A method for the hydrogenation amination of aldehydes, ketones to primary amine chemicals using a platinum group single atom doped nickel-based layered hydroxide catalyst

Abstract

The application discloses a method for preparing primary amine chemicals by hydrogenation amination of aldehyde and ketone through a platinum group single-atom doped nickel-based layered hydroxide catalyst, and belongs to the technical field of heterogeneous catalysis for preparing high-quality chemicals. The method uses aldehyde and ketone chemicals as raw materials, ammonia gas as a gas source, and under the action of the platinum group single-atom doped nickel-based layered hydroxide catalyst, hydrogenation amination reaction is carried out in a reaction solvent under a hydrogen atmosphere to prepare primary amine chemicals; the platinum group single atom is any one of palladium, platinum, ruthenium, iridium or rhodium; wherein the effective active components on the nickel-based layered hydroxide carrier are composed of nickel metal and other metals, and the other metals are one or more of zinc, magnesium, aluminum, cerium, manganese, zirconium, iron, niobium or copper. The primary amine chemicals prepared by the method have very high economic value.

Description

Technical Field

[0001] This invention belongs to the field of heterogeneous catalysis for preparing high-quality chemicals, specifically relating to a method for preparing primary amine chemicals by hydrogenating aldehydes and ketones using a platinum group single-atom doped nickel-based layered hydroxide catalyst. Background Technology

[0002] Primary amines, especially bio-based primary amine chemicals, are a crucial class of chemical intermediates, and their efficient synthesis is essential for achieving the aforementioned high-value goals. The reactive amino functional groups in primary amine molecules make them core building blocks for the preparation of agrochemicals, pharmaceuticals, surfactants, and high-performance polymers. Bio-based materials, in particular, represent a significant achievement of the integration and innovation of biotechnology and the chemical industry, and the coupled development of biochemical and traditional chemical processes, helping to reduce the petrochemical industry's dependence on fossil fuels. Utilizing the structural characteristics of biomass itself, non-traditional polymeric building blocks and scaffolds can be constructed to produce novel bio-based sustainable materials with novel structures and diverse application functions. In this context, biomass-derived aromatic primary amines (such as monocyclic or polycyclic diamines), due to their rigid structure, produce polymers with higher thermomechanical properties than flexible long-chain aliphatic amines, making them key monomers for the preparation of high-performance bio-based materials such as specialty engineering plastics and epoxy resin curing agents. Therefore, developing an efficient and highly selective catalytic route for the preparation of primary amines from biomass platform molecules (such as aldehydes and ketones) has enormous industrial demand and application prospects.

[0003] Non-precious metal catalysts are less expensive than precious metal catalysts and have shown excellent activity in reported hydrogenation amination reactions. Among transition metals, nickel (Ni) has the lowest cost and strong activation ability for H2 / NH3, and is currently considered the most promising active metal for catalyzing the hydrogenation amination of biomass feedstocks to produce high-value-added chemicals. However, traditional nickel-based catalysts often face problems such as low primary amine selectivity and easy over-alkylation to generate secondary or tertiary amines in the hydrogenation amination reactions of aldehydes, ketones, and ammonia. Therefore, developing a novel nickel-based catalyst capable of precisely controlling the reaction pathway and efficiently and selectively synthesizing primary amines has become a core challenge driving the development of this technology. Summary of the Invention

[0004] One technical problem solved by this invention is to provide a method for preparing primary amine chemicals by hydrogenating aldehydes and ketones using a platinum group single-atom doped nickel-based hydroxide catalyst. The method uses noble metals and single-atom doped modified nickel-based hydroxide catalyst to achieve the preparation of high-value primary amine chemicals from a series of aldehydes and ketones. The modification of the nickel-based hydroxide catalyst with a small amount of noble metal can effectively regulate the interaction with the nickel-based active metal, thereby improving the hydrogenation and amination activity of the catalyst.

[0005] Technical Solution: To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A method for preparing primary amine chemicals by hydrogenating aldehydes and ketones with a platinum group single-atom doped nickel-based layered hydroxide catalyst, using aldehydes and ketones as raw materials and ammonia as a gas source, and carrying out the hydrogenation amination reaction in a reaction solvent under the action of a platinum group single-atom doped nickel-based layered hydroxide catalyst and a hydrogen atmosphere to obtain primary amine chemicals.

