A FeNi@NC bimetallic catalyst and its preparation method and application

Abstract

The present invention provides a FeNi@NC bimetallic catalyst and a preparation method and application thereof. The catalyst preparation method comprises the following steps: using ferric chloride, 2-aminoterephthalic acid and nickel salt as raw materials, preparing a catalyst precursor by a solvent thermal synthesis method, and then pyrolyzing at 500°C to 1000°C to prepare a FeNi@NC catalyst. The catalyst is respectively applied to catalytic hydrogenation of levulinic acid to prepare γ-valerolactone, and catalytic reduction amination of levulinic acid and primary amine to prepare pyrrolidone derivatives, and the target product is obtained in high yield. The preparation method of the present invention is simple, and the catalyst has high activity, high selectivity and high stability, which is conducive to popularization and use.

Description

Technical Field

[0001] The present invention relates to the technical field of bioenergy and pharmaceutical chemical industry, and in particular to a FeNi@NC bimetallic catalyst and a preparation method and application thereof. Background Art

[0002] As non-renewable fossil energy sources such as coal, oil and natural gas are becoming increasingly depleted, research on the production of high-value-added chemicals and fuels using typical renewable resource biomass, especially lignocellulosic biomass, as substitutes has attracted great attention. Lignocellulose contains a variety of structural units such as pentoses, hexoses and aromatic compounds. The pentoses and hexoses obtained by degradation can easily be dehydrated to obtain the important biomass-based platform compound levulinic acid. The molecular structure of levulinic acid contains a carbonyl group and a carboxyl group. It can be used as a raw material to prepare the high-value-added chemical γ-valerolactone through catalytic hydrogenation reaction, or it can be used as a raw material to prepare N-substituted-5-methyl-2-pyrrolidone with a wide range of uses through catalytic reductive amination reaction with primary amine compounds.

[0003] However, the catalysts currently used for the preparation of γ-valerolactone and pyrrolidone derivatives from levulinic acid are mostly precious metal catalysts, which have high catalyst costs; in addition, the reaction conditions are mostly harsh. Therefore, it is crucial to develop high-performance non-precious metal catalysts to achieve the conversion of levulinic acid to prepare γ-valerolactone and pyrrolidone derivatives under relatively mild conditions. Summary of the invention

[0004] The present invention provides a FeNi@NC bimetallic catalyst and a preparation method thereof, and the prepared catalyst is respectively applied to the catalytic hydrogenation of levulinic acid to prepare γ-valerolactone, and the catalytic reduction amination of levulinic acid and primary amine to prepare pyrrolidone derivatives. The FeNi catalyst prepared by the method of the present invention has high activity, high selectivity, good stability, mild reaction conditions and high yield.

[0005] To achieve the above experimental purpose, the present invention provides the following scheme:

[0006] The preparation method of FeNi@NC bimetallic catalyst comprises the following steps:

[0007] Step 1: Dissolve FeCl3·6H2O, 2-aminoterephthalic acid and nickel salt in an organic solvent N,N-dimethylformamide (DMF) and heat to react. After cooling, filter and wash, and then vacuum dry the washed solid to obtain the catalyst precursor NH2-MIL-101 (FeNi);

[0008] Step 2: Pyrolyze the catalyst precursor NH2-MIL-101 (FeNi) in an inert gas atmosphere and cool to room temperature to obtain the FeNi@NC bimetallic catalyst. By adjusting the metal molar ratio of Fe and Ni, FeNi@NC bimetallic catalysts with different metal molar ratios were obtained.

[0009] Furthermore, the molar ratio of FeCl3·6H2O, 2-aminoterephthalic acid and nickel salt is 1:1-2:0.5-3.

[0010] Furthermore, the nickel salt is one of nickel nitrate, nickel acetate or nickel chloride.

[0011] Furthermore, the reaction temperature in step 1 is 110-180° C., and the reaction time is 12-48 hours.

[0012] Furthermore, the vacuum drying temperature in step 1 is 80-100° C., and the drying time is 8-12 hours.

[0013] Furthermore, the pyrolysis temperature in step 2 is 500-1000° C., and the pyrolysis time is 1-4 hours.

