Hydrogenation catalyst and preparation method thereof, and preparation method of gamma-valerolactone

Abstract

The invention relates to the field of hydrogenation catalytic materials, in particular to a hydrogenation catalyst, a preparation method of the hydrogenation catalyst and a preparation method of gamma-valerolactone. The hydrogenation catalyst provided by the invention comprises a carrier, wherein the carrier is a Co-Al composite oxide with an ordered mesoporous structure and a macroporous structure; zr and an auxiliary agent are loaded on the carrier, and the auxiliary agent is Fe, Sn, Si or W. The hydrogenation catalyst provided by the invention takes a large-pore-channel hierarchical-pore material as a carrier, is used for catalyzing the hydrogenation of levulinic acid or levulinate to prepare valerolactone, and has high catalytic efficiency and stability; the problem that in the prior art, a hydrogenation catalyst with a mesoporous material as a carrier has mass transfer limitation in the catalytic levulinic acid or levulinic acid ester hydro-conversion process can be solved, and the catalyst has high catalytic efficiency and stability. Tests show that the hydrogenation catalyst still keeps high activity and selectivity after being repeatedly used for three times, the preparation method is simple, and the hydrogenation catalyst has high industrial application value.

Description

Technical Field

[0001] The present invention relates to the field of hydrogenation catalytic materials, and particularly to a hydrogenation catalyst, a preparation method thereof, and a preparation method of γ-valerolactone. Background Art

[0002] With the rapid reduction of the reserves of traditional fossil resources, the conversion of renewable and carbon-neutral green biomass resources into carbon-containing chemicals and high-grade fuels has received great attention. Among them, γ-valerolactone (GVL) is considered to be a biomass-based platform compound with great application prospects, which can be used as a solvent, a food additive, and a liquid fuel, and can also be used to synthesize basic chemical raw materials and liquid fuels such as 1,4-pentanediol and 2-methyltetrahydrofuran.

[0003] Levulinic acid (LA) produced from cellulose and hemicellulose is an important biomass-based platform compound. The carbonyl and carboxyl functional groups in LA are very active and can participate in the synthesis of many high-value-added chemicals. The hydrogenation of LA to prepare the high-value-added product γ-valerolactone (GVL) is one of the most promising routes. The conversion path of levulinic acid and its esters to prepare GVL: (1) First, the carbonyl group in levulinic acid and its esters is hydrogenated to form 4-hydroxyvaleric acid or 4-hydroxyvalerate, and these intermediates are subsequently converted to GVL through an intramolecular esterification reaction. (2) Levulinic acid dehydrates to produce angelica lactone under the action of an acidic catalyst, and then angelica lactone is further hydrogenated to obtain GVL.

[0004] In the catalysts for the hydrogenation of levulinic acid to prepare γ-valerolactone, homogeneous catalysts need to use very expensive ligands and strong acidic additives, which will make it difficult to separate the catalyst system from the product after the reaction and difficult to reuse, so it is very difficult to achieve large-scale industrial applications. Heterogeneous catalysts can be separated from the product at low cost and quickly after the LA hydrogenation reaction, and do not require the use of additives and ligands, so it is relatively easy to realize industrial application.

[0005] At present, metal-loaded acidic supports are synthesized as bifunctional catalysts for the hydrogenation conversion of levulinic acid. Such catalysts contain metal hydrogenation sites and acidic sites. Among them, the metal hydrogenation sites can be divided into noble metals and non-noble metals. Noble metals include Ru, Pd, and Pt, etc., and non-noble metals include Ni, Co, Zr, and Cu, etc. Acidic supports include carbon materials, resins, molecular sieves, metal oxides, metal-organic frameworks, etc. The metal active species and acidic sites can promote the hydrogenation of levulinic acid and its esters on the metal sites and the intramolecular esterification of intermediates on the acidic sites to obtain a high yield of γ-butyrolactone.

