Preparation method of copper-based catalyst, copper-based catalyst and application

Abstract

The application discloses a preparation method of a copper-based catalyst, the copper-based catalyst and application, and the preparation method comprises the following steps: (1) mixing a mixture I containing a copper salt, an ammonia source and a silicon source, reacting, and calcining to obtain a copper-containing silicon oxide precursor; and (2) mixing a mixture II containing the copper-containing silicon oxide precursor, a template agent, an alkali source and water, and processing the mixture II by using a hydrothermal crystallization method or a dry gel crystallization method to obtain the copper-based catalyst. The raw material source of the application is lignocellulose, and the application has the advantages of rich reserves, environmental friendliness, green pollution-free and the like. Meanwhile, furfuryl alcohol and 2,5-furan dimethyl alcohol have high economy and wide utilization channels. In addition, the catalyst has the advantages of low price, high reaction selectivity, good stability, easy product separation, important economic value and industrialization prospect.

Description

Technical Field

[0001] This application relates to a method for preparing a copper-based catalyst, the copper-based catalyst and its application, belonging to the field of bioenergy chemical technology. Background Technology

[0002] With the depletion of fossil fuels and the continuous increase in global greenhouse gas emissions, there is an urgent need to obtain high-value chemicals from widely available and inexpensive biomass feedstocks. Furfural compounds, typically represented by furfural and 5-hydroxymethylfurfural, are important biomass platform compounds. Among them, furfural (selective hydrogenation product of furfural) and 2,5-furandiethanol (selective hydrogenation product of 5-hydroxymethylfurfural) both play important roles in the preparation of fine chemicals, synthetic resins, functional polymers, synthetic fibers, and pharmaceutical intermediates.

[0003] Due to the presence of reactive functional groups such as aldehyde, hydroxymethyl, and furan rings in furfural compounds, achieving highly active and selective hydrogenation of the aldehyde group is a challenge for large-scale production. Currently, among selective catalytic hydrogenation catalysts, noble metal (Hf, Ru, Rh) catalysts exhibit superior catalytic performance and milder reaction conditions, but their high cost limits their commercial application. In contrast, copper-based catalysts have abundant active components and exhibit unique advantages in the selective hydrogenation of C=O bonds. For example, Zhang Jun et al. reported using a Cu-Al catalyst to selectively convert furfural to furfuryl alcohol in methanol solvent with a yield of 94% (ACSSustainable Chem. Eng. 2017, 5, 5982-5993). Li Zhixin et al. prepared a Cu-Co-C catalyst using ZIF-8 as a sacrificial template to achieve a 97% furfuryl alcohol yield in isopropanol solvent for furfural conversion. Researchers at Guangzhou University, led by Zuo Jianliang, prepared a Cu / Cu₂O composite active copper catalyst using in-situ synthesized Cu-MOF-199 as a template through heat treatment. This catalyst achieved a selectivity of over 90% for the production of 2,5-furandimethyl from 5-hydroxymethylfurfural (CN 109794244). However, copper-based catalysts still suffer from problems such as low activity, demanding reaction conditions, and the tendency for copper particles to agglomerate at high temperatures, leading to decreased metal dispersion and shortened catalyst lifetime.

[0004] In summary, it is of great significance to develop a copper-based catalyst with high catalytic activity, good selectivity, low cost and good stability for the selective hydrogenation of furfural compounds. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing and applying a copper-based catalyst. This method has advantages such as simple operation, low catalyst cost, economic practicality, good stability, and high efficiency in producing furfuryl alcohol compounds.

[0006] According to one aspect of this application, a method for preparing a copper-based catalyst is provided, the method comprising:

[0007] (1) A mixture I containing copper salt, ammonia source and silicon source is reacted and calcined to obtain a copper-containing silicon oxide precursor;

[0008] (2) The copper-based catalyst is obtained by treating a mixture II of copper-containing silicon oxide precursor, template agent, alkali source and water by hydrothermal crystallization or dry gel crystallization.

[0009] Optionally, the copper salt is selected from at least one of copper nitrate, copper acetate, copper chloride, copper carbonate, and copper sulfate.

[0010] Optionally, the ammonia source is selected from at least one of ammonia water, liquid ammonia, ammonium salt, and urea.

[0011] Optionally, the silicon source is selected from at least one of amorphous silica, silica aerosol, silica liquid sol, and tetraethyl orthosilicate.

