process according to the invention, preferably more than 10% by weight, preferably more than 15 wt% and preferably less than 50 wt%, preferably less than 40 wt%, preferably less than 30 wt%.
• said effluent from the optional dehydration step may contain water even before it is mixed in step a) with the intermediate aqueous counter-extract 9.
• Said water may be from the dehydration step, for example, water is formed during the dehydration reaction of sugar to 5-HMF (3 moles of water generated per mole of 5-HMF produced). This water may also have been introduced with the sugar, in the case where, for practical reasons, a sugar syrup, for example at about 70% by weight in water, is used.
• a water-DMSO mixture can be recovered in the vapor phase. Said water-DMSO mixture is advantageously sent to optional step f).
• the effluent from the optional dehydration step and introduced in step a) as feed 1 may contain water, in a proportion generally between 0.1 and 30% by weight, preferably between 0. 1 and 15% by weight, preferably between 0.1 and 10% by weight.
• the effluent from the optional dehydration step and introduced in step a) as feed 1 may also contain impurities, in particular humins.
• humins refers to all the undesirable polymeric compounds formed during the synthesis of 5-HMF.
• the humins represent, in particular, less than 30% by weight of the converted sugar feed, preferably less than 20% by weight.
• the optional dehydration step can be carried out according to different embodiments.
• the step can advantageously be implemented discontinuously or continuously.
• the addition of the sugar charge can be progressive (called fed-batch according to the English terminology) in the case of a discontinuous implementation or staged in different CSTR reactors (Continuously Stirred Tank Reactor in English terminology) in series in a setting. ongoing implementation. It is possible to operate in a closed reaction chamber or in a semi-open reactor.
• the method according to the invention comprises a step a) of bringing the filler 1, optionally resulting from the dehydration step, into contact (or mixing) with at least a fraction of an intermediate aqueous counter-extract 9, so as to to obtain at least one aqueous mixture 3.
• the intermediate aqueous counter-extract 9 comes from step c) of the process according to the invention.
• the 5-HMF represents more than 1% by weight of the charge 1 introduced in step a) of the process according to the invention, preferably more than 10% by weight, preferably more than 15% by weight and preferably less 50% by weight, preferably less than 40% by weight, preferably less than 30% by weight.
• the DMSO represents between 30 and 95% by weight of the filler 1 introduced in step a), preferably between 40 and 90% by weight, preferably between 50 and 90% by weight, preferably between 55 and 85% weight.
• the filler 1 introduced in step a) may also contain water, in a proportion preferably between 0.1 and 30% by weight, preferably between 0.1 and 15% by weight and more preferably between 0.1 and 10% by weight.
• charge 1 may additionally contain humins.
• the humins represent, in particular, less than 30% by weight of the filler 1, preferably less than 20% by weight.
• the intermediate aqueous counter-extract 9 or the fraction of the intermediate aqueous counter-extract 9 is advantageously derived from step c). It includes water, DMSO and optionally 5-HMF.
• said intermediate aqueous counter-extract 9 contains more than 60 % by weight of water, preferably more than 70% by weight of water and more preferably more than 80% by weight of water.
• the aqueous mixture 3 obtained at the end of step a) contains between 10% and 90% by weight of water, preferably between 20 and 80% by weight of water, preferably between 40 and 75% by weight of 'water.
• step a) is carried out at a temperature of 0 to 60°C, preferably of 10 to 30°C and generally at ambient temperature, that is to say between 18 and 25°C.
• Step a) can optionally be additionally supplied with an aqueous stream, for example with a fraction of the aqueous solvent used in step c) for backwashing.
• step a By increasing the water content during step a), for example by introducing at least a fraction of the intermediate aqueous counter-extract 9, part of the humins possibly present in the load 1 can precipitate.
• the mixture resulting from the contact of said charge 1 with at least a fraction of the intermediate aqueous counter-extract 9 can therefore advantageously be subjected to a liquid-solid separation step, so as to obtain a liquid separated from solid particles in suspension and a residue solid comprising humins and which is preferably removed from the process.
• a liquid-solid separation step thus makes it possible to eliminate the "humins" which have precipitated.
• the liquid-solid separation step is optional. This optional liquid-solid separation step is preferably carried out at a temperature between 0 and 60°C, preferably between 10 and 30°C, preferably between 15 and 25°C and generally at room temperature (i.e. i.e. between 18 and 25°C).