[0006] At present, bifunctional catalysts mostly focus on mesoporous materials. As levulinic acid and its esters are macromolecular reactants, there are mass transfer limitations during the catalytic conversion process. Therefore, it is necessary to develop hierarchical porous materials with larger pore channels as catalyst carriers to avoid mass transfer limitations and accelerate the catalytic conversion of reactants to prepare high-value-added compounds. However, there is no relevant guidance in the existing technology on how to use hierarchical porous materials with larger pore channels as carriers to prepare hydrogenation catalysts with high catalytic efficiency and stability. Summary of the Invention

[0007] In view of this, the technical problem to be solved by the present invention is to provide a hydrogenation catalyst, its preparation method, and a preparation method of γ-valerolactone. The hydrogenation catalyst provided by the present invention is used for catalytic hydrogenation of levulinic acid or levulinic acid ester to prepare valerolactone, and has high catalytic efficiency and stability.

[0008] The present invention provides a hydrogenation catalyst, comprising:

[0009] a carrier, the carrier being a Co-Al composite oxide having an ordered mesoporous structure and a macroporous structure;

[0010] Zr and a promoter supported on the carrier, the promoter being Fe, Sn, Si, or W.

[0011] The hydrogenation catalyst of the present invention comprises a carrier, the carrier being a Co-Al composite oxide having an ordered mesoporous structure and a macroporous structure; specifically, the carrier is a Co-Al composite oxide having an ordered two-dimensional hexagonal mesoporous structure and a three-dimensional interconnected network macroporous structure. More specifically, the BET specific surface area of the carrier is 200 m 2 / g to 400 m 2 / g; the mesopore diameter of the ordered mesoporous structure is 8 nm to 10 nm; the macropore diameter of the macroporous structure is 100 nm to 300 nm.

[0012] The hydrogenation catalyst of the present invention further comprises Zr and a promoter, wherein the Zr is a metal functional component, and the promoter is Fe, Sn, Si, or W. The Zr and the promoter of the present invention are supported on the carrier. Based on the mass of the carrier, the loading amount of Zr is 5% to 12%, and the loading amount of the promoter is 1% to 5%.

[0013] The hydrogenation catalyst provided by the present invention uses an ordered mesoporous-macroporous Co-Al composite oxide as the carrier. Its regular three-dimensional interconnected network macroporous structure and highly regular two-dimensional hexagonal mesoporous structure can enhance the diffusion rate of reaction molecules and shorten the time for reactant molecules to reach the active center, and have high thermal stability and mechanical stability. Combining the functions of the metal functional component Zr and the promoter component, after a long-term continuous operation reaction, this hydrogenation catalyst can still maintain high stability and selectivity, and has the prospect of industrial application.

[0014] In some embodiments of the present invention, the carrier of the present invention is prepared by the following steps:

[0015] S1) In an ethanol solution of concentrated hydrochloric acid and citric acid, react the template agent F127, cobalt source, and aluminum source at 30 °C to 60 °C for 12 h to 48 h to obtain a reaction solution;

[0016] S2) Add polystyrene microspheres to the reaction solution obtained in step S1), volatilize the solvent, heat-treat at 100 °C to 150 °C for 24 h to 48 h, and then calcine the material obtained after heat treatment to obtain the carrier.

[0017] The present invention first reacts the template agent F127, cobalt source, and aluminum source in an ethanol solution of concentrated hydrochloric acid and citric acid at 30 °C to 60 °C for 12 h to 48 h to obtain a reaction solution. Specifically, dissolve the template agent F127 and cobalt source in an ethanol solution of concentrated hydrochloric acid and citric acid, add the aluminum source thereto, and stir and react at 30 °C to 60 °C for 12 h to 48 h to obtain a reaction solution. Preferably, stir and react at 45 °C for 48 h to obtain a reaction solution.

[0018] The ethanol in the present invention is preferably anhydrous ethanol. The concentrated hydrochloric acid in the present invention is the conventional commercially available concentrated hydrochloric acid well-known to those skilled in the art, and its mass fraction of hydrogen chloride is 36% to 38%. The cobalt source in the present invention is preferably a cobalt salt, more preferably cobalt nitrate; the aluminum source is preferably an aluminum salt, more preferably aluminum nitrate. In some embodiments of the present invention, the cobalt source is Co(NO 3 ) 2 ·6H 2 O; the aluminum source is aluminum nitrate nonahydrate. The molar ratio of the template agent F127: concentrated hydrochloric acid: citric acid: ethanol: aluminum source: cobalt source in the present invention is 1:(200 - 350):(6 - 14):(1400 - 3000):(30 - 80):(15 - 80), preferably 1:(200 - 300):(8 - 12):(2100 - 3000):(30 - 60):(15 - 45).

