Supported catalyst and application thereof in catalyzing one-step hydrogenation synthesis of cyclohexylmethylamine from cyanobenzene or derivatives thereof

Abstract

The invention discloses a supported catalyst and application thereof in catalyzing one-step hydrogenation synthesis of cyclohexylmethylamine from cyanobenzene or derivatives thereof, the supported catalyst comprises a carrier and metal and an auxiliary agent which are loaded on the carrier, and the supported catalyst provided by the invention is used for catalyzing one-step hydrogenation synthesis of cyclohexylmethylamine from cyanobenzene. The conversion rate of cyanobenzene is 100%, the selection rate of cyclohexylmethylamine is as high as 99%, and no obvious inactivation phenomenon exists after the catalyst is used for 10 times.

Description

Technical Field

[0001] The invention belongs to the technical field of supported catalysts, and particularly relates to a supported catalyst and an application thereof in catalyzing one-step hydrogenation of benzonitrile or its derivatives to synthesize cyclohexylmethylamine. Background Art

[0002] Cyclohexylmethylamine (CAS: 3218-02-8) is a methylamine derivative with a cyclohexane substituent in its molecular structure. It is widely used in medicine, pesticides, coatings, epoxy resins, polyurethanes and their curing agents, construction adhesives and other fields, and its usage is increasing year by year.

[0003] At present, cyclohexylmethylamine mainly has the following synthesis methods:

[0004] (1) Preparation by reductive amination of cyclohexylcarboxaldehyde with ammonia under hydrogen conditions. Beller Matthis et al. from the Leibniz Institute for Catalysis in Germany reported that silica prepared by thermal cracking of a complex of nickel nitrate and tartaric acid was supported on a nickel nanocatalyst (Angew. Chem. Int. Ed. 2019, 58, 5064-5068). Cyclohexylcarboxaldehyde was reductively aminized to prepare cyclohexylmethylamine (yield = 91%) at 30 mg of nickel nanocatalyst (6 mol% Ni), 120 ° C, 2 MPa of hydrogen, 5-7 bar NH3, and 3 mL of tert-butanol.

[0005] (2) Cyclohexanecarbonitrile reduction to synthesize cyclohexylmethylamine. A Chinese patent (CN112851521A) discloses a method for preparing cyclohexylmethylamine by reduction of cyclohexyl with nanoporous palladium catalyst, using ammonia boron complex as a hydrogen source, reacting at 50°C for 12 hours to obtain cyclohexylmethylamine (yield 81%).

[0006] (3) Under hydrogenation conditions, benzonitrile is hydrogenated to cyclohexylmethylamine in one step. Japanese patent (JP6748634) discloses a Ru / polydimethylsilane-supported alumina catalyst, with hydrogen (<1MPa) as the hydrogen source, to achieve one-step hydrogenation of a mixture of benzonitrile and hydrochloric acid to obtain a mixture of benzylamine hydrochloride, dibenzylamine hydrochloride, tribenzylamine hydrochloride, and cyclohexylmethylamine hydrochloride (yield is 5%, and the molar ratio of benzylamine hydrochloride, dibenzylamine hydrochloride, tribenzylamine hydrochloride, and cyclohexylmethylamine hydrochloride is 41:19:27:13).

[0007] However, the above-mentioned cyclohexylmethylamine synthesis route has the problems of expensive and difficult-to-obtain raw materials (cyclohexylcarboxaldehyde, cyclohexanecarbonitrile), the use of expensive and low-atom-economy ammonia boroalkane as a hydrogen source, or poor selectivity of benzonitrile hydrogenation products, which increases the cost of cyclohexylmethyl synthesis. Therefore, for the purpose of industrial application, it is of great significance to develop a process route that uses cheap and easily available raw materials, hydrogen as a hydrogen source, and high product selectivity. Summary of the invention

[0008] The purpose of this section is to summarize some aspects of embodiments of the present invention and to briefly introduce some preferred embodiments.