• the optional liquid-solid separation step is a simple solid-liquid separation and can be carried out by any method known to those skilled in the art, such as for example with a filter press, a belt filter, a clarifier, a decanter , a centrifuge, for example a plate centrifuge.
• the liquid-solid separation step is filtration, preferably carried out by a filter press.
• the method according to the invention comprises a step b) of liquid-liquid extraction of the aqueous mixture 3 obtained at the end of step a) in the presence of an extraction solvent 4, so as to produce an aqueous raffinate 5 and an intermediate organic extract 6.
• the liquid-liquid extraction carried out in step b) advantageously corresponds to washing the aqueous mixture with an organic extraction solvent.
• the liquid-liquid extraction carried out in step b) is a countercurrent extraction of the aqueous mixture 3 obtained in step a) with an extraction solvent.
• This technique is well known to those skilled in the art.
• the extraction can be carried out, for example, in a battery of mixer-settlers, in a column filled with bulk or structured packing, in a pulsed column, or even in a stirred column.
• Stage b) of liquid-liquid extraction is advantageously carried out at a temperature between 0 and 60° C., preferably between 5 and 50° C., preferably between 10 and 40° C., preferably between 15 and 30° C. C and generally at room temperature (i.e. between 18 and 25°C).
• the weight proportion (weight/weight) of extraction solvent relative to the aqueous mixture 3 is preferably from 0.2 to 5, preferably between 1 and 3, preferably between 1.5 and 2.5.
• the extraction solvent introduced in step b) is chosen from organic solvents immiscible with water, so as to form two liquid phases in step c) of backwashing. This property is highly dependent on the relative proportion of feed, counter-extraction water and extraction solvent flow rates used in the process.
• the extraction solvent is preferably chosen from chlorinated organic solvents, ethers, esters, ketones and aromatic compounds.
• the extraction solvent is a chlorinated solvent having between 1 and 10 carbon atoms, noted below as C1 -C10, an ether having between 2 and 10 carbon atoms (C2-C10), an ester having between 4 and 10 carbon atoms (C4-C10), a ketone having between 3 and 10 carbon atoms (C3-C10), an aldehyde between 1 and 10 carbon atoms (C1-C10), an aromatic compound C4-C10.
• the extraction solvent is chosen from dichloromethane, diethyl ether, diisopropyl ether, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, thiophene, anisole and toluene.
• the extraction solvent is methyl isobutyl ketone.
• the extraction solvent is chosen so as to:
• step e) a heterogeneous azeotrope with water, preferably rich in solvent, that is to say at more than 50% by weight of solvent, preferably at more than 60% by weight of solvent and so preferably more than 70% by weight of solvent.
• said azeotrope of the water/extraction solvent mixture has a boiling point significantly lower than that of water, preferably lower by at least 5° C. than the boiling point of water, preferably at least 8° C. below the boiling point of water and preferably at least 10° C. below the boiling point of water.
• the streams of organic solvent produced in the subsequent stages can be recycled to stage b) of extraction, as extraction solvent.
• These organic solvent streams may contain impurities possibly generated during the implementation of the process.
• the organic solvent streams produced in the subsequent stages can be distilled, for example periodically, to avoid the accumulation of said impurities.
• Step b) thus makes it possible to obtain, on the one hand, an aqueous stream depleted in 5-HMF, called aqueous raffinate 5, which contains a large part of the DMSO initially contained in the charge, and, on the other hand, a stream organic enriched in 5-HMF, called intermediate organic extract 6, which contains a large part of the 5-HMF, initially contained in the charge 1, and the extraction solvent.
• This intermediate organic extract 6 may also contain DMSO.
• said intermediate organic extract preferably contains 5-HMF and DMSO in a weight ratio, 5-HMF/DMSO, of between 50/50 and 95/05, preferably between 55/45 and 90/10, of preferably between 60/40 and 85/15 and more preferably between 65/35 and 80/20.
• the intermediate organic extract 6 is sent directly to step c) of backwashing.
• the process according to the invention comprises a step c) of backwashing, advantageously of the intermediate organic extract 6, with an aqueous solvent 7, so as to produce an intermediate aqueous counter-extract 9 and an organic raffinate 8 comprising the 5 -HMF and an organic solvent.
