A method for preparing a supported metal catalyst and a method for preparing a furan alcohol compound

Abstract

The application discloses a preparation method of a supported metal catalyst and a preparation method of a furan alcohol compound. The preparation method of the supported metal catalyst comprises the following steps: a carrier YOn is prepared; a precursor salt of an active component X, a first solvent and the carrier YOn are mixed, the active component X is loaded on the carrier YOn, and after drying treatment, a solid A is obtained; the solid A is calcined, a solid B is obtained; and the solid B is reacted with a reducing agent, and a supported metal catalyst is obtained. The application prepares the supported metal catalyst with a general formula of X / (YOn). A unique adsorption configuration formed by the active component X and the carrier YOn can make the aldehyde group of the furan aldehyde singly adsorbed on the catalyst, so that the aldehyde group of the furan aldehyde is selectively catalyzed to be hydrogenated, the conversion rate and the selectivity of the furan alcohol are improved, and the selectivity does not change with the change of temperature and pressure.

Description

Technical Field

[0001] This invention relates to the field of biomass heterogeneous catalysis technology, and in particular to a supported metal catalyst and its preparation method, as well as a method for preparing furanol compounds. Background Technology

[0002] Producing renewable chemicals from biomass resources to replace petroleum-based chemicals can effectively reduce environmental pollution and over-reliance on non-renewable fossil resources, aligning with the principles of green and sustainable development. Furan compounds derived from biomass (such as 5-hydroxymethylfurfural and 2,5-furandiethanol) can serve as platform chemicals, enabling further applications in pharmaceutical intermediates, fuel chemicals, and green solvents. For instance, 2,5-furandiethanol (BHMF), as an important bio-based platform chemical, has significant application potential in the preparation of pharmaceutical intermediates, polymers, synthetic fibers, and polyesters, and can serve as a substitute for petroleum-based chemicals, achieving high-value conversion and utilization of biomass renewable resources. Therefore, developing an efficient method for preparing furan alcohols is of great importance.

[0003] Furan alcohols can be synthesized by catalytic hydrogenation of furan aldehydes. However, furan aldehydes contain various functional groups (such as aldehyde groups, furan rings, and hydroxyl groups), which not only requires harsh reaction conditions during catalytic hydrogenation but also easily leads to hydrogenolysis, over-hydrogenation, and other byproducts. Taking the catalytic hydrogenation of 5-hydroxymethylfurfural (HMF) to BHMF as an example, HMF requires high hydrogen pressure and high temperature during catalytic hydrogenation. Studies have found that Au / Al₂O₃ catalysts can catalyze the hydrogenation of HMF at 120℃ and 6.5 MPa hydrogen conditions. Although this method achieves a high yield, the high temperature and high pressure reaction conditions increase energy consumption, which is not conducive to practical production. Furthermore, the catalytic hydrogenation of HMF also forms other hydrogenation products, such as tetrahydrofurandimethyl (BHMTHF). Using a Pd / Al₂O₃ catalyst, at 120℃ and 70 MPa, the yield of BHMTHF was 99% after 3 hours.

[0004] As can be seen from the above, the catalytic hydrogenation of furan aldehydes in existing technologies requires harsh environments and, due to the presence of multiple functional groups, easily generates other byproducts. Therefore, there is an urgent need to develop a technology with mild reaction conditions and a single hydrogenation property for furan aldehydes to obtain furan alcohols with high conversion and high selectivity. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is how to achieve catalytic hydrogenation of furan aldehyde under mild reaction conditions, avoid the generation of other by-products, and improve the conversion rate and selectivity of furan alcohol.

[0006] To address the aforementioned technical problems, the first aspect of this invention provides a method for preparing a supported metal catalyst, comprising the following steps:

[0007] S11. Prepare a support YOn, wherein the support YOn is selected from at least one of α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, OMS-2, and OMS-6;

[0008] S12. The precursor salt of active component X, the first solvent and the support YOn are mixed to load active component X onto the support YOn. The active component X is selected from at least one of iridium, rhodium, palladium, platinum, gold and silver. After drying, solid A is obtained.