[0012] Optionally, the molar ratio of the ammonia source to the copper salt is 100 to 2:1.

[0013] Optionally, the molar ratio of the copper salt to the silicon source is 0.01 to 0.5:1.

[0014] Optionally, the reaction conditions are as follows: stirring for 1 to 72 hours, raising the temperature to 70 to 100°C until the pH of mixture I is 6 to 7.5.

[0015] Optionally, the reaction conditions are as follows: the stirring time is selected from any value of 1h, 5h, 10h, 24h, 36h, 72h or a range between any two of the above points.

[0016] Optionally, the reaction conditions are as follows: the reaction temperature is selected from any value of 70℃, 75℃, 80℃, 85℃, 90℃, 100℃ or a range between any two of the above points.

[0017] Optionally, the calcination temperature is 300–600°C, and the calcination time is 0.2–72 h.

[0018] Optionally, the roasting temperature is selected from any value of 300℃, 350℃, 400℃, 450℃, 500℃, 600℃ or a range between any two of the above points.

[0019] Optionally, the roasting time is selected from any value among 0.2h, 1h, 12h, 24h, 36h, 48h, and 72h, or a range between any two of the above values.

[0020] Optionally, the roasting atmosphere is an air atmosphere.

[0021] Optionally, the molar ratio of the copper-containing silicon oxide precursor: template agent: alkali source: water is: SiO2: template agent: alkali source: H2O = 0.1~1.0: 0.02~2.5: 0~0.25: 3~200;

[0022] The amount of the copper-containing silicon oxide precursor is expressed as the molar amount of SiO2, the amount of the template agent is expressed as its own molar amount, and the molar amount of the alkali source is expressed as the molar amount of the cations in the alkali source.

[0023] Optionally, the template agent is selected from at least one of methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, choline chloride, hexamethyleneimine, 1,6-hexanediamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.

[0024] Optionally, the alkali source is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and potassium carbonate.

[0025] According to another aspect of this application, a copper-based catalyst prepared by the above-described preparation method is provided, the copper-based catalyst comprising a molecular sieve support and an active component, wherein the active component is copper.

[0026] Optionally, the molecular sieve support has one of the following topological structures: CHA, MFI, BEA, FAU, and MWW.

[0027] Optionally, the crystallinity of the molecular sieve support is above 80%.

[0028] Optionally, the copper nanoparticles of the copper-based catalyst have a size of 0.5–10 nm.

[0029] Optionally, the particle size of the copper-based catalyst is selected from any value of 0.5nm, 1nm, 3nm, 5nm, 7nm, 10nm or a range between any two of the above.

[0030] Optionally, the mass of the active component is 0.5 wt% to 25 wt% of the mass of the copper-based catalyst, wherein the mass of the active component is based on the mass of copper.

[0031] Optionally, the upper limit of the mass of copper is independently selected from 25 wt%, 20 wt%, 15 wt%, 10 wt%, and 5 wt%, and the lower limit is independently selected from 10 wt%, 5 wt%, 3 wt%, 1 wt%, and 0.5 wt%.

[0032] According to another aspect of this application, a copper-based catalyst prepared by the above-described preparation method is provided, and the application of the above-described copper-based catalyst in the transfer hydrogenation reaction of furfural compounds is provided.

[0033] Optionally, raw materials containing a copper-based catalyst, furfural compounds, and a solvent are reacted under an inactive atmosphere to generate furfuryl alcohol compounds.

[0034] Optionally, the furfural compound is selected from at least one of furfural and 5-hydroxymethylfurfural.

[0035] Optionally, the solvent is selected from at least one of methanol, ethanol, isopropanol, 2-butanol, 2-pentanol, and formic acid.

[0036] Optionally, the molar ratio of the copper-based catalyst: solvent: furfural compound is 1.0: 4.0-250: 0.2-25.0.

[0037] Optionally, the reaction temperature is 120–220°C, and the reaction time is 0.1–24 h.

[0038] Optionally, the temperature of the reaction is selected from any value of 120°C, 150°C, 180°C, 200°C, 220°C, or a range between any two of the above points.

[0039] Optionally, the reaction time is selected from any value among 0.1h, 5h, 10h, 12h, 18h, and 24h, or a range between any two of the above points.