• the intermediate aqueous counter-extract 9 is advantageously sent in part or in whole to step a).
• the organic solvent is in particular composed at least in part of extraction solvent and may optionally comprise DMSO, preferably in small quantities.
• the introduction of an aqueous solvent in step c) is carried out so as to implement backwashing, according to the general knowledge of those skilled in the art.
• the introduction of the aqueous solvent is carried out in such a way that the quantity of aqueous solvent is as low as possible so as to reduce costs, but sufficient to guarantee a content by weight of DMSO in the organic raffinate 8 which is low and preferably lower or equal to 20.0% by weight relative to the weight of the 5-HMF, preferably less than or equal to 15.0% by weight relative to the weight of the 5-HMF, preferably between 0.01 and 15.0% by weight per relative to the weight of the 5-HMF, very preferably between 0.01 and 10.0% by weight relative to the weight of the 5-HMF.
• the aqueous backwashing solvent introduced in step c) comprises more than 95% by weight of water, preferably more than 98% by weight of water (100% being the maximum).
• the aqueous solvent may optionally include DMSO.
• the effectiveness of backwashing is higher the lower the amount of DMSO present in the aqueous backwashing solvent.
• the aqueous solvent may comprise DMSO, preferably less than 1.0% by weight of DMSO, preferably less than 0.1% by weight of DMSO.
• the aqueous backwash solvent comes from an optional step f) of treatment of water-DMSO mixtures produced within the process.
• the aqueous raffinate 5 composed of water and DMSO, produced in stage b), is treated, advantageously in an optional stage f) which comprises in particular a distillation.
• the water-rich distillate thus obtained at the end of this optional step f) is advantageously used as aqueous solvent for backwashing in step c), said water-rich distillate also possibly containing a residual quantity of DMSO, preferably less than 1% by weight and preferably less than 0.1% by weight of DMSO.
• the residual quantity of DMSO in the distillate is all the lower as the distillation of optional step f) is carried out efficiently, in particular with a number of distillation stages greater than 10 and reboiling and suitable reflux.
• Step c) of backwashing is advantageously a liquid-liquid extraction of an organic stream, in particular of the intermediate organic extract 6 obtained in step b) against the current of the aqueous solvent 7.
• This technique is well known to those skilled in the art.
• the extraction can be carried out, for example, in a battery of mixer-settlers, in a column filled with bulk or structured packing, in a pulsed column, or even in a stirred column.
• Step c) is preferably carried out at a temperature between 0 and 60°C, preferably between 5 and 50°C, preferably between 10 and 40°C, preferably between 15 and 30°C and generally at a temperature ambient (i.e. between 18 and 25°C).
• the weight ratio (weight/weight) of aqueous solvent relative to the intermediate organic extract 6 is preferably from 0.04 to 5, preferably between 0.07 and 3, preferably between 0.1 and 1.
• Step c) makes it possible to obtain an aqueous stream advantageously enriched in DMSO, called intermediate aqueous counter-extract 9, preferably containing at least 60% by weight of water, preferably at least 80% by weight of water, and an organic raffinate 8, advantageously depleted in DMSO.
• Said intermediate aqueous counter-extract 9 is advantageously sent, in part or preferably in whole, to step a).
• the organic raffinate 8 obtained has a content by weight of DMSO preferably less than or equal to 20.0% by weight relative to the weight of 5-HMF, preferably less than or equal to 15.0% by weight relative to the weight of 5-HMF , preferably less than or equal to 5.0% by weight relative to the weight of 5-HMF, preferably less than or equal to 4.0% by weight relative to the weight of 5-HMF, preferably less than or equal to 3.0 wt% relative to the weight of 5-HMF.
• the organic raffinate 8 produced in stage c) is sent to stage d) of concentration.
• the method according to the invention comprises a step d) of concentration of the organic raffinate 8 resulting from step c), by elimination of part of the organic solvent, producing a concentrated organic extract 10, comprising 5-HMF and solvent residual organic material, and a stream 11 comprising, preferably consisting of organic solvent, said organic solvent being advantageously composed wholly or partly of the extraction solvent and optionally of DMSO.
• the stream 11 comprising organic solvent is recycled, in whole or in part, to stage b) of extraction.