[0019] After obtaining the reaction solution, polystyrene microspheres are added to the obtained reaction solution. After the solvent is volatilized, heat treatment is carried out at 100 °C to 150 °C for 24 h to 48 h, and then the material obtained after heat treatment is calcined to obtain a support. Specifically, polystyrene microspheres are added to the obtained reaction solution. After stirring for 4 min to 6 min, the reaction solution added with polystyrene microspheres is volatilized at 45 °C to 80 °C for 36 h to 60 h. Then the material obtained after solvent volatilization is heat treated at 100 °C to 150 °C for 24 h to 48 h, and then the material obtained after heat treatment is calcined to obtain a support. The calcination in the present invention is specifically carried out at a temperature of 400 °C to 600 °C in an air atmosphere for 3 h to 8 h. The size of the polystyrene microspheres in the present invention is 200 nm to 400 nm. The dosage of the polystyrene microspheres in the present invention is 5 wt% to 15 wt% of the dosage of the template F127 in step S1).

[0020] Preferably, polystyrene microspheres are added to the obtained reaction solution. After stirring for 5 min, the reaction solution added with polystyrene microspheres is volatilized at 60 °C for 48 h. Then the material obtained after solvent volatilization is heat treated at 100 °C for 24 h, and then the material obtained after heat treatment is calcined to obtain a support. Preferably, the calcination in the present invention is specifically carried out at a temperature of 500 °C to 600 °C in an air atmosphere for 4 h to 7 h. Preferably, the size of the polystyrene microspheres in the present invention is 300 nm. The dosage of the polystyrene microspheres in the present invention is 9.375 wt% of the dosage of the template F127 in step S1).

[0021] The present invention provides a method for preparing the hydrogenation catalyst according to any one of the above technical solutions, comprising the following steps: impregnating the support in a Zr source and an auxiliary source, and calcining the impregnated support at 400 °C to 600 °C for 2 h to 8 h to obtain a hydrogenation catalyst.

[0022] Specifically, the present invention performs equal-volume impregnation of the support in a mixed solution of a Zr source and an auxiliary source, dries the impregnated support, and then calcines it at 400 °C to 600 °C for 2 h to 8 h, preferably calcines it at 450 °C to 550 °C for 4 h to obtain a hydrogenation catalyst. The drying temperature in the present invention is 40 °C to 120 °C, and the drying time is 4 h to 24 h; preferably, the drying temperature is 80 °C to 100 °C, and the drying time is 10 h to 20 h.

[0023] The carrier of the present invention is the same as described above and will not be elaborated further. The mixed solution of the Zr source and the promoter source in the present invention is an aqueous mixed solution of the Zr source and the promoter source. The Zr source in the present invention is selected from soluble Zr salts, preferably nitrate of Zr; the promoter source is selected from soluble promoter sources, preferably nitrate of Fe, chloride of Sn, organosilicon compounds or tungstates. In certain embodiments of the present invention, the Zr source is selected from Zr(NO 3 ) 2 ·5H 2 O, and the promoter source is selected from Fe(NO 3 ) 3 ·9H 2 O, SnCl 4 ·5H 2 O, tetraethyl orthosilicate or Na 2 WO 4 , preferably selected from Fe(NO 3 ) 3 ·9H 2 O.

[0024] The present invention also provides a method for preparing γ-valerolactone, comprising the following steps: under the action of a hydrogenation catalyst, hydrogenating levulinic acid or levulinic acid ester in hydrogen to obtain γ-valerolactone; the hydrogenation catalyst is the hydrogenation catalyst described in any of the above technical solutions or the hydrogenation catalyst obtained by the preparation method described in any of the above technical solutions.

