Supported catalyst, process for its preparation and use thereof

Abstract

The application provides a supported catalyst and a preparation method and application thereof, the supported catalyst comprising a carrier and an active component, the active component comprising Pd, and the carrier being MIL-101(13%Cr) modified by a nitrogen heterocyclic compound; and the nitrogen heterocyclic compound being a nitrogen heterocyclic ligand.The application has the beneficial effect that the supported catalyst has a unique crystal structure and a unified reaction microenvironment, and is used in the preparation of benzyl alcohol from benzaldehyde by hydrogenation, so that the utilization rate of active sites of the catalyst is high, the catalytic efficiency is high, and the selectivity of benzyl alcohol is high.

Description

Technical Field

[0001] This invention belongs to the field of metal-supported catalyst preparation technology, specifically a supported catalyst, its preparation method, and its application. Background Technology

[0002] Benzyl alcohol, also known as benzyl alcohol, is one of the simplest aromatic alcohols. As a solvent, plasticizer, and preservative, benzyl alcohol is widely used in the fragrance, soap, pharmaceutical, and dye industries. Furthermore, in recent years, its application in the pharmaceutical, consumer electronics, additive materials, and home decoration industries has been increasing, driving the rapid development of my country's benzyl alcohol industry, with both production and sales volumes growing.

[0003] Currently, the main methods for preparing benzyl alcohol include benzyl chloride hydrolysis, toluene oxidation, and benzaldehyde liquid-phase hydrogenation. Benzyl chloride hydrolysis is the primary industrial method both domestically and internationally, and can be further divided into batch and continuous methods. The batch method has a lower conversion rate, while the continuous method requires harsh reaction conditions. Toluene oxidation has a low conversion rate and produces many byproducts. Liquid-phase hydrogenation of benzaldehyde to benzyl alcohol is a simple production process with mild reaction conditions and is environmentally friendly. Supported palladium catalysts have high conversion rates and are relatively ideal hydrogenation catalysts; however, due to the influence of the support surface properties, they are prone to secondary reactions that generate toluene and phenethyl ether byproducts. Improving the selectivity of benzyl alcohol at high conversion rates is a key issue that needs to be addressed in this reaction system. Summary of the Invention

[0004] To address the aforementioned issues, this application provides a catalyst, its preparation method, and its application that can improve the product selectivity of benzaldehyde liquid-phase hydrogenation to benzyl alcohol at high conversion rates.

[0005] In a first aspect, the present invention provides a supported catalyst comprising a support and an active component, wherein the active component comprises Pd, and the support is MIL-101 (13% Cr) modified with a nitrogen heterocyclic compound.

[0006] MIL-101 (13% Cr) modified with nitrogen heterocyclic compounds in the catalyst can be obtained by the following methods:

[0007] Method 1: Before impregnating palladium, modify MIL-101 (13% Cr) with a nitrogen heterocyclic compound to obtain nitrogen heterocyclic compound-modified MIL-101 (13% Cr), and then use the nitrogen heterocyclic compound-modified MIL-101 (13% Cr) to impregnate palladium and other subsequent steps.

[0008] Method 2: Add a nitrogen heterocyclic compound to the palladium impregnation solution. When MIL-101 (13% Cr) comes into contact with the palladium impregnation solution, the nitrogen heterocyclic compound in the impregnation solution coordinates with MIL-101 (13% Cr) to form nitrogen heterocyclic compound modified MIL-101 (13% Cr).

[0009] According to some embodiments of the catalyst described in this application, based on the total mass of the catalyst, the mass percentage of Pd is 0.1%-10% (e.g., 0.1%, 0.2%, 0.5%, 1.0%, 1.2%, 1.5%, 2%, 2.5%, 2.8%, 3.0%, 3.2%, 3.6%, 3.8%, 5%, 5.5%, 6.2%, 7.0%, 7.6%, 8.0%, 8.2%, 9%, 10%), preferably 0.1%-5%, more preferably 0.2%-2%, more preferably 0.3%-1.5%, and most preferably 0.5%-1%.

[0010] According to some embodiments of the catalyst described in this application, the nitrogen heterocyclic compound is at least one of pyridine, imidazole, and 4,4'-bipyridine.