• step d) part of the organic solvent is removed by vaporization, for example in a distillation column at atmospheric pressure or under vacuum, in an evaporator, or any known method of the skilled in the art.
• the vaporization of the organic solvent is advantageously carried out at atmospheric pressure or under vacuum, preferably at a pressure between 0.1 and 0.01 MPa, preferably under vacuum at a pressure between 0.09 and 0.01 MPa , so as to limit the temperature of the liquid and therefore the degradation of 5-HMF.
• the temperature of the liquid is kept below 130°C, preferably kept below 100°C, preferably kept below 70°C.
• the level of vacuum to be applied to reach these temperatures being of course dependent on the organic solvent and more particularly on the extraction solvent used and on the rate of vaporization of the organic solvent.
• the vaporization of the solvent is carried out by multi-effect evaporation or else with mechanical recompression of the vapors, or any other method known to those skilled in the art, so as to reduce the operating costs associated with the evaporation of the solvent. while limiting the risks of degradation of the product of interest, i.e. of 5-HMF.
• the temperature of the liquid is maintained below 130°C in the first effect, below 100°C in the second effect, and below 70°C in the third effect.
• the temperature of the liquid phase is reduced as the 5-HMF is concentrated in the organic solvent, limiting any risk of degradation.
• Step d) is implemented with a mass vaporization rate (or evaporation rate), corresponding to the mass of organic solvent vaporized relative to the mass of the organic raffinate 8 from step c) (more particularly the amount by mass of the stream 11 relative to the amount by mass of the organic raffinate 8), of at least 50%, preferably of at least 60%, preferably of at least 70%, preferably of at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, and preferably at most 99%.
• a mass vaporization rate or evaporation rate
• the vaporization rate is defined as a function of the extraction solvent so as not to degrade the 5-HMF, but also in order to minimize the quantity of residual solvent to be eliminated in step e) while guaranteeing the absence liquid phase separation (that is to say while ensuring that the liquid phase remains single-phase) when the concentrated organic extract 10 is brought into contact with water in step e).
• the concentrated organic extract 10 obtained at the end of the step d) very advantageously has a 5-HMF level of at least 40% by weight relative to the weight of concentrated organic extract, preferably at least 50% by weight, preferably at least 60% by weight, and preferably at most 95% by weight, preferably at most 90% by weight and preferably at most 85% by weight relative to the weight of concentrated organic extract.
• the concentrated organic extract 10 preferably has a level of residual organic solvent of at least 5% by weight relative to the weight of concentrated organic extract, preferably of at least 10% by weight, and of preferably at most 60% by weight, preferably at most 50% by weight, preferably at most 40% by weight, relative to the weight of concentrated organic extract 10.
• the organic solvent vaporized during step d) forms a stream 11 comprising, preferably consisting of, organic solvent and is preferably recycled to step b) of extraction.
• the concentrated organic extract 10 is sent to stage e) of hydrodistillation.
• the process according to the invention comprises a step e) of hydrodistillation implemented by distillation of the concentrated organic extract 10 resulting from step d) in the presence of water, so as to produce an aqueous solution 12 of 5- HMF and a stream 13 comprising, preferably consisting of, organic solvent.
• Stage e) of hydrodistillation advantageously makes it possible to eliminate, at least in part, the residual organic solvent not eliminated during stage d).
• the residual organic solvent removed during step e), that is to say stream 13, can advantageously be recycled to step b) of extraction alone or mixed with stream 11 comprising organic solvent from of step d).
• an aqueous flow 14 feeds step e) of hydrodistillation.
• the aqueous stream 14 introduced in step e) preferably contains more than 95% by weight of water, preferably more than 98% by weight of water.
• the aqueous stream 14 is pure water, optionally external to the process, which makes it possible to further minimize the residual DMSO content in the aqueous solution 12 of 5-HMF produced at the time. step e).
• isolated water within the process is used to supply step e), making it possible to limit the operating costs of the process and its environmental impact.
• the process includes the preparation of feedstock 1 and the sugar feedstock for the dehydration step is a 70% weight sugar syrup in water, around 1 tonne of water is recovered after the dehydration stage (the water in the feed and the water produced during the dehydration reaction) per tonne of 5-HMF produced. This water needs to be treated before being discharged into the environment.