[0040] Optionally, when the furfural compound is furfural, the resulting furfuryl alcohol compound is furfuryl alcohol; when the furfural compound is 5-hydroxymethylfurfural, the resulting furfuryl alcohol compound is 2,5-furandicarboxylic acid.

[0041] As a specific implementation method, the present invention is achieved through the following technical solution:

[0042] A method for preparing a copper-based catalyst includes the following steps: obtaining a copper-containing silica precursor by ammonia stripping, and treating the copper-containing silica precursor by a hydrothermal method or a dry gel crystallization method to obtain the copper-based catalyst.

[0043] The copper-based catalyst includes a molecular sieve support and an active component, copper.

[0044] The steps for preparing the copper-containing silicon oxide precursor by the ammonia stripping method are as follows:

[0045] a1) Dissolve copper salt in water and stir to obtain a copper salt solution;

[0046] a2) Add ammonia water to the copper salt solution obtained in step a1), stir, and obtain a copper ammonia solution. The molar ratio of ammonia water to copper salt is 100 to 2:1.

[0047] a3) Add the silicon source to the copper ammonia solution obtained in step a1), stir for 1 to 72 hours, then raise the temperature to 70 to 100°C to evaporate the ammonia solution until the solution pH is less than 7.5;

[0048] a4) The mixture from step a3) is filtered, washed, and dried, and then calcined in air at 300–600°C to obtain the copper-containing silicon oxide precursor.

[0049] The steps for preparing the copper-based catalyst by the hydrothermal method are as follows:

[0050] b1) A copper-containing silicon oxide precursor, a template agent, an alkali source, and water are mixed to obtain a mixture with the following molar ratio: SiO2: template agent: Na2O: H2O = 0.1~1.0: 0.02~2.5: 0~0.25: 3~200;

[0051] b2) Place the mixture obtained in step b1) in a closed reactor and crystallize it at 170–220°C for 0.2–8 days;

[0052] b3) After the crystallization in step b2) is completed, the solid product is separated, washed, dried, and then calcined in air at 400-800°C to obtain the copper-based catalyst.

[0053] The steps for preparing copper-based catalysts using the dry gel crystallization method are as follows:

[0054] c1) A copper-containing silicon oxide precursor, a template agent, an alkali source, and water are mixed to obtain a mixture with the following molar ratio: SiO2: template agent: Na2O: H2O = 0.1~1.0: 0.02~2.5: 0~0.25: 3~200;

[0055] c2) Dry the mixture obtained in step c1) at 80-150°C until the moisture content is less than 5%, then grind it into powder to obtain a dry gel precursor.

[0056] c3) The dry gel precursor obtained in step c2) is placed in a polytetrafluoroethylene-lined crystallization vessel and crystallized with water vapor at 110-170°C for 2-7 days.

[0057] c4) After the crystallization in step c3) is completed, the solid product is separated, washed, dried, and then calcined in air at 400-800°C to obtain the copper-based catalyst.

[0058] The catalyst described above is used to catalyze the transfer hydrogenation reaction of furfural compounds. The specific implementation method is as follows: a high-pressure reactor is used as the reactor for the reaction. The reaction steps are as follows: the copper-based catalyst is placed in the reactor, and a certain mass of solvent and substrate furfural compound are added to obtain a mixture with the following mass ratio: copper-based catalyst: solvent: furfural compound = 1.0: 4.0~250: 0.2~25.0; the reactor is sealed and the reaction atmosphere is replaced with inert gas, and the temperature is raised to 120~220℃ for 0.1~24 h.

[0059] Optionally, the solvent is one or more of methanol, ethanol, isopropanol, 2-butanol, 2-pentanol, and formic acid; the furfural compound is at least one of furfural and 5-hydroxymethylfurfural; and the inert gas is one or a mixture of nitrogen, argon, and helium.

[0060] Optionally, when the reaction substrate is furfural, the selectivity of the product furfuryl alcohol is greater than 90%; when the reaction substrate is 5-hydroxymethylfurfural, the selectivity of the product 2,5-furandiethanol is greater than 90%.

[0061] The beneficial effects that this application can produce include:

[0062] 1) This invention provides a method for preparing a copper-based catalyst and applying it to the transfer hydrogenation reaction of furfural compounds. The catalyst prepared by this method can significantly improve the selectivity of the target products furfuryl alcohol and 2,5-furandiethanol, reduce the generation of by-products during the reaction, and at the same time, the stability and service life of the catalyst are significantly improved. The catalyst provided by this invention has the advantages of simple operation, low catalyst cost, good stability and high reaction efficiency, which meets the requirements of sustainable development and has broad application prospects in biomass conversion.

