WO2017184545A1 - Conversion de matières premières contenant du fructose en produit contenant de l'hmf - Google Patents

Conversion de matières premières contenant du fructose en produit contenant de l'hmf Download PDF

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Publication number
WO2017184545A1
WO2017184545A1 PCT/US2017/028036 US2017028036W WO2017184545A1 WO 2017184545 A1 WO2017184545 A1 WO 2017184545A1 US 2017028036 W US2017028036 W US 2017028036W WO 2017184545 A1 WO2017184545 A1 WO 2017184545A1
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Prior art keywords
fructose
hmf
solvent
reaction zone
product
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PCT/US2017/028036
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English (en)
Inventor
Valery Sokolovskii
Eric L. Dias
Hong X. JIANG
James M. Longmire
Vincent J. Murphy
Christopher Paul DUNCKLEY
Gary M. Diamond
Thomas R. Boussie
James A.W. Shoemaker
Liza Lopez Soto
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Rennovia, Inc.
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Priority claimed from US15/132,178 external-priority patent/US20170015642A1/en
Application filed by Rennovia, Inc. filed Critical Rennovia, Inc.
Publication of WO2017184545A1 publication Critical patent/WO2017184545A1/fr

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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 generally to processes for converting fructose- containing feedstocks, for example, high fructose corn syrup-containing feedstocks, to a product comprising 5-(hydroxymethyl)furfural (HMF) and water.
  • the process comprises the step of converting a fructose-containing feedstock to HMF in a reaction zone in the presence of water, solvent and acid catalyst to attain a relatively low specified yield of HMF at a partial conversion endpoint and thereafter the conversion of fructose to HMF is quenched at the partial conversion endpoint.
  • the sum of unconverted fructose, HMF yield, and the yield of intermediates is at least 90 mol% at the partial conversion endpoint.
  • Fructose is the preferred hexose to produce HMF because it has been demonstrated to be more amenable to dehydration reactions than other hexoses including glucose.
  • High fructose com syrup HFCS
  • HFCS High fructose com syrup
  • the process comprises combining fructose, water, an acid catalyst and at least a first solvent in a reaction zone and converting in the reaction zone a portion of the fructose to HMF and water. At least a portion of the product, unconverted fructose and the first solvent are removed from the reaction zone as a combination and at least a portion of the combination is contacted with a second solvent in a fructose separator to separate at least a portion of unconverted fructose from the combination and produce an intermediate composition having a reduced fructose concentration and comprising the product and at least a portion of each of the first solvent and second solvent. At least a portion of the separated, unconverted fructose is recovered and at least a portion of the first solvent, the second solvent and the product in the intermediate composition are separated from one another.
  • Figure 2 depicts an example of a process flow diagram illustrating certain aspects of the present invention associated with the partial conversion of the fructose- containing feedstock to HMF, including separate solvent and unconverted fructose separation steps, recovery of catalyst (when applicable) and recycling of some or all of these constituents to the reaction zone or elsewhere.
  • Figure 4 depicts an example of a process flow diagram of a process wherein a liquid-liquid extraction step is employed to separate initially, and downstream of the reaction zone, at least a portion of the unconverted fructose and intermediates from the combination withdrawn from the reaction zone.
  • Figure 8 depicts an example of a process flow diagram of a process configuration employing the use of ultra-filtration and nano-filtration to enable the separation of HMF from unconverted fructose and intermediates.
  • Figure 9 graphically illustrates the conversion of fructose to HMF in a continuous flow reaction zone as a function of HC1 concentration at a fixed residence time, highlighting changes in fructose, HMF and intermediates concentrations.
  • Figure 12 graphically illustrates the removal of reaction by-products from an product effluent (organic solvent/water mixture solution) resulting from conversion of fructose to HMF, as a function of alumina surface area. The changes in fructose, HMF and intermediate concentrations are highlighted.
  • An aspect of the present invention is the partial conversion of a fructose- containing feedstock to HMF.
  • the conversion is carried out in a reaction zone that contains at least fructose-containing feedstock, water, acid catalyst and solvent.
  • an aqueous solution of fructose is used as the feedstock to the reaction zone.
