Preparation method and application of catalyst for efficiently catalyzing reaction of alcohol and organic amine

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a method for carrying out alcohol amination reaction by taking alcohol and amine as raw materials and a catalyst used in the method. The invention provides a preparation method of a catalyst for alcohol ammonification reaction, which comprises the following steps: taking fluorine-doped silicon dioxide as a catalyst carrier, and loading metal active components to be activated, the metal active components being copper, nickel, cobalt and zinc. The invention also provides a method for efficiently catalyzing the reaction of alcohol and organic amine, which comprises the following steps: activating a catalyst to be activated, mixing the alcohol and amine to be reacted to serve as a raw material to enter the gasification chamber for gasification, and enabling the gasified raw material to enter the fixed bed reactor for reaction. By adopting the catalyst provided by the invention, the alcohol amination reaction efficiency can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to a method for carrying out alcohol amination reaction using alcohol and amine as raw materials and a catalyst used therefor. Background Art

[0002] The alcohol amination reaction, using alcohols and organic amines as raw materials, is an important method for preparing nitrogen-containing fine chemicals. This method has high atom utilization efficiency and produces only water as a byproduct, making it a green chemical synthesis process.

[0003] Alcohol amination reactions typically require the presence of a catalyst, and the development of efficient catalysts is a research priority both domestically and internationally. For example, Patent CN201410809140.3 reports a γ-Al2O3-supported catalyst containing copper, nickel, zinc, and chromium as metal active components for the reaction of 2-methylimidazole and methanol to synthesize 1,2-dimethylimidazole. Patent CN201310047433.8 reports the use of ammonium metatungstate-pillared hydrotalcite as a catalyst for the reaction of methanol and imidazole to produce 1-methylimidazole. Patent CN201910461880.5 reports the use of Brønsted acids such as hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid to catalyze the reaction of 4-nitroimidazole with methanol or deuterated methanol to produce 1-methyl-5-nitroimidazole or 1-trideuteriomethyl-5-nitroimidazole. Patent CN201410722806.1 reports the use of chlorinated, brominated, or iodinated hydrocarbons corresponding to the alcohol substrate as catalysts for the reaction of alcohols and amines. In addition, there are reports on RuCl3 catalyzing the reaction of methanol and primary amines (ChemCatChem 2021, 13, 1722–1729), bimetallic nano-CuCo catalyzing the reaction of methanol and aniline (Green Chem., 2022, 24, 5965), and TiO2-loaded copper and molybdenum photocatalyzing the reaction of alcohols and secondary amines (Catal. Sci. Technol., 2015, 5, 3226–3234).

[0004] The above-mentioned literature focuses on the active sites of metal or acid catalysts and promotes the reaction by reducing the activation energy of the reaction.

[0005] In addition to catalysts, improving the reaction process is also a research focus for alcohol amination reactions. Given the characteristic of producing water as a byproduct during the reaction, developing a reaction process that promptly removes water can also promote the reaction. For example, a Dean–Stark apparatus has been introduced into the reactor of the liquid-phase alcohol amination reaction to distill off the water produced by the reaction (Angew. Chem. Int. Ed. 2019, 58, 10528–10536); and powdered molecular sieves have been added to the alcohol amination reaction to absorb the water produced by the reaction (US6423871B1; Chem. Eur. J. 2016, 22, 12316–12320).

[0006] In summary, catalyst development and reaction process improvement are the two main means to improve the conversion rate of alcohol amination reaction. Although both methods have made significant progress in alcohol amination reaction, the realization of alcohol amination reaction has reached a bottleneck, and new methods to improve the efficiency of alcohol amination reaction are urgently needed. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a preparation and application of a catalyst for efficiently catalyzing the reaction of alcohol and organic amine.

[0008] In order to solve the above technical problems, the present invention provides a method for preparing a catalyst for alcohol amination reaction (a catalyst that efficiently catalyzes the reaction of alcohol and organic amine): fluorine-doped silicon dioxide is used as a catalyst carrier to load the metal active component to be activated, wherein the metal active component is copper, nickel, cobalt, and zinc.