• the process according to the invention can then advantageously use said water resulting from the dehydration stage to produce, at the end of stage e), an aqueous solution of 5-HMF concentrated preferably at 30% by weight or more, preferentially at 40% by weight or more, and thus reduce the costs of reprocessing the process and its environmental impact.
• the aqueous stream 14 introduced in step e) may correspond to at least a fraction, possibly all, of the distillate produced in optional step f).
• Said distillate may optionally contain a residual quantity of DMSO.
• the extraction solvent used in the process forms a heterogeneous azeotrope with water, said azeotrope preferably being rich in extraction solvent, preferably comprising more than 50% by weight of extraction solvent, preferably more than 60% by weight of extraction solvent and preferably more than 70% by weight of extraction solvent.
• said water/extraction solvent azeotrope has a boiling point significantly lower than that of water, preferably lower by at least 5° C. than the boiling temperature of water, preferably lower by at least 8°C below the boiling temperature of water and preferably at least 10°C below the boiling temperature of water.
• the residual organic solvent contained in the concentrated organic extract 10 can be easily eliminated without degradation of the 5-HMF.
• Step e) of hydrodistillation can be carried out at atmospheric pressure or under vacuum and in particular at a pressure of between 0.1 MPa and 0.001 MPa, preferably under vacuum at a pressure of between 0.08 and 0.005 MPa.
• the hydrodistillation step is carried out under vacuum, in particular at a pressure of between 0.1 MPa and 0.001 MPa, preferably between 0.08 and 0.005 MPa, so as to facilitate the removal of the organic solvent residual without degradation of 5-HMF.
• step e) of hydrodistillation is carried out in a distillation column, preferably at a column bottom temperature below 140° C., preferably below 130° C., preferably below 120° C. , preferably less than 110° C. and more preferably less than 100° C., so as to facilitate the elimination of the residual organic solvent without degradation of the 5-HMF.
• the concentrated organic extract 10 and the aqueous stream 14 are mixed before introduction into a distillation column and the mixture is introduced at an intermediate point of the distillation column.
• the concentrated organic extract 10 is introduced into the upper part of the distillation column, preferably into the upper half of the distillation column, while the aqueous solvent is introduced into the lower part of distillation column, preferably in the lower half of the distillation column.
• the mixture of the concentrated organic extract and the aqueous stream is then carried out within the distillation column.
• the aqueous solution 12 of 5-HMF obtained at the end of step e) has a quantity of 5-HMF of at least 30% by weight, preferably at least 40% by weight, and preferably less than 90% by weight, preferably less than 85% by weight and preferably less than 80% by weight, the percentages being given by weight of 5-HMF relative to the weight of aqueous solution of 5-HMF obtained at the from step e).
• the process according to the invention thus makes it possible to produce an aqueous solution of 5-HMF very advantageously having a content by weight of DMSO less than or equal to 10% by weight relative to the weight of 5-HMF, preferably less than or equal to 5% by weight per relative to the weight of 5-HMF and preferably less than or equal to 3% by weight relative to the weight of 5-HMF.
• the method according to the invention may comprise an optional step f) of treatment of water-DMSO mixtures generated by the steps of the method according to the invention, to produce an aqueous effluent (also called distillate), which can be used in whole or in part in step c) of backwashing and/or in step e).
• This step can also produce a stream 16 rich in DMSO and an impurity stream 17.
• the residual quantity of DMSO in the aqueous effluent produced at the end of optional step f) is all the lower as the distillation is carried out efficiently according to the knowledge of those skilled in the art.
• the water-DMSO mixtures generated by the process designate in particular the aqueous raffinate 5 produced in stage b) and possibly the water-DMSO mixture resulting from the optional stage of dehydration of the sugars into 5-HMF when the process incorporates such a stage.
• Step f) optional treatment of water-DMSO mixtures preferably implements a section for evaporation of a water-DMSO mixture, to remove any impurities (stream 17) in particular heavy impurities such as humins , followed by a distillation section.
• the evaporation section is operated at a temperature preferably between 80 and 120° C., preferably between 100 and 110° C., and preferably at a pressure between 0.002 and 0.020 MPa, preferably between 0.005 and 0.01 OMPa.
• the evaporation section is implemented by a scraped film type evaporator (Thin film Evaporator TFE).