[0014] The FeNi@NC bimetallic catalyst prepared by the present invention can be well applied to the reaction of catalytic hydrogenation of levulinic acid to prepare γ-valerolactone, and the application method is: using levulinic acid as a raw material, in a reaction solvent, under the action of the FeNi@NC bimetallic catalyst, a catalytic hydrogenation reaction is carried out in a hydrogen atmosphere, and the reaction liquid is post-treated to prepare γ-valerolactone;

[0015] The reaction solvent is methanol, isopropanol, water, tetrahydrofuran or 1,4-dioxane; or the reaction is carried out without solvent;

[0016] The reaction conditions are: hydrogen pressure of 0.5-5 MPa, reaction temperature of 110-180° C., and reaction time of 2-8 h;

[0017] The mass dosage of the FeNi@NC bimetallic catalyst is 0.05 to 0.3 times the mass of levulinic acid, preferably 0.1 to 0.2 times;

[0018] The mass ratio of levulinic acid to reaction solvent is 1:3-30, preferably 1:5-20;

[0019] The post-treatment method of the reaction solution is: after the reaction is completed, the reaction solution is filtered, and the filtrate is distilled under reduced pressure to remove the solvent, so as to obtain γ-valerolactone.

[0020] The FeNi@NC bimetallic catalyst prepared by the present invention can be well applied to the reaction of catalytic reduction amination of levulinic acid to prepare pyrrolidone derivatives. The application method is: using levulinic acid and primary amine as raw materials, in a reaction solvent, under the action of the FeNi@NC bimetallic catalyst, a catalytic reduction amination reaction is carried out in a hydrogen atmosphere, and the reaction solution is post-treated to prepare the pyrrolidone derivative;

[0021] The primary amine includes at least one of aliphatic amine and aromatic amine;

[0022] The molar ratio of levulinic acid to primary amine is 1:1-2;

[0023] The reaction solvent is toluene, isopropanol, water, tetrahydrofuran or 1,4-dioxane;

[0024] The reaction conditions are: hydrogen pressure of 0.25-3 MPa, reaction temperature of 120-180° C., and reaction time of 5-30 h;

[0025] The mass dosage of the FeNi@NC bimetallic catalyst is 0.05 to 0.3 times the mass of levulinic acid, preferably 0.1 to 0.25 times;

[0026] The mass ratio of the levulinic acid to the reaction solvent is 1:3-30, preferably 1:5-20.

[0027] The post-treatment method of the reaction solution is: after the reaction is completed, the reaction solution is filtered, and the filtrate is distilled under reduced pressure to remove the solvent, so as to obtain the pyrrolidone derivative. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1a The XRD spectra of NH2-MIL-101-Fe, NH2-MIL-101-Fe1Ni2, Fe1Ni2@NC-500, Fe1Ni2@NC-600 and Fe1Ni2@NC-700 catalysts prepared in the present invention are compared.

[0029] Figure 1b The XRD spectra of NH2-MIL-101-Fe1Ni2 and Fe1Ni2@NC-600 catalysts prepared in the present invention are compared.

[0030] Figure 2 This is the XPS spectrum of the prepared FeNi@NC-600 catalyst. DETAILED DESCRIPTION

[0031] The technical solution of the present invention is described below with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0032] In this experiment, a series of FeNi@NC catalysts with different proportions were prepared by solvent thermal synthesis combined with high temperature pyrolysis, which were applied to the following examples. The specific preparation method is as follows:

[0033] Preparation of Fe@NC-600 catalyst: 3mmol FeCl3·6H2O was dissolved in 7.5mL N,N-dimethylformamide (DMF); 1.5mmol 2-aminoterephthalic acid was dissolved in 7.5mL DMF. The two solutions were mixed and ultrasonicated for 15min, then transferred to a hydrothermal synthesis reactor and heated at 110℃ for 24h. The obtained brown solution was filtered with a Buchner funnel and washed with methanol. The obtained brown solid was placed in a vacuum drying oven and dried at 110℃ for 12h to obtain NH2-MIL-101(Fe). The obtained NH2-MIL-101(Fe) was placed in a tubular calcining furnace and calcined at 600℃ for 2h in a nitrogen atmosphere to obtain Fe@NC-600.

