WO2020101234A1 - Procédé de préparation de 2,5-furandiméthanol et de 2,5-tétrahydrofurane diméthanol à partir de 5-hydroxyméthylfurfural - Google Patents

Procédé de préparation de 2,5-furandiméthanol et de 2,5-tétrahydrofurane diméthanol à partir de 5-hydroxyméthylfurfural Download PDF

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WO2020101234A1
WO2020101234A1 PCT/KR2019/014695 KR2019014695W WO2020101234A1 WO 2020101234 A1 WO2020101234 A1 WO 2020101234A1 KR 2019014695 W KR2019014695 W KR 2019014695W WO 2020101234 A1 WO2020101234 A1 WO 2020101234A1
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furan
based compound
producing
dimethanol
hmf
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PCT/KR2019/014695
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Korean (ko)
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김용진
미슈라디네쉬쿠마
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한국생산기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • 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
    • 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
    • B01J23/005—Spinels
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • C07D307/42—Singly bound oxygen atoms

Definitions

  • the present invention relates to a method for producing 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol from 5-hydroxymethylperfural, and more specifically, to support a spinel structure supporting precious metal nanoparticles.
  • 5-Hydroxymethylfurfural (HMF) to 2,5-furandimethanol (FDM) and 2,5-tetrahydrofuran dimethanol (2,5) -Tetrahydrofuran dimethanol, THF-DM) relates to a method for selectively producing at least one furan-based compound selected from the group consisting of.
  • plastics based on various resins began to be mass-produced as consumer goods.
  • more than 300 million tons of plastic has been produced and consumed worldwide, exceeding steel production.
  • plastic is produced using naphtha from the oil refining process, depletion of petroleum resources and carbon dioxide emissions are a problem, and as it is used as the main material for disposable products, it is used for a long time before being discarded immediately after using the product.
  • carcinogens such as dioxin are released into the atmosphere, causing environmental problems, and research on alternative materials has been continuously conducted.
  • 5-hydroxymethylfurfural is produced from carbohydrate or cellulose in the presence of an acid catalyst, and the 5-hydroxymethylfurfural is based on biomass with significant industrial applicability. It is classified as one of 10 compounds.
  • 2,5-furandimethanol FDM
  • 2,5-tetrahydrofuran dimethanol 2,5-Tetrahydrofuran dimetanol, THF-DM
  • 2,5 through catalytic hydrogenation of HMF -Dimethylfuran 2,5-dimethylfuran
  • the 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol can be used in various aspects such as the production of resins, polymers, and chemical fibers having various properties, and thus has great potential. Therefore, a hydrogenation method of HMF that can selectively produce 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol from HMF using a metal complex and a metal supported catalyst in various environments has been actively studied.
  • 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol can be selectively obtained in a single container, and 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol are respectively 90%.
  • a process that can be obtained with the above high yield is required.
  • the object of the present invention is selected from the group consisting of 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol from 5-hydroxymethylperfural using a spinel-structured support carrying precious metal nanoparticles as a catalyst. It is to provide a method for producing a furan-based compound capable of selectively obtaining 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol in a single container by preparing one or more furan-based compounds.
  • (a) 5-hydroxymethylfurfural (5-Hydroxymethylfurfural, HMF) hydrogenation reaction using a catalyst with hydrogen (H 2 ) 2,5-furandimethane (2,5 -Furandimethanol, FDM) and 2,5-tetrahydrofuran dimethanol (2,5-Tetrahydrofuran dimethanol, THF-DM) comprising the step of preparing a furan-based compound comprising at least one selected from the group consisting of, and
  • the catalyst is to provide a method for producing a furan-based compound, which comprises a spinel-structured support carrying noble metal nanoparticles.
  • the isolated 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol will contain 0.1 to 20 ppm cobalt (Co), 0.1 to 60 ppm manganese (Mn), and 0.1 to 5 ppm ruthenium (Ru). Can be.
  • the support of the spinel structure is MnCo 2 O 4 , CoMn 2 O 4 , ZnAl 2 O 4 , FeAl 2 O 4 , CuFe 2 O 4 , ZnMn 2 O 4 , MnFe 2 O 4 , Fe 3 O 4 , TiFe 2 It may include one or more selected from the group consisting of O 4 , ZnFe 2 O 4 , Mg 2 SiO 4 , Fe 2 SiO 4 .