[0009] The present invention provides a supported catalyst, wherein: the supported catalyst is composed of a carrier, a metal supported on the carrier and an auxiliary agent; the carrier is one or more of TS-1 molecular sieve, MCM-41 molecular sieve, HY molecular sieve, ZSM-5 molecular sieve, γ-Al2O3, TiO2 (anatase), CeO2; the metal is one or more of palladium, ruthenium, cobalt, nickel, copper; the auxiliary agent includes one or more of carbon, nitrogen, hydrogen. Preferably, the silicon-aluminum ratio of the ZSM-5 molecular sieve is (10-200):1, preferably (20-120):1, and more preferably (20-100):1.

[0010] Preferably, the specific surface area of ​​the supported catalyst is 200 to 2000 m 2 / g, preferably 200 to 1000 m 2 / g, more preferably 200 to 800 m 2 / g; the mass of the metal is 0.01 to 50wt% of the mass of the catalyst, preferably 0.1N40wt%, more preferably 0.1 to 20wt%; the mass of the additive is 0.01 to 50wt% of the mass of the catalyst, preferably 0.1 to 50wt%, more preferably 0.1 to 30wt%.

[0011] Preferably, the preparation method of the supported catalyst comprises the following steps: uniformly mixing a soluble metal salt, a carrier, an auxiliary agent and a solvent, then adding a reducing agent for reduction, removing the solvent, and drying to obtain the catalyst; the reducing agent comprises one or more of hydrogen, a hydrogen-argon mixed gas, a hydrogen-nitrogen mixed gas, sodium borohydride or potassium borohydride.

[0012] The soluble metal salt is one or more of nitrate, chloride, sulfate, acetylacetonate, ferrous acetate, etc.; the auxiliary agent is one or more of ammonia water, urea, o-phenanthroline, cyanamide, dicyandiamide or melamine; the solvent is one or a mixed solvent of deionized water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, tert-pentanol; the hydrogen reduction temperature is 250-800°C, preferably 250-600°C, more preferably 300-600°C; the reduction time is 0.1-12h, preferably 0.5-12h, more preferably 1-8h;.

[0013] The present invention also provides the use of the supported catalyst to catalyze the one-step hydrogenation of benzonitrile or its derivatives to synthesize cyclohexylmethylamine.

[0014] The specific steps are: adding the supported catalyst, benzonitrile, reaction aid and the like into a pressure autoclave in sequence, sealing the autoclave, and filling the autoclave with hydrogen to carry out a hydrogenation reaction.

[0015] The mass percentage of the supported catalyst and benzonitrile is: (0.001-0.5):1, preferably (0.01-0.5):1, more preferably (0.01-0.3):1;

[0016] The hydrogen is one or more of high-purity hydrogen, hydrogen-nitrogen mixed gas, hydrogen-argon mixed gas, and hydrogen-nitrogen-argon mixed gas;

[0017] The solvent is one or more of low-carbon alcohols, aromatic hydrocarbons, tetrahydrofuran, and dioxane; the low-carbon alcohol includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, and tert-pentanol; the aromatic hydrocarbon includes one or more of benzene, toluene, ethylbenzene, isopropylbenzene, and xylene.

[0018] The reaction aid is one or more of ammonia water, ammonia gas, liquid ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine; the concentration of the ammonia water is 25-28 wt%.

[0019] The pressure or partial pressure of the hydrogen is 0.1-10 MPa, preferably 0.1-6 MPa, more preferably 0.5-6 MPa;

[0020] The reaction temperature is 80-200°C, preferably 80-180°C, more preferably 100-180°C;

[0021] The reaction time is 0.1-24h, preferably 0.5-24h, more preferably 0.5-18h.