[0011] A second aspect of the present invention provides a method for preparing a Pd@MIL-101 catalyst, comprising the following steps:

[0012] (1) Preparation of palladium gel solution:

[0013] A palladium-containing compound, an organic acid, anionic surfactant, nitrogen heterocyclic compound, and water are mixed to obtain a palladium colloid solution.

[0014] (2) The palladium gel solution and the activated MIL-101 (13% Cr) were brought into contact, and after aging and reduction treatment, the reduction product was separated into solid and liquid and dried to obtain the supported catalyst.

[0015] According to some embodiments of the preparation method described in this application, in step (1), the pH value of the palladium solution is 4.0-7.0 (e.g., pH value 4.2, pH value 5.2, pH value 6.1, pH value 7.0), preferably 4.0-6.0.

[0016] According to some embodiments of the preparation method described in this application, the palladium-containing compound is one or more of palladium sulfate, palladium chloroacetic acid, or palladium phosphate.

[0017] According to some embodiments of the preparation method described in this application, the organic acid is at least one of tartaric acid, glacial acetic acid, and citric acid.

[0018] According to some embodiments of the preparation method described in this application, the anionic surfactant is potassium salt of dodecyl polyoxyethylene ether phosphate or sodium hexadecylbenzenesulfonate.

[0019] According to some embodiments of the preparation method described in this application, the nitrogen heterocyclic compound is at least one of pyridine, imidazole, and 4,4'-bipyridine.

[0020] According to some embodiments of the preparation method described in this application, the weight ratio of the palladium-containing compound, organic acid, nitrogen heterocyclic compound, anionic surfactant, and water is 0.0015-0.15:0.005-0.02:0.005-0.02:0.001-0.01, preferably 0.0050-0.10:0.008-0.012:0.010-0.015:0.005-0.008.

[0021] According to some embodiments of the preparation method described in this application, in step (1), the pH of the palladium solution is adjusted by using a sodium carbonate solution with a mass percentage of 5%-15% (e.g., 5%, 8%, 10%, 12%, 15%), preferably 8%-12%.

[0022] According to some embodiments of the preparation method described in this application, in step (2), the method of activating MIL-101 (13% Cr) is as follows: MIL-101 (13% Cr) is washed with replacement solution and solution, solid-liquid separation and drying are performed to obtain activated MIL-101 (13% Cr).

[0023] According to some embodiments of the preparation method described in this application, the replacement solution is one of N,N'-dimethylformamide and N,N'-dimethylacetamide.

[0024] According to some embodiments of the preparation method described in this application, the solution is a mixture of acetone and ethanol.

[0025] According to some embodiments of the preparation method described in this application, the drying is one of high-temperature vacuum drying or inert atmosphere drying. Preferably, the high-temperature vacuum drying temperature is 120℃-200℃ (e.g., 120℃, 130℃, 150℃, 160℃, 180℃, 200℃), and the vacuum degree is 0.5-0.9 bar.

[0026] According to some embodiments of the preparation method described in this application, the drying is performed under a nitrogen atmosphere.

[0027] According to some embodiments of the preparation method described in this application, in step (2), the mass ratio of the palladium solution to the activated MIL-101 (13% Cr) is 10:1-7 (e.g., 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7), preferably 10:3-6.

[0028] According to some embodiments of the preparation method described in this application, the aging is: aging at 15-30℃ (e.g., 15℃, 18℃, 20℃, 25℃, 28℃, 30℃) for 20-30h (e.g., 20h, 22h, 25h, 28h, 30h).

[0029] According to some embodiments of the preparation method described in this application, the reducing agent used in the reduction is selected from one or more of sodium oxalate solution, sodium sulfite solution, sodium formate solution, formic acid solution, and sodium nitrite solution.

[0030] According to some embodiments of the preparation method described in this application, the reducing agent is a sodium formate solution with a mass fraction of 5-10%.

[0031] According to some embodiments of the preparation method described in this application, the mass ratio of the amount of reducing agent added to the activated MIL-101 (13% Cr) is 0.5-2:1 (e.g., 0.5:1, 0.8:1, 1:1, 1.5:1, 2:1), preferably 0.8-1.5:1.