  • the noble metal nanoparticles may include one or more selected from the group consisting of platinum, palladium, and ruthenium.
  • the catalyst may be a MnCo 2 O 4 support having a spinel structure carrying ruthenium nanoparticles.
  • the step of preparing the furan-based compound is the reaction time, the pressure of the hydrogen, and the molar ratio (mol / mol) of 5-hydroxymethylperfural (HMF / Ru) to ruthenium (Ru) of the catalyst
  • HMF / Ru 5-hydroxymethylperfural
  • Ru ruthenium
  • the reaction time is 2.5 to 3.5 hr
  • the pressure of the hydrogen is 5 to 6 MPa
  • the molar ratio (mol / mol) of HMF / Ru is adjusted to 30 to 40 to 2,5- It may be a step of preparing furan dimethanol as a main product.
  • the reaction time is 15.5 to 16.5 hr
  • the pressure of the hydrogen is 6.5 to 9.5 MPa
  • the molar ratio (mol / mol) of HMF / Ru is adjusted to 45 to 105 to 2,5.
  • -Tetrahydrofuran may be a step of preparing methane as the main product.
  • the temperature of the step of preparing the furan-based compound may be 70 to 150 °C.
  • the precious metal nanoparticles may be 1 to 10% by weight based on the catalyst weight.
  • the precious metal nanoparticles may be 3 to 5% by weight based on the catalyst weight.
  • the precious metal nanoparticles may be 4% by weight based on the catalyst weight.
  • the step of preparing the furan-based compound may be a step performed in a single container.
  • the 5-hydroxymethylperfural may be derived from biomass including one or more selected from the group consisting of cellulose and polysaccharides.
  • the method for producing the furan-based compound is performed by a solution reaction using a solvent, and the solvent is methanol, ethanol, n-propanol, iso-propanol, butanol, pentanol, tetrahydrofuran, methyl tertiary butyl ether, hexane And it may include one or more selected from the group consisting of pentane.
  • the solvent may be methanol.
  • the average particle diameter (D 50 ) of the support having the spinel structure may be 2.0 to 4.0 ⁇ m.
  • the method for producing a furan-based compound of the present invention uses 2,5-furandimethanol and 2, in a single container by hydrogenation of 5-hydroxymethylperfural using a spinel-structured support carrying precious metal nanoparticles as a catalyst.
  • 5-Tetrahydrofuran dimethanol can be optionally obtained.
  • 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol can be obtained in high yields of 90% or more, respectively.
  • 1 shows a schematic diagram of the conversion reaction of 5-hydroxymethylperfural.
  • Figure 2 shows the aspects of the hydrogenation product of 5-hydroxymethylperfural according to the reaction conditions.
  • Figure 3 shows the XRD pattern of the spinel structure of the support prepared according to Preparation Example 1.
  • Figure 5 shows a SEM picture that can identify a number of pores in the support of the spinel structure prepared according to Preparation Example 1.
  • FIG. 6 shows an SEM photograph of a microsphere of a spinel-structured support prepared according to Preparation Example 1.
  • Figure 7 shows the XPS of the support of the spinel structure of the precious metal nanoparticles prepared according to Preparation Example 2.
  • FIG. 9 shows the 1 H-NMR spectrum of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and subsequently purified and commercially available reagent 2,5-tetrahydrofuran dimethanol.
  • FIG. 10 shows the 13 C-NMR spectrum of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and subsequently purified and commercially available reagent 2,5-tetrahydrofuran dimethanol.
  • FIG. 11 is a schematic diagram showing the conversion rate of 5-hydroxymethylperfural and the yield of 2,5-furandiethanol according to the number of catalyst reuses when preparing 2,5-furandimethane according to Example 1.
  • FIG. 12 is a schematic diagram of 5-hydroxymethylperfuran conversion and 2,5-tetrahydrofuran dimethanol yield according to the number of catalyst reuses when preparing 2,5-tetrahydrofuran dimethanol according to Example 2.
  • first and second to be used below may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from other components.
  • first component may be referred to as a second component without departing from the scope of the present invention, and similarly, the second component may be referred to as a first component.
  • a component when referred to as being “formed” or “stacked” on another component, it may be formed or stacked directly attached to the front or one side of the surface of the other component, but may be intermediate. It should be understood that there may be other components in the.
  • 1 shows a schematic diagram of the conversion reaction of 5-hydroxymethylperfural.
  • 1, 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol can be selectively obtained from 5-hydroxymethylperfural.