[0022] The benzonitrile derivatives include those shown in Formula-1 to Formula-8:

[0023]

[0024] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is independently one of hydrogen, a straight-chain alkyl group having 1 to 18 carbon atoms, an isomeric alkyl group having 1 to 18 carbon atoms, a phenyl group, a methoxy group, a phenoxy group, a nitro group, a trifluoromethyl group, a methyl group, a methanol group, fluorine, chlorine, bromine and iodine; and n is independently selected from a straight-chain alkane having 0 to 18 carbon atoms or an isomeric alkyl group having 0 to 18 carbon atoms.

[0025] Beneficial effects of the present invention: The supported catalyst provided by the present invention comprises a support and a metal and an auxiliary agent supported on the support. In the present invention, the supported catalyst realizes the hydrogenation of benzonitrile to synthesize cyclohexylmethylamine, and the molar yield of cyclohexylmethylamine is 90-99.99%, preferably 95-99.99%. The supported catalyst has the function of hydrogenating the benzene ring and the cyano bifunctional group, inhibiting the generation of some hydrogenation products (imines, benzylamine and cyclohexylcarbonitrile), the molar yield of benzylamine is 0.001-10%, preferably 0.001-5%, and the molar yield of cyclohexylcarbonitrile is 0-10%. , preferably 0-5%; at the same time, the supported catalytic system has the function of inhibiting the deamination of the product, inhibiting the occurrence of deamination byproducts (toluene, cyclohexylmethane) and deamination coupling byproducts (N, N-dicyclohexylmethylamine, N, N, N-tricyclohexylmethylamine), the molar yield of N, N-dicyclohexylmethylamine is 0.001-10%, preferably 0.001-5%, the molar yield of N, N, N-tricyclohexylmethylamine is 0-10%, preferably 0-5%. The supported catalyst provided by the present invention is used to catalyze the one-step hydrogenation of benzonitrile to synthesize cyclohexylmethylamine, the conversion rate of benzonitrile is 100%, the selectivity of cyclohexylmethylamine is as high as 99.99% or more, the catalyst is used 10 times, and there is no obvious deactivation phenomenon. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solution of the embodiment of the present invention, the following is a brief introduction to the drawings required for describing the embodiment, wherein:

[0027] Figure 1 This is the HR-TEM image of the Ru / ZSM-5 catalyst in the present invention.

[0028] Figure 2 It is a gas chromatogram of the hydrogenation reaction of benzonitrile catalyzed by Ru / ZSM-5 in the present invention. DETAILED DESCRIPTION

[0029] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with specific embodiments.

[0030] The reaction route of one-step hydrogenation of benzonitrile to cyclohexylmethylamine is as follows:

[0031]

[0032] Embodiment 1:

[0033] The preparation method of the supported catalyst Ru / TS-1 for synthesizing cyclohexylmethylamine by one-step hydrogenation of benzonitrile comprises the following steps:

[0034] Step 1: In an ice-water bath and under stirring conditions, add 3.81 g of tetraethyl silicate to 8.45 g of deionized water, and stir for 30 minutes. Subsequently, add 3.12 g of tetrapropylammonium hydroxide aqueous solution (40 wt%), and stir at 40° C. for 2 hours.

[0035] Step 2: 0.1 g of tetrabutyl titanate was dissolved in 1.0 g of isopropanol, and then added to the mixed solution obtained in step 1 at 5° C. and stirred vigorously until the mixed solution became clear.

[0036] Step 3: 0.45 g of hexadecyltrimethylammonium bromide was dissolved in 37.5 g of deionized water, and then added to the mixed solution obtained in step 2 at 5° C. and stirred vigorously for 6 hours.

[0037] Step 4: The white mixture obtained in step 3 was transferred to a polytetrafluoroethylene hydrothermal autoclave, 7.5 g of ethanol was added, and the mixture was hydrothermaled at 100° C. for 96 hours.

[0038] Step 5: Centrifuge to obtain a white solid, wash with deionized water and ethanol, and dry at 100°C overnight. Then, calcine at 550°C for 8 hours and cool naturally to room temperature to obtain TS-1 molecular sieve. The prepared TS-1 molecular sieve has a silicon-titanium ratio of 15.4:1 and a specific surface area of ​​304 m 2 / g.