[0007] The platinum group monoatoms are any one of palladium, platinum, ruthenium, iridium, or rhodium; wherein the effective active ingredient on the nickel-based layered hydroxide carrier is composed of nickel metal and other metals, and the other metals are one or more of zinc, magnesium, aluminum, cerium, manganese, zirconium, iron, niobium, or copper.

[0008] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones with a platinum group single-atom doped nickel-based layered hydroxide catalyst, wherein the catalyst is any one of Pt / NiZn-LDH, Pt / NiMg-LDH, Pt / NiCe-LDH, Pt / NiAl-LDH, Pt / NiNb-LDH, Pt / NiMn-LDH, Pt / NiZr-LDH, Pt / NiFe-LDH, Pd / NiZn-LDH, Rh / NiZn-LDH, Ru / NiZn-LDH, or Ir / NiZn-LDH; the content of noble metal platinum group single atoms in the catalyst is 0.2 wt% to 2.0 wt%, preferably 0.2 wt%; the mass ratio of the aldehyde / ketone chemical to the catalyst is 2:1 to 10:1; preferably 3:1 to 5:1; more preferably 10:3.

[0009] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones using a platinum group monoatom-doped nickel-based layered hydroxide catalyst, wherein the aldehyde or ketone chemical is furfural, 5-hydroxymethylfurfural, 1-octanal, 3-methylcyclohexanone, benzaldehyde, phenylacetaldehyde, acetophenone, p-phenylenedialdehyde, p-propylcyclohexanone, p-fluorobenzaldehyde, p-methoxybenzaldehyde, p-methylsulfonylbenzaldehyde, p-methylbenzaldehyde, p-chlorobenzaldehyde, p-nitrobenzaldehyde, p-bromobenzaldehyde, diphenylacetone, cyclohexanone, cyclopentanone, 6-undecanetone, salicylaldehyde, or vanillin. Any one of the above-mentioned aldehydes and ketones; the primary amines obtained after the above-mentioned hydrogenation amination reaction are furfurylamine, 5-hydroxymethylfurfurylamine, 1-octylamine, 3-methyl-cyclohexylamine, benzylamine, phenethylamine, 2-phenylethylamine, p-phenylenediamine, p-propylcyclohexylamine, p-fluoroanisylamine, p-methoxyanisylamine, p-methylsulfonylanisylamine, p-methylanisylamine, p-chloroanisylamine, p-nitroanisylamine, p-bromoanisylamine, diphenylpropylamine, cyclohexylamine, cyclopentylamine, 6-undecylamine, salicylamine, and vanillylamine; as shown in Table 1;

[0010] Table 1. Aldehyde and ketone chemical substrates and their corresponding primary amine products

[0011]

[0012]

[0013]

[0014] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones with platinum group monoatom-doped nickel-based layered hydroxide catalysts, wherein the reaction solvent is any one or a mixture of several of methanol, isopropanol, toluene, 1,4-dioxane, tetrahydrofuran, or tert-amyl alcohol; there are no special requirements for the amount of reaction solvent, as long as the raw materials are evenly dispersed; preferably, the reaction solvent is isopropanol.

[0015] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones with a platinum group monoatom-doped nickel-based layered hydroxide catalyst includes the following steps: during the hydrogenation amination reaction, the pressure of ammonia is 0.2~1.0 MPa, the pressure of hydrogen is 0.5~3.0 MPa, the reaction temperature is 80~200 °C, and the reaction time is 1.0~10.0 h; preferably, the pressure of ammonia is 0.7 MPa, the pressure of hydrogen is 1.0~3.0 MPa, the reaction temperature is 120~200 °C, and the reaction time is 1.0~2.0 h; more preferably, the pressure of ammonia is 0.7 MPa, the pressure of hydrogen is 1.0 MPa, the reaction temperature is 120 °C, and the reaction time is 1.0 h.

[0016] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones using the platinum group monoatom-doped nickel-based hydroxide catalyst, specifically involves the following steps: dissolving a nickel precursor and a metal chloride salt in water and stirring until homogeneous; then adding a noble metal salt precursor and dissolving it in the same way; adjusting the pH to 8.5-10 by adding sodium hydroxide solution, stirring for 8-24 h, and then washing with water and ethanol; finally, vacuum drying to obtain catalyst powder.