  • commercially available high fructose com syrup HFCS
  • HFCS-97 or HFCS- 90 may be used.
  • the reaction takes place in a reaction zone in the presence of an acid catalyst.
  • the catalyst may be a homogeneous or
  • organoboranes aluminum trihalides, phosphorus and antimony pentafluorides, rare earth metal triflates, and metal cation ether complexes.
  • Preferred acids are Bronsted acids selected from the group of HC1, HBr, H2SO4 and H 3 PO4.
  • Quantities of catalyst when homogeneous are typically in the range of from about 0.1 to about 25 mol.% vs. hexose, more typically from about 0.5 to about 10 mol.% or from about 0.5 to about 5 mol.%. Suitable
  • heterogeneous catalysts include acid-functionalized resins, acidified carbons, zeolites, micro- and meso-porous metal oxides, sulfonated and phosphonated metal oxides, clays, polyoxometallates and combinations thereof.
  • Preferred heterogeneous catalysts include acid functionalized resins.
  • the catalyst loading in the reaction mixture will depend upon the type of reactor utilized. For example, in a slurry reactor, the catalyst loading may range from about 1 g/L to about 20 g/L; in a fixed bed reactor the catalyst loading may range from about 200 g/L to about 1500 g/L.
  • off-path product including humins
  • humins As to the formation of off-path product, including humins, applicants have discovered that at a partial conversion of fructose to HMF characterized by a relatively low specified yield of HMF (for example, as shown in Figure 1 where the yield of HMF is about 50% or less at time "t"), the reaction to these undesired products is significantly reduced, as illustrated by the mass balance being > 90% .
  • off-path product at the partial conversion endpoint is maintained at not more than about 10%, more typically not more than about 8%, in various embodiments does not exceed about 5% (as illustrated in Figure 1), and in various preferred embodiments can be controlled so as not to exceed about 3%.
  • the upper end of the HMF yield at the partial conversion endpoint will depend on various factors, including the nature and concentration of the catalyst, water concentration, solvent selection and other factors that can influence the generation of off-path products.
  • operation within the ranges for HMF yield at the partial conversion endpoint as disclosed herein are consistent with the adequate control of the production of off-path intermediates while maintaining desired overall process yield of HMF.
  • the reaction zone is generally maintained at a temperature in the range of from about 50 °C to about 250 °C, more typically in the range of from about 80 °C to about 180 °C. In some embodiments, the reaction zone is maintained at a temperature in the range of from about 100 °C to about 160 °C, or in the range of from about 100 °C to about 150 °C , or in the range of about 100 °C to about 140 °C, or in the range of from about 110 °C to about 130 °C. Generally, higher temperatures increase the reaction rate and shorten the residence time necessary to reach the partial conversion endpoint.
  • the reaction constituents within the reaction zone are typically well-mixed to enhance the conversion rate and the zone is typically maintained at a pressure in the range of from about 1 atm to about 15 atm or from about 2 atm to about 10 atm.
  • the temperature and pressure within the reaction zone are maintained such that the constituents in the reaction zone are largely maintained in the liquid phase.
  • the pressure in the reaction zone can be maintained by supplying an inert gas such as nitrogen.
  • the time during which the reaction is carried out in the reaction zone prior to the partial conversion endpoint and before quenching the conversion of fructose and removal of materials from the zone is variable depending upon the specific reaction conditions employed (e.g., reaction temperature, the nature and quantity of the catalyst, solvent selection, water concentration in the reaction zone, etc.) and generally can range from about 1 to about 60 minutes.
  • the composition of the reaction mixture with respect to HMF yield from fructose and the concentration of intermediates to HMF from fructose and of unconverted fructose can be monitored using various means known to those skilled in the art to determine and establish the desired partial conversion endpoint in accordance with the present invention.
  • the dehydration reaction and conversion of fructose is typically at least partially quenched to avoid significant additional production of any off-path products (e.g., levulinic acid, formic acid, and soluble and insoluble humins).
  • any off-path products e.g., levulinic acid, formic acid, and soluble and insoluble humins.