[0039] Step 6: Add 500 mg of the TS-1 molecular sieve obtained above to 30 mL of deionized water, stir for 30 minutes, then add 1.96 mL of 5.1 mg / mL ruthenium precursor solution (RuCl3·H2O aqueous solution), stir at room temperature for 240 minutes, centrifuge, wash, and dry, and then use a hydrogen-argon mixed gas with a hydrogen molar concentration of 5% to reduce the catalyst, the hydrogen-argon mixed gas flow rate is 50 mL / min, the reduction temperature is 500°C, and the reduction time is 6 hours to obtain a Ru / TS-1 catalyst.

[0040] Embodiment 2:

[0041] The preparation method of the supported catalyst Ru / MCM-41 for one-step hydrogenation of benzonitrile to cyclohexylmethylamine comprises the following steps:

[0042] Step 1: Add 1.0 g of hexadecyltrimethylammonium bromide to 480 mL of deionized water at 80 °C and stir vigorously for 30 minutes.

[0043] Step 2: Subsequently, 3.5 mL of 2.0 mol / L sodium hydroxide solution was added to the above mixed solution, and after mixing evenly, 5.0 mL of tetraethyl silicate was added and stirred to form a white slurry.

[0044] Step 3: The white slurry obtained in step 2 was vigorously stirred at 80°C for 2h, filtered and washed with deionized water, and dried at 100°C overnight. Subsequently, the slurry was calcined at 500°C for 4h and naturally cooled to room temperature to obtain the MCM-41 molecular sieve. The specific surface area of ​​the prepared MCM-41 molecular sieve was 960m 2 / g.

[0045] Step 4: Add 500 mg of MCM-41 molecular sieve to 30 mL of deionized water, stir for 30 minutes, then add 1.96 mL of 5.1 mg / mL ruthenium precursor solution (RuCl3·H2O aqueous solution), stir at room temperature for 240 minutes, centrifuge, wash, and dry, then use a hydrogen-argon mixed gas with a hydrogen molar concentration of 5% to reduce the catalyst, the hydrogen-argon mixed gas flow rate is 50 mL / min, the reduction temperature is 500°C, and the reduction time is 6 h to obtain a Ru / MCM-41 catalyst.

[0046] Embodiment 3:

[0047] The preparation method of the supported catalyst Ru / HY for one-step hydrogenation of benzonitrile to cyclohexylmethylamine comprises the following steps:

[0048] 500 mg of HY molecular sieve (silicon to aluminum ratio of 40, specific surface area of ​​670 m 2 / g) was added into 30mL deionized water and stirred for 30 minutes, followed by the addition of 1.96mL 5.1mg / mL ruthenium precursor solution (RuCl3·H2O aqueous solution), and 4mL 6.8mg / mL sodium borohydride aqueous solution, and stirred in an ice bath for 30 minutes, centrifuged, washed, and dried to obtain a Ru / HY catalyst.

[0049] Embodiment 4:

[0050] The preparation method of the supported catalyst Ru / ZSM-5 (Si / Al=20:1) for one-step hydrogenation of benzonitrile to cyclohexylmethylamine comprises the following steps:

[0051] Step 1: In an ice-water bath and under stirring conditions, add 15 g of tetrabutyl silicate to 30 g of deionized water, and stir for 30 minutes. Subsequently, add 15 g of tetrapropylammonium hydroxide aqueous solution (40 wt%), and stir at 40° C. for 6 hours.

[0052] Step 2: Then, 350 mg of aluminum isopropoxide and 2.0 g of ammonium oxalate were added to the mixed solution obtained in step 1 and stirred vigorously for 2 h until the mixed solution became clear.

[0053] Step 3: The clarified mixture obtained in step 2 was transferred to a polytetrafluoroethylene hydrothermal reactor and hydroheated at 200°C for 72 hours.