[0009] S13. Calcining the solid A to obtain solid B;

[0010] S14. The solid B is reacted with a reducing agent to obtain a supported metal catalyst.

[0011] This invention prepares a supported metal catalyst with the general formula X / (YOn) using the above-described preparation method. The unique adsorption configuration formed by the active component X and the support YOn allows the aldehyde group of furanaldehyde to be adsorbed onto the catalyst, thereby selectively catalyzing the hydrogenation of the aldehyde group of furanaldehyde. This catalyst not only has high activity but also exhibits high selectivity for the aldehyde group of biomass aldehydes over a wide temperature and pressure range, enabling selective hydrogenation without the generation of other hydrogenation products, thus improving the conversion rate and selectivity of furanol.

[0012] Furthermore, the mass fraction of active component X in the supported metal catalyst is 0.1 wt% to 10 wt%. Using a relatively small amount of active component X in the catalyst achieves sufficient catalytic effect, which helps reduce preparation costs.

[0013] Furthermore, the average particle size of the supported metal catalyst is 0.5 nm to 5 nm. A smaller average particle size of the supported metal catalyst is beneficial for improving its catalytic activity.

[0014] Furthermore, in step S12, the loading method is selected from one of the following: impregnation method, electrostatic adsorption method, coprecipitation method, solid-phase dispersion method, and sol-gel method.

[0015] Furthermore, the precursor salt of the active component X is selected from at least one of nitrate, chloride, acetate, and acetylacetone.

[0016] Furthermore, the first solvent is selected from at least one of deionized water, methanol, ethanol, and isopropanol.

[0017] Furthermore, the reducing agent is selected from one of hydrogen, a mixture of hydrogen and an inactive gas, formic acid, sodium borohydride, vitamin C, and hydrazine hydrate.

[0018] Furthermore, in step S13, the calcination temperature is 200℃~900℃, and the time is 2h~15h. The calcination step transforms the precursor salt of the active component X into a metal oxide, which is also beneficial to the growth of metal particles. Limiting the calcination temperature can control the particle size of the metal particles.

[0019] Furthermore, in step S14, the reaction temperature is 20℃~500℃, and the time is 1h~6h. This step reduces the metal oxide to a metallic state, and an appropriate reduction temperature needs to be selected according to the metal oxide.

[0020] Further, step S11 specifically includes: reacting a mixture of manganese source and potassium permanganate using one of the following methods: solvent-free method, reflux method, or hydrothermal method to obtain support Yon, wherein the manganese source is selected from at least one of Mn(Ac)2, MnSO4, and Mn(NO3)2.

[0021] Furthermore, in step S11, the reaction temperature is 30℃~200℃, and the reaction time is 3~30h. Different temperatures and reaction times will affect the microstructure of the support and the formation of the crystal phase. The reaction conditions should be selected according to the type of support required.

[0022] A second aspect of the present invention provides a method for preparing a furanol compound, comprising the following steps:

[0023] S21. The supported metal catalyst, furanaldehyde, and second solvent prepared by any one of the preparation methods described in claims 1-6 are added to the reaction apparatus to form a mixed solution;

[0024] S22. Hydrogen gas is introduced into the reaction apparatus to carry out a hydrogenation reaction, yielding furanol compounds.

[0025] This invention utilizes a supported metal catalyst X / (YOn) for the catalytic hydrogenation of furanaldehyde to prepare furanol compounds. The above preparation method has the advantages of mild reaction conditions and few by-products, achieving high conversion and high selectivity in the preparation of furanol.

[0026] Furthermore, in step S22, the reaction temperature is 10℃~100℃, the pressure is 0.1MPa~5MPa, and the time is 0.5h~10h. The supported metal catalyst exhibits high activity, enabling catalytic hydrogenation of furanaldehyde under mild reaction conditions, which helps reduce byproducts and save energy.

[0027] Further, in step S21, the molar ratio of the supported metal catalyst to furanaldehyde is 0.2 to 5:1, and the concentration of furanaldehyde in the mixed solution is 1 g / L to 20 g / L.