  • Figure 2 shows the aspects of the hydrogenation product of 5-hydroxymethylperfural according to the reaction conditions.
  • the present invention is (a) 5-hydroxymethyl perfural (5-Hydroxymethylfurfural, HMF) hydrogenation reaction using hydrogen (H 2 ) and a catalyst to 2,5-furandiethanol (2, 5-Furandimethanol, FDM) and 2,5-tetrahydrofuran dimethanol (2,5-Tetrahydrofuran dimethanol, THF-DM) comprising the step of preparing a furan-based compound comprising at least one selected from the group consisting of,
  • the catalyst provides a method for producing a furan-based compound, which comprises a spinel-structured support carrying noble metal nanoparticles.
  • the isolated 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol will contain 0.1 to 20 ppm cobalt (Co), 0.1 to 60 ppm manganese (Mn), and 0.1 to 5 ppm ruthenium (Ru). Can be.
  • the support of the spinel structure is MnCo 2 O 4 , CoMn 2 O 4 , ZnAl 2 O 4 , FeAl 2 O 4 , CuFe 2 O 4 , ZnMn 2 O 4 , MnFe 2 O 4 , Fe 3 O 4 , TiFe 2 O 4 , ZnFe 2 O 4 , Mg 2 SiO 4 , Fe 2 SiO 4 It may include one or more selected from the group consisting of, preferably selected from the group consisting of MnCo 2 O 4 and CoMn 2 O 4 It may contain one or more, more preferably MnCo 2 O 4 .
  • the precious metal may include one or more selected from the group consisting of platinum, palladium, and ruthenium, and preferably ruthenium.
  • the particle size of the noble metal nanoparticles may be 5 to 15 nm, and the noble metal nanoparticles of the 5 to 15 nm size may be efficiently contained in the support of the spinel structure.
  • noble metal particles can be uniformly dispersed in a structure in which a number of microspheres possessed by a spinel support are integrated, it is possible to induce a stable hydrogenation reaction of a furan compound.
  • the catalyst may be a MnCo 2 O 4 support having a spinel structure carrying ruthenium nanoparticles.
  • the step of preparing the furan-based compound is the reaction time, the pressure of the hydrogen, and the molar ratio (mol / mol) of 5-hydroxymethylperfural (HMF / Ru) to ruthenium (Ru) of the catalyst
  • HMF / Ru 5-hydroxymethylperfural
  • Ru ruthenium
  • the reaction time is 2.5 to 3.5 hr
  • the pressure of the hydrogen is 5 to 6 MPa
  • the molar ratio (mol / mol) of HMF / Ru is adjusted to 30 to 40 to 2,5- It may be a step in which furan dimethanol is prepared as a main product.
  • the reaction time is less than 2.5hr, the pressure of hydrogen is less than 5MPa and the molar ratio of HMF / Ru is less than 30, the yield of 2,5-furandimethane is low, the reaction time is 3.5hr, the pressure of hydrogen is 6MPa, and HMF / Ru When the molar ratio exceeds 40, the incidence of by-product 2,5-tetrahydrofuran dimethanol may increase, which is not preferable.
  • the reaction time is 15.5 to 16.5 hr
  • the pressure of the hydrogen is 6.5 to 9.5 MPa
  • the molar ratio (mol / mol) of HMF / Ru is adjusted to 45 to 105 to 2,5 -Tetrahydrofuran may be a step of preparing methane as the main product.
  • the reaction time is 15.5h, the pressure of hydrogen is less than 6.5MPa, and the HMF / Ru molar ratio is less than 45, the yield of 2,5-tetrahydrofuran dimethanol is low, the reaction time 16.5h, the pressure of hydrogen 9.5MPa, HMF / If the Ru molar ratio exceeds 105, the incidence of by-products may increase, which is not preferable.
  • the reaction temperature of the step of preparing the furan-based compound may be 70 to 150 ° C, preferably 80 to 120 ° C, more preferably 90 to 110 ° C, even more preferably 95 to 105 ° C have.
  • the reaction temperature is less than 80 ° C, the yield of the furan-based compound is low, and when it exceeds 150 ° C, a side reaction occurs and the catalyst is decomposed at a high temperature to 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol. It is not preferable because it is difficult to prepare a furan-based compound containing one or more selected from the group consisting of.