[0025] In certain embodiments of the present invention, the hydrogenation reaction in the present invention is carried out in a stainless steel autoclave. Specifically, first, the air in the stainless steel autoclave is replaced with nitrogen several times, and then hydrogen is charged into the stainless steel autoclave. One of levulinic acid or levulinic acid ester and the hydrogenation catalyst are heated and stirred in the stainless steel autoclave for hydrogenation reaction to obtain γ-valerolactone. After the hydrogenation reaction in the present invention is completed, the reaction product is centrifuged to recover the hydrogenation catalyst and obtain the product γ-valerolactone, and the hydrogenation catalyst can be directly recycled.

[0026] The hydrogenation catalyst of the present invention is the same as described above and will not be elaborated further. The mass dosage of the hydrogenation catalyst in the present invention is 2% - 6% of the mass dosage of levulinic acid or levulinic acid ester, preferably 3% - 5.5%. The pressure of the hydrogen in the present invention is 1.0 MPa - 4.0 MPa, preferably 3.0 MPa. The temperature of the hydrogenation reaction in the present invention is 120°C - 200°C, and the time of the hydrogenation reaction is 2.0 h - 6.0 h. Preferably, the temperature of the hydrogenation reaction is 140°C - 180°C, and the time of the hydrogenation reaction is 4.0 h.

[0027] The present invention provides a hydrogenation catalyst, a preparation method thereof, and a preparation method of γ-valerolactone. The hydrogenation catalyst provided by the present invention comprises: a carrier, which is a Co-Al composite oxide having an ordered mesoporous structure and a macroporous structure; Zr and a promoter supported on the carrier, and the promoter is Fe, Sn, Si or W. The hydrogenation catalyst provided by the invention uses a hierarchical pore material with large pores as the carrier and is used for catalyzing the hydrogenation of levulinic acid or levulinate to prepare valerolactone, has high catalytic efficiency and stability, can solve the problem of mass transfer limitation existing in the hydrogenation catalyst using a mesoporous material as the carrier in the process of catalytic hydrogenation conversion of levulinic acid or levulinate, and has high catalytic efficiency and stability. Tests show that the hydrogenation catalyst provided by the present invention still maintains high activity and selectivity after being reused 3 times, has a simple preparation method, and has high industrial application value. Detailed implementation manners

[0028] The present invention discloses a hydrogenation catalyst, a preparation method thereof, and a preparation method of γ-valerolactone. Those skilled in the art can draw on the content of this article and appropriately modify the process parameters to achieve it. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all regarded as included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and those related can obviously make changes or appropriate changes and combinations to the methods and applications in this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0029] The present invention will be further described below in conjunction with embodiments:

[0030] Example 1

[0031] Step 1: Dissolve 6.4 g of template agent F127 and 2.53 g of Co(NO 3 ) 2 ·6H 2 O in 50 g of absolute ethanol containing 4.0 g of concentrated hydrochloric acid and 0.8 g of citric acid. Then, slowly add 6.52 g of aluminum nitrate nonahydrate to the above clear solution and stir strongly at 45°C for 48 h.

[0032] Step 2: Add 0.6 g of 200-nm polystyrene microspheres to the above reaction solution. After stirring strongly for 5 min, transfer the reaction mixture solution to a glass dish and place it in an oven at 60°C and 100°C successively for solvent evaporation and heat treatment for 48 h and 24 h respectively to obtain a solid product.

[0033] Step 3: Calcinate the obtained solid product in an air atmosphere at 550°C for 6 h to obtain the carrier CA-1.

[0034] Step 4: An aqueous solution containing 0.63 g of Zr(NO 3 ) 2 ·5H 2 O and 0.27 g of Fe(NO 3 ) 3 ·9H 2 O was impregnated onto the CA-1 support in equal volumes. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 6Zr-2Fe / CA-1.

[0035] Example 2

[0036] Compared with Example 1, the difference is that 0.6 g of 300-nm polystyrene microspheres were added in Step 2 to obtain the support CA-2, and the other conditions remained unchanged, obtaining the catalyst 6Zr-2Fe / CA-2.

[0037] Example 3

[0038] Compared with Example 1, the difference is that 0.6 g of 400-nm polystyrene microspheres were added in Step 2 to obtain the support CA-3, and the other conditions remained unchanged, obtaining the catalyst 6Zr-2Fe / CA-3.