• the distillation section for its part advantageously implements a distillation column or else several separate pieces of equipment.
• the distillation section of optional step f) is advantageously implemented in a distillation column, at a temperature at the top of the column preferably between 25 and 60° C., preferably between 45 and 55° C., for example about 50°C, preferably at a temperature at the bottom of the column of between 80 and 120°C, preferably between 105 and 115°C, for example of about 110°C, preferably at a pressure of between 0.001 and 0.05 MPa, preferably between 0.005 and 0.02 MPa and preferably between 0.008 and 0.012 MPa, and preferably with a reflux ratio between 0.01 and 0.50, preferably between 0.05 and 0.10.
• the aqueous raffinate 5 produced in step b) and comprising water and DMSO and optionally the water-DMSO mixture recovered in the optional dehydration step are evaporated, then the gaseous phase is recovered and distilled, from preferably under vacuum, so as to produce a residue 16 rich in DMSO on the one hand and a distillate 15 rich in water (corresponding to the aqueous effluent) on the other hand. Rich here means more than 95% by weight, preferably more than 98% by weight.
• Part or all of the water-rich distillate, or aqueous effluent can advantageously be recycled to step c) as aqueous solvent to carry out the backwashing step and/or to step e) of hydrodistillation as an aqueous stream.
• Said water-rich distillate can also be, in whole or in part, recycled as water introduced in step a).
• the DMSO-rich residue can advantageously be introduced at the optional dehydration stage, directly or after distillation, allowing the heavy products which could accumulate to be evacuated.
• FIG. 1 illustrates a particular embodiment of the method according to the invention.
• Charge 1 containing 5-HMF, DMSO and humins is sent to step a) and is brought into contact with the intermediate aqueous counter-extract 9 from step c) then the humins 2 which have precipitated are removed from the mixture by liquid-solid filtration.
• the aqueous mixture 3 obtained at the end of stage a) is sent to stage b) of extraction and placed in the presence of an extraction solvent 4 recycled from stage d) and e), in order to extract the 5 -HMF of the aqueous mixture with the extraction solvent and to obtain an aqueous raffinate 5 and an intermediate organic extract 6.
• the intermediate organic extract 6 is placed in the presence of an aqueous solvent 7 in step c) against -washing.
• the organic raffinate 8 obtained is concentrated in stage d) by elimination of the stream 11 recycled in stage b).
• the concentrated organic extract 10 obtained at the end of stage d) is treated in a stage e) of hydrodistillation in order to eliminate the residual organic solvent 13, recycled in stage b), and to obtain a aqueous solution 12 of 5-HMF.
• FIG. 2 illustrates another particular embodiment of the method according to the invention which differs from that of FIG. 1 in that the method comprises a step f) of treatment of the water-DMSO mixtures produced within the method, and in particular aqueous raffinate 5, to produce an aqueous effluent 15, part of which is recycled to stage c) as aqueous solvent 7 and another part to stage e) of hydrodistillation as aqueous stream 14, a residue 16 rich in DMSO and an impurities stream 17.
• the method comprises a step f) of treatment of the water-DMSO mixtures produced within the method, and in particular aqueous raffinate 5, to produce an aqueous effluent 15, part of which is recycled to stage c) as aqueous solvent 7 and another part to stage e) of hydrodistillation as aqueous stream 14, a residue 16 rich in DMSO and an impurities stream 17.
• Example 1 preparation of an organic extract 8 according to the invention.
• An acid catalyst methanesulfonic acid
• DMSO molar ratio with the sugar charge (catalyst/sugar charge) is 1% mol, and they are brought to a temperature of 120°C.
• the fructose is introduced in the form of an aqueous solution, at 70% sugar weight (syrup), in a DMSO/fructose mass ratio of 2.3.
• the pressure is maintained at 0.035 MPa. Under these pressure and temperature conditions, the reaction medium is above the bubble point of the mixture, so the vapor phase can be withdrawn from the reactor, and condensed to form the condensates.
• the sugar dehydration step is implemented discontinuously with a gradual addition of charge for 2 hours.
• the reaction medium is maintained at the temperature and pressure indicated above for an additional 2 h after the end of the addition.