[0017] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones with a platinum group monoatom-doped nickel-based layered hydroxide catalyst includes the following: the nickel precursor is nickel chloride hexahydrate or nickel chloride; the metal chloride is any one or a mixture of several of magnesium chloride, aluminum chloride, zirconium chloride, manganese chloride, zinc chloride, copper chloride, ferric chloride, niobium chloride, or their chloride hydrates; the noble metal salt precursor is any one of palladium chloride, rhodium chloride, platinum chloride, iridium chloride, or ruthenium chloride; the mass ratio of nickel precursor to metal chloride is 1.0:1 to 3.0:1; when calculating the mass ratio, if nickel chloride is used as the calculation standard for the nickel precursor, then the chloride standard is also used for other metal salts; if nickel chloride hydrate is used as the calculation standard for the nickel precursor, then chloride hydrate is also used as the calculation standard for other metal salts.

[0018] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones with platinum group single-atom doped nickel-based layered hydroxide catalyst includes stirring at room temperature for 2-8 h; vacuum drying at 60-80 ℃ for 4-12 h; preferably, stirring for 2 h and vacuum drying at 80 ℃ for 4 h.

[0019] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones using a platinum group monoatom-doped nickel-based layered hydroxide catalyst requires the catalyst to undergo reduction treatment before use. Specifically, the platinum group monoatom-doped nickel-based layered hydroxide catalyst is reduced at 200-300°C in a hydrogen atmosphere for 2-4 h with a hydrogen flow rate of 50-80 mL / min; preferably, reduction is performed at 200°C for 3 h with a hydrogen flow rate of 50 mL / min.

[0020] The method for preparing primary amine chemicals by hydrogenating aldehydes and ketones with a platinum group single-atom doped nickel-based layered hydroxide catalyst includes the following steps:

[0021] (1) Dissolve nickel chloride and metal chloride salt in deionized water and stir until the solution is homogeneous. Then add noble metal salt precursor and stir at room temperature for 2 h. Adjust the pH to 8.5 with sodium hydroxide solution, then wash with water and ethanol 4-5 times. After washing, vacuum dry at 80 ℃ for 4 h to obtain catalyst powder. The catalyst is any one of Pt / NiZn-LDH, Pt / NiMg-LDH, Pt / NiCe-LDH, Pt / NiAl-LDH, Pt / NiNb-LDH, Pt / NiMn-LDH, Pt / NiZr-LDH, Pt / NiFe-LDH, Pd / NiZn-LDH, Rh / NiZn-LDH, Ru / NiZn-LDH or Ir / NiZn-LDH. The content of noble metal platinum group monoatoms in the catalyst is 0.2 wt%.

[0022] (2) The obtained catalyst powder was reduced at 200 °C for 3 h with a hydrogen flow rate of 50 mL / min to obtain the reduced catalyst;

[0023] (3) Dissolve 0.1 g of the aldehyde or ketone chemical and 0.03 g of the reduced catalyst from step (2) in 10 mL of reaction solvent, then add them to a reaction vessel and carry out a hydrogenation amination reaction to obtain a primary amine chemical; the aldehyde or ketone chemical is any one of furfural, 5-hydroxymethylfurfural, 1-octanal, 3-methyl-cyclohexanone, benzaldehyde, phenylacetaldehyde, acetophenone, p-phenylenedialdehyde, p-propylcyclohexanone, p-fluorobenzaldehyde, p-methoxybenzaldehyde, p-methylsulfonylbenzaldehyde, p-methylbenzaldehyde, p-chlorobenzaldehyde, p-nitrobenzaldehyde, p-bromobenzaldehyde, diphenylacetone, cyclohexanone, cyclopentanone, 6-undecanetone, salicylaldehyde, or vanillin; the primary amination obtained after the above aldehyde or ketone chemical undergoes the hydrogenation amination reaction is... The chemicals are furfurylamine, 5-hydroxymethylfurfurylamine, 1-octylamine, 3-methyl-cyclohexylamine, benzylamine, phenethylamine, 2-phenylethylamine, p-phenylenediamine, p-propylcyclohexylamine, p-fluorobenzylamine, p-methoxybenzylamine, p-methylsulfonylbenzylamine, p-methylbenzylamine, p-chlorobenzylamine, p-nitrobenzylamine, p-bromobenzylamine, diphenylpropylamine, cyclohexylamine, cyclopentylamine, 6-undecylamine, salicylamine, and vanillylamine; the reaction solvent is any one or a mixture of several of methanol, isopropanol, toluene, 1,4-dioxane, tetrahydrofuran, or tert-amyl alcohol; the hydrogenation amination reaction process is carried out at an ammonia pressure of 0.7 MPa, a hydrogen pressure of 1.0~3.0 MPa, a reaction temperature of 120~200 °C, and a reaction time of 1.0~2.0 h.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0025] (1) This invention successfully doped platinum group single atoms onto nickel-based layered hydroxide catalysts by doping with platinum group single atoms through a simple “co-precipitation” process to obtain hydrogenation amination catalysts.