[0039] Example 4

[0040] Compared with Example 2, the difference is that the addition amount of Co(NO 3 ) 2 ·6H 2 O in Step 1 was 0.51 g to obtain the support CA-4. In Step 4, an aqueous solution containing 0.42 g of Zr(NO 3 ) 2 ·5H 2 O and 0.18 g of Fe(NO 3 ) 3 ·9H 2 O was impregnated onto the CA-4 support in equal volumes. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 6Zr-2Fe / CA-4.

[0041] Example 5

[0042] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.42 g of Zr(NO 3 ) 2 ·5H 2 O and 0.21 g of tetraethyl orthosilicate was impregnated onto the CA-2 support in equal volumes. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 6Zr-3Si / CA-2.

[0043] Example 6

[0044] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.42 g of Zr(NO 3 ) 2 ·5H 2 O and 0.04 g of SnCl 4 ·5H 2 O was impregnated onto the CA-2 support in equal volumes. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 8Zr-Sn / CA-2.

[0045] Example 7

[0046] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.56 g of Zr(NO 3 ) 2 ·5H 2 O and 0.05 g of Na 2 WO 4 was impregnated onto the CA-2 support in equal volumes. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 6Zr-2W / CA-2.

[0047] Example 8

[0048] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.56 g of Zr(NO 3 ) 2 ·5H 2 O and 0.18 g of Fe(NO 3 ) 3 ·9H 2 O was impregnated onto the CA-2 support in equal volumes. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 8Zr-2Fe / CA-2.

[0049] Example 9

[0050] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.84 g of Zr(NO 3 ) 2 ·5H 2 O and 0.18 g of Fe(NO 3 ) 3 ·9H 2 O was impregnated onto the CA-2 support in equal volumes. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 12Zr-2Fe / CA-2.

[0051] Example 10

[0052] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.56 g of Zr(NO3 ) 2 ·5H 2 O and 0.36 g of Fe(NO 3 ) 3 ·9H 2 O aqueous solution was impregnated onto the CA-2 support in equal volume. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 8Zr-4Fe / CA-2.

[0053] Comparative Example 1

[0054] Compared with Example 1, the difference is that polystyrene microspheres were not added in Step 2 to obtain the support CA-5. The other conditions remained unchanged, and the catalyst 6Zr-2Fe / CA-5 was obtained.

[0055] Comparative Example 2

[0056] Compared with Example 2, the difference is that no promoter source was added in Step 4 to obtain the catalyst 6Zr / CA-2.

[0057] Comparative Examples 3-5

[0058] After the catalyst of Example 2 prepared above was used in the catalytic hydrogenation of levulinic acid to γ-valerolactone reaction, it was separated by centrifugation, and the obtained catalyst was continued to be used in the catalytic hydrogenation of levulinic acid to γ-valerolactone reaction. The catalyst was recycled 3 times, and the 1st, 2nd, and 3rd times were used as Comparative Examples 3-5 respectively.

[0059] The physical characterization data of the above CA-1 to CA-5 supports are shown in Table 1:

[0060] Table 1

[0061] vector CA-1 CA-2 CA-3 CA-4 CA-5 <![CDATA[S BET , m 2 / g]]> 312 364 304 340 258 <![CDATA[D mes ,nm]]> 8.3 9.5 9.6 9.4 9.7 <![CDATA[D mac ,nm]]> 130 156 260 162 /

[0062] It can be seen from Table 1 that the relatively ordered mesoporous-macroporous Co-Al composite oxide supports (CA-1, CA-2, CA-3, and CA-4) have relatively high specific surface areas and macropore diameters.

[0063] Comparative Example 6

[0064] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.42 g of Zr(NO 3 ) 2 ·5H 2 O and 0.17 g of tetrabutyl titanate was impregnated onto the CA-2 support in equal volume. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 6Zr-2Ti / CA-2.

[0065] Comparative Example 7

[0066] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.42 g of Zr(NO 3 ) 2 ·5H 2 O and 0.15 g of Ni(NO 3 ) 2 ·6H 2 O was impregnated onto the CA-2 support in an equal volume. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 6Zr-2Ni / CA-2.