[0063] 2) This invention uses furfural and 5-hydroxymethylfurfural as substrates. The raw materials are widely available and produced in large quantities. The products have high added value and are widely used in multiple fields.

[0064] 3) The copper-based catalyst prepared by this invention has the following structural advantages: the catalyst support molecular sieve possesses excellent hydrothermal stability, nanoscale pores, and a highly crystalline framework structure, which not only effectively confines the sintering and agglomeration of metallic copper within it but also enhances reaction selectivity through pore shape-selectivity. Furthermore, the ammonia stripping process used to prepare the copper-containing silica precursor allows for stronger interactions between the copper species and the silica-based support. In summary, the catalyst exhibits higher stability and reactivity. Attached Figure Description

[0065] Figure 1The image shows the XRD pattern of the Cu1-air SiO2-AE-Silicalite-1-HT catalyst prepared in Example 1 of this application.

[0066] Figure 2 The attached diagram shows the nitrogen adsorption-desorption process of Cu1-air SiO2-AE-Silicalite-1-HT prepared in Example 1 of this application. Detailed Implementation

[0067] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0068] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0069] XRD characterization was performed using a PANalytical X'Pert PRO X-ray characterizer, and nitrogen adsorption-desorption was performed using a Micromeritics ASAP 2020 adsorption characterizer.

[0070] Example 1

[0071] Weigh 0.76 g of copper nitrate and add it to a flask containing 50 mL of deionized water. Stir until completely dissolved, then slowly add 10 mL of 25% ammonia solution. At this point, the solution pH is 12. Seal and stir for 2 hours. Then weigh 10 g of silica aerosol powder and add it to the flask. Continue stirring at 20–25 °C for 8 hours. Use a super-constant temperature water bath to heat to 80 °C and place the flask open to allow the ammonia in the system to evaporate until the pH of the slurry is less than 7.5. Stop stirring. After naturally cooling to room temperature, filter, dry at 100 °C for 12 hours, and calcine at 400 °C for 4 hours to obtain the copper-containing silica precursor Cu1-air SiO2-AE.

[0072] 8 g of Cu1-air SiO2-AE was mixed with 21.4 g of tetrapropylammonium hydroxide (25 wt% aqueous solution), 0.11 g of NaOH, and 31.5 g of deionized water and stirred at room temperature for 4 h to form a mixture with a molar concentration of SiO2:tetrapropylammonium hydroxide:Na2O:H2O = 1.0:0.2:0.04:20. This mixture was then crystallized in a 100 mL sealed reactor at 170 °C under autogenous pressure for 4 days. After washing, filtering, drying at 100 °C for 12 h, and calcining at 550 °C for 4 h, the Cu1-air SiO2-AE-Silicalite-1-HT catalyst was obtained. Figure 1 It can be seen that the catalyst has a highly crystalline MFI framework structure. Figure 2 It can be seen that the catalyst has a rich pore structure.

[0073] Example 2

[0074] Weigh 0.76 g of copper nitrate and add it to a flask containing 50 mL of deionized water. Stir until completely dissolved, then slowly add 10 mL of 25% ammonia solution. At this point, the solution pH is 12. Seal and stir for 2 hours. Then weigh 10 g of silica aerosol powder and add it to the flask. Continue stirring at 20-25℃ for 8 hours. Use a super constant temperature water bath to heat to 80℃ and place the flask open to allow the ammonia in the system to evaporate until the pH of the slurry is less than 7.5. Stop stirring. After naturally cooling to room temperature, filter, dry at 100℃ for 12 hours, and calcine at 400℃ for 4 hours to obtain the copper-containing silica precursor Cu1-air SiO2-AE.

[0075] 8 g of Cu1-air SiO2-AE was mixed with 21.4 g of tetrapropylammonium hydroxide (25 wt% aqueous solution), 0.11 g of NaOH, and 31.5 g of deionized water and stirred at room temperature for 4 h to form a mixture with a molar concentration of SiO2:tetrapropylammonium hydroxide:Na2O:H2O = 1.0:0.2:0.04:20. The mixture was then dried in a 100 °C oven for 24 h to prepare a copper-containing silica precursor until the moisture content was less than 5%, and then ground into powder. The dried gel precursor was placed in a 100 mL crystallization vessel lined with polytetrafluoroethylene (PTFE), with 5 mL of deionized water added outside the liner. Crystallization was carried out at 170 °C for 4 days with steam assistance, followed by washing, filtration, drying at 100 °C for 12 h, and calcination at 550 °C for 4 h to obtain the Cu1-air SiO2-AE-Silicalite-1-VP catalyst.