[0032] According to some embodiments of the preparation method described in this application, the reduction reaction conditions are as follows: reduction treatment for 30-90 min (e.g., 30 min, 40 min, 45 min, 50 min, 55 min, 76 min, 80 min, 85 min, 88 min, 90 min, 100 °C, 105 °C, 110 °C, 112 °C, 120 °C, 125 °C, 128 °C, 130 °C, 135 °C, 136 °C, 138 °C, 140 °C, 150 °C) at 50-150 °C (e.g., 50 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 80 min, 90 min).

[0033] According to some embodiments of the preparation method described in this application, the drying is performed by drying at a temperature of 100-200°C for 10-30 hours.

[0034] A third aspect of the present invention provides the application of the catalyst described in the first aspect of the present invention or the catalyst obtained by the preparation method described in the second aspect of the present invention in the hydrogenation of benzaldehyde to benzyl alcohol.

[0035] In a fourth aspect, the present invention provides a method for preparing benzyl alcohol by hydrogenation of benzaldehyde, wherein benzaldehyde is hydrogenated with hydrogen in the presence of the catalyst described in the first aspect of the present invention or the catalyst obtained by the preparation method described in the second aspect of the present invention to obtain benzyl alcohol.

[0036] According to some embodiments of the method for preparing benzyl alcohol by hydrogenation of benzaldehyde according to the present invention, the solvent for the hydrogenation reaction is ethanol, isopropanol or n-butanol, preferably ethanol.

[0037] According to some embodiments of the method for preparing benzyl alcohol by hydrogenation of benzaldehyde according to the present invention, the temperature of the hydrogenation reaction is 20-100℃ (e.g., 20℃, 30℃, 35℃, 38℃, 40℃, 45℃, 50℃, 55℃, 58℃, 60℃, 65℃, 68℃, 70℃, 75℃, 78℃, 80℃, 85℃, 90℃, 95℃, 100℃).

[0038] According to some embodiments of the method for preparing benzyl alcohol by hydrogenation of benzaldehyde according to the present invention, the pressure of the hydrogenation reaction is 0.1-1.0 MPa (0.1 MPa, 0.2 MPa, 0.3 MPa, 0.6 MPa, 0.8 MPa, 0.9 MPa, 1 MPa).

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows: the supported catalyst of the present invention has a unique crystalline structure and a uniform reaction microenvironment. When used in the hydrogenation of benzaldehyde to prepare benzyl alcohol, the catalyst has high utilization of active sites, high catalytic efficiency, and high selectivity for benzyl alcohol. Attached Figure Description

[0040] Figure 1 The image shows the microstructure of the 1% Pd@MIL-101 (13% Cr) catalyst synthesized in Example 2.

[0041] Figure 2 The PXRD pattern of the 1% Pd@MIL-101 (13% Cr) catalyst synthesized in Example 2 is shown. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention in any way. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concepts of this disclosure. Such structures and techniques have also been described in many publications.

[0043] The synthesis of the carrier MIL-101 (13% Cr) was based on the preparation method described in the literature Férey, G.; Melott-Draznieks, C.; Serre, C., et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area[J]. Science, 2005, 309:2040-2042. MIL-101 (13% Cr) is a crystalline porous material with three-dimensional channels and good thermal and chemical stability.

[0044] Solution washing and drying activation method for MIL-101 (13% Cr): Add 5 equivalents of DMF to MIL-101 (13% Cr), stir at 80°C for 4 hours, and filter to collect the solid. Wash with a mixture of ethanol and acetone at 70°C for 4 hours, filter to collect the solid, and dry at 120°C for 24 hours to obtain activated MIL-101 (13% Cr).

[0045] Catalyst activity evaluation conditions:

[0046] Samples were loaded into the autoclave and evaluated.

[0047] Catalyst dosage: The amount of catalyst to be added is determined by adding 1 mg of palladium;

[0048] Reactant benzaldehyde: 10.00g;

[0049] Solvent: Ethanol, 100.00g;

[0050] Hydrogen pressure: 0.5 MPa;

[0051] Reaction temperature: 50℃;

[0052] Samples were taken 1 hour later and analyzed by gas chromatography.

[0053]

[0054]

[0055] The present invention will be further illustrated below through examples.