[0067] Comparative Example 8

[0068] Compared with Example 2, the difference is that in Step 4, an aqueous solution containing 0.42 g of Zr(NO 3 ) 2 ·5H 2 O and 0.1 g of Ce(NO 3 ) 3 ·6H 2 O was impregnated onto the CA-2 support in an equal volume. After drying at 100 °C for 12 h, it was calcined at 500 °C for 4 h to obtain the catalyst 6Zr-2Ce / CA-2.

[0069] The catalytic performances of the catalysts obtained in the above examples and comparative examples are compared as shown in Table 2:

[0070] Table 2

[0071]

[0072]

[0073] Table 2 gives the data of levulinic acid conversion rate and γ-valerolactone yield (calculated by gas chromatography detection). According to the comparison, it can be seen that using an ordered mesoporous-macroporous Co-Al composite oxide support and doping with promoter metals can improve the conversion rate of levulinic acid, the yield of γ-valerolactone, and good stability.

[0074] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

Claims

1. A hydrogenation catalyst, characterized in that include: A carrier, wherein the carrier is a Co-Al composite oxide having an ordered mesoporous structure and a macroporous structure; The Zr and the auxiliary agent are loaded on the carrier, and the auxiliary agent is Fe, Sn, Si or W.

2. The hydrogenation catalyst according to claim 1, characterized in that The BET specific surface area of ​​the carrier is 200 m 2 / g~400m 2 / g; The mesopore diameter of the ordered mesoporous structure is 8nm to 10nm; The macropore diameter of the macroporous structure is 100nm to 300nm.

3. The hydrogenation catalyst according to claim 1, characterized in that Calculated on the basis of the mass of the carrier, the loading amount of the Zr is 5% to 12%, and the loading amount of the auxiliary agent is 1% to 5%.

4. The hydrogenation catalyst according to any one of claims 1 to 3, characterized in that The carrier is prepared by the following steps: S1) reacting the template F127, the cobalt source and the aluminum source in an ethanol solution of concentrated hydrochloric acid and citric acid at 30° C. to 60° C. for 12 h to 48 h to obtain a reaction solution; S2) adding polystyrene microspheres to the reaction solution obtained in step S1), volatilizing the solvent, heat-treating the solution at 100° C. to 150° C. for 24 h to 48 h, and then calcining the material obtained after the heat treatment to obtain a carrier.

5. The hydrogenation catalyst according to claim 4, characterized in that In step S1), the molar ratio of the template F127, concentrated hydrochloric acid, citric acid, ethanol, aluminum source and cobalt source is 1: (200-350): (6-14): (1400-3000): (30-80): (15-80); In step S2), the amount of the polystyrene microspheres used is 5wt% to 15wt% of the amount of the template F127 used in step S1).

6. The hydrogenation catalyst according to claim 4, characterized in that In step S2), the size of the polystyrene microspheres is 200nm to 400nm.

7. The method for preparing the hydrogenation catalyst according to any one of claims 1 to 6, characterized in that: The following steps are involved: The carrier is impregnated in a Zr source and an auxiliary agent source, and the impregnated carrier is calcined at 400° C. to 600° C. for 2 h to 8 h to obtain a hydrogenation catalyst.

8. The method for preparing a hydrogenation catalyst according to claim 7, characterized in that: The Zr source is selected from Zr nitrate; The auxiliary agent source is selected from Fe nitrate, Sn chloride, organic silicon compound or tungstate.

9. A method for preparing γ-valerolactone, characterized in that: The following steps are involved: Under the action of a hydrogenation catalyst, levulinic acid or levulinic ester is subjected to a hydrogenation reaction in hydrogen to obtain γ-valerolactone; The hydrogenation catalyst is the hydrogenation catalyst according to any one of claims 1 to 6 or the hydrogenation catalyst obtained by the preparation method according to claim 7 or 8.

10. The method for preparing γ-valerolactone according to claim 9, characterized in that: The mass amount of the hydrogenation catalyst is 2% to 6% of the mass amount of the levulinic acid or levulinic ester.

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