[0054] Step 4: Centrifuge to obtain a white solid, wash with deionized water, and dry at 100°C overnight. Subsequently, calcine at 550°C for 4 hours and cool naturally to room temperature to obtain ZSM-5 molecular sieve. The prepared ZSM-5 molecular sieve has a silicon-aluminum ratio of 20:1 and a specific surface area of ​​381 m 2 / g.

[0055] Step 5: Add 500 mg of ZSM-5 (Si / Al=20:1) molecular sieve to 30 mL of deionized water, stir for 30 minutes, then add ruthenium precursor solution (1.96 mL of 5.1 mg / mL RuCl3·H2O aqueous solution), add 4 mL of 6.8 mg / mL sodium borohydride aqueous solution, stir for 30 minutes in an ice bath, centrifuge, wash, and dry to obtain a Ru / ZSM-5 catalyst.

[0056] Embodiment 5:

[0057] The preparation method of the supported catalyst Ru / ZSM-5 (Si / Al=40:1) for one-step hydrogenation of benzonitrile to cyclohexylmethylamine comprises the following steps:

[0058] 500 mg of the prepared ZSM-5 (Si / Al=40:1) molecular sieve was added to 30 mL of deionized water and stirred for 30 minutes. Subsequently, 1.96 mL of 5.1 mg / mL ruthenium precursor solution (RuCl3·H2O aqueous solution) was added and stirred at room temperature for 240 minutes. The mixture was centrifuged, washed, and dried. The catalyst was then reduced using a hydrogen-argon mixed gas with a hydrogen molar concentration of 5%. The hydrogen-argon mixed gas flow rate was 50 mL / min, the reduction temperature was 500°C, and the reduction time was 6 h.

[0059] Embodiment 6:

[0060] The preparation method of the supported catalyst Ru / γ-Al2O3 for one-step hydrogenation of benzonitrile to cyclohexylmethylamine comprises the following steps:

[0061] Add 500 mg of γ-Al2O3 (CAS: 1344-28-1) to 30 mL of deionized water and stir for 30 minutes. Then add 1.96 mL of 5.1 mg / mL ruthenium precursor solution (RuCl3·H2O aqueous solution), add 4 mL of 6.8 mg / mL sodium borohydride aqueous solution, stir in an ice bath for 30 minutes, centrifuge, wash, and dry to obtain a Ru / γ-Al2O3 catalyst.

[0062] Embodiment 7:

[0063] The preparation method of the supported catalyst Ru / TiO2 (anatase) for one-step hydrogenation of benzonitrile to cyclohexylmethylamine comprises the following steps:

[0064] Add 500 mg of TiO2 (anatase, CAS: 1317-70-0) to 30 mL of deionized water and stir for 30 minutes. Then add 1.96 mL of 5.1 mg / mL ruthenium precursor solution (RuCl3·H2O aqueous solution), add 4 mL of 6.8 mg / mL sodium borohydride aqueous solution, stir in an ice bath for 30 minutes, centrifuge, and wash to obtain a Ru / TiO2 (anatase) catalyst.

[0065] Embodiment 8:

[0066] The preparation method of the supported catalyst Ru / CeO2 for one-step hydrogenation of benzonitrile to cyclohexylmethylamine comprises the following steps:

[0067] Add 500 mg of CeO2 (20-50 nm spherical, CAS: 1306-38-3) to 30 mL of deionized water and stir for 30 minutes. Then add 1.96 mL of 5.1 mg / mL ruthenium precursor solution (RuCl3·H2O aqueous solution) and 4 mL of 6.8 mg / mL sodium borohydride aqueous solution. Stir in an ice bath for 30 minutes, centrifuge, wash, and dry to obtain a Ru / CeO2 catalyst.