[0056] Example 1

[0057] Weigh 20g of dried and activated MIL-101 (13% Cr). Weigh 0.5g of chloropalladium acid aqueous solution (palladium mass fraction 20%), add 5.0g of deionized water, then add 0.05g of tartaric acid, 0.05g of glacial acetic acid, 0.10g of pyridine, 0.02g of potassium dodecyl polyoxyethylene ether phosphate, and 0.10g of citric acid. Adjust the pH to 5.1 with 10% sodium carbonate solution, and add deionized water to a final volume of 14.0g to obtain palladium gel solution.

[0058] Palladium colloid solution was sprayed into the activated MIL-101 (13% Cr) support in a rotary kiln. After thorough impregnation, the solid was placed in a beaker and aged at room temperature for 24 hours. Then, 200 g of 2% sodium formate aqueous solution was added, and reduction was carried out at 100°C for 1 hour. After washing, filtration, and drying at 150°C, the catalyst product 0.5% Pd@MIL-101 (13% Cr) was obtained.

[0059] Example 2

[0060] In Example 1, the amount of chloropalladium acid aqueous solution (palladium mass fraction 20%) added was changed to 1g, while other conditions remained unchanged, to synthesize the catalyst product 1% Pd@MIL-101 (13% Cr).

[0061] Example 3

[0062] In Example 1, the amount of chloropalladium acid aqueous solution (palladium mass fraction 20%) added was changed to 2g, while other conditions remained unchanged, to synthesize the catalyst product 2% Pd@MIL-101 (13% Cr).

[0063] Example 4

[0064] In Example 1, the amount of chloropalladium acid aqueous solution (palladium mass fraction 20%) added was changed to 4g, while other conditions remained unchanged, to synthesize the catalyst product 4% Pd@MIL-101 (13% Cr).

[0065] Example 5

[0066] In Example 1, the amount of chloropalladium acid aqueous solution (palladium mass fraction 20%) added was changed to 5g, while other conditions remained unchanged, to synthesize the catalyst product 5% Pd@MIL-101 (13% Cr).

[0067] Comparative Example 1

[0068] Weigh 20g of activated carbon for later use. Weigh 1.0g of chloropalladium acid aqueous solution (palladium mass fraction 20%), add 5g of deionized water, then add 0.05g of tartaric acid, 0.05g of glacial acetic acid, 0.02g of potassium dodecyl polyoxyethylene ether phosphate, and 0.10g of citric acid. Adjust the pH to 5.1 with 10% sodium carbonate solution, and add deionized water to a final volume of 10.0g to obtain palladium gel solution. Spray the palladium gel solution into the activated carbon carrier in a rotary kiln, and after thorough impregnation, place the solid in a beaker and age at room temperature for 24h. Add 200g of 2% sodium formate aqueous solution and reduce at 100℃ for 1h. Wash, filter, and dry at 150℃ to obtain the catalyst product 1% Pd@Carbon.

[0069] Comparative Example 2

[0070] According to the literature Chui, SS, et al., A chemically functionalizable nanoporous material. Science, 1999, 283(5405): p.1148-50, a metal-organic framework Cu3(BTC)2(H2O)3 (also known as HKUST-1) was synthesized, with a Cu content of 19 wt%.

[0071] Weigh 20g of HKUST-1. Weigh 1.0g of chloropalladium acid aqueous solution (palladium mass fraction 20%), add 4.0g of deionized water, then add 0.05g of tartaric acid, 0.05g of glacial acetic acid, 0.02g of potassium dodecyl polyoxyethylene ether phosphate, and 0.10g of citric acid. Adjust the pH to 5.1 with 10% sodium carbonate solution, and add deionized water to a final volume of 6.6g to obtain a palladium gel solution. Spray the palladium gel solution into the HKUST-1 support in a rotary kiln. After thorough impregnation, place the solid in a beaker and age at room temperature for 24h. Add 200g of 2% sodium formate aqueous solution and reduce at 100℃ for 1h. Wash, filter, and dry at 150℃ to obtain the catalyst product 1% Pd@HKUST-1 (19% Cu).

[0072] Comparative Example 3

[0073] According to the literature Cavka, JH; Jakobsen, S.; Olsbye, U., et al. A new zirconium-organic building brick forming metal-organic frameworks with exceptional stability[J]. J. Am. Chem. Soc., 2008, 130: 13850-13851, a metal-organic framework Zr24O120C192H96 (also known as UIO-66) was synthesized, with a Zr content of 33 wt%.