[0009] The improvement of the preparation method of the catalyst for alcohol amination reaction of the present invention comprises the following steps:

[0010] 1) Add tetraethoxysilane (TEOS) and fluorosilane to the solvent at room temperature, slowly add deionized water (addition time is 50 to 70 minutes) under stirring, and then use acid (HNO3) to adjust the pH to 2 to 4 to obtain a sol;

[0011] The mass ratio of tetraethoxysilane to fluorosilane is 2 to 6:1 (preferably 2.5 to 5:1);

[0012] Deionized water: solvent = 1: (15 ± 5) volume ratio;

[0013] Tetraethoxysilane (TEOS): solvent = 1g: (15±5)ml material-liquid ratio;

[0014] 2) Stirring at room temperature (preferably at 25-30°C for 2-4 hours) to allow the sol to gradually form a gel; then aging the gel at room temperature for 24-36 hours, and drying (to remove the solvent) to obtain a xerogel;

[0015] Disperse the dry gel in deionized water to prepare a slurry with a solid content of 20-40% (to maintain fluidity and achieve pumpability, preferably 30-40%);

[0016] Solid content = weight ratio of xerogel / (xerogel + deionized water);

[0017] 3) spray drying the slurry obtained in step 2) to form fluorine-doped porous silica microspheres;

[0018] 4) Dissolving the modified silane in a solvent to obtain a modified silane solution with a concentration of 1 to 3 M;

[0019] The fluorine-doped porous silica microspheres obtained in step 3) are immersed in the modified silane solution for 3 to 5 hours (after the immersion, it is necessary to ensure that the fluorine-doped porous silica microspheres are still immersed in the modified silane solution), and then taken out, dried, and then calcined at 350±20° C. for 2±0.2 hours. The calcined product (fluorine-doped porous silica microspheres are formed after calcination) is used as a catalyst support;

[0020] 5) dissolving a mixed metal salt consisting of a soluble copper salt, a soluble nickel salt, a soluble cobalt salt and a soluble zinc salt in deionized water according to a molar ratio of soluble copper salt: soluble nickel salt: soluble cobalt salt: soluble zinc salt = 0.8-1.2: 0.2-0.4: 0.1-0.3: 0.1-0.3 (preferably 0.8-1: 0.3-0.4: 0.1-0.2: 0.15-0.3), and controlling the total concentration of metal ions in the mixed metal salt to be 0.2-1 M (preferably 0.5-1.0 M); and then adding urea to obtain a metal precursor solution;

[0021] Urea: metal salt = 2±0.1:1 mass ratio;

[0022] 6) Immersing the catalyst support in the metal precursor solution, stirring after ultrasonic dispersion (about 8 to 24 hours) until the metal precursor solution is completely absorbed by the catalyst support; obtaining the impregnated catalyst support;

[0023] 7) The impregnated catalyst carrier is dried first, and then calcined in an inert atmosphere (including N2) at 300-500°C for 3-6 hours to obtain a catalyst loaded with the metal active component to be activated (granular, referred to as: activated catalyst).

[0024] As a further improvement to the preparation method of the catalyst for alcohol amination reaction of the present invention: the fluorosilane in step 1) is 4-fluorophenyltriethoxysilane, trifluoropropyltrimethoxysilane, or perfluorooctylethyltrichlorosilane.

[0025] As a further improvement to the method for preparing the catalyst for alcohol amination reaction of the present invention: the modified silane in step 4) is methyltriethoxysilane, octadecyltriethoxysilane, or phenyltriethoxysilane.

[0026] As a further improvement of the method for preparing the catalyst for alcohol amination reaction of the present invention: in the step 5):

[0027] The soluble copper salt is: Cu(NO3)2·3H2O, the soluble nickel salt is: Ni(NO3)2·6H2O, the soluble cobalt salt is: Co(NO3)2·6H2O, and the soluble zinc salt is: Zn(NO3)2·6H2O.

[0028] As a further improvement of the preparation method of the catalyst for alcohol amination reaction of the present invention: in the step 6), the solid-liquid ratio of the catalyst support: metal precursor solution = 1g:5-15ml (preferably 1g:8-10ml), and ultrasonic dispersion is carried out for 30-60min;

[0029] The drying in step 2) is as follows: drying at 60-80° C. for 12-24 hours (to remove the solvent);

[0030] In the spray drying step 3), the air inlet temperature is controlled at 160-180°C, the air outlet temperature is controlled at 90-100°C, the nozzle diameter is 0.7-2 mm, and the nozzle pressure of the spray drying is 0.15-0.3 MPa;

[0031] The drying step 4) is as follows: drying at 120±20°C for 1 to 2 hours;

[0032] The drying in step 7) is performed at 60-120° C. for 12-24 hours.

