CN104209120A - Metal clusters stabilized by mesoporous zirconium-silicon nanospheres and their preparation methods and applications - Google Patents

Abstract

The invention discloses a metal cluster stabilized by mesoporous zirconium silicon nanospheres, a preparation method and application thereof. Composed of Zr-embedded mesoporous silicon nanospheres and transition metal cluster particles with stable surface, it has the characteristics of uniform hexagonal channels, small and uniform distribution of metal particles (0.6-2.0nm), high stability and high catalytic activity. Wherein, the transition metal particles are one or more of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au. The material adopts a sol-gel method to synthesize nanospheres, and an impregnation-hydrogen reduction method to load metal cluster particles. Using this material as a catalyst for aqueous phase hydrogenation conversion of furan derivatives can achieve high activity of hydrogenation at normal temperature and pressure, and high selectivity to obtain hydrogenation products or ring-opened products.

Description

Metal clusters stabilized by mesoporous zirconium-silicon nanospheres and their preparation methods and applications

technical field

The invention relates to the field of materials and energy, in particular to a metal cluster stabilized by mesoporous zirconium-silicon nanospheres and a preparation method thereof, and also relates to the application of the above-mentioned material in the hydrogenation reaction of biomass-based furan derivatives.

Background technique

Metal clusters exhibit high catalytic activity and selectivity due to their unique metal-bonding structures, and their stability during the reaction has always been a common concern of researchers. Many methods have been reported to suppress the agglomeration of metal clusters in the catalytic process, including loading metal clusters in microporous molecular sieve supercages [J.Am.Chem.Soc.2012,134,17688], carbon nanotubes [ACS Appl.Mater.Interfaces2012,4,6302], hollow shell materials [Small2008,4,1694] and polymer dispersion protection [Adv.Synth.Catal.2006,348,857], etc. However, polymer materials and metal clusters anchored by microporous materials have the problems of low thermal stability and limited diffusion of substrate molecules.

Mesoporous molecular sieves have a large pore size and are widely applicable to macromolecular organic substances. In order to obtain stable metal cluster materials for mesoporous molecular sieves, Mihalcik et al. grafted metal clusters onto the channel surface of mesoporous molecular sieves by means of organic ligand anchoring [Angew.Chem.Int.Ed.2008,47,6229], but high temperature conditions The decomposition of organic ligands can easily deactivate metal clusters by sintering; Liu et al. used mesoporous silicon-based molecular sieves doped with titanium and other metals to increase the dispersion of nickel nanoparticles, but the optimal particle size is 16nm [J.Catal.2009,266,380] . Therefore, highly dispersed and stable metal nanoparticles can be obtained by designing mesoporous silicon-based materials doped with high surface area metals.

With the continuous consumption of fossil energy such as petroleum, the conversion and utilization of biomass will be one of the effective ways to supplement energy. As a biomass-based platform compound, furan derivatives can be used to produce liquid fuel molecules (2,5-dimethylfuran, etc.) and high value-added chemicals (2,5-dimethyloltetrahydrofuran, 1 , 6-hexanediol and other polymer monomers) [Chem.Rev.2013,113,1499]. Most of the currently used heterogeneous hydrogenation catalysts require high temperature or high pressure reaction conditions [Green Chem.2012, 14, 1413; Catal.Commun. Reaction, reduce selectivity and raw material utilization. Therefore, there is an urgent need to develop highly active and highly selective heterogeneous hydrogenation catalysts.

Within the scope of the applicant's search, the use of mesoporous zirconium-silicon nanospheres to directly stabilize metal clusters and use them as heterogeneous catalysts for catalytic hydrogenation reactions of furan derivatives has not yet been reported.

Contents of the invention

The purpose of the present invention is to provide a metal cluster material stable with mesoporous zirconium silicon nanospheres and a preparation method thereof. The material contains mesoporous zirconium-silicon nanospheres with uniform hexagonal channels and highly dispersed and stable metal cluster particles (less than 2nm) on the surface.

In order to achieve the above-mentioned purpose, the present invention adopts an equal-volume impregnation-hydrogen reduction method to immobilize metal clusters in mesoporous zirconium-silicon nanospheres.

The material has a uniform hexagonal pore structure with an average pore diameter of 2.0-3.0nm; metal clusters are immobilized in mesoporous zirconium-silicon nanospheres, and the mass loading of metal clusters on the material is 0.01-50%. Metal cluster particles It is one or more than two kinds of transition metal elements, and the particle size is 0.6-2.0nm.