[0034] Preparation of Fe1Ni1@NC-600 catalyst: 1.5mmol FeCl3·6H2O and 1.5mmol Ni(NO3)2·6H2O were dissolved in 7.5mL N,N-dimethylformamide (DMF); 1.5mmol 2-aminoterephthalic acid was dissolved in 7.5mL DMF. The two solutions were mixed and ultrasonicated for 15min, then transferred to a hydrothermal synthesis reactor and heated at 110℃ for 24h. The brown solution was filtered with a Buchner funnel and washed with methanol. The brown solid was placed in a vacuum drying oven and dried at 110℃ for 12h to obtain NH2-MIL-101(Fe1Ni1). The obtained NH2-MIL-101(Fe1Ni1) was placed in a tubular calcining furnace and calcined at 600℃ in a nitrogen atmosphere for 2h to obtain Fe1Ni1@NC-600 catalyst.

[0035] Preparation of Fe1Ni2@NC-600: 1mmol FeCl3·6H2O and 2mmol Ni(NO3)2·6H2O were dissolved in 7.5mL N,N-dimethylformamide (DMF); 1.5mmol 2-aminoterephthalic acid was dissolved in 7.5mL DMF. The two solutions were mixed and ultrasonicated for 15min, then transferred to a hydrothermal synthesis reactor and heated at 110℃ for 24h. The brown solution was filtered with a Buchner funnel and washed with methanol. The brown solid was placed in a vacuum drying oven and dried at 110℃ for 12h to obtain NH2-MIL-101(Fe1Ni2). The obtained NH2-MIL-101(Fe1Ni2) was placed in a tubular calcining furnace and calcined at 600℃ in a nitrogen atmosphere for 2h to obtain Fe1Ni2@NC-600. When different calcination temperatures (500℃, 700℃) are adopted, Fe1Ni2@NC-500 and Fe1Ni2@NC-700 can be obtained respectively.

[0036] Preparation of Fe1Ni3@NC-600: 0.75mmol FeCl3·6H2O and 2.25mmol Ni(NO3)2·6H2O were dissolved in 7.5mL N,N-dimethylformamide (DMF); 1.5mmol 2-aminoterephthalic acid was dissolved in 7.5mL DMF. The two solutions were mixed and ultrasonicated for 15min, then transferred to a hydrothermal synthesis reactor and heated at 110℃ for 24h. The brown solution was filtered with a Buchner funnel and washed with methanol. The brown solid was placed in a vacuum drying oven and dried at 110℃ for 12h to obtain NH2-MIL-101(Fe1Ni3). The obtained NH2-MIL-101(Fe1Ni3) was placed in a tubular calcining furnace and calcined at 600℃ in a nitrogen atmosphere for 2h to obtain Fe1Ni3@NC-600.

[0037] The XRD spectrum of the catalyst prepared by the present invention is as follows: Figure 1a-1b As shown. Compared with NH2-MIL-101-Fe and NH2-MIL-101-Fe1Ni2, both are Fe-based MOFs materials doped with N. The XRD spectra of the catalyst precursors MIL-101-NH2-Fe1Ni2 and MIL-101-NH2-Fe prepared after adding Ni(NO3)2·6H2O remain unchanged.

[0038] The XRD patterns of the catalyst precursor NH2-MIL-101-Fe1Ni2 and the Fe1Ni2@NC catalyst calcined at different temperatures (500-700℃) in N2 atmosphere were analyzed. In the catalyst directly calcined in N2, four types of diffraction peaks can be observed: belonging to Ni, NiO, Fe2O3 and Fe-Ni alloy. Among them, 2θ=44.5°, 51.8° and 76.4° are attributed to the diffraction peaks of Ni (111), (200) and (220). 2θ=30.2°, 35.6°, 57.3° and 62.9° are attributed to the diffraction peaks of Fe2O3. The positions of the other two diffraction peaks are 43.6° and 50.7°, respectively, which can be attributed to Fe-Ni alloy (PDF 38-0419). The intensity of the diffraction peaks of Fe-Ni alloy and metal Ni increases with the increase of calcination temperature, and is basically completely reduced at 600℃. At 500°C, the diffraction peak intensity of Fe-Ni alloy and metallic Ni is relatively low, and diffraction peaks of (111), (200) and (220) belonging to NiO appear at 2θ=37.2°, 43.3° and 62.9°. Due to the low calcination temperature, the catalyst cannot be completely reduced, and NiO exists in it. This shows that the active metal content in the catalyst is insufficient, which is also the reason why the catalyst calcined at this temperature has a poor effect. The diffraction peaks of Fe-Ni alloy and metallic Ni (220) calcined at 600°C and 700°C are stronger, but in comparison, the diffraction peaks of the active metal of the catalyst calcined at 600°C are sharper. Therefore, when calcined at this temperature, the catalyst exhibits better catalytic activity.

