WO2020190043A1 - Method for producing 5-alkoxy-methylfurfural and 2,5-furandicarboxylic acid from fructose - Google Patents

Method for producing 5-alkoxy-methylfurfural and 2,5-furandicarboxylic acid from fructose Download PDF

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WO2020190043A1
WO2020190043A1 PCT/KR2020/003741 KR2020003741W WO2020190043A1 WO 2020190043 A1 WO2020190043 A1 WO 2020190043A1 KR 2020003741 W KR2020003741 W KR 2020003741W WO 2020190043 A1 WO2020190043 A1 WO 2020190043A1
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fructose
catalyst
alkoxymethylfurfural
oxide
producing
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PCT/KR2020/003741
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French (fr)
Korean (ko)
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황동원
황영규
홍도영
판다리나스 우파레프라빈
이마음
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한국화학연구원
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Priority claimed from KR1020190032162A external-priority patent/KR102337169B1/en
Priority claimed from KR1020190151543A external-priority patent/KR102278268B1/en
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2020190043A1 publication Critical patent/WO2020190043A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • 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
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

  • the present invention relates to a method for preparing 2,5-furandicarboxylic acid from fructose, and more particularly, to an intermediate 5 from fructose using a solid acid catalyst.
  • -It relates to a method of preparing alkoxy-methylfurfural and preparing 2,5-furandicarboxylic acid therefrom.
  • 2,5-Furandicarboxylic acid (hereinafter referred to as'FDCA') is an organic compound in which two carboxylic acids are bonded to the furan ring, and as an alternative to petroleum-derived terephthalic acid, interest has recently increased. It is a chemical substance.
  • FDCA can be manufactured from renewable resources and is an intermediate used in various fields such as pesticides, pharmaceuticals, pesticides, pharmaceuticals or antibacterial agents.
  • FDCA synthesizes FDCA by oxidizing 5-hydroxymethylfurfural (hereinafter'HMF'), which is induced by dehydration of hexose derivatives, through a catalyst.
  • HMF' 5-hydroxymethylfurfural
  • DFF diformylfuran
  • HFCA hydroxymerylfurancarboxylic acid
  • FCA formylfurancarboxylic acid
  • fructose is a monosaccharide having a ketone as a reducing group, one of the hexose and widely present in the plant world, it is contained in fruit with glucose in a free form or combined with glucose to exist as sucrose.
  • HMF is prepared through a fructose dehydration reaction in one step, and HMF is oxidized in a second step.
  • Patent Document 1 Korean Laid-Open Patent Publication No. 10-2018-7018309.
  • HMF in order to prepare FDCA from fructose in high yield, HMF must be prepared in a high boiling point organic solvent and then HMF must be separated from the organic solvent before the HMF oxidation reaction.
  • reaction temperature in the case of removing the solvent by evaporation, the reaction temperature must be kept below 50°C in order not to decompose HMF.
  • the present invention is to provide a method for economically producing FDCA from fructose.
  • a catalytic process technology for producing FDCA without the process of separating the intermediate after fructose dehydration using a solid acid catalyst.
  • a catalyst with high economic efficiency by using a heterogeneous catalyst instead of a homogeneous catalyst in the FDCA generation step It provides a method of manufacturing FDCA by replacing it with a substance.
  • the organic solvent may be methanol or ethanol.
  • the solid acid catalyst may include sulfonic acid (-SO 3 H) as a functional group.
  • the filtration may be performed using a filter paper after cooling the 5-alkoxymethylfurfural solution to room temperature of 20 to 30°C.
  • the 5-alkoxymethylfurfural solution may be pressurized, heated, and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid.
  • the pressurization may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150 °C.
  • the oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ), gold, platinum , It may be characterized in that any one metal selected from the group consisting of palladium and ruthenium is supported.
  • the oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, It may be characterized in that the transition metal oxide is supported on any one support selected from the group consisting of cerium oxide and aluminum oxide (Al 2 O 3 ).
  • the organic solvent may be methanol or ethanol.
  • the solid acid catalyst may include sulfonic acid (-SO 3 H) as a functional group.
  • the pressurization may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150°C.
  • the oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ), gold, platinum, Any one metal selected from the group consisting of palladium and ruthenium may be supported.
  • the oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite,
  • the transition metal oxide may be supported on any one support selected from the group consisting of cerium oxide and aluminum oxide (Al 2 O 3 ).
  • Crystallization or distillation may be used to recover 2,5-furandicarboxylic acid crystals from the filtrate.
  • 2,5-furandicarboxylic acid can be economically prepared from fructose, which is very abundant in the plant world.
  • the oxidation reaction can proceed immediately without additional post-treatment.
  • 2,5-furandicarboxylic acid can be prepared and recovered in high yield using a more economical heterogeneous oxidation catalyst.
  • 2,5-furandicarboxylic acid can be prepared and recovered through a one-pot process without a separate process of separating the intermediate.
  • FIG. 1 is a process flow diagram showing a process of a method for producing 5-alkoxymethylfurfural using a solid acid catalyst according to an embodiment of the present invention.
  • FIG. 2 is a process flow diagram showing a process of a method for producing 2,5-furandicarboxylic acid using a catalyst according to another embodiment of the present invention.
  • the present inventors believe that when the dehydration reaction of fructose is performed in an aqueous solution, the resulting 5-hydroxymethyl-2-furfural (hereinafter referred to as'HMF') is a secondary reaction with water.
  • 5-alkoxymethylfurfural was first prepared using a solid acid catalyst in the presence of alcohol, and a solid acid catalyst was prepared. After removing by filtration, it is immediately oxidized using a heterogeneous oxidation catalyst without any separate treatment, and the final product, 2,5-furandicarboxylic acid (hereinafter referred to as'FDCA'), in high yield through oxidation reaction.
  • 'FDCA' 2,5-furandicarboxylic acid
  • FIG. 1 is a process flow diagram showing a process of a method for producing 5-alkoxymethylfurfural from fructose according to an embodiment of the present invention
  • FIG. 2 is a process flow diagram showing the process of a method for producing 5-alkoxymethylfurfural from fructose according to an embodiment of the present invention. It is a process flow diagram showing the process of the 2,5-furandicarboxylic acid production method.
  • the present invention relates to a method of preparing 5-alkoxymethylfurfural, an intermediate, from fructose, using a solid acid catalyst, and reacting the intermediate, 5-alkoxymethylfurfural, with a heterogeneous oxidation catalyst, to produce 2,5-furan in high yield. It provides a method for preparing 2,5-furandicarboxylic acid from fructose, including a method for preparing dicarboxylic acid.
  • a mixed solution is prepared by mixing fructose and an organic solvent (S10).
  • the fructus is a carbohydrate and is converted to 5-alkoxymethylfurfural by dehydration.
  • the 5-alkoxymethylfurfural is 5-methoxymethylfurfural (“MMF”) or 5-ethoxymethylfurfural (“EMF”).
  • the organic solvent is methanol or ethanol.
  • C 3 or more alcohols other than methanol or ethanol are difficult to convert to 5-alkoxymethylfurfural by dehydrating fructose using a solid acid catalyst, and there is a problem of generating by-products after the reaction.
  • the mixed solution may be heated and reacted under a solid acid catalyst to prepare 5-alkoxymethylfurfural (S20).
  • the solid acid catalyst acts as a proton donor or electron acceptor and is used as a catalyst for dehydration.
  • the solid acid catalyst may be an ion exchange resin containing sulfonic acid (-SO 3 H) as a functional group.
  • the solid acid catalyst may be graphene oxide, activated carbon, or a polymer in which a sulfonic acid (-SO 3 H) is bonded to a functional group.
  • GO-SO 3 H means that sulfonic acid is bonded to graphene oxide
  • AC-SO 3 H means that sulfonic acid is bonded to activated carbon
  • the sulfonic acid functional group acts as a Bronsted acidic function.
  • the solid acid catalyst has very high catalytic activity and is very advantageous for dehydration reaction.
  • the heating may be performed at 60 to 120 °C.
  • fructose may be converted to 100%, and EMF or MMF may be prepared in a yield of 70 to 90%.
  • the solid acid catalyst is separated from the mixed solution containing 5-alkoxymethylfurfural through filtration (S30).
  • the filtration may be performed using a filter paper after cooling the 5-alkoxymethylfurfural solution to room temperature at 20 to 30°C.
  • the reaction catalyst may be removed through the filtration.
  • EMF or MMF can be prepared by using a solid acid catalyst, and unlike a separate treatment process for separating the conventional high boiling point organic solvent phase, the solid acid catalyst is very effectively removed through filtration, and 5-alkoxymethyl peroxide is used in high yield.
  • Fural (5-alkoxymethylfurfural) can be prepared.
  • the 5-alkoxymethylfurfural solution may be pressurized, heated, and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid.
  • the pressurization may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150 °C.
  • FDCA can be produced with high efficiency by using an oxidation catalyst within the pressurized and heated range, and if it is not within the above range, the yield due to the oxidation reaction is low, and if it exceeds the above range, the reaction yield is not increased. There is a problem that more energy is consumed.
  • the oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ) gold, platinum, palladium on the support And any one metal selected from the group consisting of ruthenium may be supported.
  • the oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, or activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, oxidation
  • the transition metal oxide may be supported on any one support selected from the group consisting of cerium and aluminum oxide (Al 2 O 3 ).
  • the oxidation catalyst is a heterogeneous catalyst, and since it is easier to separate the catalyst from the FDCA after an oxidation reaction compared to a conventional homogeneous catalyst, it is environmentally friendly and can greatly reduce the process cost.
  • fructose is mixed with ethanol under a solid acid catalyst to generate EMF, an intermediate, and is converted to FDCA by reacting with a Pt/C oxidation catalyst under oxygen pressure.
  • a mixed solution is prepared by mixing fructose and an organic solvent (S100).
  • the organic solvent may be methanol or ethanol.
  • C 3 or more alcohols other than methanol or ethanol are difficult to convert to 5-alkoxymethylfurfural by dehydrating fructose using a solid acid catalyst, and there is a problem of generating by-products after the reaction.
  • the mixed solution is heated and reacted under a solid acid catalyst to prepare 5-alkoxymethylfurfural (S200).
  • the solid acid catalyst may be an ion exchange resin containing sulfonic acid (-SO 3 H) as a functional group.
  • the solid acid catalyst may be graphene oxide, activated carbon, or a polymer in which a sulfonic acid (-SO 3 H) is bonded to a functional group.
  • the solid acid catalyst in which the sulfonic acid is bonded to a functional group acts as a proton donor or electron acceptor and is used as a catalyst for dehydration reaction.
  • the sulfonic acid functional group acts as a Bronsted acidic function.
  • the solid acid catalyst has very high catalytic activity and is very advantageous for dehydration reaction.
  • the conversion rate of fructose is low, and a reaction temperature of 90° C. or higher is required during the heating reaction, thereby reducing process efficiency.
  • the heating may be performed at 60 to 120 °C.
  • fructose may be converted to 100%, and EMF or MMF may be prepared in a yield of 70 to 90%.
  • the solid acid catalyst is filtered and separated from the 5-alkoxymethylfurfural solution in which the solid acid catalyst is mixed (S300).
  • the reaction catalyst can be removed through the filtration.
  • EMF or MMF can be prepared using a solid acid catalyst, and unlike a separate treatment process for separating the conventional high boiling point organic solvent phase, the solid acid catalyst is very effectively removed through filtration, and EMF or MMF is obtained at a high conversion rate. 5-alkoxymethylfurfural can be prepared.
  • the pressurization and heating may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150°C.
  • FDCA can be manufactured with high efficiency by using an oxidation catalyst within the pressurized and heated range, and if it is not within the above range, the yield due to the oxidation reaction is low. There is a problem that more energy is consumed.
  • the oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ) gold, platinum, palladium on the support And any one metal selected from the group consisting of ruthenium may be supported.
  • the oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite,
  • the transition metal oxide may be supported on any one support selected from the group consisting of cerium oxide and aluminum oxide (Al 2 O 3 ).
  • a heterogeneous catalyst can be prepared to perform an oxidation reaction, and the catalyst can be easily recovered and reused, thereby reducing the overall process cost, thereby increasing the efficiency of the process.