  • the conversion of fructose can be suitably quenched after the partial conversion endpoint is attained by reducing the temperature of the reaction constituents either within the reaction zone or after being withdrawn from the zone using various industrial means known to those skilled in the art.
  • the reaction constituents may be cooled by flash evaporation, contact with a cooling inert gas, mixing with a liquid diluent, passage through an indirect heat exchanger or a combination of these and other techniques.
  • the reaction constituents are cooled to a temperature below about 100 °C, more typically, below about 60 or 50 °C. It should be understood that other means for quenching the conversion of fructose may be employed without departing from the present invention.
  • the conversion of fructose at the partial conversion endpoint can be quenched by withdrawing some or all of the combination produced from the reaction zone.
  • FIG. 2 illustrates basic process steps employed for the partial conversion of fructose-containing feedstocks to HMF in accordance with the present invention.
  • feedstock is added as an aqueous solution to the reaction zone, or feedstock and water may be added separately.
  • catalyst heterogeneous or homogeneous
  • the catalyst is typically added to the reaction zone prior to the addition of the feedstock, water and solvent.
  • the catalyst may be pre-mixed with the feedstock and/or solvent before being supplied to the reaction zone (see Figure 3 et seq.) or may be added before, simultaneously with or after the feedstock, water and/or solvent is added to the reaction zone. Further, solvent may be added to the reaction zone before, simultaneously with or after addition to the reaction zone of one or more of the other reaction zone constituents.
  • solvent may be added to the reaction zone before, simultaneously with or after addition to the reaction zone of one or more of the other reaction zone constituents.
  • some or all of the reaction constituents may be mixed prior to addition to the reaction zone or mixed in the reaction zone, all so as to enhance the conversion rate in the reaction zone. Mixing can be undertaken by any of a variety of means well known in the art.
  • the conversion step can be carried out in one or more reaction zones.
  • the figures depict only one reaction zone.
  • the process may be carried out in batch, semi-continuously or substantially continuous manner.
  • Any of a variety of well known reactor designs defining at least one reaction zone is suitable for carrying out the process of the present invention.
  • useful reactors include tank reactors, continuously stirred tank reactors (CSTRs), flow through continuous reactors, fixed bed continuous reactors, slurry type reactors and loop reactors, among others. Single reactors may be employed or combinations of several reactors. Again, reactors may comprise one or more reaction zones.
  • reaction zones in series may be employed using, for example, cascading tank reactors or continuous reactors, or one continuous reactor provided with multiple, separated reaction zones.
  • cascading tank reactors or continuous reactors or one continuous reactor provided with multiple, separated reaction zones.
  • the output from the reaction zone is a combination comprising HMF, unconverted fructose, intermediates produced during the conversion step, solvent, water and off-path products which may result from the conversion step. Additionally, when
  • the output from the reactor will include catalyst.
  • Output from the reactor i.e., the combination removed from the reaction zone at the partial conversion endpoint
  • FIG. 3 illustrates an embodiment of the partial conversion process of the present invention using a homogeneous catalyst and employing a combination of a solvent separator 300, a catalyst recovery unit 500, and a product recovery unit 600 to separate and remove unconverted fructose and intermediates from the desired product, HMF in water, and enable recycling of certain reaction constituents.
  • an aqueous stream of fructose-containing feedstock is supplied via 301 to mixer 100 for mixing reaction constituents (e.g., a stirred tank).
  • reaction constituents e.g., a stirred tank
  • Also provided to mixer 100 via 302 is fresh and make up solvent, water via 303, and catalyst via 304.
  • catalyst may also be provided to a reaction zone 200 via 304a.
  • supply of catalyst to mixer 100 and reaction zone 200 need not be exclusive to either; instead, it may be supplied to both.
  • the mixed reaction constituents are supplied to the reaction zone via 305.
  • fructose is converted to HMF until the partial conversion endpoint is attained and then the conversion reaction is suitably quenched as described above.
  • At least a portion of the reaction constituents, product (HMF and water), intermediates to HMF, solvent (in this embodiment the solvent is preferably polar) and off-path products (such as levulinic acid, formic acid, and soluble and insoluble humins, among others) are removed from the reaction zone as a combination and supplied via 306 to solvent separator 300 for separating at least a portion of solvent from the combination.