[0074] The metal-organic framework support in the above (Comparative Example 2) was replaced with UIO-66, and the catalyst was synthesized as 1% Pd@UIO-66 (33% Zr).

[0075] Comparative Example 4

[0076] According to the literature Cavka, JH; Jakobsen, S.; Olsbye, U., et al. A new zirconium-organic building brick forming metal-organic frameworks with exceptional stability[J]. J. Am. Chem. Soc., 2008, 130: 13850-13851, a metal-organic framework C84H8O32Zr6 (also known as UIO-67) was synthesized, with a Zr content of 23 wt%.

[0077] The metal-organic framework support in the above (Comparative Example 2) was replaced with UIO-67, and the catalyst was synthesized as 1% Pd@UIO-67 (23% Zr).

[0078] Comparative Example 5

[0079] According to the literature Férey, G.; Serre, C.; Melott-Draznieks, C., et al. A hybrid solid with giant pores prepared by a combination of targeted chemistry, simulation, and powder diffraction[J]. Angew. Chem. Int. Ed., 2004, 43: 6296-6301, a metal-organic framework Cr3F(H2O)3O[C6H3-(CO2)3]2.28H2O (also known as MIL-100(Cr)) was synthesized, with a Cr content of 17 wt%.

[0080] The metal-organic framework support in the above (Comparative Example 2) was replaced with MIL-100 (Cr), and the catalyst was synthesized as 1% Pd@MIL-100 (17% Cr).

[0081] Comparative Example 6

[0082] Weigh 20g of dried and activated MIL-101 (13% Cr). Weigh 1.0g of chloropalladium acid aqueous solution (palladium mass fraction 20%), add 5.0g of deionized water, then add 0.05g of tartaric acid, 0.05g of glacial acetic acid, 0.02g of potassium dodecyl polyoxyethylene ether phosphate, and 0.10g of citric acid. Adjust the pH to 5.1 with 10% sodium carbonate solution, and add deionized water to a final volume of 14.0g to obtain palladium gel solution.

[0083] Palladium colloid solution was sprayed into the activated MIL-101 (13% Cr) support in a rotary kiln. After thorough impregnation, the solid was placed in a beaker and aged at room temperature for 24 hours. Then, 200 g of 2% sodium formate aqueous solution was added, and reduction was carried out at 100°C for 1 hour. After washing, filtration, and drying at 150°C, the catalyst product 1% Pd@MIL-101 (13% Cr)-Pyridine free was obtained.

[0084] The content of catalyst metal element components in each embodiment and comparative example, as well as the evaluation results of benzaldehyde hydrogenation under the above-mentioned activity evaluation conditions, are shown in Table 1.

[0085] Table 1

[0086] Example 1 0.5％ 13％Cr 99.1％ 99.3％ Example 2 1％ 13％Cr 99.9％ 99.8％ Example 3 2％ 13％Cr 92.3％ 95.3％ Example 4 4％ 13％Cr 85.7％ 96.0％ Example 5 5％ 13％Cr 74.9％ 91.2％ Comparative Example 1 1％ / 31.2％ 51.3％ Comparative Example 2 1％ 19% Cu 51.8％ 63.1％ Comparative Example 3 1％ 33％Zr 37.4％ 57.2％ Comparative Example 4 1％ 23％Zr 43.2％ 52.9％ Comparative Example 5 1％ 17％Cr 55.3％ 48.3％ Comparative Example 6 1％ 13％Cr 25.6％ 51.8％

[0087] As can be seen from Table 1, the supported palladium catalysts prepared in the various embodiments and comparative examples of the present invention, using MIL-101 (13% Cr) as a support and impregnated and reduced by an equal volume of palladium solution, have a unique pore structure and high utilization rate of metal active sites, which can significantly improve the conversion rate of benzaldehyde and the selectivity of the product benzyl alcohol. Among them, the 1% Pd@MIL-101 (13% Cr) catalyst with a palladium mass percentage of 1% in Example 2 has the best conversion rate and selectivity.