[0026] (2) The synergistic effect of platinum group single-atom metals and nickel-based layered hydroxide supports can greatly enhance the interaction between the support and single atoms. When applied to the catalytic hydrogenation and amination of aldehydes and ketones to prepare primary amine platform compounds, the catalyst has high conversion efficiency and has broad application potential as a key component of pharmaceuticals, agrochemicals, polyamides and other fine chemicals. Attached Figure Description

[0027] Figure 1 Here is an HR-TEM image of the catalyst Pt / NiZn-LDH;

[0028] Figure 2 XRD patterns of catalysts Rh / NiZn-LDH, Pt / NiZn-LDH, and NiZn-LDH;

[0029] Figure 3The image shows the GC-MS chromatograms of furfural and furfuralamine in test group 8 of Example 2. Detailed Implementation

[0030] The present invention will be further illustrated below with reference to specific embodiments. These embodiments are implemented based on the technical solutions of the present invention, and it should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0031] In this embodiment of the invention, both substrate conversion and product selectivity were detected using gas chromatography-mass spectrometry (GC-MS) under the same detection conditions: column: HP-5MS (30 m × 0.25 mm × 0.25 μm); carrier gas: high-purity helium (99.999%); flow rate: 1.5 mL / min; splitless injection; the GC-MS (Agilent 7890B GC / 5977MS) temperature program was set as follows: injection temperature 250 °C, initial column temperature 50 °C held for 1 min, ramped up to 280 °C at 20 °C / min, held for 4 min. Electron ionization (EI=70Ev) mass spectra were recorded in the range of 35–700 m / z in full scan mode. The detected compounds were identified based on the NIST database.

[0032] Example 1

[0033] The preparation of platinum group single-atom doped nickel-based layered hydroxide catalysts is as follows:

[0034] (1) Dissolve 5.09 g of nickel chloride hexahydrate and 0.974 g of zinc chloride in 20 mL of deionized water and stir until the solution is mixed evenly. Then add 0.012 g of platinum tetrachloride and stir at room temperature for 2 h. Then adjust the pH to 8.5 with sodium hydroxide solution and wash with water and ethanol 4 times. After washing, vacuum dry at 80 °C for 4 h to obtain catalyst powder.

[0035] (2) The obtained catalyst powder was reduced at 200 °C for 3 h with a hydrogen flow rate of 50 mL / min to obtain the catalyst Pt / NiZn-LDH.

[0036] Using the above method, catalysts Pt / NiMg-LDH, Pt / NiCe-LDH, Pt / NiAl-LDH, Pt / NiNb-LDH, Pt / NiMn-LDH, Pt / NiZr-LDH, Pt / NiFe-LDH, Pd / NiZn-LDH, Rh / NiZn-LDH, Ru / NiZn-LDH, and Ir / NiZn-LDH were prepared by modifying the metal chloride and noble metal salt precursors. In all of these catalysts, the nickel precursor and metal chloride are chlorides of the corresponding metals, and the noble metal content is 0.2 wt%.