[0076] Examples 3-7

[0077] Example 3 differs from Example 2 only in that 0.20 g of copper nitrate was used in the preparation of the copper-containing silicon oxide precursor to obtain Cu3-air SiO2-AE-Silicalite-1-HT;

[0078] Example 4 differs from Example 3 only in that an equimolar amount of silica sol is used as the silicon source in the process of preparing the copper-containing silicon oxide precursor, resulting in Cu1-SiO2 sol-AE-Silicalite-1-VT.

[0079] Example 5 differs from Example 3 only in that the template agent is replaced with tetraethylammonium hydroxide, resulting in a molecular sieve support with a BEA structure, Cu1-air SiO2-AE-beta-VT.

[0080] Example 6 differs from Example 2 only in that the process of preparing the copper-containing silicon oxide precursor involves evaporating ammonia at 90°C to obtain Cu1-air SiO2-AE90-Silicalite-1-HT;

[0081] Example 7 differs from Example 2 only in that 0.44 g of copper nitrate was used in the preparation of the copper-containing silicon oxide precursor, and an equimolar amount of tetraethyl orthosilicate was used as the silicon source to obtain Cu5-TEOS-AE-Silicalite-1-HT.

[0082] Comparative Example 1

[0083] Comparative Example 1 differs from Example 2 only in that the copper-containing silicon oxide precursor was prepared by loading copper onto the surface of a silicon-based support using an equal-volume impregnation method, ultimately yielding Cu1-air SiO2-IM-Silicalite-1-HT.

[0084] Comparative Example 2

[0085] Comparative Example 2 differs from Example 2 only in that the copper-containing silicon oxide precursor was directly calcined at 550°C for 4 hours after preparation, omitting subsequent steps, and finally obtained Cu1-air SiO2-AE-550.

[0086] Reaction Example 1

[0087] The catalytic conversion experiments were conducted in a stainless steel reactor under the following conditions: Furfural transfer hydrogenation was carried out using catalysts prepared in Examples 1-7 and Comparative Examples 1-2, with a catalyst dosage of 1.0 g, isopropanol of 10 g, and furfural of 4.0 g as solvent. The reactor was sealed, and the atmosphere was replaced with nitrogen. The temperature was raised to 170 °C and the reaction was carried out for 4 h. The results of the furfural transfer hydrogenation catalyzed by different copper-based catalysts are shown in Table 1.

[0088] Table 1 Results of furfural transfer hydrogenation catalyzed by different copper-based catalysts

[0089]

[0090]

[0091] Table 1 compares the results of furfural transfer hydrogenation on different copper-based catalysts. The reaction data show that the catalyst with copper-containing silica precursor-guided molecular sieve support coated with copper prepared by the ammonia stripping method exhibits better reactivity and higher furfuryl alcohol selectivity compared to the copper-containing silica precursor-guided catalyst prepared by the impregnation method or the uncrystallized catalyst.

[0092] Reaction Example 2

[0093] The effects of reaction temperature and reaction pressure on the catalytic results were investigated. Except for the reaction conditions specifically noted in Table 2, the other reaction conditions were the same as in Reaction Example 1. The results of the catalytic furfural transfer hydrogenation reaction in Examples 1-2 are shown in Table 2:

[0094] Table 2. Results of furfural transfer hydrogenation catalyzed by catalysts under different temperatures and solvent conditions.

[0095]

[0096] As can be seen from the reaction data in Table 2, the catalysts of Examples 1-2 all exhibited a selectivity of not less than 90% for furfuryl alcohol under different reaction temperatures and reaction solvents.

[0097] Reaction Example 3

[0098] The effect of the reaction substrate on the catalytic results was investigated. Specific conditions were as follows: 5-hydroxymethylfurfural transfer hydrogenation was carried out using the catalysts prepared in Examples 1-7, with a catalyst dosage of 1.0 g, isopropanol solvent of 24 g, and a certain mass of 5-hydroxymethylfurfural. The reaction vessel was sealed, and the atmosphere was replaced with nitrogen. The temperature was raised to 150 °C and the reaction was carried out for 6 h. The results of the catalytic 5-hydroxymethylfurfural transfer hydrogenation reaction on different copper-based catalysts are shown in Table 3.