[0028] Furthermore, the furanaldehyde is selected from at least one of furfural, 2,5-furandicarboxaldehyde, benzaldehyde, cinnamaldehyde, 5-hydroxymethylfurfural, 4-hydroxymethylfurfural, and 5-methylfurfural.

[0029] Further, the second solvent is water and / or an organic solvent selected from at least one of γ-butyrolactone, γ-valerolactone, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, and tetrahydrofuran.

[0030] In summary, compared with the prior art, the present invention has the following beneficial effects:

[0031] This invention provides a supported metal catalyst prepared via a specific method. The unique adsorption configuration formed between the active component X and the support YOn allows for the singular adsorption of the aldehyde group of furanaldehyde onto the catalyst, maintaining selectivity for the hydrogenation product regardless of temperature and pressure changes. This results in highly selective catalytic hydrogenation, improving the conversion and selectivity of furanol. Using the supported metal catalyst for the catalytic hydrogenation of furanaldehyde requires mild reaction conditions, is easy to implement, consumes little energy, and is suitable for industrial application. Attached Figure Description

[0032] Figure 1 This is a schematic diagram illustrating the principle of supported metal catalyst catalysis of furanaldehyde in a specific embodiment of the present invention;

[0033] Figure 2 This is a high-angle annular dark-field-scanning transmission electron microscope image of the supported metal prepared in Example 1 of this invention.

[0034] Figure 3 This is a high-resolution transmission electron microscope image of the supported metal catalyst prepared in Example 1 of this invention.

[0035] Figure 4 This is the XRD pattern of the supported metal catalyst prepared in Example 1 of this invention. Detailed Implementation

[0036] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0037] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0038] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This application specification and embodiments are merely exemplary.

[0039] This invention provides a supported metal catalyst suitable for the catalytic hydrogenation of furanaldehyde to furanol compounds. The supported metal catalyst has the general formula X / (YOn), where the active component X can be selected from iridium, rhodium, palladium, platinum, gold, silver, etc., and the support YOn can be selected from α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, OMS-2, OMS-6, etc. The unique adsorption configuration formed by the active component X and the support YOn in the supported metal catalyst allows the aldehyde group of furanaldehyde to be adsorbed singly onto the catalyst, thereby selectively catalyzing the hydrogenation of the aldehyde group of furanaldehyde.

[0040] In specific embodiments, the mass fraction of active component X in the supported metal catalyst is 0.1 wt% to 10 wt%, with typical mass fractions such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, 5.0 wt%, 5.5 wt%, 6.0 wt%, 6.5 wt%, 7.0 wt%, 7.5 wt%, 8.0 wt%, 8.5 wt%, 9.0 wt%, 9.5 wt%, and 10.0 wt%.

[0041] In specific embodiments, the average particle size of the supported metal catalyst is 0.5 nm to 5 nm, with typical particle sizes such as 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 4 nm, and 5 nm.

[0042] The preparation method of the above-mentioned supported metal catalyst includes the following steps:

[0043] S11. Prepare the support YOn. The preparation method can be solvent-free method, reflux method, hydrothermal method, etc. The support can be obtained by reacting a mixture of manganese source and potassium permanganate.

[0044] In specific embodiments, the manganese source is selected from Mn(Ac)2, MnSO4, Mn(NO3)2, etc.; the reaction conditions are a temperature of 30℃~200℃ and a time of 3~30h, with typical reaction temperatures including 30℃, 50℃, 70℃, 90℃, 110℃, 140℃, 170℃, 200℃, etc.

[0045] S12. Mix the precursor salt of active component X, the first solvent and the support YOn obtained in step S11 to load active component X onto support YOn, and then dry to obtain solid A.

[0046] In a specific embodiment, the loading method is selected from one of the following: impregnation method, electrostatic adsorption method, coprecipitation method, solid-phase dispersion method, and sol-gel method.

[0047] In a specific embodiment, the active component X is selected from iridium, rhodium, palladium, platinum, gold, silver, etc., and the precursor salt is selected from nitrate, chloride, acetate, acetylacetone, etc.; the first solvent is selected from deionized water, methanol, ethanol, isopropanol, etc.