  • the oxidation reaction of EMF or MMF may be performed by pressurization within the above range, and FDCA may be prepared in a yield of 90% or more.
  • the oxidation catalyst is separated by filtration from the 2,5-furandicarboxylic acid solution in which the oxidation catalyst is mixed, and then 2,5-furandicarboxylic acid is recovered from the filtrate (S500).
  • Crystallization or distillation may be used in order to recover 2,5-furandicarboxylic acid crystals from the filtrate.
  • the content of the sulfone group (S-density, mmol/g) was confirmed through elemental analysis of the sulfonated material.
  • AC-SO 3 H contained 2.5 mmol/g -SO 3 H group, which was confirmed to be about twice as much as 1.2 mmol/g of GO-SO 3 H, so that AC-SO 3 H has a stronger acidic point (acidic site).
  • AC-SO 3 H and GO-SO 3 H have higher S-density than that of MTS-GO (methoxytrimethylsiliane-graphene oxide) or Zr(SO 4 ) 2 catalyst, so it was predicted to be very effective in fructose dehydration reaction.
  • the EMF/ethanol solution obtained through the above process was heated to 60° C., maintained for 48 hours, and then cooled to room temperature.
  • EMF when EMF is prepared in an ethanol solvent using an AC-SO 3 H catalyst, EMF can be obtained in a high yield of 90% or more, and when the catalyst is removed after the catalytic reaction is completed, the secondary reaction of EMF can be suppressed. You can see that there is.
  • fructose 1 g was mixed with 9 ml of methanol and 1.0 g of a GO-SO 3 H catalyst, heated to 60° C., and reacted for 30 hours. After the reaction, the sample was cooled to room temperature, and the GO-SO 3 H catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the MMF yield was 91%.
  • the MMF/methanol solution obtained through the above process was heated to 60° C., maintained for 48 hours, and then cooled to room temperature. As a result of analyzing the solution through liquid chromatography, there was almost no change in the concentration of MMF.
  • MMF when MMF is prepared in a methanol solvent using a GO-SO 3 H catalyst, MMF can be obtained in a high yield of 90% or more, and when the catalyst is removed after the catalytic reaction is completed, the secondary reaction of MMF can be suppressed. You can see that you can.
  • fructose 1 g was mixed with 9 ml of methanol and 1.5 g of a catalyst (hereinafter referred to as “AC-SO 3 H”) in which a sulfonic acid was bonded to a functional group on an activated carbon support, heated to 60° C., and reacted for 21 hours.
  • AC-SO 3 H a catalyst in which a sulfonic acid was bonded to a functional group on an activated carbon support, heated to 60° C., and reacted for 21 hours.
  • the sample was cooled to room temperature, and the AC-SO 3 H catalyst was separated from the solution through filtration.
  • fructose 1 g was mixed with 9 ml of methanol and 1.0 g of an AC-SO 3 H catalyst, heated to 80° C., and reacted for 12 hours.
  • the sample was cooled to room temperature, and the AC-SO 3 H catalyst was separated from the solution through filtration.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with platinum on an activated carbon support (hereinafter'Pt(5%)/C'), heated to 100° C., and then heated to 15 bar using O 2 gas. After raising the pressure, the reaction was carried out for 2 hours.
  • a catalyst coated with platinum on an activated carbon support hereinafter'Pt(5%)/C'
  • the sample was cooled to room temperature of 27° C., and the solid mixture was separated from the solution through filtration.
  • the solid mixture was mixed with 10 ml of a dimethylformamide (hereinafter referred to as'DMF') solvent, and then the catalyst was separated from the solution through filtration.
  • a dimethylformamide hereinafter referred to as'DMF'
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with gold on a hydrotalcite support (hereinafter, referred to as'Au(5%)/hydrotalcite'), heated to 100° C., and then used O 2 gas. After raising the pressure to 15 bar, the reaction was carried out for 2 hours.
  • a catalyst coated with gold on a hydrotalcite support hereinafter, referred to as'Au(5%)/hydrotalcite'
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 95%.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of Au (5%)/hydrotalcite catalyst, heated to 100° C., and the pressure was raised to 10 bar using O 2 gas, and the reaction was carried out for 2 hours.
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 90%.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a ruthenium-coated catalyst (hereinafter referred to as'Ru(5%)/C') on an activated carbon support, heated to 100° C., and then heated to 15 bar using O 2 gas. After raising the pressure, the reaction was carried out for 2 hours.
  • a ruthenium-coated catalyst hereinafter referred to as'Ru(5%)/C'
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • the catalyst was separated from the solution through filtration.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with ruthenium on a cerium oxide support (hereinafter, referred to as'Ru(5%)/CeO 2 '), heated to 100° C., and then 15 using O 2 gas. After raising the pressure to bar, the reaction was carried out for 2 hours.
  • a catalyst coated with ruthenium on a cerium oxide support hereinafter, referred to as'Ru(5%)/CeO 2 '
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • the catalyst was separated from the solution through filtration.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with palladium on an activated carbon support (hereinafter referred to as'Pd(5%)/C'), heated to 100° C., and then 15 bar using O 2 gas. After raising the pressure, the reaction was carried out for 2 hours.
  • a catalyst coated with palladium on an activated carbon support hereinafter referred to as'Pd(5%)/C'
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with platinum on an activated carbon support (hereinafter, referred to as'Pt(5%)/C'), heated to 100° C., and then pressurized to 20 bar using air. After raising the reaction was carried out for 2 hours.
  • a catalyst coated with platinum on an activated carbon support hereinafter, referred to as'Pt(5%)/C'
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of Ru-Sn (5%)/CeO2 catalyst, heated to 100° C., and the pressure was raised to 15 bar using O 2 gas, and the reaction was carried out for 2 hours. I did.
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 90%.
  • Example 2 The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of MnOx/CeO2 (Mn/Ce molar ratio 6) catalyst, heated to 100° C., and then increased the pressure to 15 bar using O 2 gas, and reacted for 2 hours. Proceeded.
  • MnOx/CeO2 Mn/Ce molar ratio 6
  • the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
  • an EMF oxidation catalyst not only noble metal catalysts such as Pt/C, Ru/C, Pd/C, Ru/CeO2, Ru-Sn/ZnO, but also transition metal catalysts such as MnOx/CeO2 are used. This is possible. In particular, transition metal catalysts such as MnOx/CeO2 are advantageous in economically producing FDCA because the price is much lower than that of precious metal catalysts.
  • fructose 1 g was mixed with 9 ml of 1-butanol and 1.0 g of Amberlsyt-15 resin, heated to 100° C., and reacted for 5 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
  • fructose 1 g was mixed with 9 ml of isopropyl alcohol and 1.0 g of Amberlsyt-15 resin, heated to 100° C., and reacted for 5 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
  • Example 1 The EMF/ethanol solution prepared in Example 1 was heated to 100° C. without an oxidation catalyst, and the pressure was raised to 20 bar using air, and the reaction was carried out for 2 hours.
  • the sample was cooled to room temperature, the solid mixture was mixed with 10 ml of a DMF solvent, and analyzed by liquid chromatography. As a result, the EMF conversion was found to be 15% and the FDCA yield was 10%.
  • 2,5-furandicarboxylic acid can be economically prepared from fructose, which is very abundant in the plant world.
  • the oxidation reaction can proceed immediately without additional post-treatment.

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Abstract

The present invention provides a method for producing 2,5-furandicarboxylic acid using catalysts, the method comprising: (a) a step for mixing fructose and an organic solvent to prepare a mixed solution; (b) a step for heating and reacting the mixed solution in the presence of a solid-acid catalyst to prepare alkoxy-methylfurfural; (c) a step for filtering and separating the solid-acid catalyst from a 5-alkoxy-methylfurfural solution in which the solid-acid catalyst is mixed; (d) a step for pressurizing, heating, and reacting, in the presence of an oxidation catalyst, the solution from which the solid-acid catalyst has been separated, to prepare 2,5-furandicarboxylic acid; and (e) a step for filtering and separating the oxidation catalyst from the 2,5-furandicarboxylic acid solution in which the oxidation catalyst is mixed, and then recovering 2,5-furandicarboxylic acid from the filtrate. Accordingly, 2,5-furandicarboxylic acid can be economically produced from fructose.

Description

프룩토스로부터 5-알콕시메틸퍼퓨랄 및 2,5-퓨란디카르복실산의 제조방법Method for producing 5-alkoxymethylfurfural and 2,5-furandicarboxylic acid from fructose
본 발명은 프룩토스(fructose)로부터 2,5-퓨란디카복실산 (2,5-Furandicarboxylic acid)을 제조하는 방법에 관한 것으로서, 더욱 상세하게는 고체산촉매를 사용하여 프룩토스(fructose)로부터 중간체인 5-알콕시메틸퍼퓨랄(alkoxy-methylfurfural)을 제조하고, 이로부터 2,5-퓨란디카르복실산을 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing 2,5-furandicarboxylic acid from fructose, and more particularly, to an intermediate 5 from fructose using a solid acid catalyst. -It relates to a method of preparing alkoxy-methylfurfural and preparing 2,5-furandicarboxylic acid therefrom.
2,5-퓨란디카복실산 (2,5-Furandicarboxylic acid, 이하 'FDCA')은 두개의 카르복시산이 퓨란고리에 결합된 유기화합물이고, 석유유래 테레프탈산(terephthalic acid)의 대안으로 최근에 관심이 증가되고 있는 화학 물질이다. 2,5-Furandicarboxylic acid (hereinafter referred to as'FDCA') is an organic compound in which two carboxylic acids are bonded to the furan ring, and as an alternative to petroleum-derived terephthalic acid, interest has recently increased. It is a chemical substance.
또한 FDCA는 재생가능한 자원으로부터 제조할 수 있으며, 농약, 의약품, 살충제, 약제 또는 항균제 등의 다양한 분야에서 사용되는 중간체이다. In addition, FDCA can be manufactured from renewable resources and is an intermediate used in various fields such as pesticides, pharmaceuticals, pesticides, pharmaceuticals or antibacterial agents.
일반적으로 FDCA는 헥소스 유도체의 탈수반응(dehydration of hexose derivatives)으로 유도되는 5-하이드록시메틸퍼퓨랄(5-hydroxymethylfurfural, 이하 'HMF')을 촉매를 통하여 산화하여 FDCA를 합성한다.In general, FDCA synthesizes FDCA by oxidizing 5-hydroxymethylfurfural (hereinafter'HMF'), which is induced by dehydration of hexose derivatives, through a catalyst.
HMF의 산화는 디포르밀퓨란 (diformylfuran, DFF) 또는 하이드록시메릴푸란카르복실산 (5-hydroxymethyl-2-furancarboxylic acid, HFCA)을 중간산물로 생성하고 다음 공정에서 포르밀푸란카르복실산 (5-formyl-2-furancarboxylic acid, FCA)을 거쳐서 FDCA를 생성한다. The oxidation of HMF produces diformylfuran (DFF) or hydroxymerylfurancarboxylic acid (5-hydroxymethyl-2-furancarboxylic acid, HFCA) as an intermediate product, and formylfurancarboxylic acid (5 -formyl-2-furancarboxylic acid, FCA) to produce FDCA.
한편 프룩토스(Fructose)는 환원기로 케톤을 가지는 단당류이며, 헥소스의 하나이고 식물계에 널리 존재하여, 포도당과 함께 과일 속에 유리 형태로 들어있거나 포도당과 결합하여 슈크로스로 존재한다. On the other hand, fructose (Fructose) is a monosaccharide having a ketone as a reducing group, one of the hexose and widely present in the plant world, it is contained in fruit with glucose in a free form or combined with glucose to exist as sucrose.
프룩토스로부터 FDCA를 제조하기 위해서는 1단계로 프룩토스 탈수반응을 통해 HMF를 제조하고, 2단계로 HMF의 산화반응을 통해 진행된다. In order to prepare FDCA from fructose, HMF is prepared through a fructose dehydration reaction in one step, and HMF is oxidized in a second step.