[0033] As a further improvement to the method for preparing the catalyst for alcohol amination reaction of the present invention: the solvent is ethanol.

[0034] The present invention also provides a method for efficiently catalyzing the reaction of alcohols and organic amines: using the catalyst to be activated (catalyst loaded with a metal active component to be activated) prepared by any of the above methods, the method comprises the following steps:

[0035] 1) The activated catalyst particles are ground (to a mesh size of 25-45 mesh) and loaded into a fixed bed reactor (quartz sand inert filler is laid on the bottom of the bed and the top of the catalyst) and activated using H2 to serve as a catalyst layer;

[0036] After activation is completed, an inert gas (N2 or Ar, etc.) is introduced to flush the fixed bed reactor, and the fixed bed reactor is set to a reaction temperature (200-400°C, preferably 250-300°C) and a reaction pressure (0.1-3 MPa);

[0037] 2) The alcohol and amine to be reacted are mixed in a molar ratio of 1.1 to 1.3:1 and then enter the gasification chamber as raw materials for gasification. The gasified raw materials enter the fixed bed reactor and react at a temperature of 200 to 400° C. (preferably 250 to 300° C.) and a reaction pressure of 0.1 to 3 MPa. The residence time of the gasified raw materials in the catalyst layer is 10 to 30 minutes.

[0038] The reaction product was cooled in a condenser (20°C) to form a liquid phase, which was separated by distillation to obtain the product;

[0039] The alcohol is The amine is

[0040] As an improvement of the method for efficiently catalyzing the reaction of alcohol and organic amine of the present application:

[0041] R1, R3 is substituted heteroaryl or substituted alkyl;

[0042] The substituted heteroaryl is furan, thiophene, pyridine, morpholine, piperidine, pyrrolidine, and the substituted alkyl is alkyl with carbon chain length and branch substitution;

[0043] The R2 is hydrogen.

[0044] As a further improvement of the method for efficiently catalyzing the reaction of alcohol and organic amine of the present application:

[0045] When the catalyst is activated, first, inert gas (N2 or Ar, etc.) is purged (20-40 minutes), then the fixed bed reactor is heated to 300±30℃, and H2 / N2 mixed gas with H2 content of 4-6% (volume%) is introduced, so as to carry out the reduction activation of the catalyst, until no water is produced, and the flow rate of H2 / N2 mixed gas is about 1.5-2.5 times the volume of the volume of the catalyst to be activated per min.

[0046] The inner diameter of the fixed bed reactor is 10-20mm, and the effective volume of the catalyst layer (catalyst bed) is 25-100mL.

[0047] The reaction equation of the present application is as follows:

[0048]

[0049] Wherein R1, R3 can be various functional groups substituted on 2-, 3- or 4-phenyl or various substituted heteroaryl such as substituted furan, substituted thiophene, substituted pyridine, substituted morpholine, substituted piperidine, substituted pyrrolidine, etc. or various alkyl with carbon chain length and branch substitution; R2 is hydrogen or the same as or different from R3.

[0050] The catalyst of the present application uses the fluorine-doped silicon dioxide solid specially provided in the present application as the carrier, and simultaneously loads active components of metals such as copper, nickel, cobalt and zinc. It is found in the actual use process of the present application that the catalyst surface has hydrophobicity, and the water molecules generated in the reaction are repelled, so as to avoid covering the active sites of the catalyst and promote the forward progress of the reaction, thereby improving the efficiency of the alcohol amine reaction. The present application no longer needs to add molecular sieves for water removal during the reaction operation, thereby simplifying the reaction operation process.

[0051] The present application uses non-noble metals such as copper, nickel, cobalt and zinc as active metal catalysts, which can achieve good reaction effect.

[0052] The method of the present invention has the characteristics of low catalyst preparation cost, simple reaction operation, mild conditions, high yield, wide substrate adaptability, etc. DETAILED DESCRIPTION

[0053] The following products obtained by the present invention have all been verified by conventional nuclear magnetic resonance, proving the correctness of the names of the obtained products.

[0054] Room temperature generally refers to 10-30℃.