[0037] The reduced catalyst was tested, and the HR-TEM image of the reduced Pt / NiZn-LDH catalyst is shown below. Figure 1 As shown, the synchrotron radiation diagrams of the reduced catalysts Rh / NiZn-LDH, Pt / NiZn-LDH, and NiZn-LDH are as follows: Figure 2 As shown, from Figure 1 and Figure 2 It can be seen that the Pt single atoms are uniformly dispersed on the nickel-based hydroxide support, indicating that the catalyst synthesis was successful.

[0038] Example 2

[0039] 0.1 g of furfural and 0.03 g of the catalyst prepared in Example 1 were dissolved in 10 mL of reaction solvent and then added to a stainless steel reactor for hydrogenation amination reaction to obtain furfurylamine. The conversion efficiency and furfurylamine yield obtained under different reaction conditions are shown in Table 2. Figure 3 The GC-MS chromatograms for furfural and furfuralamine in test group 8 are shown below. Figure 3 It is known that coupling products exist in the reaction products, but the yield of furfurylamine is very high, indicating that the method of the present invention can obtain primary amine chemicals with high selectivity.

[0040] .

[0041] Table 2. Reaction efficiency results for the preparation of furfural-based furfural by hydrogenation amination.

[0042]

[0043] Example 3

[0044] 0.1 g of aldehydes and ketones and 0.03 g of the catalyst Pt / NiZn-LDH prepared in Example 1 were dissolved in 10 mL of isopropanol, and then added to a stainless steel reactor. The mixture was subjected to hydrogenation amination for 1 h to obtain various primary amine products. The conversion efficiency and yield are shown in Table 3. The aldehydes and ketones in Table 3 were obtained commercially.

[0045] In Table 3, the reaction conditions for group 5 were 180 ℃, 0.7 MPa NH3, 2.0 MPa H2, 1 h; for group 10, 180 ℃, 0.7 MPa NH3, 1.0 MPa H2, 1 h; for group 16, 150 ℃, 0.7 MPa NH3, 3.0 MPa H2, 2 h; for group 18, 120 ℃, 0.7 MPa NH3, 1.0 MPa H2, 2 h; for group 19, 200 ℃, 0.7 MPa NH3, 1.0 MPa H2, 1 h; and for the other groups, 120 ℃, 0.7 MPa NH3, 1.0 MPa H2, 1 h.

[0046] Table 3. Results of the efficiency of the hydrogenation amination reaction of aldehydes and ketones in series 3.

[0047]

[0048]

[0049]

[0050] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A process for the hydrogenation amination of aldehydes, ketones to primary amines chemicals using a platinum group single atom doped nickel based layered hydroxide catalyst characterized in that, The primary amine chemical is prepared by hydrogenation amination reaction of aldehyde and ketone chemicals as raw materials, ammonia gas as gas source, under the action of Pt / NiZn-LDH catalyst, in a reaction solvent under hydrogen atmosphere; the content of platinum in the catalyst is 0.2 wt%-2.0 wt%; The preparation method of the catalyst is as follows: dissolving a nickel precursor and a metal chloride salt in water and stirring to mix uniformly; then adding a noble metal salt precursor and dissolving; Then, the pH is adjusted to 8.5-10 by adding sodium hydroxide solution, and stirring for 8-24 h, and then washing with water and ethanol; finally, vacuum drying to obtain catalyst powder; the nickel precursor is nickel chloride hexahydrate or nickel chloride, the metal chloride salt is zinc chloride, and the noble metal salt precursor is platinum chloride; The catalyst needs to be reduced before use, specifically: the catalyst is reduced at 200-300 ℃ under hydrogen atmosphere for 2-4 h; the hydrogen flow rate is 50-80 mL / min.

2. The method of claim 1, wherein, The mass ratio of the aldehyde and ketone chemicals to the catalyst is 2:1-10:

1.