[0039] The XPS spectrum results of FeNi@NC-600 catalyst are as follows Figure 2 As shown, the valence state and elemental composition of the metal on the catalyst surface. XPS full spectrum ( Figure 2 a) shows the apparent peaks corresponding to the binding energies of C1s, O 1s, N 1s, Ni 2p, and Fe 2p. Figure 2 In b), the peak at 284.7 eV is attributed to CC, the peaks at 285.7 eV and 286.4 eV are attributed to C=N and CN respectively, and the peak at 289.5 eV is attributed to OC=O. The existence of the CN bond confirms that the N atom is successfully doped into the carbon skeleton. The XPS spectrum of N 1s ( Figure 2 c) The peaks with binding energies of approximately 398.8 eV, 399.9 eV, 401.1 eV, 402.6 eV, and 406.1 eV are attributed to pyridine N, Fe-N X , pyrrolic N, graphitic N and pyridinium-nitride oxide (NX). In the XPS spectrum of Fe 2p ( Figure 2 d), the peaks at 711.9 eV and 726.5 eV are attributed to Fe2+ The peaks with binding energies of 714.7 eV and 732.2 eV are attributed to Fe 3+ The peaks with binding energies of 720.6 eV and 707.1 eV are attributed to Fe 0 In addition, the XPS spectrum of Ni1s ( Figure 2 e) Confirmed that Ni 0 (2p 3 / 2 : 853.6eV and 2p 1 / 2 :871.4eV)、NiO(2p 3 / 2 : 856.2eV and 2p 1 / 2 :874.3eV) and Ni(OH)2(2p 3 / 2 : 861.1eV and 2p 1 / 2 :881eV).

[0040] In the reaction of levulinic acid catalytic hydrogenation to produce γ-valerolactone:

[0041] Embodiment 1:

[0042] Take 0.464g (4mmol) of levulinic acid and put it in a beaker, add 5mL 1,4-dioxane to dissolve it, add the solution into a 25mL high-pressure reactor, add 0.035g Fe1Ni2@NC-600 catalyst (the molar ratio of Fe and Ni is 1:2), pass hydrogen to purge five times, the reaction temperature is 150°C, the hydrogen pressure is 2.0MPa, and the reaction is carried out for 4h. After the reaction is completed, the reaction liquid is filtered, and the filtrate is distilled under reduced pressure to remove the solvent to obtain γ-valerolactone. The conversion rate of levulinic acid is 74.5%, and the yield of γ-valerolactone is 74.5% (the catalyst selectivity is 100%).

[0043] Embodiment 2:

[0044] Take 0.464g (4mmol) of levulinic acid and put it in a beaker. Add 5mL of 1,4-dioxane to dissolve it. Add the solution into a 25mL high-pressure reactor, add 0.075g of Fe1Ni2@NC-600 catalyst (the molar ratio of Fe and Ni is 1:2), pass hydrogen to purge five times, the reaction temperature is 150°C, the hydrogen pressure is 2.0MPa, and the reaction is carried out for 3h. After the reaction is completed, the reaction liquid is filtered, and the filtrate is distilled under reduced pressure to remove the solvent to obtain γ-valerolactone. The conversion rate of levulinic acid is 83.1%, and the yield of γ-valerolactone is 83.1% (the catalyst selectivity is 100%).