• the liquid effluent from the dehydration step contains 74% by weight of DMSO, 21% by weight of 5-HMF, 3% by weight of water, ie a molar yield of 5-HMF relative to the fructose involved of 81%.
• Polymeric compounds (called humins) soluble in the reaction medium were formed up to 5% by weight.
• a water-DMSO mixture is recovered in the vapor phase. Said water-DMSO mixture has a composition of 32% by weight of DMSO and 68% water. This water-DMSO mixture is distilled under vacuum to produce water containing only traces of DMSO.
• the liquid effluent from the dehydration step corresponding to charge 1 is engaged in a step a) of bringing into contact with a stream containing water, at ambient temperature, so as to obtain a mixture which contains a ratio mass DMSO/water equal to 1.
• the mixture from step a) is subjected to a liquid-solid separation step, on a Büchner filter equipped with a polypropylene cloth filter with a pore size of 10 ⁇ m.
• This liquid-solid separation step is carried out at room temperature.
• 7.5 g of a “humin” solid residue/kg of filtered mixture are recovered, as well as a homogeneous liquid phase corresponding to the aqueous mixture 3.
• the aqueous mixture 3 is composed of 43% by weight of DMSO, 12% by weight of 5-HMF and 43% by weight of water and includes impurities (approximately 2% by weight of humins).
• the aqueous mixture 3 resulting from stage a) is subjected to a stage b) of countercurrent liquid-liquid extraction in a stirred column (Kühni or ECR type) made of glass comprising 8 sections 225 mm high and internal diameter of 32 mm, as well as a lower decanter and an upper decanter.
• the useful height is approximately 1.8 m and the total height of the column is 2.60 m.
• the total volume is about 3 liters.
• the organic extraction solvent is methyl isobutyl ketone (or MIBK for methyl isobutyl ketone in Anglo-Saxon terms).
• Said aqueous mixture 3 is introduced into the upper part of the device and dispersed in the ascending organic phase.
• the column inlet flow rates are set at 2.2 kg/h for the DMSO-water phase and at 4.1 kg/h for the organic extraction solvent.
• the proportion (weight/weight) of MIBK solvent is 1.9 relative to the aqueous mixture 3 from step a).
• the temperature is 20°C and the stirring speed is 300 rpm.
• the extraction yield is 97% for 5-HMF and 13% for DMSO.
• the intermediate organic extract 6 resulting from stage b) of liquid-liquid extraction is subjected to a stage c) of backwashing in the same extraction device (stirred column Kühni type or ECR). Said organic extract is dispersed in the pure water phase, at 21.5°C.
• the column inlet flow rates are set at 5 kg/h for the organic extract and at 1.5 kg/h for the aqueous phase.
• the proportion (weight/weight) of water introduced as aqueous backwash solvent relative to the intermediate organic extract is 0.3.
• the organic raffinate 8 produced according to example 1 is sent to stage d) of concentration.
• the vaporization of the solvent is carried out under vacuum.
• the liquid temperature is set at 60°C, and the vacuum level at 0.02 MPa.
• Step d) is implemented with a mass rate of vaporization of 95%, corresponding to the mass of organic solvent vaporized relative to the mass of organic raffinate resulting from step c) engaged.
• the concentrated organic extract obtained at the end of step d) has a mass content of 5-HMF of 84% by weight, 2% by weight in DMSO and 9% by weight in MIBK.
• the 5-HMF content of the concentrated organic extract (84% by weight) conforms to what is expected (at least 40% by weight and at most 95% by weight), as is its residual solvent content of 11% by weight ( sum of 9% of MIBK + 2% of DMSO) which conforms to the expected value (at least 5% by weight and at most 60% by weight).
• the concentrated organic extract obtained at the end of step d) also includes humin impurities (5% by weight).
• the recovered distillate essentially contains MIBK and water, eliminated in the form of an azeotrope with the MIBK, which separates into two immiscible phases upon condensation.
• the concentrated organic extract from stage d) is brought into contact with pure water, with a water/concentrated extract mass proportion of 0.95, then sent to a stage e) of hydrodistillation implemented by distillation.
• Stage e) of hydrodistillation is carried out at a column bottom temperature of 35° C., and under a vacuum of 0.01 MPa, so as to facilitate the elimination of the residual MIBK organic solvent, in the form of a water/MIBK azeotrope without degradation of 5-HMF.