Metal cluster elements are preferably one or more of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au;

The mass ratio of metal clusters loaded on the material is 0.01%-50%, preferably 0.05%-30%, and most preferably 0.1%-10%.

The specific preparation method is as follows:

1) Preparation of mesoporous zirconium-silicon nanospheres: Dissolve 0.58g of cetyltrimethylammonium bromide (CTAB) template in 300mL of ammonia (pH 10-12) solution, and heat in a water bath to 40- 60°C, under stirring, add dilute ethyl orthosilicate (TEOS ⁾ ethanol solution with a concentration of 0.1-0.5mol ^L Ethanol solution mixed with tetraethyl orthosilicate (TEOS) and zirconium n-propoxide (Zr( ^On Pr) ₄ ), (the molar ratio of zirconium to silicon of the mixed species is 0.01-0.5); aged for 20 hours after stirring, Solid-liquid separation, solid matter washed with water, dried overnight at 110°C, and roasted at 550°C for 10 hours to obtain MSN-Zr;

2) Prepare mesoporous zirconium-silicon nanosphere-stabilized metal clusters (M/MSN-Zr) by impregnation-hydrogen reduction method: weigh 1 g of MSN-Zr carrier, and dissolve metal salt with 0.1-10% metal loading in 3.5 g in a water-soluble solvent, ultrasonically dispersed, left standing at room temperature for 12-48 hours, dried at 100-120°C, placed in a tube furnace, and treated with hydrogen reduction at 100-800°C for 0.5-10 hours to obtain M/ MSN-Zr. In step 1 of the above method, the molar ratio of each raw material in the mixture is Zr/Si=0.01-0.50, CTAB/Si=0.05-1.0, H ₂ O/Si=500-5000; preferably Zr/Si=0.01 -0.20, CTAB/Si=0.05-0.50, H ₂ O/Si=1000-3500; the best is Zr/Si=0.01-0.10, CTAB/Si=0.20-0.30, H ₂ O/Si=2000-3000.

The concentration of the dilute TEOS ethanol solution is preferably 0.1-0.5mol·L ^-1 , most preferably 0.2-0.4mol·L ^-1 ; the concentration of the mixed ethanol solution of concentrated TEOS and Zr( ^On Pr) ₄ is relatively Preferably it is 0.6-2.5 mol·L ^-1 , most preferably 1-2 mol·L ^-1 .

In the dilute ammonia solution, the pH value is 8-14, preferably 9-13, most preferably 10-12.

In step 2 of the above method, the metal cluster is selected from at least one transition metal element in the periodic table, preferably Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au At least one; the metal ion is selected from its organometallic compounds (ruthenium acetylacetonate, iridium dicarbonyl acetylacetonate, cobalt acetate, etc.), metal inorganic salts (ferric nitrate, nickel nitrate, ruthenium chloride, chloroauric acid, etc.); wherein, The mass ratio of metal clusters to be loaded is 0.01%-50%, preferably 0.05%-30%, and most preferably 0.1%-10%.

The water-soluble solvent is at least one selected from water, methanol, ethanol, propanol, isopropanol and acetone.

In the hydrogen reduction treatment conditions described above, hydrogen is provided in a flowing form, the flow rate of which is 1-70mL·min ^-1 , preferably 5-50mL·min ^-1 , most preferably 10-40mL·min ^-1 ; the reduction temperature is 100-800°C, preferably 100-700°C, most preferably 100-600°C; reduction time is 0.5-10 hours, preferably 1-8 hours, most preferably 1-6 hours.

Another object of the present invention is to provide such metal cluster materials stabilized by mesoporous zirconium-silicon nanospheres as catalysts in the hydrogenation conversion of furan derivatives.

In order to achieve the above purpose, the hydrogenation reaction of furan derivatives in the present invention is carried out under the combined action of molecular hydrogen and metal cluster catalysts. Specific steps are as follows:

Add a certain amount of furan derivative aqueous solution and hydrogen newly reduced M/MSN-Zr catalyst to the autoclave, seal the autoclave and replace the air in the autoclave several times, fill the autoclave with hydrogen to the specified pressure, and stir the reaction at a specific temperature for several hours .