[0045] Embodiment 3:

[0046] 0.464 g (4 mmol) of levulinic acid was placed in a beaker, 3 mL of 1,4-dioxane was added to dissolve it, the solution was added into a 25 mL high pressure reactor, 0.075 g of Fe1Ni2@NC-600 catalyst (the molar ratio of Fe to Ni was 1:2) was added, hydrogen was introduced for five times, the reaction temperature was 180 ° C, the hydrogen pressure was 3.0 MPa, the reaction was carried out for 2.5 hours, and after the reaction was completed, the reaction liquid was filtered, and the filtrate was distilled under reduced pressure to remove the solvent to obtain γ-valerolactone. The conversion rate of levulinic acid was 100%, and the yield of γ-valerolactone was 100% (the catalyst selectivity was 100%).

[0047] Embodiment 4:

[0048] Take 0.464g (4mmol) of levulinic acid and put it in a beaker, add 3mL of water to dissolve it, add the solution into a 25mL high-pressure reactor, add 0.075g of Fe1Ni2@NC-600 catalyst (the molar ratio of Fe and Ni is 1:2), pass hydrogen to purge five times, the reaction temperature is 150°C, the hydrogen pressure is 2.0MPa, and the reaction is carried out for 3h. After the reaction, the reaction liquid is filtered, and the filtrate is distilled under reduced pressure to remove the solvent to obtain γ-valerolactone. The conversion rate of levulinic acid is 100%, and the yield of γ-valerolactone is 100% (the catalyst selectivity is 100%).

[0049] Embodiment 5:

[0050] 0.464 g (4 mmol) of levulinic acid was placed in a beaker. Under solvent-free conditions, the solution was added to a 25 mL high-pressure reactor, and 0.075 g of Fe1Ni2@NC-600 catalyst (the molar ratio of Fe and Ni was 1:2, and the catalyst was prepared by hydrothermal synthesis) was added. Hydrogen was passed through for five times. The reaction temperature was 160 ° C, the hydrogen pressure was 2.0 MPa, and the reaction was carried out for 3.5 hours to obtain γ-valerolactone. The conversion rate of levulinic acid was 100%, and the yield of γ-valerolactone was 100% (the catalyst selectivity was 100%).

[0051] In the reaction of reductive amination of levulinic acid to prepare pyrrolidone derivatives:

[0052] Embodiment 6:

[0053] 2mmol of levulinic acid and 3mmol of n-butylamine were placed in a beaker, 3mL of tetrahydrofuran was added to dissolve, the solution was added to a 25mL high-pressure reactor, 0.05g of Fe1Ni1@NC-600 catalyst (the molar ratio of Fe to Ni was 1:1) was added, hydrogen was introduced for five times, the reaction temperature was 140°C, the hydrogen pressure was 3.0MPa, the reaction was carried out for 12h, and after the reaction was completed, the reaction liquid was filtered, and the filtrate was distilled under reduced pressure to remove the solvent to obtain N-butyl-5-methyl-2-pyrrolidone, the conversion rate of levulinic acid was 100%, and the yield of N-butyl-5-methyl-2-pyrrolidone was 90.1%.

[0054] Embodiment 7:

[0055] 2 mmol of levulinic acid and 3 mmol of n-butylamine were placed in a beaker, 3 mL of tetrahydrofuran was added to dissolve, the solution was added into a 25 mL high pressure reactor, 0.05 g of Fe1Ni1@NC-600 catalyst (the molar ratio of Fe to Ni was 1:1) was added, hydrogen was introduced for five times, the reaction temperature was 150 ° C, the hydrogen pressure was 3.0 MPa, the reaction was carried out for 12 hours, and after the reaction was completed, the reaction liquid was filtered, and the filtrate was distilled under reduced pressure to remove the solvent to obtain N-butyl-5-methyl-2-pyrrolidone, the conversion rate of levulinic acid was 100%, and the yield of N-butyl-5-methyl-2-pyrrolidone was 92.4%.

[0056] Embodiment 8:

[0057] 2 mmol of levulinic acid and 3 mmol of n-butylamine were placed in a beaker, 3 mL of tetrahydrofuran was added to dissolve, the solution was added to a 25 mL high-pressure reactor, 0.05 g of Fe1Ni1@NC-600 catalyst (the molar ratio of Fe to Ni was 1:1) was added, hydrogen was introduced for five times, the reaction temperature was 150°C, the hydrogen pressure was 0.5 MPa, the reaction was carried out for 12 hours, and after the reaction was completed, the reaction liquid was filtered, and the filtrate was distilled under reduced pressure to remove the solvent to obtain N-butyl-5-methyl-2-pyrrolidone, the conversion rate of levulinic acid was 100%, and the yield of N-butyl-5-methyl-2-pyrrolidone was 95.8%.