• the aqueous solution of 5-HMF obtained at the end of step e) has a composition of 45% by weight of 5-HMF, 53.3% by weight of water, 1% by weight of DMSO (i.e. 2.2% weight of DMSO relative to the weight of 5-HMF) and 0.7% by weight of MIBK.
• Example 3 implementation of steps d) and e) according to the invention
• the organic raffinate 8 produced according to example 1 is sent to stage d) of concentration.
• the vaporization of the solvent is carried out under vacuum.
• the liquid temperature is set at 60°C, and the vacuum level at 0.02 MPa.
• Step d) is implemented with a mass rate of vaporization of 93%, corresponding to the mass of organic solvent vaporized relative to the mass of organic raffinate resulting from step c) engaged.
• the concentrated organic extract obtained at the end of step d) has a mass content of 5-HMF of 59% by weight, 1% by weight in DMSO and 34% by weight in MIBK.
• the 5-HMF content of the concentrated organic extract (59% by weight) conforms to what is expected (at least 40% by weight and at most 95% by weight), as is its residual solvent content of 35% by weight (sum of 34% of MIBK + 1% of DMSO) which conforms to the expected value (at least 5% by weight and at most 60% by weight).
• the concentrated organic extract obtained at the end of step d) also includes humin impurities (approximately 6% by weight).
• the recovered distillate essentially contains MIBK and water, eliminated in the form of an azeotrope with the MIBK, which separates into two immiscible phases upon condensation.
• the concentrated organic extract from step d) is brought into contact with pure water, with a water/concentrated extract mass proportion of 0.83, to proceed to a step e) of hydrodistillation implemented by distillation.
• Stage e) of hydrodistillation is carried out at a column bottom temperature of 49° C., and under a vacuum of 0.008 MPa, so as to facilitate the elimination of the residual MIBK organic solvent, in the form of a water/MIBK azeotrope without 5-HMF degradation.
• the aqueous solution of 5-HMF obtained at the end of step e) has a composition of 42% by weight of 5-HMF, 56.5% by weight of water, 0.9% by weight of DMSO (i.e. 2. 1% by weight of DMSO relative to the weight of 5-HMF) and 0.6% by weight of MIBK.
• the organic raffinate 8 produced according to example 1 is sent to stage d) of concentration.
• the vaporization of the solvent is carried out under vacuum.
• the liquid temperature is set at 60°C, and the vacuum level at 0.02 MPa.
• Step d) is implemented with a mass rate of vaporization of 70%, corresponding to the mass of organic solvent vaporized relative to the mass of organic raffinate resulting from step c) engaged.
• the concentrated organic extract obtained at the end of step d) has a mass content of 5-HMF of 15% by weight, 0.5% by weight in DMSO and 79% by weight in MIBK.
• the concentrated organic extract obtained at the end of step d) also comprises humin impurities (5.5% by weight).
• the concentrated organic extract obtained at the end of step d) still comprises 79.5% by weight of residual solvent (79% of MIBK+0.5% of DMSO).
• the recovered distillate contains mainly MIBK and water, eliminated in the form of an azeotrope with the MIBK, which separates into two immiscible phases upon condensation.
• the 5-HMF content of the 15% weight concentrated organic extract is lower than expected (at least 40% weight and at most 95% weight).
• the residual solvent content of the concentrated organic extract is 79.5% by weight (sum of 79% of MIBK + 0.5% of DMSO) and therefore much higher than the expected value (at least 5% by weight and at most 60% weight).
• the concentrated organic extract from step d) is brought into contact with pure water, with a water/concentrated extract mass proportion of 0.45, to proceed to a step e) of hydrodistillation implemented by distillation.
• Stage e) of hydrodistillation is carried out at a column bottom temperature of 49° C., and under a vacuum of 0.008 MPa, so as to facilitate the elimination of the residual MIBK organic solvent, in the form of a water/MIBK azeotrope without 5-HMF degradation.
• step d) of concentration which still comprises 79.5% by weight of organic solvent (value which is well above the target limit value of 60% weight)
• step e) of hydrodistillation induces a phase separation of the liquid phase, to generate an aqueous phase and an organic phase which are mutually immiscible, not allowing step e) of hydrodistillation to be carried out.

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• 2021
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