  • the precious metal nanoparticles may be 1 to 10% by weight based on the catalyst weight, preferably 3 to 5% by weight, more preferably 4% by weight. If the noble metal nanoparticles are contained in less than 1% by weight, the yield of the furan-based compound may be lowered, and when it is included in 10% by weight or more, the furan-based compound may be rapidly hydrogenated to cause problems in process stability, and the noble metal particles Excessive use of is undesirable as it can affect the price increase of the catalyst.
  • the step of preparing the furan-based compound may be a step performed in a single container.
  • the HMF may be derived from biomass containing at least one selected from the group consisting of cellulose and polysaccharides.
  • the method for producing the furan-based compound is performed by a solution reaction using a solvent, and the solvent is methanol, ethanol, n-propanol, iso-propanol, butanol, pentanol, tetrahydrofuran, methyl tertiary butyl ether, hexane And it may include one or more selected from the group consisting of pentane, preferably may include methanol.
  • the average particle diameter (D 50 ) of the support having the spinel structure may be 2.0 to 4.0 ⁇ m.
  • the pale pink precipitate was collected by filtration, washed with distilled water and anhydrous ethanol, and then dried at 60 ° C. for 12 hours.
  • the obtained carbonate precursor (MnCo 2 CO 3 ) is calcined in an air (20% O 2 , 80% N 2 ) atmosphere at 425 ° C. (2 ° C./min) for 8 hours, and then naturally cooled to room temperature over 8 hours to cobalt- A manganese-based spinel structure support (MnCo 2 O 4 ) was prepared.
  • the mixture was purged with hydrogen at a pressure of 0.55 MPa and the atmosphere was evacuated three times. Thereafter, the mixture was stirred at 650 rpm, heated to 100 ° C., and the carbon dioxide pressure was raised to 8.2 MPa, and then reacted for 16 hours while maintaining the pressure at 8.2 MPa, and 2,5-tetrahydrofuran dimethanol (THF-DM) was used as the main product. It was prepared.
  • THF-DM was prepared as a main product in the same manner as in Example 2, except that the reaction temperature was performed at 80 ° C instead of 100 ° C.
  • THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction temperature was performed at 120 ° C instead of 100 ° C.
  • THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction pressure was performed at 5.5 MPa instead of 8 MPa.
  • THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction pressure was performed at 6.8 MPa instead of 8 MPa.
  • THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction pressure was performed at 8.85 MPa instead of 8 MPa.
  • Example 1 2,5-furandiethanol 8.0 0.40 33.6 20 100 5.5 3
  • Example 2 2,5-tetrahydrofuran dimethanol 8.0 0.40 50 20 100 8.2 16
  • Example 3 2,5-tetrahydrofuran dimethanol 8.0 0.40 50 30 80 8 16
  • Example 4 2,5-tetrahydrofuran dimethanol 8.0 0.40 50 30 120 8 16
  • Example 5 2,5-tetrahydrofuran dimethanol 8.0 0.40 50 30 100 5.5 16
  • Example 6 2,5-tetrahydrofuran dimethanol 8.0 0.40 50 30 100 6.8 16
  • Example 7 2,5-tetrahydrofuran dimethanol 8.0 0.40 50 30 100 8.85 16
  • Example 8 2,5-tetrahydrofuran dimethanol 8.0 0.27 75 30 100 8 16
  • Example 9 2,5-tetrahydrofuran dimethanol 8.0 0.27 75 30 100 8 16
  • Example 9 2,5-tetrahydrofuran dimethanol 8.0 0.27 75 30 100 8 16
  • Example 9 2,
  • FIG. 3 shows the XRD pattern of the cobalt-manganese-based spinel structure support (MnCo 2 O 4 ) prepared according to Preparation Example 1
  • Figure 4 is a cobalt-manganese-based spinel structure support according to Preparation Example 1 ( SEM image of MnCo 2 O 4 ).
  • FIG. 5 is a SEM image of confirming a number of pores on a support (MnCo 2 O 4 ) of a cobalt-manganese-based spinel structure prepared according to Preparation Example 1
  • FIG. 6 is a cobalt-manganese base prepared according to Preparation Example 1
  • the SEM photograph of the microspheres of the spinel structure support (MnCo 2 O 4 ) is shown.
  • MnCo 2 O 4 as a spinel structure has an average particle diameter (D 50 ) of 2.0 to 4.0 ⁇ m, and the structure is a structure in which a large number of microspheres of 30 to 60 nm are integrated. Can be.