[0099] Table 3 Results of the catalytic hydrogenation of 5-hydroxymethylfurfural under different substrate mass conditions

[0100]

[0101] As can be seen from the reaction data in Table 3, when 5-hydroxymethylfurfural is used as the substrate, the catalysts all exhibit a selectivity of not less than 90% for 2,5-furandiethanol and good catalytic activity.

[0102] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing a copper-based catalyst, characterized in that, The preparation method includes: (1) Mixture I containing copper salt, ammonia source and silicon source is subjected to ammonia stripping reaction and calcined in air atmosphere at 300~600℃ to obtain copper-containing silicon oxide precursor; (2) The copper-containing silicon oxide precursor, template agent, alkali source and water mixture II is treated by hydrothermal crystallization or dry gel crystallization, and after separation, drying and calcination in air atmosphere, the copper-based catalyst is obtained.

2. The preparation method according to claim 1, characterized in that, The copper salt is selected from at least one of copper nitrate, copper acetate, copper chloride, copper carbonate, and copper sulfate; The ammonia source is selected from at least one of ammonia water, liquid ammonia, ammonium salt, and urea; The silicon source is selected from at least one of amorphous silica, silica aerosol, silica liquid sol, and tetraethyl orthosilicate; The molar ratio of the ammonia source to the copper salt is 100~2:1; The molar ratio of the copper salt to the silicon source is 0.01 to 0.5:

1.

3. The preparation method according to claim 1, characterized in that, The reaction conditions are as follows: stirring for 1-72 hours, raising the temperature to 70-100 °C until the pH of mixture I is 6-7.5; In step (1), the roasting time is 0.2 to 72 h.

4. The preparation method according to claim 1, characterized in that, The molar ratio of the copper-containing silicon oxide precursor, template agent, alkali source, and water is: SiO2: Template agent: Alkali source: H2O = 0.1~1.0: 0.02~2.5: 0~0.25: 3~200; The amount of the copper-containing silicon oxide precursor is expressed as the molar amount of SiO2, the amount of the template agent is expressed as its own molar amount, and the molar amount of the alkali source is expressed as the molar amount of the cations in the alkali source.

5. The preparation method according to claim 3, characterized in that, The template agent is selected from at least one of methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, choline chloride, hexamethyleneimine, 1,6-hexanediamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; The alkali source is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and potassium carbonate.

6. The copper-based catalyst prepared by the preparation method according to any one of claims 1 to 5, characterized in that, The copper-based catalyst includes a molecular sieve support and an active component, wherein the active component includes copper active element; The molecular sieve support has one of the following topological structures: CHA, MFI, BEA, FAU, and MWW. The crystallinity of the molecular sieve support is above 80%; The copper nanoparticles in the copper-based catalyst have a size of 0.5~10 nm; The mass of the active component is 0.5 wt% to 25 wt% of the mass of the copper-based catalyst, wherein the mass of the active component is based on the mass of copper.

7. The application of the copper-based catalyst prepared by the preparation method according to any one of claims 1 to 5, and the copper-based catalyst according to claim 6, in the transfer hydrogenation reaction of furfural compounds.

8. The application according to claim 7, characterized in that, In an inactive atmosphere, raw materials containing a copper-based catalyst, furfural compounds, and a solvent are reacted to produce furfuryl alcohol compounds.

9. The application according to claim 8, characterized in that, The furfural compound is selected from at least one of furfural and 5-hydroxymethylfurfural; The solvent is selected from at least one of methanol, ethanol, isopropanol, 2-butanol, 2-pentanol, and formic acid.

10. The application according to claim 8, characterized in that, The molar ratio of the copper-based catalyst, solvent, and furfural compound is 1.0:4.0~250:0.2~25.

0. The reaction temperature is 120~220℃, and the reaction time is 0.1~24h; When the furfural compound is furfural, the resulting furfuryl alcohol compound is furfuryl alcohol; when the furfural compound is 5-hydroxymethylfurfural, the resulting furfuryl alcohol compound is 2,5-furandiethanol.

Images