[0048] S13. Calcining the solid A obtained in step S12 to obtain solid B.

[0049] In specific embodiments, the calcination temperature is 200℃~900℃, and the time is 2h~15h. Typical calcination temperatures include 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, 650℃, 700℃, etc.

[0050] S14. React the solid B obtained in step S13 with a reducing agent to prepare a supported metal catalyst.

[0051] In specific embodiments, the reducing agent can be selected from hydrogen, a mixture of hydrogen and inert gases, formic acid, sodium borohydride, vitamin C, hydrazine hydrate, etc. The reaction conditions are a temperature of 20℃ to 500℃ and a time of 1h to 6h. Typical reduction temperatures include 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, 300℃, 340℃, 380℃, 420℃, 460℃, and 500℃.

[0052] The supported metal catalyst prepared by the above method has a unique adsorption configuration. The active component X is supported on the support Yon, which allows the aldehyde group of furanaldehyde to be adsorbed onto the catalyst, thereby selectively catalyzing the hydrogenation of the aldehyde group of furanaldehyde. This catalyst not only has high activity, but also high selectivity for the aldehyde group of biomass aldehydes over a wide temperature and pressure range.

[0053] A specific embodiment of the present invention also provides a method for preparing furanol compounds, which specifically includes the following steps:

[0054] S21. The supported metal catalyst, furanaldehyde, and second solvent prepared in this invention are added to the reaction apparatus to form a mixed solution.

[0055] Preferably, the molar ratio of the supported metal catalyst to furanaldehyde is 0.2–5:1, and the concentration of furanaldehyde in the mixed solution is 1 g / L–20 g / L. In a specific embodiment, the ratio of the amount of supported metal catalyst, furanaldehyde, and second solvent is (10 mg–100 mg): (10 mg–150 mg): (5 mL–50 mL).

[0056] In a specific embodiment, furfural can be selected from furfural, 2,5-furandicarboxaldehyde, benzaldehyde, cinnamaldehyde, 5-hydroxymethylfurfural, 4-hydroxymethylfurfural, 5-methylfurfural, etc.; the second solvent is water and / or an organic solvent, and the organic solvent can be selected from γ-butyrolactone, γ-valerolactone, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, tetrahydrofuran, etc.

[0057] S22. Hydrogen gas is introduced into the reaction apparatus to carry out a hydrogenation reaction, yielding furanol compounds.

[0058] In a specific embodiment, the reaction conditions are as follows: temperature 10℃~100℃, pressure 0.1MPa~5MPa, and time 0.5h~10h. Typical reaction temperatures include 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, and 100℃. Typical reaction times include 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, and 10h. Typical reaction pressures include 0.1MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3.5MPa, 4MPa, 4.5MPa, and 5MPa.

[0059] The above method utilizes a specific supported metal catalyst for catalytic hydrogenation, requiring mild reaction conditions, being easy to implement, and consuming little energy. The reaction principle is as follows: Figure 1 As shown, changes in temperature and pressure do not alter the catalyst's selectivity for hydrogenation products, thus achieving high conversion and high selectivity in the preparation of furan alcohol compounds.

[0060] The technical effects of the present invention will be described below with reference to specific embodiments. Unless otherwise specified, the raw materials used in the embodiments of this application were all purchased through commercial channels. The conversion rate and selectivity are calculated in the embodiments as follows:

[0061] HMF conversion rate = (concentration of HMF converted / initial concentration of HMF) × 100%;

[0062] BHMF selectivity = (Concentration of BHMF generated / Concentration of HMF converted) × 100%;

[0063] Example 1

[0064] (1) Dissolve an appropriate amount of MnSO4·H2O in 20 ml of deionized water, and add concentrated nitric acid dropwise to prepare mixed solution A; then add a solution B of KMnO4 dissolved in deionized water of appropriate concentration to mixed solution A to form mixed solution C. Reflux the resulting mixed solution C at 110℃ for 5 h, and further wash and dry the product to obtain the OMS-2 support.