  • the remaining constituents from the combination withdrawn from reaction zone 200 are delivered via 308 to a filtration unit 400.
  • filtration unit 400 insoluble, typically solid, humins are removed from the stream 308 and disposed of via 308a.
  • the remaining liquid from filtration unit 400 is delivered via 309 to catalyst recovery unit 500 (e.g., an ion exchange unit) designed, for example when HC1 or H2SO4 is the catalyst, to capture the chloride or sulfate ions on the exchange resin prior to the separation of the unconverted fructose from the product.
  • catalyst recovery unit 500 e.g., an ion exchange unit
  • the "catalyst free" eluent from the catalyst recovery unit 500 is supplied via 310 to product recovery unit 600, which in the illustrated
  • embodiment is a continuous chromatographic separation (e.g., simulated moving bed, liquid chromatography or, for short, SMB) unit in which the typically more difficult separation of the unconverted fructose from the product is carried out.
  • SMB units are well known to those of ordinary skill in the art of separations; for example, SMB units are industrially employed in the separation of similar products such as, for example, glucose from fructose.
  • water is added to the bed via 312 and the mixture of HMF, unconverted fructose and water flows through the multiple columns of the SMB unit to separate HMF from fructose.
  • catalyst may also be provided to a reaction zone 200 via 404b.
  • supply of catalyst to mixer 100 and reaction zone 200 need not be exclusive to either; instead, it may be supplied to both.
  • the mixed reaction constituents are supplied to the reaction zone via 405.
  • fructose is converted to HMF until the partial conversion endpoint is attained and then the conversion reaction is suitably quenched as described above.
  • reaction constituents, product (HMF and water), intermediates to HMF, solvent in this embodiment the solvent may be polar or non-polar, preferably polar
  • off-path products such as levulinic acid, formic acid, and soluble and insoluble humins, among others
  • the solvent used to extract unconverted fructose can be used as a cooling medium to quench the conversion of fructose.
  • An unexpected advantage of embodiments of the present invention in which liquid-liquid separation is employed is that the homogeneous acid catalyst is readily recovered and easily resupplied to the reaction zone with, for example, the unconverted fructose.
  • the partitioned unconverted fructose and at least a portion of the acid catalyst are removed via 407.
  • a part of the partitioned unconverted fructose may optionally be purged via 407a for any of a variety of reasons.
  • Figure 5 illustrates a preferred embodiment of the partial conversion process of the present invention using a homogeneous catalyst and employing two solvents, one of which is employed to provide enhanced partitioning in fructose separator 700 for separating unconverted fructose from the combination removed from the reaction zone, for example, by employing liquid-liquid extraction technology.
  • the configuration of major aspects of the process illustrated in Figure 5 is the same as illustrated in Figure 4.
  • an aqueous stream of fructose-containing feedstock is supplied via 501 to mixer 100 for mixing reaction constituents (e.g., a stirred tank).
  • reaction constituents e.g., a stirred tank
  • Also provided to mixer 100 via 502 is fresh and make up solvent, water provided via 503, and catalyst via 504.
  • catalyst may also be provided to a reaction zone 200 via 504a.
  • Supply of catalyst to mixer 100 and reaction zone 200 need not be exclusive to either; instead, it may be supplied to both.
  • the mixed reaction constituents are supplied to the reaction zone via 505.
  • fructose is converted to HMF until the partial conversion endpoint is attained and then the conversion reaction is suitably quenched as described above.
  • fructose separator 700 is a liquid-liquid extraction apparatus.
  • the partitioned unconverted fructose (and catalyst) is removed via 610 and recycled to the mixer 100 as described in more detail hereinafter.
  • a part of the liquid for any of a variety of reasons may be purged via 710a.
  • means may be provided (not illustrated) to remove, for example, by another separation means (such as for example evaporation), a portion of the water that may have been partitioned with the unconverted fructose.
  • the "catalyst free" eluent from the ion exchange unit 500 is supplied via 712 to a second solvent separator 300a for separating the second solvent from the product.
  • a flash evaporation unit may be utilized to vaporize the second solvent and some water, preferably essentially only the second solvent.