The furan derivatives described in the present invention are furan and compounds substituted by organic groups on the furan ring. One or more of the following compounds: furan, 5-methylfuran, 2,5-dimethylfuran, furfural, 5-methylfurfural, 5-hydroxymethylfurfural, 5-ethoxy methylfurfural, furandicarbaldehyde, and furandicarboxylic acid; the corresponding hydrogenation products are furan ring hydrogenation products (2,5-dimethyltetrahydrofuran, 2,5-dimethyloltetrahydrofuran and other tetrahydrofuran-based compounds), Hydrogenation products of substituents on the furan ring (5-methylfurfuryl alcohol, furan dimethanol and other furyl compounds), hydrogenation ring-opening products (2,5-hexanediol, 1,4-butanediol and other polyol compounds) one or more of them.

The ratio of the amount of catalyst to substrate added in the present invention is 0.01%-100% based on metal mass, preferably 0.1%-50%, and most optimally 0.1%-10%.

According to the catalytic reaction conditions of the present invention, the hydrogenation reaction temperature is 20-240°C, preferably 25-150°C, the best 25-100°C; the hydrogen pressure is 0.1-10MPa, preferably 0.1 -5MPa, preferably 0.5-3MPa; reaction time is 0.1-10 hours, preferably 0.5-5 hours, most preferably 1-4 hours.

In summary, the present invention provides a sol-gel method and impregnation-hydrogen reduction method to synthesize mesoporous zirconium-silicon nanospheres with uniform hexagonal channels and highly dispersed and stable metal cluster particles on the surface. The metal cluster particles are transition metal elements, the particle size is small and evenly distributed (0.6-2.0nm), and it has the characteristics of high-temperature anti-sintering stability and high catalytic activity. The preparation method is simple and convenient, and the raw materials are widely available. It is an easy-to-use Materials for industrialized production and application. The invention also provides that the material is used as a novel catalyst for the hydrogenation reaction of furan derivatives, which has the characteristics of high activity and high selectivity, and can be obtained with high selectivity by simply adjusting reaction conditions such as time and temperature. Hydrogenation products or ring-opened products.

Description of drawings

Figure 1 is the small-angle XRD pattern of the mesoporous zirconium-silicon nanospheres (MSN-Zr) and their stable Ru metal clusters (Ru/MSN-Zr) in Examples 1 and 2;

Figure 2 is a) high-resolution transmission electron microscope image (HRTEM) and b) high-angle annular dark field image (HAADF) of the Ru metal clusters stabilized by mesoporous zirconium-silicon nanospheres in Example 2;

FIG. 3 is a transmission electron microscope image (TEM) of Ru/MSN-Zr-20 calcined in air in Example 5. FIG.

Detailed ways

The following examples are helpful for understanding the present invention, but the content of the invention is not limited thereto.

Synthesis of Example 1 Mesoporous Zirconium Silicon Nanospheres

Dilute 12g of concentrated ammonia water (25wt%) with deionized water to 300g (pH=11.4), add 0.58g of CTAB, stir and dissolve in a 50°C water bath. Prepare dilute tetraethyl orthosilicate (TEOS) ethanol solution A: medium (Si) concentration 0.2mol L ^-1 , and mixed solution of concentrated TEOS and n-propoxide zirconium (Zr( ^On Pr) ₄ ) B: medium (Si) concentration 1.0mol·L ^-1 (respectively prepared so that in B: Zr/Si=0.025, 0.05, 0.1). Quickly add 5mL of A solution to the above mixed solution under stirring, seal the reactor, stir for 5 hours, open the reactor, add 5mL of B solution dropwise, continue stirring for 1 hour, stop stirring, and stand in a 50°C water bath for 20 hours. The reaction mixture was centrifuged, washed with deionized water to neutrality, washed with ethanol for 1 to 2 times, dried overnight at 80°C, and roasted at 550°C for 10 hours to obtain mesoporous zirconium-silicon nanoparticles with different atomic ratios of zirconium to silicon. Ball MSN-Zr-x (x=Si/Zr=10,20,40). Its structural properties are shown in Table 1 and Figure 1.