[0065] (2) Using the impregnation method, a 0.15M aqueous solution of chloroplatinic acid was mixed with 500g of OMS-2 carrier, impregnated, and then dried in an oven for 12h to obtain solid A.

[0066] (3) Solid A was calcined in air for 12 hours at a temperature of 300°C to obtain solid B.

[0067] (4) Solid B was reduced to 300℃ for 3h under normal pressure H2 atmosphere to obtain the supported metal catalyst Pt / OMS-2.

[0068] The microstructure of the supported metal catalyst prepared in Example 1 is as follows: Figure 1 and Figure 2 As shown in the figure, the active component Pt is loaded on the support OMS-2, forming an adsorption configuration.

[0069] Figure 3 The XRD pattern of the supported metal catalyst prepared in Example 1 shows that the product is a Pt / OMS-2 catalyst.

[0070] The supported metal catalyst prepared in the above examples was applied to the reaction of catalytic hydrogenation of HMF to prepare BHMF. The specific operation method is as follows:

[0071] 0.05 g of catalyst, 10 ml of deionized water, and 0.1 g of HMF were added to a 50 ml reactor lined with polytetrafluoroethylene and sealed. H2 was repeatedly introduced into the reactor to displace the air, followed by the introduction of 1.5 MPa of H2. The temperature was set to 30 °C and the reaction was carried out for 2 h. After the reaction, the reactor was immediately removed and placed in ice water for cooling. The catalyst and reaction solution were separated by filtration. The reaction solution was diluted with isopropanol, and the diluted filtrate was added to a 2 ml sample vial for quantitative analysis using high-performance gas chromatography. The performance evaluation results are shown in Table 1 below. The results indicate that the catalyst has excellent performance, achieving catalytic hydrogenation of furanaldehyde under mild reaction conditions. The measured HMF conversion and BHMF selectivity were 98.1% and 98.5%, respectively.

[0072] Example 2

[0073] (1) The α-MnO2 support was prepared by reacting a mixture of manganese source and potassium permanganate at 140℃ for 10h using a hydrothermal method.

[0074] (2) The impregnation method was adopted. A 0.1M platinum nitrate aqueous solution was mixed with 500g of α-MnO2 support, impregnated, and then placed in an oven to dry for 12h to obtain solid A.

[0075] (3) Solid A was calcined in air for 10 hours at a temperature of 400°C to obtain solid B.

[0076] (4) Solid B was reduced to 220℃ for 4h under normal pressure H2 atmosphere to obtain the supported metal catalyst Pt / α-MnO2.

[0077] The supported metal catalyst prepared in the above examples was applied to the reaction of catalytic hydrogenation of HMF to prepare BHMF. The operation steps were the same as in Example 1. The HMF conversion rate and BHMF selectivity of the reaction were measured to be 96% and 92%, respectively.

[0078] Example 3

[0079] (1) The δ-MnO2 support was prepared by reacting a mixture of manganese source and potassium permanganate at 90°C for 30 h using a solvent-free method.

[0080] (2) Mix 0.1M acetylacetone platinum isopropanol with 1000g of δ-MnO2 support and prepare solid A by electrostatic adsorption.

[0081] (3) Solid A was calcined in air for 6 hours at a temperature of 650°C to obtain solid B.

[0082] (4) Solid B was reduced to 300℃ for 2h under normal pressure H2 atmosphere to obtain the supported metal catalyst Pt / δ-MnO2.

[0083] The supported metal catalyst prepared in the above examples was applied to the reaction of catalytic hydrogenation of HMF to prepare BHMF. The operation steps were the same as in Example 1. The HMF conversion rate and BHMF selectivity of the reaction were measured to be 92% and 90.1%, respectively.

[0084] Example 4

[0085] (1) The OMS-6 support was prepared by reacting a mixture of manganese source and potassium permanganate at 200℃ for 3h using the reflux method.

[0086] (2) Mix 0.2M chloroplatinic acid aqueous solution with 700g of OMS-6 carrier and prepare solid A by coprecipitation.