  • the bottoms fraction, now comprised of product and off-path materials can be withdrawn via 714.
  • separated first solvent from solvent separator 300 is supplied via 710b as a component of the recycled mixture provided to mixer 100 via 710c.
  • Separated second solvent from second solvent separator 300a is recovered via 713 and resupplied to the fructose separator 700. Make-up second solvent, if needed, may be added via 713a.
  • the remaining product and off- path materials withdrawn from second solvent separator 300a via 714 are delivered via
  • the aqueous combination removed from the reaction zone intended for selective membrane separation treatment may be collected in an optional feed tank (not shown).
  • the suspended solids content in the aqueous combination removed from the reaction zone is optionally controlled.
  • the aqueous combination will contain less than about 10,000 ppm of suspended solids.
  • the suspended solids content of the aqueous combination subj ected to membrane separation may be reduced to less than about 1000 ppm, less than about 500 ppm, or less than about 100 ppm.
  • Suitable continuous filters include cross-flow filters and continuous back-pulse filters wherein a portion of the filtrate is used to periodically back-pulse the filter media to dislodge and remove separated solids.
  • the filter media employed is capable of separating and removing suspended solids greater than about 250 ⁇ in size from the aqueous combination. It should be understood that any optional solids reduction stage may comprise a combination of dilution, filtration and/or other operations to attain the desired solids content in the aqueous combination prior to selective membrane separation treatment.
  • the suspended solids content of the aqueous combination removed from the reaction zone can be readily determined by analytical methods known in the art such as by turbidity measurement (e.g., nephelometric turbidity units or NTU) and correlation of the turbidity reading to a known standard or by other methods known to those skilled in the art.
  • analytical methods known in the art such as by turbidity measurement (e.g., nephelometric turbidity units or NTU) and correlation of the turbidity reading to a known standard or by other methods known to those skilled in the art.
  • the reaction product is fed through the spiral wound nanofiltration membrane assembly with a flow of > 20 cms "1 .
  • the dehydration reactor can be designed such that the fructose can be fed through the continuous reactor at the same velocity of > 20 cms "1 in which the fructose conversion is controlled within the range of 10 - 50%, or more preferably within the range of 10 - 35%.
  • the surface area of the membrane with the spiral wound assembly (or multiplexed assemblies) is chosen such that recovery of the HMF produced in the partial conversion reaction reaches a minimum of 85% (for example greater than about 85%, preferably greater than about 90%, or greater than about 95%, more preferably greater than about 97%) in the combined permeate streams.
  • the retentate from the membrane filtration which contains the unconverted fructose, and optionally the acid catalyst, is recycled back to the dehydration reactor.
  • the retentate from the membrane filtration is subj ected to a purge prior to its recycling to the dehydration reactor.
  • the purge stream can serve to enable removal of unwanted components that could otherwise build up in the recycle loop from the reaction, such as low levels of unwanted reaction products such as humins, or unwanted components that may be present in the fructose feedstock (e.g glucose or disaccharides or oligosaccharides).
  • Feed 1 10 wt% HFCS-90, dissolved in Dioxane/H 2 0 (4/1 by volume); and Feed 2: 10 wt% HFCS-90, 0.12 wt% HCl dissolved in Dioxane/H 2 0 (4/1 by volume).
  • reaction conversion was controlled by varying the amount of HCl through changes in the flow ratio of Feed 1 and Feed 2.
  • Reaction progress was monitored and product composition was determined by HPLC analysis on a Thermo Ultimate 3000 analytical chromatography system using a porous graphitic stationary phase (Hypercarb, 3.0 x 100mm, 5um) at 30°C. Fructose and glucose were eluted under isocratic conditions of 0.005% v/v NH 4 OH in H 2 0 at a flow rate of 0.6 mL/min.
  • cross-flow filtration was performed by circulating 1L of the opaque dark brown aqueous product mixture through a 2.6 m 2 spiral wound H series membrane having a MWCO of 150-300 available from GE Water & Process Technologies, Inc. After 20.0 minutes, the collected permeate was analyzed by HPLC. The permeate consisted primarily of HMF with a very small amount of fructose and no detectable quantity of glucose or intermediates. The colored bodies (humins) were substantially removed. The collected permeate was a clear pale yellow solution.