Table 1 Structural properties of mesoporous zirconium silicon nanospheres

Example 2 Synthesis of Ru metal clusters stabilized by mesoporous zirconium silicon nanospheres

Dissolve 0.1442g RuCl ₃ (36.5wt%Ru) in 3.5g water, add 1g MSN-Zr-20, ultrasonically disperse, let stand at room temperature for 24 hours, and dry at 110°C. The dried powder sample was placed in a tube furnace in 30mL·min ^-1 flowing hydrogen, and reduced at 350°C for 6 hours to obtain Ru/MSN-Zr-20 (Ru loading 5wt%). Based on the transmission electron microscope (TEM) image, the average particle size of the statistical Ru particles is 1.1 nm, and the results are shown in Figure 2.

Embodiment 3 ruthenium acetylacetonate synthesizes ruthenium metal clusters

Dissolve 0.2072g Ru(acac) ₃ in 3.5g acetone, add 1g MSN-Zr-20, ultrasonically disperse, let stand at room temperature for 24 hours, and dry at 110°C. The dried powder sample was placed in a tube furnace under 30mL·min ^-1 flowing hydrogen, and reduced at 350°C for 6 hours to obtain Ru/MSN-Zr-20. The average diameter of the Ru particles is 0.8nm.

The synthesis of embodiment 4 nickel metal clusters

Dissolve 0.5505g Ni(NO ₃ ) ₂ ·6H ₂ O in 3.5g water, add 1g MSN-Zr-20, ultrasonically disperse, let stand at room temperature for 24 hours, and dry at 110°C. The dried powder sample was placed in a tube furnace in 25mL·min ^-1 flowing hydrogen, and reduced at 450°C for 3 hours to obtain Ni/MSN-Zr-20 (10wt% Ni loading). The average particle diameter of Ni particles is 1.8nm.

The stability of Ru metal cluster in embodiment 5Ru/MSN-Zr-20

After the catalyst Ru/MSN-Zr-20 in Example 2 was calcined in air for 3 hours, its particle size was characterized by TEM, and the average value was still 1.1 nm. The result is shown in FIG. 3 .

Embodiment 65-Hydroxymethylfurfural (HMF) catalytic hydrogenation reaction activity

Add 0.1g HMF, 9.9g water and 0.1g newly reduced catalyst Ru/MSN-Zr-20 in the embodiment 2 in the 50mL autoclave, replace the air after sealing, charge into hydrogen to 0.5MPa, adjust the temperature to be stable at 25°C, after stirring for a certain period of time, stop the reaction. The HMF conversion rate and product selectivity are shown in Table 2 (the hydrogenation products are 2,5-dimethylolfuran (DHMF) and 2,5-dimethyloltetrahydrofuran (DHMTHF); the ring-opening product is 1 ,2,6-hexanetriol (1,2,6-HT), 1,2,5-hexanetriol (1,2,5-HT)).

Table 2 The results of the hydrogenation reaction of HMF catalyzed by Ru metal clusters

The influence of embodiment 7 reaction temperature on metal cluster catalytic performance

Catalyst Ru/MSN-Zr-10 was prepared according to Example 2, and subjected to hydrogen reduction treatment, the average particle diameter of Ru particles was 1.4nm.

Add 0.1g HMF, 9.9g water and 50mg newly reduced catalyst Ru/MSN-Zr-10 into a 50mL autoclave, replace the air after sealing, fill with hydrogen to 0.5MPa, adjust different reaction temperatures, stir for 4 hours, Stop responding. HMF conversion rate and product selectivity are shown in Table 3 (the hydrogenation products are 2,5-dimethylolfuran (DHMF) and 2,5-dimethyloltetrahydrofuran (DHMTHF); the ring-opening product is 1 -Hydroxy-2,5-hexanedione (HHD), 1,2,5-hexanetriol (1,2,5-HT)).

The influence of table 3 reaction temperature on catalyst reaction performance

DHMF DHMTHF HHD 1,2,5-HT 25 98.1 92.1 5.2 2.2 0 50 95.2 91.8 3.3 4.8 0 75 90.8 57.3 4.6 31.7 0 100 100 0 14.2 2.5 56.5

The influence of embodiment 8 reaction pressure on metal cluster catalytic performance

Add 0.1g HMF, 9.9g water and 50mg newly reduced catalyst Ru/MSN-Zr-10 in Example 6 to a 50mL autoclave, replace the air after sealing, fill with hydrogen to a certain pressure, and adjust the temperature to be stable at 25 °C, after stirring for 4 hours, the reaction was stopped. HMF conversion rate and product selectivity are shown in Table 4 (the hydrogenation products are 2,5-dimethylolfuran (DHMF) and 2,5-dimethyloltetrahydrofuran (DHMTHF); the ring-opening product is 1 ,2,6-hexanetriol (1,2,6-HT), 1,2,5-hexanetriol (1,2,5-HT)).