1단계인 프룩토스 탈수반응을 수용액상에서 수행하는 경우, 생성된 HMF가 물과의 2차반응에 의해 Levulinic acid와 formic acid로 쉽게 분해되기 때문에, HMF 수율을 높이기 위해서는 수용액 보다는 고비점 유기 용매 (ex. 1-Butanol, GVL, DMF 등)를 사용하는 것이 유리하다(비특허문헌 1, Green Chem., 비특허문헌 2 2015, 17, 3310; Green Chem., 2011, 13, 754).When the first step, fructose dehydration, is carried out in an aqueous solution, the generated HMF is easily decomposed into levulinic acid and formic acid by a secondary reaction with water, so in order to increase the HMF yield, a high boiling point organic solvent (ex. It is advantageous to use 1-Butanol, GVL, DMF, etc.) (Non-Patent Document 1, Green Chem., Non-Patent Document 2 2015, 17, 3310; Green Chem., 2011, 13, 754).
HMF의 산화반응에서 FDCA 수율을 높이기 위해서는 수용액상에서 반응을 수행하는 것이 유리하다(특허문헌 1, 대한민국 공개특허공보 제10-2018-7018309호).In order to increase the FDCA yield in the oxidation reaction of HMF, it is advantageous to perform the reaction in an aqueous solution (Patent Document 1, Korean Laid-Open Patent Publication No. 10-2018-7018309).
따라서, 프룩토스로부터 고수율로 FDCA를 제조하기 위해서는 고비점 유기 용매상에서 HMF를 제조 후에 HMF 산화반응 전에 HMF를 유기용매로부터 분리해야 한다. Therefore, in order to prepare FDCA from fructose in high yield, HMF must be prepared in a high boiling point organic solvent and then HMF must be separated from the organic solvent before the HMF oxidation reaction.
하지만, HMF로부터 유기 용매를 분리하는 데에는 많은 노력이 필요하며, 분리과정에서 HMF의 손실을 피할 수 없다. However, much effort is required to separate the organic solvent from HMF, and loss of HMF in the separation process cannot be avoided.
예를 들어, 증발법에 의해 용매를 제거하는 경우에는 HMF가 분해되지 않기 위해서는 반응 온도를 50℃ 미만으로 유지해야 한다. For example, in the case of removing the solvent by evaporation, the reaction temperature must be kept below 50°C in order not to decompose HMF.
이에 따라 고비점 용매를 제거하기 위해서는 매우 낮은 압력이 필요하며, 이는 대규모 산업 공정에서 수행하는 것은 거의 불가능하고 경제적이지 않다.Accordingly, very low pressure is required to remove the high boiling point solvent, which is almost impossible and not economical to carry out in large-scale industrial processes.
또 다른 방법으로, 유기 용매 추출제를 이용하여 HMF를 고비점 유기 용매로부터 분리하는 기술들이 소개되고 있으나, 유기 용매 추출제에서 HMF 용해도의 한계로 인해 효율이 떨어지는 문제점이 있어, 이 역시 경제적이지 않다(비특허문헌 3. Nature, 2007, 447, 982).As another method, techniques for separating HMF from a high boiling point organic solvent using an organic solvent extractant have been introduced, but there is a problem in that the efficiency is inferior due to the limitation of HMF solubility in the organic solvent extractant, which is also not economical. (Non-Patent Document 3. Nature, 2007, 447, 982).
따라서, 프룩토스로부터 경제적으로 FDCA를 제조하기 위해서는 1단계 프룩토스 탈수반응 후 추가적인 후처리 없이 바로 산화반응을 진행하는 방법이 이상적이다. Therefore, in order to economically manufacture FDCA from fructose, it is ideal to proceed with the oxidation reaction immediately after the first step fructose dehydration reaction without additional post-treatment.
또한 HMF 산화반응에서 아세트산 배지에서 Co/Mn/Br과 같은 균질 촉매를 사용하여 FDCA를 생성하는 방법이 알려져 있으나, 촉매 회수 및 재사용이 어렵고 폐기물 발생으로 인한 환경 오염 문제가 있어 바람직하지 않다. In addition, a method of generating FDCA using a homogeneous catalyst such as Co/Mn/Br in an acetic acid medium in the HMF oxidation reaction is known, but it is difficult to recover and reuse the catalyst, and there is a problem of environmental pollution due to waste generation, which is not preferable.
따라서 균질계 촉매 기술에 대한 대안으로, 불균일계 촉매를 이용하여 FDCA 수율을 높이는 제조방법의 개발이 매우 필요한 실정이다. Therefore, as an alternative to the homogeneous catalyst technology, it is very necessary to develop a manufacturing method that increases the FDCA yield using a heterogeneous catalyst.
따라서, 본 발명은 프룩토스로부터 경제적으로 FDCA를 제조하는 방법을 제공하는데 있다. Accordingly, the present invention is to provide a method for economically producing FDCA from fructose.
구체적으로는, 고체산촉매를 사용하여 프룩토스 탈수반응 후 중간체를 분리하는 과정 없이 FDCA를 제조하는 촉매 공정 기술을 제공하며, 또한 FDCA 생성 단계에서 균일계 촉매 대신 불균일계 촉매를 활용하여 경제성이 높은 촉매 물질로 대체하여 FDCA를 제조하는 방법을 제공한다.Specifically, it provides a catalytic process technology for producing FDCA without the process of separating the intermediate after fructose dehydration using a solid acid catalyst.In addition, a catalyst with high economic efficiency by using a heterogeneous catalyst instead of a homogeneous catalyst in the FDCA generation step It provides a method of manufacturing FDCA by replacing it with a substance.
본 발명이 해결하고자 하는 과제는 이상에서 언급한 과제(들)로 제한되지 않으며, 언급되지 않은 또 다른 과제(들)는 이하의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The problem to be solved by the present invention is not limited to the problem(s) mentioned above, and another problem(s) that is not mentioned will be clearly understood by those skilled in the art from the following description.
상기 과제를 해결하기 위해, 본 발명의 일 실시예에 따른 프룩토스로부터 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural) 제조방법은 In order to solve the above problems, a method for preparing 5-alkoxymethylfurfural from fructose according to an embodiment of the present invention is
(a-1) 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조하는 단계; (a-1) preparing a mixed solution by mixing fructose and an organic solvent;
(a-2) 상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조하는 단계; 및(a-2) heating the mixed solution under a solid acid catalyst and reacting to prepare 5-alkoxymethylfurfural; And
(a-3) 상기 5-알콕시메틸퍼퓨랄 용액으로부터 여과를 통해 고체산촉매를 분리하는 단계;를 포함한다.and (a-3) separating the solid acid catalyst from the 5-alkoxymethylfurfural solution through filtration.
또한 상기 유기용매는 메탄올 또는 에탄올일 수 있다. In addition, the organic solvent may be methanol or ethanol.
또한 상기 고체산촉매는 술폰산(-SO 3H)을 작용기로 포함할 수 있다. In addition, the solid acid catalyst may include sulfonic acid (-SO 3 H) as a functional group.
또한 상기 여과는 상기 5-알콕시메틸퍼퓨랄 용액을 20 내지 30 ℃ 상온으로 냉각한 이후에 여과지를 사용하여 수행될 수 있다. In addition, the filtration may be performed using a filter paper after cooling the 5-alkoxymethylfurfural solution to room temperature of 20 to 30°C.
본 발명의 다른 실시예에 따른 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산을 제조하는 방법은A method for preparing 2,5-furandicarboxylic acid from 5-alkoxymethylfurfural according to another embodiment of the present invention
상기 5-알콕시메틸퍼퓨랄 용액을 산화촉매 하에서 가압 및 가열하고 반응시켜 2,5-퓨란디카르복실산을 제조할 수 있다. The 5-alkoxymethylfurfural solution may be pressurized, heated, and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid.
또한 상기 가압은 산소 가스 또는 공기를 10 내지 50 bar로 가압하고 80 내지 150 ℃로 가열할 수 있다. In addition, the pressurization may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150 °C.
또한 상기 산화촉매는 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)에서 선택된 어느 하나인 지지체에, 금, 백금, 팔라듐 및 루테늄으로 이루어진 군에서 선택된 어느 하나의 금속이 담지된 것을 특징으로 할 수 있다.In addition, the oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ), gold, platinum , It may be characterized in that any one metal selected from the group consisting of palladium and ruthenium is supported.
또한 상기 산화촉매는 산화크롬, 산화망간, 산화철, 및 산화코발트로 이루어지는 전이금속 산화물 중 어느 하나 이상이거나, 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)로 이루어진 군에서 선택된 어느 하나의 지지체에 상기 전이금속 산화물이 담지된 것을 특징으로 할 수 있다.In addition, the oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, It may be characterized in that the transition metal oxide is supported on any one support selected from the group consisting of cerium oxide and aluminum oxide (Al 2 O 3 ).
본 발명의 또 다른 실시예에 따른 프룩토스로부터 2,5-퓨란디카르복실산 제조방법은A method for preparing 2,5-furandicarboxylic acid from fructose according to another embodiment of the present invention
(a) 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조하는 단계; (a) preparing a mixed solution by mixing fructose and an organic solvent;
(b) 상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조하는 단계;(b) heating the mixed solution under a solid acid catalyst and reacting to prepare 5-alkoxymethylfurfural;
(c) 상기 고체산촉매가 혼합된 5-알콕시메틸퍼퓨랄 용액에서 상기 고체산촉매를 여과하여 분리하는 단계; (c) filtering and separating the solid acid catalyst from the 5-alkoxymethylfurfural solution in which the solid acid catalyst is mixed;
(d) 상기 고체산촉매가 분리된 용액을 산화촉매 하에서 가압 및 가열하고 반응시켜 2,5-퓨란디카르복실산을 제조하는 단계; 및(d) preparing 2,5-furandicarboxylic acid by pressing and heating the solution from which the solid acid catalyst was separated and reacting under an oxidation catalyst; And
(e) 상기 산화촉매가 혼합된 2,5-퓨란디카르복실산 용액에서 상기 산화촉매를 여과하여 분리한 후 여액에서 2,5-퓨란디카르복실산을 회수하는 단계;를 포함한다. and (e) filtering and separating the oxidation catalyst from the 2,5-furandicarboxylic acid solution in which the oxidation catalyst is mixed, and then recovering the 2,5-furandicarboxylic acid from the filtrate.
또한 상기 유기용매는 메탄올 또는 에탄올일 수 있다. In addition, the organic solvent may be methanol or ethanol.
또한 상기 고체산촉매는 술폰산(-SO 3H)을 작용기로 포함할 수 있다. In addition, the solid acid catalyst may include sulfonic acid (-SO 3 H) as a functional group.
또한 상기 가압은 산소 가스 또는 공기를 10 내지 50 bar로 가압하고, 80 내지 150 ℃로 가열할 수 있다. Further, the pressurization may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150°C.
또한 상기 산화촉매는 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)에서 선택된 어느 하나인 지지체에 금, 백금, 팔라듐 및 루테늄으로 이루어진 군에서 선택된 어느 하나의 금속이 담지된 것일 수 있다. In addition, the oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ), gold, platinum, Any one metal selected from the group consisting of palladium and ruthenium may be supported.
또한 상기 산화촉매는 산화크롬, 산화망간, 산화철, 및 산화코발트로 이루어지는 전이금속 산화물 중 어느 하나 이상이거나, 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)로 이루어진 군에서 선택된 어느 하나의 지지체에 상기 전이금속 산화물이 담지된 것일 수 있다.In addition, the oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, The transition metal oxide may be supported on any one support selected from the group consisting of cerium oxide and aluminum oxide (Al 2 O 3 ).
상기 여액에서 2,5-퓨란디카르복실산 결정을 회수하기 위해서 결정화 또는 증류법을 이용할 수 있다.Crystallization or distillation may be used to recover 2,5-furandicarboxylic acid crystals from the filtrate.
본 발명에 따르면, 식물계에 매우 풍부한 프룩토스(fructose)로부터 2,5-퓨란디카복실산(2,5-furandicarboxylic acid)을 경제적으로 제조할 수 있다. According to the present invention, 2,5-furandicarboxylic acid can be economically prepared from fructose, which is very abundant in the plant world.
또한 프룩토스를 고체산촉매를 이용하여 탈수한 이후에 추가적인 후처리 없이 바로 산화반응을 진행할 수 있다. In addition, after dehydration of fructose using a solid acid catalyst, the oxidation reaction can proceed immediately without additional post-treatment.