  • aluminum oxide is used as an adsorbant to remove humins, 2-hydroxyacetylfuran (HAF), and unreacted glucose from an organic solvent/water product effluent resulting from conversion of fructose to HMF.
  • HMF and the by-product furfural are not adsorbed on alumina and can be recovered from the purified solution.
  • the adsorbed by-products can be desorbed from the solid aluminum oxide using aqueous NaOH solution. This allows a facile method for regenerating the adsorbant for use in additional product purification reactions.
  • humins are not significantly desorbed from alumina spheres using dioxane/water, acetone or methanol solutions.
  • alumina spheres When alumina spheres are treated with 0.1N NaOH (aq.), humins are immediately desorbed.
  • Higher surface area alumina spheres SA > 80 absorb humins (color) without adsorbing HMF or furfural.
  • the HAF by- product is completely adsorbed and removed from solution.
  • Al oxide (Sasol 0.5/200) is used as an adsorbant to remove humins, 2-hydroxyacetylfuran (HAF), and unreacted glucose from a reaction solution effluent resulting from conversion of fructose to HMF.
  • 0.28 g Sasol 0.5/200 was added to a 2.6 g reaction solution containing fructose (5.7 wt%; 0.293 M), HC1 (0.1 wt%), water (18.5 wt%), and dimethoxy ethane (75.7 wt%) at pH 1.81. It was observed that the pH of the solution became more acidic (pH lowered) over time after removal of alumina from the solution. The results from this experiment are shown in Table 8 below.
  • activated carbon (Norit GAC 1240+) is used as an adsorbant to remove humins, 2-hydroxyacetylfuran (HAF), and unreacted glucose from a reaction solution effluent resulting from conversion of fructose to HMF.
  • 0.28 g Norit GAC 1240+ was added to a reaction solution containing fructose (5 wt%), HC1 (0.1 wt%), water (18.5 wt%), and dimethoxyethane (76.4 wt%) at pH 1.65. The results of this experiment are shown in Table 9 below.
  • a heterogeneous solid acid catalyst Purolite 482 was used (supplied by Puriolite, containing a proton loading of 4.82 meq./g).
  • a heterogeneous reduction catalyst comprising lwt.% Pt supported on Fe2C>3 was prepared as follows: 0.5 g of Fe2C>3 (supplied by Baker) was impregnated with a 0.25 mL of a solution prepared by combining 0.08 mL of a solution of (NH 3 ) 4 Pt(OH) 2 (63.2mg/ml Pt) with 0.17 mL of deionized water. The resultant material was dried at 120°C for 2 hours, calcined at 300°C for 4 hours and then reduced under a flow of forming gas at 350°C for a further 3 hours.
  • the glass vial was removed and a reaction aliquot was sampled for analysis by both GC and HPLC.
  • the reaction product from the control vial was a dark brown solution indicative of the presence of humins.
  • the principal products detected by GC and HPLC from the control vial were HMF and levulinic acid.
  • the reaction product from the vial containing the reduction catalyst was a light orange color indicative of lower levels of humins.
  • the principal reaction products detected by GC and HPLC were BHMF and HMF, demonstrating that BHMF can be prepared by in situ reduction of HMF prepared from the catalytic dehydration of fructose.
  • This example describes a dehydration reaction, converting fructose to HMF using tetraethylammonium bromide.
  • An aqueous stock solution was prepared by combining Fructose (1.2g, 6.66 mmol), tetraethylammonium bromide (0.6g, 2.86 mmol), H 2 0 (3.8 g) and IN aqueous HCl (0.669g).
  • a glass reaction vial was charged with 0.786g of this aqueous solution followed by addition of 1,4-dioxane (2.23g). The resulting
  • This example describes a dehydration reaction, converting fructose to HMF without using tetraethylammonium bromide (comparison example).
  • An aqueous stock solution was prepared by combining Fructose (1.2g, 6.66 mmol), H 2 0 (3.8 g) and IN aqueous HCl (0.669g).