The influence of table 4 reaction pressure on catalyst reaction performance

Example 9 Metal Cluster Catalyzed Hydrogenation Reaction Activity of Furan Derivatives

Furfural, 5-methylfurfural, 5-hydroxymethylfurfural, 5-ethoxymethylfurfural, furan, 5-methylfuran, and 2,5-dimethylfuran are selected as reaction substrates in the embodiments, wherein , Furfuryl hydrogenation products and furan ring hydrogenation products refer to furfuryl alcohol and tetrahydrofurfuryl alcohol, 5-methylfurfuryl alcohol and 5-methyltetrahydrofurfuryl alcohol, 2,5-dimethylfuran and 2,5-dihydroxyfurfuryl alcohol, respectively Methyltetrahydrofuran, 5-ethoxymethylfurfuryl alcohol, and 5-ethoxymethyltetrahydrofurfuryl alcohol; furan ring hydrogenation products and ring-opening products refer to tetrahydrofuran, 1,4-butanediol, and 5-methyltetrahydrofuran, respectively and 1,4-pentanediol, 2,5-dimethyltetrahydrofuran and 2,5-hexanediol.

Add 0.1g substrate, 9.9g water and 50mg newly reduced catalyst Ru/MSN-Zr-10 in Example 6 to the 50mL autoclave, replace the air after sealing, fill with hydrogen to 0.5MPa, and adjust the temperature to be stable at 25°C, after stirring for 4 hours, stop the reaction. The conversion rate and product selectivity of furan derivatives are shown in Table 5.

Table 5-1 Hydrogenation performance of furfuryl derivatives catalyzed by Ru metal clusters

Furfural 88.5 87.5 11.8 5-Methylfurfural 87.4 68.9 9.1 5-Hydroxymethylfurfural 98.1 92.1 5.3 5-Ethoxymethylfurfural 100 84.1 12.5

Table 5-2Ru metal clusters catalyzed hydrogenation reaction performance of furan derivatives

In summary, the metal cluster particles stabilized by mesoporous zirconium-silicon nanospheres provided by the present invention have highly dispersed and highly stable metal cluster particles (0.6-2.0nm) and uniform The hexagonal mesoporous structure (pore size 2.0-3.0nm) facilitates the diffusion of macromolecular substrates. In the catalytic hydrogenation reaction of furan derivatives, it shows high catalytic activity for hydrogenation at normal temperature and pressure, and high selectivity to obtain hydrogenated products or ring-opened products. In addition, the preparation method is simple and convenient, the elements cover most transition metals, and the raw materials are widely available, etc., it will be a class of materials that are easy to realize industrial production and application.

Claims (11)