[0055] Example 1

[0056] 1. A method for preparing a catalyst for the reaction of alcohols and amines, comprising the following steps:

[0057] 1) Using ethanol as the solvent, 20 g of tetraethoxysilane and 5 g of 4-fluorophenyltriethoxysilane were added to 300 ml of ethanol, and 20 mL of deionized water was slowly added dropwise (addition time: 60 minutes) under stirring. HNO3 was then added dropwise to adjust the pH to 2.0 to form a sol.

[0058] 2) Stirring at 25°C for 2 hours to allow the sol to gradually form a gel; aging the gel at room temperature for 24 hours, and then drying at 70°C for 12 hours to remove the solvent (ethanol) to obtain a xerogel;

[0059] 22 g of the above-mentioned dry gel was dispersed in 40 g of deionized water (dispersion time was about 0.5 h) to prepare a slurry (solid content was about 35.5%). The slurry had fluidity and could be pumped.

[0060] 3) The slurry obtained in step 2 was subjected to conventional spray drying, with the air inlet temperature controlled at 160-180° C., the air outlet temperature at 90-100° C., the nozzle diameter at 0.7 mm, and the spray drying nozzle pressure at 0.3 MPa to form fluorine-doped porous silica microspheres.

[0061] 4) The fluorine-doped porous silica microspheres obtained in step 3) were immersed in a 1M ethanol solution of methyltriethoxysilane and taken out after 4 hours (after 4 hours, the fluorine-doped porous silica microspheres were still immersed in the 1M ethanol solution of methyltriethoxysilane), dried at 120°C for 2 hours and calcined at 350°C for 2 hours to form fluorine-doped porous silica microspheres, which were used as catalyst supports.

[0062] 5) the mixed metal salt consists of Cu(NO3)2·3H2O, Ni(NO3)2·6H2O, Co(NO3)2·6H2O, and Zn(NO3)2·6H2O in a molar ratio of 1:0.4:0.2:0.15;

[0063] The mixed metal salt is dissolved in deionized water, and the total concentration of metal ions in the mixed metal salt is controlled to be 0.5 M; that is, the sum of the concentrations of Cu ions, Ni ions, Co ions, and Zn ions is 0.5 mol / L. Then, urea is added (urea: mixed metal salt ≈ 2:1 mass ratio) to obtain a metal precursor solution (total metal ion concentration 0.5 M).

[0064] 6) The catalyst carrier is immersed in the metal precursor solution, the solid-liquid ratio is 1:10 (g / ml), ultrasonic dispersion is performed for 45 min, and stirring is performed for 8-24 h until the metal precursor solution is completely absorbed by the catalyst carrier.

[0065] 7) The impregnated catalyst carrier obtained in step 6) is first dried at 100°C for 12-24 h, and then calcined at 400°C for 5 h in a N2 atmosphere to obtain a catalyst particle loaded with a to-be-activated metal active component (a to-be-activated catalyst).

[0066] II. A method for synthesizing methylmorpholine by reacting methanol and morpholine, the following steps are performed in sequence:

[0067] 1) The to-be-activated catalyst particles obtained in step I are ground (25-45 mesh), and then loaded into a fixed bed reactor with an inner diameter of 15 mm and an effective bed volume of 50 mL (that is, the volume of the to-be-activated catalyst is 50 mL), and quartz sand inert fillers are laid at the bottom of the bed and on the top of the catalyst.

[0068] 2) After purging with inert gas (N2 or Ar, etc.) for 30 min, the fixed bed reactor is heated to 300°C, H2 / N2 mixed gas (H2 content 5%) is introduced at a flow rate of 100 mL / min for 2 h to reduce and activate the catalyst. After activation, no water is generated.

[0069] 3) After activation, the fixed bed reactor is set to a reaction temperature of 250°C and a reaction pressure of 0.2 MPa after purging with inert gas (N2 or Ar, etc.) for 20 min.

[0070] 4) The alcohol and amine to be reacted are mixed in a molar ratio of 1.1:1 (methanol 40 g, morpholine 100 g), and then introduced into a gasification chamber for gasification (gasification temperature 180°C). The gasified raw materials are introduced into the fixed bed reactor to react at the set reaction temperature and reaction pressure, and the residence time is 20 min. The reaction equation is as follows.

[0071]

[0072] 5) After the reaction gas is cooled to 20°C by a condenser, a mixed solution (mainly methanol, methylmorpholine, and morpholine) is obtained, and then subjected to rectification:

[0073] First, under normal pressure, the component collected at a distillation temperature of 64-66°C is methanol; at a distillation pressure of 20kPa, the component collected at a distillation temperature of 85-90°C is methylmorpholine, and the component collected at a distillation temperature of 100-105°C is morpholine.