또한 프룩토스를 고체산촉매와 반응시켜 매우 높은 수율로 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural)을 제조할 수 있다. Also, by reacting fructose with a solid acid catalyst, 5-alkoxymethylfurfural can be prepared in a very high yield.
또한 5-알콕시메틸퍼퓨랄을 제조한 이후에 보다 경제적인 불균일계 산화촉매를 이용하여 높은 수율로 2,5-퓨란디카복실산을 제조하여 회수할 수 있다. In addition, after preparing 5-alkoxymethylfurfural, 2,5-furandicarboxylic acid can be prepared and recovered in high yield using a more economical heterogeneous oxidation catalyst.
또한 프룩토스로부터 탈수반응 후 중간체를 분리하는 별도의 과정 없이 원-팟(one pot)공정으로 2,5-퓨란디카복실산을 제조하여 회수할 수 있다. In addition, after the dehydration reaction from fructose, 2,5-furandicarboxylic acid can be prepared and recovered through a one-pot process without a separate process of separating the intermediate.
또한 프룩토스로부터 2,5-퓨란디카복실산의 제조과정을 매우 감소시켜 제조비용을 매우 감소시킬 수 있다. In addition, the manufacturing process of 2,5-furandicarboxylic acid from fructose can be greatly reduced, thereby greatly reducing the manufacturing cost.
발명의 효과는 상기한 효과로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 특허청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.The effects of the invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the invention.
도 1은 본 발명의 일 실시예에 따른 고체산촉매를 이용한 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural) 제조방법의 공정을 나타낸 공정흐름도이다. 1 is a process flow diagram showing a process of a method for producing 5-alkoxymethylfurfural using a solid acid catalyst according to an embodiment of the present invention.
도 2는 본 발명의 다른 실시예에 따른 촉매를 이용한 2,5-퓨란디카르복실산 제조방법의 공정을 나타낸 공정흐름도이다. 2 is a process flow diagram showing a process of a method for producing 2,5-furandicarboxylic acid using a catalyst according to another embodiment of the present invention.
이하 첨부된 도면을 참조하면서 본 발명에 따른 바람직한 실시예를 상세히 설명하기로 한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
발명의 이점 및 특징, 그리고 그것을 달성하는 방법은 첨부된 도면과 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다.Advantages and features of the invention, and a method of achieving the same will become apparent with reference to the embodiments described below in detail together with the accompanying drawings.
그러나 본 발명은 이하에 개시되는 실시예들에 의해 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다.However, the present invention is not limited by the embodiments disclosed below, but will be implemented in a variety of different forms, only these embodiments are intended to complete the disclosure of the present invention, and common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims.
또한, 본 발명을 설명함에 있어 관련된 공지 기술 등이 본 발명의 요지를 흐리게 할 수 있다고 판단되는 경우 그에 관한 자세한 설명은 생략하기로 한다.In addition, when it is determined that related well-known technologies or the like may obscure the subject matter of the present invention in describing the present invention, detailed descriptions thereof will be omitted.
본 발명자들은 프룩토스(fructose)의 탈수반응을 수용액 상에서 수행하는 경우 생성된 5-하이드록시메틸-2-퍼퓨랄(5-hydroxymethyl-2-furfural, 이하 'HMF')이 물과의 2차 반응에 의하여 레불린산(levulinic acid)과 포름산(formic acid)으로 쉽게 분해되는 것을 확인하여, 알콜 존재 하에서 고체산촉매를 이용하여 5-알콕시메틸퍼퓨랄(alkoxy-methylfurfural)을 먼저 제조하고, 고체산촉매를 여과하여 제거한 이후에 별도 처리과정 없이 이를 바로 불균일계 산화촉매를 이용하여 산화반응을 통해 높은 수율로 최종산물인 2,5-퓨란디카르복실산(2,5-furandicarboxylic acid, 이하 'FDCA')을 수득할 수 있는 것을 확인하여 본 발명을 완성하였다. The present inventors believe that when the dehydration reaction of fructose is performed in an aqueous solution, the resulting 5-hydroxymethyl-2-furfural (hereinafter referred to as'HMF') is a secondary reaction with water. By confirming that it is easily decomposed into levulinic acid and formic acid, 5-alkoxymethylfurfural was first prepared using a solid acid catalyst in the presence of alcohol, and a solid acid catalyst was prepared. After removing by filtration, it is immediately oxidized using a heterogeneous oxidation catalyst without any separate treatment, and the final product, 2,5-furandicarboxylic acid (hereinafter referred to as'FDCA'), in high yield through oxidation reaction. By confirming that it can be obtained, the present invention was completed.
본 발명자들이 아는 한 프룩토스로부터 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural)을 제조 후 5-알콕시메틸퍼퓨랄(alkoxy-methylfurfural) 분리과정 없이 바로 불균일계 산화촉매를 이용하여 산화반응을 통해 FDCA를 제조하는 방법은 개시된 바가 없다. As far as the present inventors know, after preparing 5-alkoxymethylfurfural from fructose, FDCA was prepared through an oxidation reaction using a heterogeneous oxidation catalyst immediately without separation of 5-alkoxy-methylfurfural. There is no disclosed method of manufacturing.
도 1은 본 발명의 일 실시예에 따른 프룩토스로부터 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural) 제조방법의 공정을 나타낸 공정흐름도이고, 도 2는 본 발명의 또 다른 실시예에 따른 프룩토스로부터 2,5-퓨란디카르복실산 제조방법의 공정을 나타낸 공정흐름도이다. 1 is a process flow diagram showing a process of a method for producing 5-alkoxymethylfurfural from fructose according to an embodiment of the present invention, and FIG. 2 is a process flow diagram showing the process of a method for producing 5-alkoxymethylfurfural from fructose according to an embodiment of the present invention. It is a process flow diagram showing the process of the 2,5-furandicarboxylic acid production method.
본 발명은 고체산촉매를 이용하여 프룩토스로부터 중간체인 5-알콕시메틸퍼퓨랄을 제조하는 방법과, 상기 중간체인 5-알콕시메틸퍼퓨랄을 불균일계 산화촉매와 반응시켜 높은 수율로 2,5-퓨란디카르복실산을 제조하는 방법을 포함하여 프룩토스로부터 2,5-퓨란디카르복실산 제조방법을 제공한다. The present invention relates to a method of preparing 5-alkoxymethylfurfural, an intermediate, from fructose, using a solid acid catalyst, and reacting the intermediate, 5-alkoxymethylfurfural, with a heterogeneous oxidation catalyst, to produce 2,5-furan in high yield. It provides a method for preparing 2,5-furandicarboxylic acid from fructose, including a method for preparing dicarboxylic acid.
우선 도 1을 참조하면, 본 발명의 일 실시예에 따른 프룩토스로부터 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural) 제조방법은 First, referring to FIG. 1, a method for preparing 5-alkoxymethylfurfural from fructose according to an embodiment of the present invention is
(a-1) 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조하는 단계; (a-1) preparing a mixed solution by mixing fructose and an organic solvent;
(a-2) 상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조하는 단계; 및(a-2) heating the mixed solution under a solid acid catalyst and reacting to prepare 5-alkoxymethylfurfural; And
(a-3) 상기 5-알콕시메틸퍼퓨랄을 함유하는 혼합용액을 여과하여 고체산촉매를 분리하는 단계;를 포함한다.and (a-3) separating the solid acid catalyst by filtering the mixed solution containing the 5-alkoxymethylfurfural.
우선 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조한다(S10).First, a mixed solution is prepared by mixing fructose and an organic solvent (S10).
상기 프룩투스는 탄수화물이며, 탈수반응으로 5-알콕시메틸퍼퓨랄로 전환된다. The fructus is a carbohydrate and is converted to 5-alkoxymethylfurfural by dehydration.
상기 5-알콕시메틸퍼퓨랄은 5-메톡시메틸퍼퓨랄(5-methoxymethylfurfural, 이하 'MMF') 또는 5-에톡시메틸퍼퓨랄(5-ethoxymethylfurfural, 이하 'EMF') 이다. The 5-alkoxymethylfurfural is 5-methoxymethylfurfural (“MMF”) or 5-ethoxymethylfurfural (“EMF”).
상기 유기용매는 메탄올(methanol) 또는 에탄올(ethanol)이다. The organic solvent is methanol or ethanol.
상기 메탄올 또는 에탄올 이외 C 3 이상의 알코올은 고체산촉매를 이용하여 프룩토스를 탈수시켜 5-알콕시메틸퍼퓨랄로 전환시키기 어려우며, 반응 후 부산물을 생성하는 문제가 있다. C 3 or more alcohols other than methanol or ethanol are difficult to convert to 5-alkoxymethylfurfural by dehydrating fructose using a solid acid catalyst, and there is a problem of generating by-products after the reaction.
상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조할 수 있다(S20). The mixed solution may be heated and reacted under a solid acid catalyst to prepare 5-alkoxymethylfurfural (S20).
상기 고체산촉매는 양성자 공여체 또는 전자 수용체로 작용하여 탈수반응의 촉매로 사용된다. The solid acid catalyst acts as a proton donor or electron acceptor and is used as a catalyst for dehydration.
상기 고체산촉매는 술폰산(-SO 3H)을 작용기로 포함하는 이온교환수지인 것 일 수 있다. The solid acid catalyst may be an ion exchange resin containing sulfonic acid (-SO 3 H) as a functional group.
상기 고체산촉매는 그래핀 산화물(graphene oxide), 활성탄 (activated carbon) 또는 고분자를 지지체로 하여 술폰산(-SO 3H)이 작용기로 결합된 것일 수 있다. The solid acid catalyst may be graphene oxide, activated carbon, or a polymer in which a sulfonic acid (-SO 3 H) is bonded to a functional group.
이하에서 GO-SO 3H는 그래핀 산화물에 술폰산이 결합한 것을 의미하고, AC-SO 3H 는 활성탄에 술폰산이 결합한 것으로 의미한다. Hereinafter, GO-SO 3 H means that sulfonic acid is bonded to graphene oxide, and AC-SO 3 H means that sulfonic acid is bonded to activated carbon.
상기 그래핀 산화물과 활성탄에서 술폰산 작용기는 브뢴스테드 산 작용기(Bronsted acidic function)로 작용한다. In the graphene oxide and activated carbon, the sulfonic acid functional group acts as a Bronsted acidic function.
따라서 상기 고체산촉매는 촉매활성이 매우 높으며 탈수반응에 매우 유리하다. Therefore, the solid acid catalyst has very high catalytic activity and is very advantageous for dehydration reaction.
상기 고체산촉매 이외에는 프룩토스의 전환율이 낮으며, 부산물 생성이 높아 EMF 수율을 감소시키는 문제가 있다. Except for the solid acid catalyst, there is a problem in that the conversion rate of fructose is low, and the generation of by-products is high, thereby reducing the EMF yield.
상기 가열은 60 내지 120 ℃에서 수행될 수 있다. The heating may be performed at 60 to 120 °C.
상기 가열 범위에서 프룩토스를 100 %로 전환할 수 있으며, EMF 또는 MMF를 70 내지 90 % 수율로 제조할 수 있다. In the above heating range, fructose may be converted to 100%, and EMF or MMF may be prepared in a yield of 70 to 90%.
상기 가열온도가 60 ℃ 보다 낮은 경우, 프룩토스의 탈수 반응속도가 낮은 단점이 있으며, 120 ℃ 보다 높은 경우, 상압 반응 중 알코올의 증발에 의한 손실 및 고압 반응 중 부반응이 발생하는 문제점이 있다.When the heating temperature is lower than 60° C., the dehydration reaction rate of fructose is low, and when it is higher than 120° C., there is a problem of loss due to evaporation of alcohol during normal pressure reaction and side reactions during high pressure reaction.
상기 5-알콕시메틸퍼퓨랄을 함유하는 혼합용액으로부터 여과를 통해 고체산촉매를 분리한다(S30).The solid acid catalyst is separated from the mixed solution containing 5-alkoxymethylfurfural through filtration (S30).
상기 여과는 상기 5-알콕시메틸퍼퓨랄 용액을 20 내지 30 ℃ 상온으로 냉각한 이후에 여과지를 사용하여 수행할 수 있다. The filtration may be performed using a filter paper after cooling the 5-alkoxymethylfurfural solution to room temperature at 20 to 30°C.