[0068] Embodiment 9-16:

[0069] The supported catalyst prepared in Example 1-8 was used for one-step hydrogenation of benzonitrile to synthesize cyclohexylmethylamine, and the specific steps were as follows:

[0070] Benzonitrile, one of the supported catalysts obtained in Examples 1-8, an auxiliary agent (methylamine), and a solvent (toluene) were added into an autoclave, wherein the molar ratio of benzonitrile: supported catalyst: ammonia: toluene was 1:0.06:0.1:25. After the autoclave was sealed, 0.5 MPa argon was introduced for replacement three times, and then hydrogen was introduced to 2 MPa. The temperature was set at 120° C. and the reaction was carried out for 12 h. After the reaction was completed, the reaction was cooled to room temperature. The liquid product was collected by centrifugation.

[0071] The product distribution was analyzed by gas chromatography.

[0072] Table 1 Study on the hydrogenation performance of benzonitrile with different supported catalysts in Examples 9-16

[0073]

[0074]

[0075] As can be seen from Table 1, the invention has the highest conversion rate of benzonitrile and yield of cyclohexylmethylamine under the catalytic reaction of Ru / ZSM-5 (Si / Al=40:1).

[0076] Embodiment 17-20:

[0077] Using the supported catalyst Ru / ZSM-5 of Example 12 and the same other reaction conditions as Example 11, a one-step hydrogenation of benzonitrile to cyclohexylmethylamine was conducted at different temperatures. The results are listed in Table 2.

[0078] Table 2 Reaction conditions and reaction results of Examples 17 to 20

[0079] Example Reaction temperature Benzonitrile conversion rate (%) Cyclohexylmethylamine yield (%) 17 100 100 90 18 120 100 99.99 19 140 100 98 20 160 100 82

[0080] Embodiment 21-25:

[0081] Using the supported catalyst Ru / ZSM-5 of Example 12 and the same other reaction conditions as Example 11, different hydrogen pressures were examined to study the selective catalytic hydrogenation reaction of benzonitrile. The results are listed in Table 3.

[0082] Table 3 Reaction conditions and reaction results of Examples 21 to 254

[0083] Example Hydrogen pressure (MPa) Benzonitrile conversion rate (%) Cyclohexylmethylamine yield (%) 21 1 100 82 22 2 100 99.99 23 3 100 97 24 4 100 97 25 5 100 92

[0084] Embodiment 26-36:

[0085] Using the supported catalyst Ru / ZSM-5 of Example 12 and the same other reaction conditions as Example 12, different application times were examined to study the selective catalytic hydrogenation reaction of benzonitrile. The results are listed in Table 4.

[0086] Table 4 Reaction conditions and reaction results of Examples 26 to 35

[0087] Example Number of applications Benzonitrile conversion rate (%) Cyclohexylmethylamine yield (%) 26 1 100 99.99 27 2 100 99.99 28 3 100 99.99 29 4 100 99.99 30 5 100 99.9 31 6 100 99.9 32 7 100 99 33 8 100 99 34 9 100 98 35 10 100 96

[0088] As shown in Table 4, the supported catalyst provided by the invention is still not significantly deactivated after repeated cycles for 10 times, the conversion rate of benzonitrile in the 10th reaction can reach 100%, and the yield of cyclohexylmethylamine can reach 96%.

[0089] Embodiment 36-39:

[0090] Using the supported catalyst Ru / ZSM-5 of Example 12 and the same other reaction conditions as Example 12, different substrates were examined to study the selective catalytic hydrogenation reaction of organic nitriles. The results are listed in Table 5.

[0091] Table 5 Universality study of supported catalyst Ru / ZSM-5

[0092]

[0093] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A supported catalyst, characterized in that: The supported catalyst is composed of a carrier, a metal supported on the carrier and an auxiliary agent; the carrier is one or more of TS-1 molecular sieve, MCM-41 molecular sieve, HY molecular sieve, ZSM-5 molecular sieve, γ-Al2O3, TiO2 (anatase), CeO2, wherein the silicon-aluminum ratio of the ZSM-5 molecular sieve is (10-200): 1; the metal is one or more of palladium, ruthenium, cobalt, nickel, and copper; the auxiliary agent includes one or more of carbon, nitrogen, and hydrogen elements.