[0087] (3) Solid A was calcined in air for 6 hours at a temperature of 650°C to obtain solid B.

[0088] (4) Solid B was reduced to 500℃ for 1h under normal pressure H2 atmosphere to obtain the supported metal catalyst Pt / OMS-6.

[0089] The supported metal catalyst prepared in the above examples was applied to the reaction of catalytic hydrogenation of HMF to prepare BHMF. The operation steps were the same as in Example 1. The HMF conversion rate and BHMF selectivity of the reaction were measured to be 92.5% and 88.4%, respectively.

[0090] Example 5

[0091] (1) The mixture of manganese source and potassium permanganate was reacted at 140℃ for 10h by reflux method to obtain β-MnO2 support.

[0092] (2) Mix 0.25M chloroplatinic acid aqueous solution with 750g of β-MnO2 support and prepare solid A by solid-phase dispersion method.

[0093] (3) Solid A was calcined in air for 10 hours at a temperature of 700°C to obtain solid B.

[0094] (4) Solid B was reduced to 260℃ for 5h under normal pressure H2 atmosphere to obtain the supported metal catalyst Pt / β-MnO2.

[0095] The supported metal catalyst prepared in the above examples was applied to the reaction of catalytic hydrogenation of HMF to prepare BHMF. The operation steps were the same as in Example 1. The HMF conversion rate and BHMF selectivity of the reaction were measured to be 93% and 87.1%, respectively.

[0096] Example 6

[0097] (1) The mixture of manganese source and potassium permanganate was reacted at 140℃ for 10h by reflux method to obtain γ-MnO2 support.

[0098] (2) Mix 0.15M chloroplatinic acid aqueous solution with 800g of γ-MnO2 support and prepare solid A by sol-gel method.

[0099] (3) Solid A was calcined in air for 12 hours at a temperature of 450°C to obtain solid B.

[0100] (4) Solid B was reduced to 180℃ for 3h under normal pressure H2 atmosphere to obtain the supported metal catalyst Pt / γ-MnO2.

[0101] The supported metal catalyst prepared in the above examples was applied to the reaction of catalytic hydrogenation of HMF to prepare BHMF. The operation steps were the same as in Example 1. The HMF conversion rate and BHMF selectivity of the reaction were measured to be 86.5% and 88.6%, respectively.

[0102] Table 1. Performance test results of catalysts in Examples 1-6 for the catalytic hydrogenation of HMF to BHMF.

[0103] Test sample catalyst HMF conversion rate (%) BHMF selection (%) Example 1 Pt / OMS-2 96 92 Example 2 Pt / α-MnO2 92 90.1 Example 3 <![CDATA[Pt / δ-MnO2]]> 98.1 98.5 Example 4 Pt / OMS-6 92.5 88.4 Example 5 <![CDATA[Pt / β-MnO2]]> 93 87.1 Example 6 <![CDATA[Pt / γ-MnO2]]> 86.5 88.6

[0104] Example 7

[0105] (1) Preparation of OMS-6 vector.

[0106] (2) A solid A was prepared by mixing a 0.1 M palladium chloride ethanol solution with 1000 g of OMS-2 carrier and impregnating it.

[0107] (3) Solid A was calcined in air for 8 hours at a temperature of 600°C to obtain solid B.

[0108] (4) Solid B was reduced to 340℃ for 3h under normal pressure H2 atmosphere to obtain the supported metal catalyst Pd / OMS-6.

[0109] Example 8

[0110] (1) Preparation of OMS-2 vector.

[0111] (2) Mix 0.1M silver nitrate aqueous solution with 300g of OMS-2 carrier and prepare solid A by impregnation method.

[0112] (3) Solid A was calcined in air for 6 hours at a temperature of 650°C to obtain solid B.

[0113] (4) Solid B was reduced to 420℃ for 2.5h under normal pressure H2 atmosphere to obtain supported metal catalyst Ag / OMS-2.