  • the cobalt-manganese-based spinel structure support (MnCo 2 O 4 ) prepared according to Preparation Example 1 of the present invention has a unique structure and size, so that when the precious metal nanoparticles are reduced and included in the support, the nano It can be seen that the particles have an efficient structure that can be formed evenly distributed in the support.
  • XPS X-ray photoelectron spectroscopy
  • TLC Thin-layer chromatography
  • 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol were not read by TLC (Thin-layer chromatography) using a UV lamp, so a KMnO 4 solution was used.
  • dilute 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol solutions were measured after concentration because they were unreadable in the KMnO 4 solution.
  • FIG. 9 shows the 1 H-NMR spectrum (DMSO-d 6 ) of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and subsequently purified and commercially available reagent 2,5-tetrahydrofuran dimethanol
  • Figure 10 shows the 13 C-NMR spectrum of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and then purified separately and commercially available reagent 2,5-tetrahydrofuran dimethanol.
  • the conversion method of 5-hydroxymethylperfural (HMF), the yield and selectivity of 2,5-furandimethane (FDM), and the yield and selectivity calculation method of 2,5-tetrahydrofuran dimethanol (THF-DM) may be using the following equations 1 to 5.
  • C HMF in Tables 2 to 5 below represents the conversion rate of 5-hydroxymethylperfural
  • Y FDM is the yield of 2,5-furandimethane
  • Y THF -DM is the yield of 2,5-tetrahydrofuran dimethanol Indicates.
  • FIG. 11 is a schematic diagram of HMF conversion and FDM yield according to the number of catalyst reuses when manufacturing FDM according to Example 1
  • FIG. 12 is HMF conversion and THF according to catalyst reuse frequency when manufacturing THF-DM according to Example 2 -It is a diagram of DM yield.
  • the catalyst was simply recovered by filtration and reused.
  • Co Co
  • Mn manganese
  • 2,5-tetrahydrofuran dimethanol prepared according to Example 1 and then separated and purified according to Example 2 and then purified separately according to Example 2 and
  • the ruthenium (Ru) content was analyzed using an inductively coupled plasma mass spectrometer (ICP-MS) and the results are shown in Table 6.
  • the method for producing a furan-based compound of the present invention uses 2,5-furandimethanol and 2, in a single container by hydrogenation of 5-hydroxymethylperfural using a spinel-structured support carrying precious metal nanoparticles as a catalyst.
  • 5-Tetrahydrofuran dimethanol can be optionally obtained.
  • 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol can be obtained in high yields of 90% or more, respectively.

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Abstract

La présente invention concerne un procédé de préparation de composés à base de furane, comprenant une étape de préparation d'un ou de plusieurs composés à base de furane choisis dans le groupe constitué par le 2,5-furandiméthanol (FDM) et le 2,5-tétrahydrofurane diméthanol (THF-DM) par hydrogénation de 5-hydroxyméthylfurfural (HMF) à l'aide d'hydrogène (H2) et d'un catalyseur, le catalyseur comprenant un support ayant une structure de spinelle, des nanoparticules de métal noble étant supportées. Par conséquent, du 2,5-FDM et du 2,5-THF-DM peuvent être obtenus de manières sélective et respective avec des rendements élevés de 90 % ou plus dans un récipient unique.
PCT/KR2019/014695 2018-11-16 2019-11-01 Procédé de préparation de 2,5-furandiméthanol et de 2,5-tétrahydrofurane diméthanol à partir de 5-hydroxyméthylfurfural WO2020101234A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN112742482A (zh) * 2021-01-15 2021-05-04 广州大学 一种催化加氢的催化剂及其制备方法与应用
CN113651780A (zh) * 2021-09-27 2021-11-16 浙江糖能科技有限公司 一种2，5-四氢呋喃二甲醇的制备方法
CN114573527A (zh) * 2022-03-11 2022-06-03 湖南师范大学 一种5-羟甲基糠醛转移加氢制备2,5-二羟甲基呋喃的方法
CN115490652A (zh) * 2022-07-14 2022-12-20 中科国生(杭州)科技有限公司 一种氢转移催化5-羟甲基糠醛制备2,5-四氢呋喃二甲醇的方法
CN115490652B (zh) * 2022-07-14 2023-09-19 中科国生(杭州)科技有限公司 一种氢转移催化5-羟甲基糠醛制备2,5-四氢呋喃二甲醇的方法

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