상기 여과를 통하여 반응촉매를 제거할 수 있다. The reaction catalyst may be removed through the filtration.
상기 고체산촉매를 여과하여 분리하지 않으면, 후속 5-알콕시메틸퍼퓨랄을 산화촉매 하에서 FDCA를 생성하는 단계에서 부산물이 발생하거나 FDCA 생성 속도가 저하되는 문제가 있다. If the solid acid catalyst is not separated by filtration, there is a problem that by-products are generated or the FDCA generation rate is lowered in the step of generating FDCA in the subsequent 5-alkoxymethylfurfural oxidation catalyst.
따라서 고체산촉매를 사용하여 EMF 또는 MMF를 제조할 수 있으며, 종래 고비점 유기 용매상을 분리하기 위한 별도의 처리과정과 상이하게 여과를 통하여 매우 효과적으로 고체산촉매를 제거하고 높은 수율로 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural)을 제조할 수 있다. Therefore, EMF or MMF can be prepared by using a solid acid catalyst, and unlike a separate treatment process for separating the conventional high boiling point organic solvent phase, the solid acid catalyst is very effectively removed through filtration, and 5-alkoxymethyl peroxide is used in high yield. Fural (5-alkoxymethylfurfural) can be prepared.
본 발명의 다른 실시예에 따른 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산을 제조하는 방법은A method for preparing 2,5-furandicarboxylic acid from 5-alkoxymethylfurfural according to another embodiment of the present invention
상기 5-알콕시메틸퍼퓨랄 용액을 산화촉매 하에서 가압 및 가열하고 반응시켜 2,5-퓨란디카르복실산을 제조할 수 있다. The 5-alkoxymethylfurfural solution may be pressurized, heated, and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid.
상기 가압은 산소 가스 또는 공기를 10 내지 50 bar로 가압하고 80 내지 150 ℃로 가열할 수 있다. The pressurization may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150 °C.
상기 가압 및 가열 범위 내에서 산화촉매를 사용하여 FDCA를 높은 효율로 제조할 수 있으며, 상기 범위에 미치지 못하는 경우에는 산화반응에 따른 수율이 낮고, 상기 범위를 초과하는 경우 반응 수율이 증가되지 않으면서 에너지가 더 소모되는 문제가 있다. FDCA can be produced with high efficiency by using an oxidation catalyst within the pressurized and heated range, and if it is not within the above range, the yield due to the oxidation reaction is low, and if it exceeds the above range, the reaction yield is not increased. There is a problem that more energy is consumed.
상기 산화촉매는 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)에서 선택된 어느 하나인 지지체에 금, 백금, 팔라듐 및 루테늄으로 이루어진 군에서 선택된 어느 하나의 금속이 담지된 것일 수 있다. The oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ) gold, platinum, palladium on the support And any one metal selected from the group consisting of ruthenium may be supported.
상기 산화촉매는 산화크롬, 산화망간, 산화철, 및 산화코발트로 이루어지는 전이금속 산화물 중 어느 하나 이상이거나, 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)로 이루어진 군에서 선택된 어느 하나의 지지체에 상기 전이금속 산화물이 담지된 것일 수 있다.The oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, or activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, oxidation The transition metal oxide may be supported on any one support selected from the group consisting of cerium and aluminum oxide (Al 2 O 3 ).
상기 산화촉매는 불균일계 촉매로 종래의 균일계 촉매 대비 산화반응 후 FDCA로부터 촉매의 분리가 용이하기 때문에 친환경적이면서 공정비용을 크게 감소시킬 수 있다.The oxidation catalyst is a heterogeneous catalyst, and since it is easier to separate the catalyst from the FDCA after an oxidation reaction compared to a conventional homogeneous catalyst, it is environmentally friendly and can greatly reduce the process cost.
도 2를 참조하면, 본 발명의 또 다른 실시예에 따른 촉매를 이용한 2,5-퓨란디카르복실산 제조방법은 Referring to Figure 2, a method for preparing 2,5-furandicarboxylic acid using a catalyst according to another embodiment of the present invention
(a) 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조하는 단계; (a) preparing a mixed solution by mixing fructose and an organic solvent;
(b) 상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조하는 단계;(b) heating the mixed solution under a solid acid catalyst and reacting to prepare 5-alkoxymethylfurfural;
(c) 상기 고체산촉매가 혼합된 5-알콕시메틸퍼퓨랄 용액에서 상기 고체산촉매를 여과하여 분리하는 단계; (c) filtering and separating the solid acid catalyst from the 5-alkoxymethylfurfural solution in which the solid acid catalyst is mixed;
(d) 상기 고체산촉매가 분리된 용액을 산화촉매 하에서 가압 및 가열하고 반응시켜 2,5-퓨란디카르복실산을 제조하는 단계; 및(d) preparing 2,5-furandicarboxylic acid by pressing and heating the solution from which the solid acid catalyst was separated and reacting under an oxidation catalyst; And
(e) 상기 산화촉매가 혼합된 2,5-퓨란디카르복실산 용액에서 상기 산화촉매를 여과하여 분리한 후 여액에서 2,5-퓨란디카르복실산을 회수하는 단계를 포함한다. (e) filtering and separating the oxidation catalyst from the 2,5-furandicarboxylic acid solution in which the oxidation catalyst is mixed, and recovering the 2,5-furandicarboxylic acid from the filtrate.
또한 상기 고체산촉매 및 산화촉매를 이용한 프룩투스로부터 FDCA제조방법은 하기 반응식 1에 따라 수행될 수 있다. In addition, the method for producing FDCA from fructus using the solid acid catalyst and the oxidation catalyst may be performed according to the following Scheme 1.
[반응식 1][Scheme 1]
Figure PCTKR2020003741-appb-img-000001
Figure PCTKR2020003741-appb-img-000001
본 발명의 일 실시예에서 프룩토스는 고체산촉매 하에서 에탄올과 혼합되어 중간체인 EMF를 생성하고 산소 가압 하에서 Pt/C 산화촉매와 반응하여 FDCA로 전환된다. In one embodiment of the present invention, fructose is mixed with ethanol under a solid acid catalyst to generate EMF, an intermediate, and is converted to FDCA by reacting with a Pt/C oxidation catalyst under oxygen pressure.
우선 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조한다(S100).First, a mixed solution is prepared by mixing fructose and an organic solvent (S100).
상기 유기용매는 메탄올 또는 에탄올일 수 있다. The organic solvent may be methanol or ethanol.
상기 메탄올 또는 에탄올 이외 C 3 이상의 알코올은 고체산촉매를 이용하여 프룩토스를 탈수시켜 5-알콕시메틸퍼퓨랄로 전환시키기 어려우며, 반응 후 부산물을 생성하는 문제가 있다. C 3 or more alcohols other than methanol or ethanol are difficult to convert to 5-alkoxymethylfurfural by dehydrating fructose using a solid acid catalyst, and there is a problem of generating by-products after the reaction.
상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조한다(S200).The mixed solution is heated and reacted under a solid acid catalyst to prepare 5-alkoxymethylfurfural (S200).
상기 고체산촉매는 술폰산(-SO 3H)을 작용기로 포함하는 이온교환수지일 수 있다. The solid acid catalyst may be an ion exchange resin containing sulfonic acid (-SO 3 H) as a functional group.
상기 고체산촉매는 그래핀 산화물(graphene oxide), 활성탄 (activated carbon) 또는 고분자를 지지체로 하여 술폰산(-SO 3H)이 작용기로 결합된 것일 수 있다. The solid acid catalyst may be graphene oxide, activated carbon, or a polymer in which a sulfonic acid (-SO 3 H) is bonded to a functional group.
상기 지지체 이외에는 술폰산이 작용기로 결합되기 어렵다.It is difficult for sulfonic acid to be bonded to functional groups other than the support.
상기 술폰산이 작용기로 결합된 고체산촉매는 양성자 공여체 또는 전자 수용체로 작용하여 탈수반응의 촉매로 사용된다. The solid acid catalyst in which the sulfonic acid is bonded to a functional group acts as a proton donor or electron acceptor and is used as a catalyst for dehydration reaction.
상기 그래핀 산화물과 활성탄에서 술폰산 작용기는 브뢴스테드 산 작용기(Bronsted acidic function)로 작용한다. In the graphene oxide and activated carbon, the sulfonic acid functional group acts as a Bronsted acidic function.
따라서 상기 고체산촉매는 촉매활성이 매우 높으며 탈수반응에 매우 유리하다. Therefore, the solid acid catalyst has very high catalytic activity and is very advantageous for dehydration reaction.
상기 고체산촉매 이외에는 프룩토스의 전환율이 낮으며, 가열반응 시 90 ℃ 이상의 반응온도가 요구되어 공정 효율을 감소시키는 문제가 있다. Except for the solid acid catalyst, the conversion rate of fructose is low, and a reaction temperature of 90° C. or higher is required during the heating reaction, thereby reducing process efficiency.
상기 가열은 60 내지 120 ℃에서 수행될 수 있다. The heating may be performed at 60 to 120 °C.
상기 가열 범위에서 프룩토스를 100 %로 전환할 수 있으며, EMF 또는 MMF를 70 내지 90 % 수율로 제조할 수 있다. In the above heating range, fructose may be converted to 100%, and EMF or MMF may be prepared in a yield of 70 to 90%.
상기 고체산촉매가 혼합된 5-알콕시메틸퍼퓨랄 용액에서 상기 고체산촉매를 여과하여 분리한다(S300).The solid acid catalyst is filtered and separated from the 5-alkoxymethylfurfural solution in which the solid acid catalyst is mixed (S300).
상기 여과를 통하여 반응촉매를 제거할 수 있다. The reaction catalyst can be removed through the filtration.
고체산촉매를 사용하여 EMF 또는 MMF를 제조할 수 있으며, 종래 고비점 유기 용매상을 분리하기 위한 별도의 처리과정과 상이하게 여과를 통하여 매우 효과적으로 고체산촉매를 제거하고 높은 전환율로 EMF 또는 MMF을 수득하여 5-알콕시메틸퍼퓨랄(5-alkoxymethylfurfural)을 제조할 수 있다. EMF or MMF can be prepared using a solid acid catalyst, and unlike a separate treatment process for separating the conventional high boiling point organic solvent phase, the solid acid catalyst is very effectively removed through filtration, and EMF or MMF is obtained at a high conversion rate. 5-alkoxymethylfurfural can be prepared.
상기 고체산촉매가 분리된 용액을 산화촉매 하에서 가압 및 가열하고 반응시켜 2,5-퓨란디카르복실산을 제조한다(S400).The solution from which the solid acid catalyst was separated is pressurized, heated, and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid (S400).
상기 가압 및 가열은 산소 가스 또는 공기를 10 내지 50 bar로 가압하고, 80 내지 150 ℃로 가열할 수 있다. The pressurization and heating may pressurize oxygen gas or air to 10 to 50 bar and heat to 80 to 150°C.
상기 가압 및 가열 범위 내에서 산화촉매를 사용하여 FDCA를 높은 효율로 제조할 수 있으며, 상기 범위에 미치지 못하는 경우에는 산화반응에 따른 수율이 낮고, 상기 범위를 초과하는 경우 반응 수율을 증가되지 않으면서 에너지가 더 소모되는 문제가 있다. FDCA can be manufactured with high efficiency by using an oxidation catalyst within the pressurized and heated range, and if it is not within the above range, the yield due to the oxidation reaction is low. There is a problem that more energy is consumed.
상기 산화촉매는 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)에서 선택된 어느 하나인 지지체에 금, 백금, 팔라듐 및 루테늄으로 이루어진 군에서 선택된 어느 하나의 금속이 담지된 것일 수 있다. The oxidation catalyst is any one selected from activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ) gold, platinum, palladium on the support And any one metal selected from the group consisting of ruthenium may be supported.
또한 상기 산화촉매는 산화크롬, 산화망간, 산화철, 및 산화코발트로 이루어지는 전이금속 산화물 중 어느 하나 이상이거나, 활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)로 이루어진 군에서 선택된 어느 하나의 지지체에 상기 전이금속 산화물이 담지된 것일 수 있다.In addition, the oxidation catalyst is any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, The transition metal oxide may be supported on any one support selected from the group consisting of cerium oxide and aluminum oxide (Al 2 O 3 ).