[0058] Embodiment 9:

[0059] 2 mmol of levulinic acid and 3 mmol of n-butylamine were placed in a beaker, 3 mL of tetrahydrofuran was added to dissolve, the solution was added into a 25 mL high pressure reactor, 0.05 g of Fe1Ni1@NC-600 catalyst (the molar ratio of Fe to Ni was 1:1) was added, hydrogen was introduced for five times, the reaction temperature was 150 ° C, the hydrogen pressure was 0.5 MPa, the reaction was carried out for 6 hours, and after the reaction was completed, the reaction liquid was filtered, and the filtrate was distilled under reduced pressure to remove the solvent to obtain N-butyl-5-methyl-2-pyrrolidone, the conversion rate of levulinic acid was 99.8%, and the yield of N-butyl-5-methyl-2-pyrrolidone was 78.6%.

[0060] Embodiment 10~12:

[0061] The other operations were the same as in Example 1, and the Fe / Ni molar ratio was changed to obtain the following reaction results (Table 1):

[0062] Table 1

[0063]

[0064] (The selectivity of the catalyst is 100%, so the conversion rate of levulinic acid and the yield of γ-valerolactone are the same, the same below).

[0065] Embodiment 13~15:

[0066] The other operations were the same as in Example 1, and the calcination temperature of Fe1Ni2@NC was changed to obtain the following reaction results (Table 2):

[0067] Table 2

[0068]

[0069]

[0070] Embodiments 16 to 20:

[0071] The other operations were the same as in Example 2, and the hydrogen pressure was changed to obtain the following reaction results (Table 3):

[0072] Table 3

[0073]

[0074] Embodiments 21 to 25:

[0075] The other operations were the same as in Example 2, but the solvent was changed to obtain the following reaction results (Table 4):

[0076] Table 4

[0077]

[0078]

[0079] Embodiment 27-42:

[0080] The other operations were the same as those in Example 3, 1,4-dioxane was used as the solvent, and the number of times the catalyst was recycled was changed (after each reaction, the reaction solution was filtered, and the filter cake was recycled as the catalyst, the same below), and the following reaction results were obtained (Table 5):

[0081] Table 5

[0082]

[0083]

[0084] Embodiment 44-51:

[0085] Other operations were the same as in Example 4, with water as the solvent and the number of times the catalyst was recycled being changed, and the following reaction results were obtained (Table 6):

[0086] Table 6

[0087]

[0088] Embodiment 52-54:

[0089] Other operations were the same as in Example 5. Under solvent-free conditions, the number of catalyst cycles was changed to obtain the following reaction results (Table 7):

[0090] Table 7

[0091]

[0092] Embodiments 55 to 59:

[0093] The other operations were the same as in Example 6, but the solvent was changed to obtain the following reaction results (Table 8):

[0094] Table 8

[0095]

[0096] Embodiment 60~63:

[0097] The other operations were the same as in Example 7, and the reaction temperature was changed to obtain the following reaction results (Table 9):

[0098] Table 9

[0099]

[0100]

[0101] Embodiments 64 to 68:

[0102] The other operations were the same as in Example 8, and the hydrogen pressure was changed to obtain the following reaction results (Table 10):

[0103] Table 10

[0104]

[0105] Examples 69-74:

[0106] The other operations were the same as those in Example 9, tetrahydrofuran was used as the solvent, and the number of times the catalyst was recycled was changed to obtain the following reaction results (Table 11):

[0107] Table 11

[0108]

[0109] Embodiment 75-84:

[0110] The other operations were the same as those in Example 9, except that the type of primary amine compound was changed, and the following reaction results were obtained (Table 12):

[0111] Table 12

[0112]

[0113]