[0088] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a supported catalyst, comprising the following steps: (1) A palladium-containing compound, an organic acid, an anionic surfactant, a nitrogen heterocyclic compound, and water are mixed to obtain a palladium gel solution; (2) The palladium gel solution and the activated MIL-101(Cr) phase are brought into contact, aged, and reduced. The reduction product is then separated into solid and liquid phases and dried to obtain a supported catalyst. The Cr content in the MIL-101(Cr) is 13 wt%. The organic acid is at least one of tartaric acid, glacial acetic acid, and citric acid; The anionic surfactant is potassium salt of dodecyl polyoxyethylene ether phosphate or sodium hexadecylbenzene sulfonate. The nitrogen heterocyclic compound is at least one of pyridine, imidazole, and 4,4'-bipyridine; In step (2), the mass ratio of the palladium solution to the activated MIL-101(Cr) is 10:1-7.

2. The preparation method according to claim 1, characterized in that, In step (1), the pH value of the palladium solution is 4.0-7.

0.

3. The preparation method according to claim 1, characterized in that, In step (1), the pH value of the palladium solution is 4-6.

4. The preparation method according to claim 1, characterized in that, In step (1), the palladium-containing compound is one or more of palladium sulfate, palladium chloroacetic acid, or palladium phosphate.

5. The preparation method according to claim 2, characterized in that, In step (1), the pH of the palladium colloid solution is adjusted using a sodium carbonate solution with a mass percentage of 5%-15%.

6. The preparation method according to claim 2, characterized in that, In step (1), the pH of the palladium colloid solution is adjusted using a sodium carbonate solution with a mass percentage of 8%-12%.

7. The preparation method according to claim 1, characterized in that, In step (2), the method for activating MIL-101(Cr) is as follows: MIL-101(Cr) is washed with replacement solution and solution, solid-liquid separation and drying are performed to obtain activated MIL-101(Cr); And / or, the solution is a mixture of acetone and ethanol; And / or, the drying is one of high-temperature vacuum drying or inert atmosphere drying.

8. The preparation method according to claim 7, characterized in that, The replacement solution is one of N,N'-dimethylformamide and N,N'-dimethylacetamide.

9. The preparation method according to claim 7, characterized in that, The high-temperature vacuum drying temperature is 120℃-200℃, and the vacuum degree is 0.5-0.9 bar.

10. The preparation method according to claim 7, characterized in that, The inert atmosphere drying is nitrogen atmosphere drying.

11. The preparation method according to claim 1, characterized in that, In step (2), the aging process is: aging at 15-30℃ for 20-30 hours; And / or, the reducing agent used in the reduction is selected from one or more of sodium oxalate solution, sodium sulfite solution, sodium formate solution, formic acid solution, and sodium nitrite solution; And / or, the reduction reaction conditions are: reduction treatment at 50-150℃ for 30-90 min; And / or, the drying is performed by drying at a temperature of 100-200°C for 10-30 hours.

12. The preparation method according to claim 1, characterized in that, In step (2), the mass ratio of the palladium solution to the activated MIL-101(Cr) is 10:3-6.

13. The preparation method according to claim 11, characterized in that, The reducing agent is a 5-10% sodium formate solution.

14. The preparation method according to claim 11, characterized in that, The mass ratio of the reducing agent added to the activated MIL-101(Cr) is 0.5-2:

1.

15. The preparation method according to claim 11, characterized in that, The mass ratio of the reducing agent to the activated MIL-101(Cr) is 0.8-1.5:

1.

16. The use of the catalyst obtained by the preparation method according to any one of claims 1-15 in the hydrogenation of benzaldehyde to prepare benzyl alcohol.

17. A method for preparing benzyl alcohol by hydrogenation of benzaldehyde, wherein benzaldehyde is reacted with hydrogen in the presence of a catalyst obtained by the preparation method according to any one of claims 1-15 to obtain benzyl alcohol; And / or, the temperature of the hydrogenation reaction is 20-100°C; And / or, the pressure of the hydrogenation reaction is 0.1-1.0 MPa.

18. The method according to claim 17, characterized in that, The solvent for the hydrogenation reaction is ethanol, isopropanol, or n-butanol.

19. The method according to claim 17, characterized in that, The solvent for the hydrogenation reaction is ethanol.

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