  • a glass reaction vial was charged with 0.71 lg of this aqueous solution followed by addition of 1,4-dioxane (2.33g).
  • the resulting homogeneous monophasic reaction solution was sealed and heated at 120°C for lh with magnetic stirring. After cooling to room temperature, an aliquot was removed and diluted with H 2 0 for HPLC analysis. Quantification of fructose and HMF was made using external calibration standards. The molar yield of HMF was 77.8% at 98% Fructose conversion.
  • This example describes an experiment in which an ultrafiltration ceramic membrane is used to remove humins from a reaction solution containing HMF, fructose, glucose, and humins, in a solvent combination containing water and a water miscible organic solvent using H 2 SC>4 as a catalyst.
  • a ceramic PFM ultrafiltration membrane module with a 800 Dalton molecular weight cut off (MWCO) supplied by Cerahelix was used (see www. cerahelix. com; website April 9 th 2016).
  • the membrane was housed in a 1 meter multi-channel filter tube developed by Cerahelix with a usable surface area of 0.18 m 2 and was deployed with a cross-flow velocity of 10 cms "1 and an applied pressure of 160 - 200 psi.
  • the separation started with 2.575 L of a reaction product generated from a 10 wt.% solution (in 4/1 v/v Dioxane/H 2 0) of high fructose corn syrup 90 (HFCS-90) in which 90% of the fructose was converted using H 2 SC>4 as a dehydration catalyst (0.4 wt %) to a darkly colored reaction mixture comprising HMF, humins, unconverted fructose and unconverted glucose.
  • HFCS-90 high fructose corn syrup 90
  • This example describes an experiment in which membrane separations using polymeric membranes were conducted using a cross-flow filtration through a flat sheet membrane (surface are 42cm 2 ) deployed in a cross-flow membrane testing cell supplied by Sterlitech (see www, sterli tech .com website April 9 th 2016). Unless otherwise stated, a cross- flow velocity of 12 cms "1 was used with an applied pressure of 400 psi across the membrane.
  • the testing cell was used to test 17 polymer membranes in the following manner: A darkly colored reaction product was generated from a 10 wt.% solution (in 4/1 v/v Dioxane/H 2 0) of HFCS-90 in which all of the fructose was converted using a very low concentration of HC1 as a dehydration catalyst (0.01 wt.%) to a reaction mixture comprising HMF, humins, and glucose. The reaction product was first neutralized by the addition of NaOH (1 stoichimetric equivalent with respect to the HC1 present in the starting solution). A cross-flow velocity of 12 cms "1 was used with an applied pressure of 100-400 psi across the membrane within the membrane testing cell.
  • Membranes were tested for compatibility with the reaction solvent by measuring the flux of the permeation. Membranes that showed very low or no measurable flux were considered incompatible. Membranes that showed very high fluxes with no separation were also considered incompatible. The ability of the membrane to reject humins which was assessed by the color of the permeate solution and/or UV/Vis spectroscopy. Membranes capable of humins removal produced a permeate solution that was light yellow or light orange in color, and a retentate solution that was darker in color than in the reaction product. A list of the membranes tested and the results are shown in Table 10 below.
  • PolAn_Pol_oNF_Ml_2 (see www.poly-an.de website April 8 th 2016) was secured in place in the testing cell.
  • the separation started with 3.842 L of a darkly colored reaction product generated from a 10 wt.% solution (in 4/1 v/v Dioxane/H 2 0) of HFCS-90 in which almost all of the fructose was converted using a very low concentration of HC1 (0.01 wt.%) as a dehydration catalyst.
  • the reaction product was first neutralized by the addition of NaOH (1 stoichimetric equivalent with respect to the HC1 present in the starting solution). 3.428 L of the neutralized reaction solution was filtered through the ultrafiltration membrane (90% single pass recovery).
  • Example 16 the testing cell described in Example 16 was used to test 7 polymer membranes in the following manner: A darkly colored reaction product was generated from a 10 wt.% solution (in 4/1 v/v Dioxane/H 2 0) of HFCS-90 in which all of the fructose was converted using a very low concentration of HCl as a dehydration catalyst (0.01 wt.%). The reaction product was first neutralized by the addition of Ca(OH) 2 (1 stoichimetric equivalent with respect to the HCl present in the starting solution). A cross-flow velocity of 12 cms "1 was used with an applied pressure of 400 psi across the membrane within the membrane testing cell.