상기 지지체를 사용하여 불균일계 촉매를 제조하여 산화반응을 수행할 수 있으며, 촉매의 회수 및 재사용이 용이하여 전체 공정 비용을 감소시켜 공정의 효율을 증가시킬 수 있다. By using the support, a heterogeneous catalyst can be prepared to perform an oxidation reaction, and the catalyst can be easily recovered and reused, thereby reducing the overall process cost, thereby increasing the efficiency of the process.
상기 산화촉매 하에서 상기 범위 내 가압으로 EMF 또는 MMF의 산화반응을 수행하고, 90 % 이상의 수율로 FDCA를 제조할 수 있다. Under the oxidation catalyst, the oxidation reaction of EMF or MMF may be performed by pressurization within the above range, and FDCA may be prepared in a yield of 90% or more.
상기 산화촉매가 혼합된 2,5-퓨란디카르복실산 용액에서 상기 산화촉매를 여과하여 분리한 후 여액에서 2,5-퓨란디카르복실산을 회수한다(S500).The oxidation catalyst is separated by filtration from the 2,5-furandicarboxylic acid solution in which the oxidation catalyst is mixed, and then 2,5-furandicarboxylic acid is recovered from the filtrate (S500).
상기 여액에서 2,5-퓨란디카르복실산 결정을 회수하기 위해서 결정화 또는 증류법을 이용할 수 있다.Crystallization or distillation may be used in order to recover 2,5-furandicarboxylic acid crystals from the filtrate.
상기 유기용매로 에탄올을 이용하는 경우 2,5-퓨란디카르복실산의 에탄올에 대한 용해도가 작기 때문에 단순 여과를 통해서 2,5-퓨란디카르복실산을 에탄올 용매로부터 쉽게 분리할 수 있다.When ethanol is used as the organic solvent, the solubility of 2,5-furandicarboxylic acid in ethanol is small, and thus 2,5-furandicarboxylic acid can be easily separated from the ethanol solvent through simple filtration.
상기 유기용매로 메탄올을 이용하는 경우 2,5-퓨란디카르복실산의 메탄올에 대한 용해도가 크기 때문에 증류를 통해 2,5-퓨란디카르복실산을 메탄올 용매로부터 쉽게 분리할 수 있다.When methanol is used as the organic solvent, the solubility of 2,5-furandicarboxylic acid in methanol is large, and thus 2,5-furandicarboxylic acid can be easily separated from the methanol solvent through distillation.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
실험예 1. 고체산촉매 제조Experimental Example 1. Preparation of solid acid catalyst
문헌(P.P. Upare, J.-W. Yoon, H.-Y. Kang, D.W. Hwang, Y.K. Hwang, H.H. Kung, J.-S. Chang, Green Chem. 15 (2013) 2935-2943)에 따라 그래핀 산화물과 활성탄의 술폰화를 수행하여 고체산 촉매인 GO-SO 3H 및 AC-SO 3H를 제조하였다. Graphene according to the literature (PP Upare, J.-W. Yoon, H.-Y. Kang, DW Hwang, YK Hwang, HH Kung, J.-S. Chang, Green Chem. 15 (2013) 2935-2943) Sulfonation of the oxide and activated carbon was performed to prepare solid acid catalysts GO-SO 3 H and AC-SO 3 H.
술폰화된 물질에 대한 원소분석을 통하여 술폰기의 함량(S-density, mmol/g)을 확인하였다. The content of the sulfone group (S-density, mmol/g) was confirmed through elemental analysis of the sulfonated material.
AC-SO 3H 는 2.5 mmol/g -SO 3H 기를 함유하였으며, 이는 GO-SO 3H의 1.2 mmol/g에 비해 약 2배 이상인 것으로 확인되어 AC-SO 3H가 더 강한 산성점(acidic site)을 가지는 것을 확인하였다. AC-SO 3 H contained 2.5 mmol/g -SO 3 H group, which was confirmed to be about twice as much as 1.2 mmol/g of GO-SO 3 H, so that AC-SO 3 H has a stronger acidic point (acidic site).
또한 AC-SO 3H 및 GO-SO 3H는 MTS-GO(methoxytrimethylsiliane-graphene oxide) 또는 Zr(SO 4) 2 촉매에 비하여 S-density가 높아서 프룩토스의 탈수반응에 매우 효과적일 것으로 예측되었다. In addition, AC-SO 3 H and GO-SO 3 H have higher S-density than that of MTS-GO (methoxytrimethylsiliane-graphene oxide) or Zr(SO 4 ) 2 catalyst, so it was predicted to be very effective in fructose dehydration reaction.
실시예 1. fructose로부터 5-ethoxymethylfurfural (EMF) 제조 Example 1. Preparation of 5-ethoxymethylfurfural (EMF) from fructose
프룩토스 1 g을 ethanol 9 ml, 그래핀산화물에 술폰산이 결합된 고체산촉매(GO-SO 3H) 1.0 g과 혼합 후 70 ℃로 가열 후 24 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 GO-SO 3H 촉매를 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of a solid acid catalyst (GO-SO 3 H) in which sulfonic acid is bound to graphene oxide, and heated to 70° C., followed by reaction for 24 hours. After the reaction, the sample was cooled to room temperature, and the GO-SO 3 H catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, EMF 수율은 72 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 72%.
실시예 2. fructose로부터 5-ethoxymethylfurfural (EMF) 제조 Example 2. Preparation of 5-ethoxymethylfurfural (EMF) from fructose
프룩토스 1 g을 ethanol 9 ml, GO-SO 3H 촉매 1.0 g과 혼합 후 70 ℃로 가열 후 30 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 GO-SO 3H 촉매를 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of a GO-SO 3 H catalyst, heated to 70° C., and reacted for 30 hours. After the reaction, the sample was cooled to room temperature, and the GO-SO 3 H catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100%, EMF 수율은 90%로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 90%.
실시예 3. fructose로부터 5-ethoxymethylfurfural (EMF) 제조 Example 3. Preparation of 5-ethoxymethylfurfural (EMF) from fructose
프룩토스 1 g을 ethanol 9 ml, AC-SO 3H 촉매 1.0 g과 혼합 후 70 ℃로 가열 후 32 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 AC-SO3H 촉매를 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of AC-SO 3 H catalyst, heated to 70° C., and reacted for 32 hours. After the reaction, the sample was cooled to room temperature, and the AC-SO3H catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, EMF 수율은 91 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 91%.
상기 과정을 통해 얻은 EMF/ethanol 용액을 60 ℃로 가열 후 48시간 동안 유지 후 상온으로 냉각하였다. The EMF/ethanol solution obtained through the above process was heated to 60° C., maintained for 48 hours, and then cooled to room temperature.
용액을 liquid chromatography로 분석한 결과 EMF의 농도 변화는 거의 없었다.As a result of analyzing the solution through liquid chromatography, there was almost no change in the concentration of EMF.
따라서 AC-SO 3H 촉매를 이용하여 ethanol 용매상에서 EMF를 제조하는 경우, EMF를 90% 이상 고수율로 얻을 수 있을 뿐 아니라 촉매 반응 완료 후 촉매를 제거한 경우에는 EMF의 2차 반응을 억제할 수 있음을 알 수 있다.Therefore, when EMF is prepared in an ethanol solvent using an AC-SO 3 H catalyst, EMF can be obtained in a high yield of 90% or more, and when the catalyst is removed after the catalytic reaction is completed, the secondary reaction of EMF can be suppressed. You can see that there is.
실시예 4. fructose로부터 5-methoxymethylfurfural (MMF) 제조 Example 4. Preparation of 5-methoxymethylfurfural (MMF) from fructose
프룩토스 1 g을 methanol 9 ml, GO-SO 3H 촉매 1.0 g과 혼합 후 60 ℃로 가열 후 30 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 GO-SO 3H 촉매를 용액과 분리하였다. 분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, MMF 수율은 91 %로 확인되었다.1 g of fructose was mixed with 9 ml of methanol and 1.0 g of a GO-SO 3 H catalyst, heated to 60° C., and reacted for 30 hours. After the reaction, the sample was cooled to room temperature, and the GO-SO 3 H catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the MMF yield was 91%.
상기 과정을 통해 얻은 MMF/methanol 용액을 60 ℃로 가열 후 48시간 동안 유지 후 상온으로 냉각하였다. 용액을 liquid chromatography로 분석한 결과 MMF의 농도 변화는 거의 없었다. The MMF/methanol solution obtained through the above process was heated to 60° C., maintained for 48 hours, and then cooled to room temperature. As a result of analyzing the solution through liquid chromatography, there was almost no change in the concentration of MMF.
따라서, GO-SO 3H 촉매를 이용하여 methanol 용매상에서 MMF를 제조하는 경우, MMF를 90 % 이상 고수율로 얻을 수 있을 뿐 아니라 촉매 반응 완료 후 촉매를 제거한 경우에는 MMF의 2차 반응을 억제할 수 있음을 알 수 있다.Therefore, when MMF is prepared in a methanol solvent using a GO-SO 3 H catalyst, MMF can be obtained in a high yield of 90% or more, and when the catalyst is removed after the catalytic reaction is completed, the secondary reaction of MMF can be suppressed. You can see that you can.
실시예 5. fructose로부터 5-Methoxymethylfurfural (MMF) 제조 Example 5. Preparation of 5-Methoxymethylfurfural (MMF) from fructose
프룩토스 1 g을 methanol 9 ml, 활성탄 지지체에 술폰산이 작용기로 결합된 촉매(이하 'AC-SO 3H') 1.5 g과 혼합 후 60 ℃로 가열 후 21 시간 동안 반응을 진행하였다. 1 g of fructose was mixed with 9 ml of methanol and 1.5 g of a catalyst (hereinafter referred to as “AC-SO 3 H”) in which a sulfonic acid was bonded to a functional group on an activated carbon support, heated to 60° C., and reacted for 21 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 AC-SO 3H 촉매를 용액과 분리하였다. After the reaction, the sample was cooled to room temperature, and the AC-SO 3 H catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, MMF 수율은 90 %로 확인되었다. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the MMF yield was 90%.
따라서 AC-SO 3H 촉매를 이용하여 methanol 용매상에서 MMF를 제조하는 경우, AC-SO 3H 촉매의 양이 증가함에 따라 MMF 생성속도가 빠름을 알 수 있으며, 이를 통해 AC-SO 3H 촉매의 양을 조절함으로써 MMF 수율 및 반응시간을 조절할 수 있다. Thus, the AC-SO case of preparing MMF on a methanol solvent using a 3 H catalyst, AC-SO 3 as H is increased amount of catalyst, and the MMF production rate to find out faster, this AC-SO 3 H catalyst with MMF yield and reaction time can be controlled by adjusting the amount.
실시예 6. fructose로부터 5-methoxymethylfurfural (MMF) 제조 Example 6. Preparation of 5-methoxymethylfurfural (MMF) from fructose
프룩토스 1 g을 methanol 9 ml, AC-SO 3H 촉매 1.0 g과 혼합 후 80 ℃로 가열 후 12 시간 동안 반응을 진행하였다. 1 g of fructose was mixed with 9 ml of methanol and 1.0 g of an AC-SO 3 H catalyst, heated to 80° C., and reacted for 12 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 AC-SO 3H 촉매를 용액과 분리하였다. After the reaction, the sample was cooled to room temperature, and the AC-SO 3 H catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, MMF 수율은 79 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the MMF yield was 79%.
실시예 1 내지 6을 확인하면, 프룩토스를 고체산 촉매와 혼합하고 가열반응으로 높은 전환율로 5-알콕시메틸퍼퓨랄인 EMF 또는 MMF를 수득할 수 있는 것을 알 수 있다.When confirming Examples 1 to 6, it can be seen that by mixing fructose with a solid acid catalyst and heating reaction, 5-alkoxymethylfurfural, EMF or MMF, can be obtained with a high conversion rate.