Claims

1. An application of a FeNi@NC bimetallic catalyst in the reaction of catalytic hydrogenation of levulinic acid to produce γ-valerolactone or catalytic reductive amination of levulinic acid to produce pyrrolidone derivatives, characterized in that: The preparation method of the catalyst comprises the following steps: Step 1: Dissolve iron salt, 2-aminoterephthalic acid and nickel salt in N , N - dimethylformamide (DMF), heating for solvent thermal reaction; after cooling, filtering and washing, and then vacuum drying the washed solid to obtain the catalyst precursor NH2-MIL-101-FeNi; Step 2: Pyrolyze the catalyst precursor NH2-MIL-101-FeNi in an inert gas atmosphere and cool to room temperature to obtain the FeNi@NC bimetallic catalyst.

2. The use according to claim 1, characterized in that In the preparation method of the catalyst, the molar ratio of the iron salt, 2-aminoterephthalic acid and the nickel salt is 1:1-2:0.5-3; The nickel salt is one of nickel nitrate, nickel acetate or nickel chloride, and the iron salt is ferric chloride.

3. The use according to claim 1, characterized in that In the preparation method of the catalyst, the reaction temperature in step 1 is 110-180°C, and the reaction time is 12-48 h.

4. The use according to claim 1, characterized in that In the catalyst preparation method, the vacuum drying temperature in step 1 is 80-100° C., and the drying time is 8-12 h.

5. The use according to claim 1, characterized in that In the preparation method of the catalyst, the pyrolysis temperature in step 2 is 500-1000°C, and the pyrolysis time is 1-4 h.

6. The use according to claim 1, characterized in that The catalyst is used in the reaction of catalytic hydrogenation of levulinic acid to prepare γ-valerolactone, taking levulinic acid as a raw material, in a reaction solvent, under the action of a FeNi@NC bimetallic catalyst, a catalytic hydrogenation reaction is carried out in a hydrogen atmosphere, and the reaction liquid is post-treated to prepare γ-valerolactone; The reaction solvent is methanol, isopropanol, water, tetrahydrofuran or 1,4-dioxane; or the reaction is carried out without solvent; The reaction conditions are: hydrogen pressure of 0.5-5 MPa, reaction temperature of 110-180 o C, reaction time is 2~8 h; The mass dosage of the FeNi@NC bimetallic catalyst is 0.05-0.3 times the mass of levulinic acid; The mass ratio of levulinic acid to reaction solvent is 1:3-30; The post-treatment method of the reaction solution is: after the reaction is completed, the reaction solution is filtered, and the filtrate is distilled under reduced pressure to remove the solvent, so as to obtain γ-valerolactone.

7. The use according to claim 6, characterized in that The mass dosage of the FeNi@NC bimetallic catalyst is 0.1-0.2 times the mass of levulinic acid; the mass ratio of levulinic acid to the reaction solvent is 1:5-20.

8. The use according to claim 1, characterized in that The catalyst is used in the reaction of catalytic reduction amination of levulinic acid to prepare pyrrolidone derivatives, taking levulinic acid and primary amine as raw materials, in a reaction solvent, under the action of FeNi@NC bimetallic catalyst, catalytic reduction amination reaction is carried out in a hydrogen atmosphere, and the reaction solution is post-treated to prepare the pyrrolidone derivatives; The primary amine includes at least one of aliphatic amine and aromatic amine; The molar ratio of levulinic acid to primary amine is 1:1-2; The reaction solvent is toluene, isopropanol, water, tetrahydrofuran or 1,4-dioxane; The reaction conditions are: hydrogen pressure of 0.25-3 MPa, reaction temperature of 120-180 o C, reaction time is 5~30 h; The mass dosage of the FeNi@NC bimetallic catalyst is 0.05-0.3 times the mass of levulinic acid; The mass ratio of levulinic acid to reaction solvent is 1:3-30; The post-treatment method of the reaction solution is: after the reaction is completed, the reaction solution is filtered, and the filtrate is distilled under reduced pressure to remove the solvent, so as to obtain the pyrrolidone derivative.

9. The use according to claim 8, characterized in that The mass dosage of the FeNi@NC bimetallic catalyst is 0.1-0.25 times the mass of levulinic acid; the mass ratio of levulinic acid to the reaction solvent is 1:5-20.

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