1. Metal clusters stabilized by mesoporous zirconium-silicon nanospheres, characterized in that: the material has a uniform hexagonal pore structure with an average pore diameter of 2.0-3.0nm; metal clusters are immobilized in mesoporous zirconium-silicon nanospheres, and the metal clusters The mass loading on the material is 0.01-50%, the metal cluster particles are one or more than two kinds of transition metal elements, and the particle size is 0.6-2.0nm. 2. Metal cluster according to claim 1, characterized in that: Metal cluster elements are preferably one or more of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au; The mass ratio of metal clusters loaded on the material is 0.01%-50%, preferably 0.05%-30%, and most preferably 0.1%-10%. 3. a method for preparing the stable metal cluster of mesoporous zirconium silicon nanospheres according to claim 1 or 2, characterized in that: 1) Preparation of mesoporous zirconium-silicon nanospheres (MSN-Zr): Dissolve 0.58 g of cetyltrimethylammonium bromide (CTAB) template in 300 mL of ammonia (pH 10-12) solution, Heat it in a water bath to 40-60°C, add 5mL of dilute ethyl orthosilicate (TEOS) ethanol solution with a concentration of 0.1-0.5mol L ^-1 under stirring, and add silicon concentration of 0.6-2.5mol dropwise after 5 hours of reaction 5mL ethanol solution mixed with concentrated tetraethyl orthosilicate (TEOS) and zirconium n-propoxide (Zr( ^On Pr) ₄ ) in L ^-1 (the molar ratio of zirconium to silicon in the mixture is 0.01-0.5); Aging for 20 hours after stirring, solid-liquid separation, solid matter washed with water, dried overnight at 110°C, and roasted at 550°C for 10 hours to obtain MSN-Zr; 2) Prepare mesoporous zirconium-silicon nanosphere-stabilized metal clusters (M/MSN-Zr) by impregnation-hydrogen reduction method: Weigh 1 g of MSN-Zr carrier, and dissolve the required loading amount of metal salt in 3.5 g of water-soluble In a solvent, ultrasonically disperse, stand at room temperature for 12-48 hours, dry at 100-120°C, place in a tube furnace, and perform hydrogen reduction treatment at 100-800°C for 0.5-10 hours to obtain M/MSN-Zr . 4. The method according to claim 3, characterized in that: in step 1), the molar ratio of each raw material in the mixture is Zr/Si=0.01-0.50, CTAB/Si=0.05-1.0, H ₂ O/Si= 500-5000; better Zr/Si=0.01-0.20, CTAB/Si=0.05-0.50, H ₂ O/Si=1000-3500; best Zr/Si=0.01-0.10, CTAB/Si=0.20- 0.30, H ₂ O/Si=2000-3000. 5. The method according to claim 3, characterized in that: the concentration of silicon in the dilute TEOS ethanol solution is preferably 0.1-0.5mol·L ^-1 , most preferably 0.2-0.4mol·L ^-1 ; concentrated TEOS and The concentration of silicon in the ethanol solution mixed with Zr( ^On Pr) ₄ is preferably 0.6-2.5 mol·L ^-1 , most preferably 1-2 mol·L ^-1 . 6. according to the described method of claim 3, it is characterized in that: metal cluster element is selected from one or more than two kinds of transition metal elements in the periodic table, preferably Fe, Co, Ni, Ru, Rh, Pd, Os, Ir , Pt, Cu, Ag, Au in one or two or more; The metal salt is selected from one or more of the following compounds: ruthenium acetylacetonate, iridium dicarbonyl acetylacetonate, or cobalt acetate in organometallic compounds, iron nitrate, nickel nitrate, ruthenium chloride in metal inorganic salts , palladium chloride, chloroplatinic acid or chloroauric acid. 7. The method according to claim 3, characterized in that: the water-soluble solvent is selected from one or more than two of water, methanol, ethanol, propanol, isopropanol, and acetone. 8. The method according to claim 3, characterized in that: in the hydrogen reduction treatment condition, the hydrogen is provided in a flow form, and the flow rate is 1-70mL·min ^-1 , preferably 5-50mL·min ^-1 , most preferably Preferably 10-40mL·min ^-1 ; reduction temperature is 100-800°C, preferably 100-700°C, most preferably 100-600°C; reduction time is 0.5-10 hours, preferably 1- 8 hours, the best is 1-6 hours. 9. The application of the stable metal clusters of mesoporous zirconium silicon nanospheres described in claim 1 or 2 in the hydrogenation reaction of furan derivatives, which uses the stable metal clusters of mesoporous zirconium silicon nanospheres as a catalyst, with molecular Hydrogen is used as the hydrogen source, and the aqueous phase is hydroconverted. 10. according to the described application of claim 9, it is characterized in that: based on the metal mass in the catalyst, the added quality of the catalyst is 0.01%-100% of the raw material substrate quality, preferably 0.1%-50%, the best is 0.1%-10%; In the catalytic reaction conditions, the hydrogenation reaction temperature is 20-240°C, preferably 25-150°C, the best is 25-100°C; the hydrogen pressure is 0.1-10MPa, preferably 0.1-5MPa, the best 0.5-3MPa; the reaction time is 0.1-10 hours, preferably 0.5-5 hours, most preferably 1-4 hours. 11. according to the described application of claim 9, it is characterized in that: furan derivative is furan and the compound that the organic group on the furan ring replaces; One or more than two kinds are selected from the following compounds: furan, 5-methano Furan, 2,5-Dimethylfuran, Furfural, 5-Methylfurfural, 5-Hydroxymethylfurfural, 5-Ethoxymethylfurfural, 5-Methoxymethylfurfural, Furandicarbaldehyde, Furan Diformic acid.