실시예 7. fructose로부터 5-ethoxymethylfurfural (EMF) 제조 Example 7. Preparation of 5-ethoxymethylfurfural (EMF) from fructose
프룩토스 1g을 ethanol 9 ml, Amberlsyt-131 resin 1.0 g과 혼합 후 80 ℃로 가열 후 46 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 amberlyst-15 resin을 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of Amberlsyt-131 resin, heated to 80°C, and reacted for 46 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, EMF 수율은 86 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 86%.
실시예 8. fructose로부터 5-ethoxymethylfurfural (EMF) 제조 Example 8. Preparation of 5-ethoxymethylfurfural (EMF) from fructose
프룩토스 1g을 ethanol 9 ml, Amberlsyt-16 resin 1.0 g과 혼합 후 80 ℃로 가열 후 30 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 amberlyst-15 resin을 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of Amberlsyt-16 resin, heated to 80°C, and reacted for 30 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, EMF 수율은 81 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 81%.
실시예 9. fructose로부터 5-ethoxymethylfurfural (EMF) 제조 Example 9. Preparation of 5-ethoxymethylfurfural (EMF) from fructose
프룩토스 1g을 ethanol 9 ml, Amberlsyt-36 resin 1.0 g과 혼합 후 80 ℃로 가열 후 25 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 amberlyst-15 resin을 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of Amberlsyt-36 resin, heated to 80°C, and reacted for 25 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, EMF 수율은 78 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 78%.
실시예 10. fructose로부터 5-ethoxymethylfurfural (EMF) 제조 Example 10. Preparation of 5-ethoxymethylfurfural (EMF) from fructose
프룩토스 1g을 ethanol 9 ml, Amberlsyt-15 resin 1.0 g과 혼합 후 80 ℃로 가열 후 60 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 amberlyst-15 resin을 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of Amberlsyt-15 resin, heated to 80° C., and reacted for 60 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 98 %, EMF 수율은 75 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 98% and the EMF yield was 75%.
실시예 11. EMF로부터 FDCA 제조 Example 11. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 활성탄 지지체에 백금이 도포된 촉매(이하 'Pt(5%)/C') 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 15 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with platinum on an activated carbon support (hereinafter'Pt(5%)/C'), heated to 100° C., and then heated to 15 bar using O 2 gas. After raising the pressure, the reaction was carried out for 2 hours.
반응 후 샘플을 상온 27 ℃로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature of 27° C., and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 디메틸포름아미트(dimethylformamide, 이하'DMF') 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. The solid mixture was mixed with 10 ml of a dimethylformamide (hereinafter referred to as'DMF') solvent, and then the catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 97 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 97%.
활성탄 지지체에 소량의 백금이 도포된 불균일계 산화촉매를 사용하는 경우 FDCA 생성 후 여과를 통하여 FDCA와 용이하게 분리할 수 있기 때문에 반응용액과 촉매의 분리가 용이하여 촉매를 재사용할 수 있는 장점을 갖는다.In the case of using a heterogeneous oxidation catalyst coated with a small amount of platinum on the activated carbon support, it has the advantage of being able to reuse the catalyst because it is easy to separate the reaction solution from the catalyst because it can be easily separated from FDCA through filtration after FDCA generation. .
실시예 12. EMF로부터 FDCA 제조 Example 12. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 하이드로탈사이트 지지체에 금이 도포된 촉매(이하 'Au(5%)/hydrotalcite') 촉매 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 15 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with gold on a hydrotalcite support (hereinafter, referred to as'Au(5%)/hydrotalcite'), heated to 100° C., and then used O 2 gas. After raising the pressure to 15 bar, the reaction was carried out for 2 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. 분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 95 %로 확인되었다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 95%.
실시예 13. EMF로부터 FDCA 제조 Example 13. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 Au(5%)/hydrotalcite 촉매 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 10 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of Au (5%)/hydrotalcite catalyst, heated to 100° C., and the pressure was raised to 10 bar using O 2 gas, and the reaction was carried out for 2 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. 분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 90 %로 확인되었다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 90%.
실시예 8과 실시예 9를 참조하면, 동일한 Au(5%)/hydrotalcite 촉매를 사용하여 EMF로부터 FDCA를 제조하는 경우 압력증가에 따라 FDCA의 수율이 증가되는 것을 확인하였다. Referring to Examples 8 and 9, it was confirmed that when FDCA was prepared from EMF using the same Au (5%)/hydrotalcite catalyst, the yield of FDCA increased with increasing pressure.
실시예 14. EMF로부터 FDCA 제조 Example 14. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 활성탄 지지체에 루테늄이 도포된 촉매(이하 ' Ru(5%)/C') 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 15 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a ruthenium-coated catalyst (hereinafter referred to as'Ru(5%)/C') on an activated carbon support, heated to 100° C., and then heated to 15 bar using O 2 gas. After raising the pressure, the reaction was carried out for 2 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100%, FDCA 수율은 96%로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 96%.
실시예 15. EMF로부터 FDCA 제조 Example 15. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 산화세륨 지지체에 루테늄이 도포된 촉매(이하 'Ru(5%)/CeO 2 ') 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 15 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with ruthenium on a cerium oxide support (hereinafter, referred to as'Ru(5%)/CeO 2 '), heated to 100° C., and then 15 using O 2 gas. After raising the pressure to bar, the reaction was carried out for 2 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 95 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 95%.
실시예 16. EMF로부터 FDCA 제조 Example 16. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 활성탄 지지체에 팔라듐이 도포된 촉매(이하 'Pd(5%)/C') 촉매 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 15 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with palladium on an activated carbon support (hereinafter referred to as'Pd(5%)/C'), heated to 100° C., and then 15 bar using O 2 gas. After raising the pressure, the reaction was carried out for 2 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. 분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 92 %로 확인되었다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 92%.
실시예 17. EMF로부터 FDCA 제조 Example 17. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 활성탄 지지체에 백금이 도포된 촉매(이하 'Pt(5%)/C') 촉매 0.5 g과 혼합하고 100 ℃로 가열 후 공기를 이용하여 20 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with platinum on an activated carbon support (hereinafter, referred to as'Pt(5%)/C'), heated to 100° C., and then pressurized to 20 bar using air. After raising the reaction was carried out for 2 hours.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. 분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 93 %로 확인되었다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 93%.
실시예 18. EMF로부터 FDCA 제조 Example 18. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 Ru-Sn(5%)/CeO2 촉매 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 15 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of Ru-Sn (5%)/CeO2 catalyst, heated to 100° C., and the pressure was raised to 15 bar using O 2 gas, and the reaction was carried out for 2 hours. I did.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. 분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 90 %로 확인되었다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 90%.
실시예 19. EMF로부터 FDCA 제조 Example 19. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 MnOx/CeO2 (Mn/Ce 몰비 6) 촉매 0.5 g과 혼합하고 100 ℃로 가열 후 O 2 가스를 이용하여 15 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of MnOx/CeO2 (Mn/Ce molar ratio 6) catalyst, heated to 100° C., and then increased the pressure to 15 bar using O 2 gas, and reacted for 2 hours. Proceeded.
반응 후 샘플을 상온으로 냉각 후 여과를 통해 고체 혼합물을 용액으로부터 분리하였다. After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.
상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 여과를 통해 촉매를 용액과 분리하였다. 분리한 용액을 liquid chromatography로 분석한 결과 EMF 전환율은 100 %, FDCA 수율은 92 %로 확인되었다. After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 92%.
상기 실시예들을 참조하면, EMF 산화반응 촉매로는 Pt/C, Ru/C, Pd/C, Ru/CeO2, Ru-Sn/ZnO와 같은 귀금속 촉매 뿐 아니라 MnOx/CeO2와 같은 전이금속 촉매도 활용이 가능하다. 특히, MnOx/CeO2와 같은 전이금속 촉매는 귀금속 촉매 대비 가격이 훨씬 더 저렴하기 때문에 경제적으로 FDCA를 생산하는데 유리한 장점이 있다.Referring to the above embodiments, as an EMF oxidation catalyst, not only noble metal catalysts such as Pt/C, Ru/C, Pd/C, Ru/CeO2, Ru-Sn/ZnO, but also transition metal catalysts such as MnOx/CeO2 are used. This is possible. In particular, transition metal catalysts such as MnOx/CeO2 are advantageous in economically producing FDCA because the price is much lower than that of precious metal catalysts.
비교예 1: 무기산 촉매를 이용하여 EMF 제조 Comparative Example 1: Preparation of EMF using an inorganic acid catalyst
프룩토스 1g을 ethanol 9 ml, 무기산 촉매로 황산(H 2SO 4) 0.03 g과 혼합 후 25bar에서 90 ℃로 가열 후 6 시간 동안 반응을 진행하였다. 반응 후 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 85%, EMF 수율은 32 %로 확인되었다.After mixing 1 g of fructose with 9 ml of ethanol and 0.03 g of sulfuric acid (H 2 SO 4 ) as an inorganic acid catalyst, the reaction was carried out for 6 hours after heating at 25 bar to 90° C. After the reaction, the solution was analyzed through liquid chromatography, and it was found that the fructose conversion rate was 85% and the EMF yield was 32%.
비교예 2. fructose로부터 5-hydroxymethylfurfural (HMF) 제조 Comparative Example 2. Preparation of 5-hydroxymethylfurfural (HMF) from fructose
프룩토스 1g을 1-butanol 9 ml, Amberlsyt-15 resin 1.0 g과 혼합 후 100 ℃로 가열 후 5 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 amberlyst-15 resin을 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of 1-butanol and 1.0 g of Amberlsyt-15 resin, heated to 100° C., and reacted for 5 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, HMF 수율은 86 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the HMF yield was 86%.
비교예 3. fructose로부터 5-hydroxymethylfurfural (HMF) 제조 Comparative Example 3. Preparation of 5-hydroxymethylfurfural (HMF) from fructose
프룩토스 1g을 isopropyl alcohol 9 ml, Amberlsyt-15 resin 1.0 g과 혼합 후 100 ℃로 가열 후 5 시간 동안 반응을 진행하였다. 반응 후 샘플을 상온으로 냉각 후 여과를 통해 amberlyst-15 resin을 용액과 분리하였다. 1 g of fructose was mixed with 9 ml of isopropyl alcohol and 1.0 g of Amberlsyt-15 resin, heated to 100° C., and reacted for 5 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.
분리한 용액을 liquid chromatography로 분석한 결과 프룩토스 전환율은 100 %, HMF 수율은 42 %로 확인되었다.As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the HMF yield was 42%.
또한 메탄올 또는 에탄올이 아닌 이소프로필알코올 또는 1-부탄올을 용매로 사용한 경우에는 5-알콕시메틸퍼퓨랄이 생성되지 않고, 5-하이드록시메틸퍼퓨랄(5-hydroxymethylfurfural; HMF)이 주로 생성되는 것을 알 수 있다.In addition, when isopropyl alcohol or 1-butanol other than methanol or ethanol is used as a solvent, 5-alkoxymethylfurfural is not produced, and 5-hydroxymethylfurfural (HMF) is mainly produced. I can.
또한, 프룩토스로부터 에탄올과의 반응에서 고체산 촉매 대신 무기산을 촉매로 사용한 경우 EMF 수율이 매우 낮은 것을 확인하였다.In addition, it was confirmed that the EMF yield was very low when an inorganic acid was used as a catalyst instead of a solid acid catalyst in the reaction with ethanol from fructose.
비교예 4. EMF로부터 FDCA 제조 Comparative Example 4. Preparation of FDCA from EMF
실시예 1에서 제조한 EMF/ethanol 용액을 산화촉매 없이 100 ℃로 가열 후 공기를 이용하여 20 bar로 압력을 올린 후 2 시간 동안 반응을 진행하였다. The EMF/ethanol solution prepared in Example 1 was heated to 100° C. without an oxidation catalyst, and the pressure was raised to 20 bar using air, and the reaction was carried out for 2 hours.
반응 후 샘플을 상온으로 냉각 후 상기 고체 혼합물을 DMF 용매 10 ml와 혼합 후 liquid chromatography로 분석한 결과 EMF 전환율은 15 %, FDCA 수율은 10 %로 확인되었다.After the reaction, the sample was cooled to room temperature, the solid mixture was mixed with 10 ml of a DMF solvent, and analyzed by liquid chromatography. As a result, the EMF conversion was found to be 15% and the FDCA yield was 10%.