3. The method of claim 1, wherein, The aldehyde and ketone chemicals are any one of furfural, 5-hydroxymethylfurfural, 1-octanal, 3-methyl-cyclohexanone, benzaldehyde, phenylacetaldehyde, acetophenone, p-benzaldehyde, p-propylcyclohexanone, p-fluorobenzaldehyde, p-methoxybenzaldehyde, p-methylsulfonylbenzaldehyde, p-methylbenzaldehyde, p-chlorobenzaldehyde, p-nitrobenzaldehyde, p-bromobenzaldehyde, diphenylpropyl ketone, cyclohexanone, cyclopentanone, 6-undecanone, salicylaldehyde or vanillin; the primary amine chemicals obtained after the hydrogenation amination reaction of the above aldehyde and ketone chemicals are furfurylamine, 5-hydroxymethylfurfurylamine, 1-octylamine, 3-methyl-cyclohexylamine, benzylamine, phenethylamine, 2-phenethylamine, p-xylene diamine, p-propylcyclohexylamine, p-fluorobenzylamine, p-methoxybenzylamine, p-methylsulfonylbenzylamine, p-methylbenzylamine, p-chlorobenzylamine, p-nitrobenzylamine, p-bromobenzylamine, diphenylpropylamine, cyclohexylamine, cyclopentylamine, 6-undecylamine, salicylamine and vanillylamine.

4. The method of claim 1, wherein, The reaction solvent is any one of methanol, isopropanol, toluene, 1,4-dioxane, tetrahydrofuran or tertiary amyl alcohol or a mixture of several thereof.

5. The method of claim 1, wherein, In the hydrogenation amination reaction process, the pressure of ammonia gas is 0.2-1.0 MPa, the pressure of hydrogen gas is 0.5-3.0 MPa, the reaction temperature is 80-200 ℃, and the reaction time is 1.0-10.0 h.

6. The method of claim 1, wherein, The mass ratio of the nickel precursor to the metal chloride salt is 1.0:1-3.0:

1.

7. The method of claim 1, wherein, The stirring and mixing during catalyst preparation are carried out at room temperature, and the stirring time is 2-8 h; the vacuum drying temperature is 60-80 ℃, and the time is 4-12 h.

8. The method of claim 1, wherein, The method comprises the following steps: (1) dissolving nickel chloride and zinc chloride in deionized water, stirring until the solution is uniformly mixed, then adding platinum chloride, stirring at room temperature for 2 h, then adjusting the pH to 8.5 with sodium hydroxide solution, and then washing with water and ethanol for 4-5 times, and then vacuum drying at 80 ℃ for 4 h to obtain catalyst powder; the catalyst is Pt / NiZn-LDH; the content of platinum in the catalyst is 0.2 wt%; (2) The obtained catalyst powder is reduced at 200 ℃ for 3 h with a hydrogen flow rate of 50 mL / min to obtain a reduced catalyst; (3) 0.1 g of an aldehyde or ketone chemical and 0.03 g of the reduced catalyst in step (2) are dissolved in 10 mL of a reaction solvent, and then added into a reaction container to perform a hydroaminomerization reaction to obtain a primary amine chemical; the aldehyde or ketone chemical is any one of furfural, 5-hydroxymethylfurfural, 1-octanal, 3-methyl-cyclohexanone, benzaldehyde, phenylacetaldehyde, acetophenone, p-xylylformaldehyde, p-propylcyclohexanone, p-fluorobenzaldehyde, p-methoxybenzaldehyde, p-methylsulfonylbenzaldehyde, p-methylbenzaldehyde, p-chlorobenzaldehyde, p-nitrobenzaldehyde, p-bromobenzaldehyde, benzophone, cyclohexanone, cyclopentanone, 6-undecanone, salicylaldehyde or vanillin; the primary amine chemical obtained after the hydroaminomerization reaction of the above aldehyde or ketone chemical is furfurylamine, 5-hydroxymethylfurfurylamine, 1-octylamine, 3-methyl-cyclohexylamine, benzylamine, phenethylamine, 2-phenethylamine, p-xylylamine, p-propylcyclohexylamine, p-fluorobenzylamine, p-methoxybenzylamine, p-methylsulfonylbenzylamine, p-methylbenzylamine, p-chlorobenzylamine, p-nitrobenzylamine, p-bromobenzylamine, benzophone, cyclohexylamine, cyclopentylamine, 6-undecylamine, salicylamine and vanillylamine, respectively; the reaction solvent is any one or a mixture of two or more of methanol, isopropanol, toluene, 1,4-dioxane, tetrahydrofuran or t-amyl alcohol; the hydroaminomerization reaction is performed at an ammonia pressure of 0.7 MPa, a hydrogen pressure of 1.0-3.0 MPa, a reaction temperature of 120-200 ℃ and a reaction time of 1.0-2.0 h.

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