2. The supported catalyst according to claim 1, characterized in that: The specific surface area of ​​the supported catalyst is 200 to 2000 m 2 / g; the mass of the metal is 0.01-50wt% of the mass of the catalyst; the mass of the auxiliary agent is 0.01-50wt% of the mass of the catalyst.

3. The supported catalyst according to claim 1 or 2, characterized in that: The preparation method of the supported catalyst comprises the following steps: uniformly mixing a soluble metal salt, a carrier, an auxiliary agent precursor and a solvent, then adding a reducing agent for reduction, removing the solvent and drying to obtain a supported catalyst; The soluble metal salt is one or more of nitrate, chloride, sulfate, acetylacetonate, ferrous acetate, etc.; the auxiliary agent precursor is one or more of ammonia water, urea, o-phenanthroline, cyanamide, dicyandiamide or melamine; the solvent is one or a mixed solvent of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, tert-pentanol; the mass of the soluble metal salt is 0.02-80wt% of the mass of the carrier; the mass of the auxiliary agent is 0.01-80wt% of the mass of the carrier; The reducing agent includes one or more of hydrogen, hydrogen-argon mixed gas, hydrogen-nitrogen mixed gas, sodium borohydride or potassium borohydride; when the reducing agent is one or more of hydrogen, hydrogen-argon mixed gas, hydrogen-nitrogen mixed gas, the reduction temperature is 250-800° C.; when the reducing agent is one or more of sodium borohydride or potassium borohydride, the reduction temperature is 0-80° C.; and the reduction time is 0.1-12 hours.

4. The use of the supported catalyst according to claim 1 to catalyze the one-step hydrogenation of benzonitrile or its derivatives to synthesize cyclohexylmethylamine, wherein the molar yield of cyclohexylmethylamine is 90-99.99%, the molar yield of benzylamine is 0.001-10%, the molar yield of cyclohexylcarbonitrile is 0-10%, the molar yield of N,N-dicyclohexylmethylamine is 0.001-10%, and the molar yield of N,N,N-tricyclohexylmethylamine is 0-10%.

5. The use according to claim 4, characterized in that: Add benzonitrile, the supported catalyst, the reaction aid and the solvent into a pressure autoclave in sequence, fill with hydrogen, and carry out a hydrogenation reaction; wherein the mass ratio of benzonitrile: supported catalyst: reaction aid: solvent is: 1: (0.001-0.5): (0.01-50): (0.1-100).

6. The use according to claim 5, characterized in that: The reaction aid is one or more of ammonia water, ammonia gas, liquid ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine; the concentration of the ammonia water is 25-28 wt%.

7. The use according to claim 5, characterized in that: The hydrogen is charged, wherein the hydrogen pressure is 0.1-10MPa; the hydrogenation reaction time is 0.1-24h; and the hydrogenation reaction temperature is 80-200°C.

8. The use according to claim 5 or 6, characterized in that: The solvent is one or more of low-carbon alcohols, aromatic hydrocarbons, tetrahydrofuran, and dioxane.

9. The use according to claim 8, characterized in that: The low-carbon alcohol includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, and tert-pentanol; the aromatic hydrocarbon includes one or more of benzene, toluene, ethylbenzene, isopropylbenzene, and xylene.

10. The use according to claim 4, characterized in that: The benzonitrile derivatives include those shown in Formula-1 to Formula-8: R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is independently one of hydrogen, a straight-chain alkyl group having 1 to 18 carbon atoms, an isomeric alkyl group having 1 to 18 carbon atoms, a phenyl group, a methoxy group, a phenoxy group, a nitro group, a trifluoromethyl group, a methyl group, a methanol group, fluorine, chlorine, bromine and iodine; and n is independently selected from a straight-chain alkane having 0 to 18 carbon atoms or an isomeric alkyl group having 0 to 18 carbon atoms.

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