지금까지 본 발명에 실시예에 따른 프룩토스로부터 5-알콕시메틸퍼퓨랄을 제조방법, 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산을 제조하는 방법 및 프룩토스로부터 2,5-퓨란디카르복실산 제조방법에 관한 구체적인 실시예에 관하여 설명하였으나, 본 발명의 범위에서 벗어나지 않는 한도 내에서는 여러 가지 실시 변형이 가능함은 자명하다.So far, a method for preparing 5-alkoxymethylfurfural from fructose according to an embodiment of the present invention, a method for preparing 2,5-furandicarboxylic acid from 5-alkoxymethylfurfural, and 2,5-from fructose Although specific examples of the method for producing furandicarboxylic acid have been described, it is obvious that various embodiments can be modified without departing from the scope of the present invention.
그러므로 본 발명의 범위는 설명된 실시예에 국한되어 정해져서는 안 되며, 후술하는 특허청구범위뿐만 아니라 이 특허청구범위와 균등한 것들에 의해 정해져야 한다.Therefore, the scope of the present invention is limited to the described embodiments and should not be defined, and should be defined by the claims and equivalents as well as the claims to be described later.
즉, 전술된 실시예는 모든 면에서 예시적인 것이며, 한정적인 것이 아닌 것으로 이해되어야 하며, 본 발명의 범위는 상세한 설명보다는 후술될 특허청구범위에 의하여 나타내어지며, 그 특허청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.That is, it should be understood that the above-described embodiments are illustrative in all respects and not limiting, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims and All changes or modified forms derived from the equivalent concept should be interpreted as being included in the scope of the present invention.
본 발명에 따르면, 식물계에 매우 풍부한 프룩토스(fructose)로부터 2,5-퓨란디카복실산(2,5-furandicarboxylic acid)을 경제적으로 제조할 수 있다. According to the present invention, 2,5-furandicarboxylic acid can be economically prepared from fructose, which is very abundant in the plant world.
또한 프룩토스를 고체산촉매를 이용하여 탈수한 이후에 추가적인 후처리 없이 바로 산화반응을 진행할 수 있다. In addition, after dehydration of fructose using a solid acid catalyst, the oxidation reaction can proceed immediately without additional post-treatment.

Claims (15)

  1. (a-1) 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조하는 단계; (a-1) preparing a mixed solution by mixing fructose and an organic solvent;
    (a-2) 상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조하는 단계; 및(a-2) heating the mixed solution under a solid acid catalyst and reacting to prepare 5-alkoxymethylfurfural; And
    (a-3) 상기 5-알콕시메틸퍼퓨랄을 함유하는 혼합용액을 여과하여 고체산촉매를 분리하는 단계;를 포함하는 프룩토스로부터 5-알콕시메틸퍼퓨랄을 제조하는 방법.(a-3) separating the solid acid catalyst by filtering the mixed solution containing the 5-alkoxymethylfurfural; Method for producing 5-alkoxymethylfurfural from fructose comprising.
  2. 제1항에 있어서, The method of claim 1,
    상기 유기용매는 The organic solvent is
    메탄올 또는 에탄올인 것을 특징으로 하는 프룩토스로부터 5-알콕시메틸퍼퓨랄을 제조하는 방법.Method for producing 5-alkoxymethylfurfural from fructose, characterized in that methanol or ethanol.
  3. 제1항에 있어서, The method of claim 1,
    상기 고체산촉매는 The solid acid catalyst is
    술폰산(-SO 3H)을 작용기로 포함하는 것을 특징으로 하는 프룩토스로부터 5-알콕시메틸퍼퓨랄을 제조하는 방법.A method for producing 5-alkoxymethylfurfural from fructose, comprising sulfonic acid (-SO 3 H) as a functional group.
  4. 제1항에 있어서, The method of claim 1,
    상기 여과는 The filtration is
    상기 5-알콕시메틸퍼퓨랄 용액을 20 내지 30 ℃ 상온으로 냉각한 이후에 여과지를 사용하여 수행하는 것을 특징으로 하는 프룩토스로부터 5-알콕시메틸퍼퓨랄을 제조하는 방법.A method of producing 5-alkoxymethylfurfural from fructose, characterized in that the 5-alkoxymethylfurfural solution is cooled to room temperature at 20 to 30°C and then performed using a filter paper.
  5. 청구항 제1항 내지 제4항 중 어느 한 항의 방법으로 제조된 5-알콕시메틸퍼퓨랄 용액을 산화촉매 하에서 가압 및 가열하고 반응시켜 2,5-퓨란디카르복실산을 제조하는 것을 특징으로 하는 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산을 제조하는 방법.5, characterized in that the 5-alkoxymethylfurfural solution prepared by the method of any one of claims 1 to 4 is pressurized, heated, and reacted under an oxidation catalyst to produce 2,5-furandicarboxylic acid. -Method for producing 2,5-furandicarboxylic acid from alkoxymethylfurfural.
  6. 제5항에 있어서, The method of claim 5,
    상기 가압 및 가열은 산소 가스 또는 공기를 10 내지 50 bar로 가압하고 80 내지 150 ℃로 가열하는 것을 특징으로 하는 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산의 제조방법.The pressurization and heating is a method for producing 2,5-furandicarboxylic acid from 5-alkoxymethylfurfural, characterized in that oxygen gas or air is pressurized to 10 to 50 bar and heated to 80 to 150°C.
  7. 제5항에 있어서, The method of claim 5,
    상기 산화촉매는 The oxidation catalyst is
    활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)에서 선택된 어느 하나인 지지체에,Activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide and aluminum oxide (Al 2 O 3 ) to any one selected from the support,
    금, 백금, 팔라듐 및 루테늄으로 이루어진 군에서 선택된 어느 하나의 금속이 담지된 것을 특징으로 하는 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산의 제조방법.Method for producing 2,5-furandicarboxylic acid from 5-alkoxymethylfurfural, characterized in that any one metal selected from the group consisting of gold, platinum, palladium and ruthenium is supported.
  8. 제5항에 있어서, The method of claim 5,
    상기 산화촉매는 The oxidation catalyst is
    산화크롬, 산화망간, 산화철, 및 산화코발트로 이루어지는 전이금속 산화물 중 어느 하나 이상이거나, Any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, or
    활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)로 이루어진 군에서 선택된 어느 하나의 지지체에 상기 전이금속 산화물이 담지된 것을 특징으로 하는 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산의 제조방법.The transition metal oxide is supported on any one support selected from the group consisting of activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide, and aluminum oxide (Al 2 O 3 ). Method for producing 2,5-furandicarboxylic acid from 5-alkoxymethylfurfural, characterized in that.
  9. (a) 프룩토스(fructose)와 유기용매를 혼합하여 혼합용액을 제조하는 단계; (a) preparing a mixed solution by mixing fructose and an organic solvent;
    (b) 상기 혼합용액을 고체산촉매 하에서 가열하고 반응시켜 5-알콕시메틸퍼퓨랄을 제조하는 단계;(b) heating the mixed solution under a solid acid catalyst and reacting to prepare 5-alkoxymethylfurfural;
    (c) 상기 고체산촉매가 혼합된 5-알콕시메틸퍼퓨랄 용액에서 상기 고체산촉매를 여과하여 분리하는 단계; (c) filtering and separating the solid acid catalyst from the 5-alkoxymethylfurfural solution in which the solid acid catalyst is mixed;
    (d) 상기 고체산촉매가 분리된 용액을 산화촉매 하에서 가압 및 가열하고 반응시켜 2,5-퓨란디카르복실산을 제조하는 단계; 및(d) preparing 2,5-furandicarboxylic acid by pressing and heating the solution from which the solid acid catalyst was separated and reacting under an oxidation catalyst; And
    (e) 상기 산화촉매가 혼합된 2,5-퓨란디카르복실산 용액에서 상기 산화촉매를 여과하여 분리한 후 여액에서 2,5-퓨란디카르복실산을 회수하는 단계;(e) filtering and separating the oxidation catalyst from the 2,5-furandicarboxylic acid solution in which the oxidation catalyst is mixed, and recovering the 2,5-furandicarboxylic acid from the filtrate;
    를 포함하는 프룩토스로부터 2,5-퓨란디카르복실산 제조방법.Method for producing 2,5-furandicarboxylic acid from fructose comprising a.
  10. 제9항에 있어서, The method of claim 9,
    상기 유기용매는 The organic solvent is
    메탄올 또는 에탄올인 것을 특징으로 하는 프룩토스로부터 2,5-퓨란디카르복실산 제조방법. Method for producing 2,5-furandicarboxylic acid from fructose, characterized in that it is methanol or ethanol.
  11. 제9항에 있어서, The method of claim 9,
    상기 고체산촉매는 The solid acid catalyst is
    술폰산(-SO 3H)을 작용기로 포함하는 것을 특징으로 하는 프룩토스로부터 2,5-퓨란디카르복실산 제조방법. A method for producing 2,5-furandicarboxylic acid from fructose, comprising a sulfonic acid (-SO 3 H) as a functional group.
  12. 제9항에 있어서, The method of claim 9,
    상기 (d) 단계의 가압 및 가열은 The pressurization and heating of step (d)
    산소 가스 또는 공기를 10 내지 50 bar로 가압하고, 80 내지 150 ℃로 가열하는 것을 특징으로 하는 촉매를 이용한 프룩토스로부터 2,5-퓨란디카르복실산 제조방법.A method for producing 2,5-furandicarboxylic acid from fructose using a catalyst, characterized in that oxygen gas or air is pressurized to 10 to 50 bar and heated to 80 to 150°C.
  13. 제9항에 있어서, The method of claim 9,
    상기 산화촉매는 The oxidation catalyst is
    활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)에서 선택된 어느 하나인 지지체와,Activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide, and a support selected from aluminum oxide (Al 2 O 3 ),
    상기 지지체에 금, 백금, 팔라듐 및 루테늄으로 이루어진 군에서 선택된 어느 하나의 금속이 담지된 것을 특징으로 하는 프룩토스로부터 2,5-퓨란디카르복실산 제조방법. Method for producing 2,5-furandicarboxylic acid from fructose, characterized in that any one metal selected from the group consisting of gold, platinum, palladium and ruthenium is supported on the support.
  14. 제9항에 있어서, The method of claim 9,
    상기 산화촉매는 The oxidation catalyst is
    산화크롬, 산화망간, 산화철, 및 산화코발트로 이루어지는 전이금속 산화물 중 어느 하나 이상이거나, Any one or more of transition metal oxides consisting of chromium oxide, manganese oxide, iron oxide, and cobalt oxide, or
    활성탄, 실리카, 산화아연, 이산화규소, 지르코늄디옥사이드(ZrO 2), 하이드로탈사이트, 제올라이트, 산화세륨 및 산화알루미늄(Al 2O 3)로 이루어진 군에서 선택된 어느 하나의 지지체에 상기 전이금속 산화물이 담지된 것을 특징으로 하는 프룩토스로부터 2,5-퓨란디카르복실산 제조방법. The transition metal oxide is supported on any one support selected from the group consisting of activated carbon, silica, zinc oxide, silicon dioxide, zirconium dioxide (ZrO 2 ), hydrotalcite, zeolite, cerium oxide, and aluminum oxide (Al 2 O 3 ). Method for producing 2,5-furandicarboxylic acid from fructose, characterized in that the
  15. 제9항에 있어서, The method of claim 9,
    상기 (e) 단계는 상기 여액에서 2,5-퓨란디카르복실산 결정을 회수하기 위해서 결정화 또는 증류법을 이용하는 것을 특징으로 하는 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산 제조방법.Step (e) is a method for producing 2,5-furandicarboxylic acid from 5-alkoxymethylfurfural, characterized in that a crystallization or distillation method is used to recover 2,5-furandicarboxylic acid crystals from the filtrate. .
PCT/KR2020/003741 2019-03-21 2020-03-19 Method for producing 5-alkoxy-methylfurfural and 2,5-furandicarboxylic acid from fructose WO2020190043A1 (en)

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WO2009030511A1 (en) * 2007-09-07 2009-03-12 Furanix Technologies B.V. Mixture of furfural and 5-(alkoxymethyl)furfural derivatives from sugars and alcohols
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