[0114] Example 9

[0115] The supported metal catalyst Pt / OMS-2 prepared in Example 1 above was used to catalyze the hydrogenation of BHMF to prepare BHMTHF. The specific operation method is as follows:

[0116] BHMF, catalyst, and water were added to a reaction vessel lined with polytetrafluoroethylene at a ratio of 100 mg: 50 mg: 10 mL and then sealed. H2 was repeatedly added to the reaction vessel to replace the air inside. Then, 3.0 MPa of H2 was added to the vessel, the temperature was set to 120 °C, and the reaction was carried out for 2 hours.

[0117] After the reaction was complete, the reactor was immediately removed and placed in ice water for cooling. The catalyst and reaction solution were separated by filtration. The reaction solution was diluted with isopropanol, and the diluted filtrate was added to a 2 ml sample vial for quantitative analysis using high-performance gas chromatography (HPLC). The test results showed that the starting material BHMF did not undergo conversion.

[0118] The above results indicate that the catalyst prepared in Example 1 will not undergo reactions such as furan ring hydrogenation or ring opening, even under harsh environmental conditions.

[0119] Example 10

[0120] The supported metal catalyst Pt / OMS-2 prepared in Example 1 above was used for the catalytic hydrogenation of HMF to BHMF. The specific operation method is as follows:

[0121] HMF, catalyst, and water were added to a reaction vessel lined with polytetrafluoroethylene at a ratio of 100 mg: 50 mg: 10 mL and then sealed. H2 was repeatedly added to the reaction vessel to replace the air inside. Then, 3.0 MPa of H2 was added to the vessel, the temperature was set to 120 °C, and the reaction was carried out for 2 hours.

[0122] After the reaction was completed, the reactor was immediately removed and placed in ice water for cooling. The catalyst and reaction solution were separated by filtration. The reaction solution was diluted with isopropanol, and the diluted filtrate was added to a 2 ml sample vial for quantitative analysis using high-performance gas chromatography. The HMF conversion and BHMF yield were found to be 100% and 99%, respectively.

[0123] The above results indicate that the catalyst also exhibits superior performance under these harsh reaction conditions, and no other hydrogenation byproducts such as complete hydrogenation of the furan ring or ring-opening are generated except for the product BHMF.

[0124] While the present invention has been disclosed above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of this disclosure, and all such changes and modifications will fall within the scope of protection of this invention.

Claims

1. A method for producing a furan alcohol compound, characterized by, The method comprises the following steps: S11, a carrier YOn is prepared, the carrier YOn is at least one of α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, OMS-2 and OMS-6; S12, a precursor salt of an active component X, a first solvent and the carrier YOn are mixed, the active component X is platinum, and after drying treatment, a solid A is obtained, and the loading method is selected from one of an impregnation method, an electrostatic adsorption method, a coprecipitation method, a solid dispersion method and a sol-gel method; S13, the solid A is calcined to obtain a solid B, the calcination temperature is 200-900 DEG C, and the time is 2-15 hours; S14, the solid B is reacted with a reducing agent, the reaction temperature is 180-500 DEG C, the time is 1-5 hours, and a supported metal catalyst is obtained, the mass fraction of the active component X in the supported metal catalyst is 0.1-10 wt%; S21, the supported metal catalyst, 5-hydroxymethyl furfural and a second solvent are added into a reaction device to form a mixed solution; S22, hydrogen is introduced into the reaction device to perform a hydrogenation reaction, the reaction temperature is 30 DEG C, the pressure is 1.5 MPa, the time is 2 hours, and a furan alcohol compound is obtained.

2. The method for preparing the furanol compound according to claim 1, characterized in that, The step S11 specifically comprises: a mixture of a manganese source and potassium permanganate is reacted by one of a solvent-free method, a reflux method and a hydrothermal method to obtain the carrier YOn, the manganese source is at least one of Mn(Ac)2, MnSO4 and Mn(NO3)2.

3. The method for preparing the furanol compound according to claim 1, characterized in that, In the step S21, the molar ratio of the supported metal catalyst to furan aldehyde is 0.2-5:1, and the concentration of furan aldehyde in the mixed solution is 1-20 g / L.

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