  • the ability of the membrane to reject humins was assessed by the color of the permeate solution and/or UV -Visible spectroscopy. Membranes capable of humins removal produced a permeate solution that was light yellow or light orange in color, and a retentate solution that was darker in color than in the reaction product. In all cases, humins were rejected by the membranes while HMF permeated through the membrane.
  • the ability of the membrane to rej ect the calcium salt was determined by ICP by measuring the calcium concentration of the permeate solution relative to the neutralized reaction product. The calcium content of the retentate was consistent with the expected value from the neutralization. In all cases the calcium content of the permeate was consistent with background calcium concentrations. The results are shown in Table 1 1.

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  • Furan Compounds (AREA)

Abstract

La présente invention concerne de manière générale des procédés de conversion de matières premières contenant du fructose en un produit comprenant du 5-(hydroxyméthyl) furfural (HMF) et de l'eau en présence d'eau, de solvant et d'un catalyseur acide. Dans des modes de réalisation, la conversion de fructose en HMF est commandée au niveau d'un point d'extrémité de conversion partielle caractérisé par un rendement d'HMF à partir de fructose qui ne dépasse pas environ 80 % en moles. Dans ces modes de réalisation et dans d'autres, les procédés fournissent des techniques de séparation pour séparer et récupérer le produit, du fructose non converti, un solvant et un catalyseur acide pour permettre la récupération et la réutilisation efficaces de composants réactionnels.
PCT/US2017/028036 2016-04-18 2017-04-18 Conversion de matières premières contenant du fructose en produit contenant de l'hmf WO2017184545A1 (fr)

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US15/132,178 US20170015642A1 (en) 2014-01-27 2016-04-18 Conversion of fructose-containing feedstocks to hmf-containing product
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WO2019229080A1 (fr) * 2018-05-29 2019-12-05 Südzucker AG Production de hmf catalysée par un mélange de sels et d'acides
CN110551639A (zh) * 2019-09-09 2019-12-10 南京工业大学 一种短梗霉菌株及其在2,5-二羟甲基呋喃合成中的应用
CN111909123A (zh) * 2019-05-07 2020-11-10 中国石油化工股份有限公司 一种连续分离提纯5-羟甲基糠醛及其衍生物的方法及装置
CN112047907A (zh) * 2020-09-22 2020-12-08 浙江大学 一种甲酸供氢、金属卤化物协同催化下葡萄糖一锅法制备2,5-呋喃二甲醇的方法
US20210292290A1 (en) * 2018-07-13 2021-09-23 Novamont S.P.A. Process for the production and separation of 5-hydroxymethylfurfural with quaternary ammonium salts

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019229080A1 (fr) * 2018-05-29 2019-12-05 Südzucker AG Production de hmf catalysée par un mélange de sels et d'acides
JP2021525732A (ja) * 2018-05-29 2021-09-27 ズートツッカー アーゲー 塩と酸との混合物により触媒されるｈｍｆの製造
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US20210292290A1 (en) * 2018-07-13 2021-09-23 Novamont S.P.A. Process for the production and separation of 5-hydroxymethylfurfural with quaternary ammonium salts
CN111909123A (zh) * 2019-05-07 2020-11-10 中国石油化工股份有限公司 一种连续分离提纯5-羟甲基糠醛及其衍生物的方法及装置
CN110551639A (zh) * 2019-09-09 2019-12-10 南京工业大学 一种短梗霉菌株及其在2,5-二羟甲基呋喃合成中的应用
CN112047907A (zh) * 2020-09-22 2020-12-08 浙江大学 一种甲酸供氢、金属卤化物协同催化下葡萄糖一锅法制备2,5-呋喃二甲醇的方法
CN112047907B (zh) * 2020-09-22 2024-03-19 浙江大学 一种甲酸供氢、金属卤化物协同催化下葡萄糖一锅法制备2,5-呋喃二甲醇的方法

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