[0074] The obtained products include 110 g of methylmorpholine, 4.2 g of methanol and 2 g of morpholine.

[0075] Then, the conversion rate of morpholine is: (100-2) / 100=98%.

[0076] The yield of methylmorpholine is:

[0077] Example 2 series, Comparative Example 1 series, Comparative Example 2 series: The preparation process of the catalyst support in Example 1 was changed, with the addition amount of 4-fluorophenyltriethoxysilane and the concentration conditions of the ethanol solution of methyltriethoxysilane. The remaining steps were the same as in Example 1, and the Example 2 series, Comparative Example 1 series, and Comparative Example 2 series were obtained, respectively. The morpholine conversion rate and methylmorpholine yield are shown in Table 1.

[0078] Table 1

[0079]

[0080] Example 3 series: The types of fluorosilane and modified silane in the preparation process of the catalyst support in Example 1 were changed; the remaining steps were the same as Example 1, and Example 3 series were obtained, and their morpholine conversion rates and methylmorpholine yields were shown in Table 2.

[0081] Table 2

[0082]

[0083] Example 4 series, the molar concentration ratio of each metal and the total metal ion concentration in the metal precursor solution in Example 1 were changed, and the remaining steps were the same as Example 1 to obtain Example 4 series, whose morpholine conversion rate and methylmorpholine yield are shown in Table 3.

[0084] Table 3

[0085]

[0086]

[0087] Example 5 series,

[0088] The reaction substrate and reaction temperature conditions in Example 1 were changed, while the reaction pressure and reaction time remained unchanged; the rest were the same as in Example 1, and Example 5 series were obtained. The amine conversion rates and product yields thereof are shown in Table 4.

[0089] Table 4

[0090]

[0091]

[0092] Note: The chemical names of the alcohols, amines and products in Table 4 correspond to the structural formulas as shown in Table 5 to Table 7 below.

[0093] Table 5, alcohols

[0094]

[0095] The CAS of the above alcohols: 67-56-1, 100-51-6, 111-27-3, 98-00-0.

[0096] Table 6, amines

[0097]

[0098]

[0099] The CAS of the above amines: 111-86-4, 62-53-3, 504-24-5, 108-91-8, 110-89-4, 288-32-4, 110-91-8.

[0100] Table 7, products

[0101]

[0102]

[0103] The CAS of the above products: 2439-54-5, 100-61-8, 1121-58-0, 100-60-7, 626-67-5, 616-47-7, 10316-00-4, 31866-75-8, 71897-72-8.

[0104] Comparative Example 3-1, steps 1) to 4) in the "Preparation method of catalyst for alcohol and amine reaction" of Example 1 were omitted, i.e., commercially available silica (30 mesh ± 5 mesh) was directly used instead of fluorine-doped porous silica microspheres as the catalyst carrier, and the remaining preparation steps of the catalyst were identical to those of Example 1. The catalyst thus obtained was used to synthesize methylmorpholine according to the "Method for synthesizing methylmorpholine by reacting methanol and morpholine" of Example 1, and the conversion rate of morpholine was 72% and the yield of methylmorpholine was 67%.

[0105] Comparative Example 3-2, instead of the steps 1) to 4) in the "Preparation method of catalyst for alcohol and amine reaction" of Example 1, i.e., directly using commercially available alumina (30 mesh ± 10 mesh) instead of fluorine-doped porous silica microspheres as the catalyst carrier, the remaining preparation steps of the catalyst are the same as those of Example 1. The obtained catalyst is used to synthesize methylmorpholine according to the "Method for synthesizing methylmorpholine by using methanol and morpholine reaction" of Example 1, and the conversion rate of morpholine is 76% and the yield of methylmorpholine is 73%.

[0106] Comparative Example 4, which is different from Comparative Example 3-1 in that:

[0107] The prepared to-be-activated catalyst (volume amount is the same as 50 mL of Example 1) of Comparative Example 3-1 is placed in a fixed bed reactor for activation (activation conditions are the same as those of Example 1), and after the activation is completed, the molecular sieve is added for mixing, and the obtained is named as a composite catalyst. The mass ratio of molecular sieve: activated catalyst is 0.3:1.

[0108] The obtained composite catalyst is used to synthesize methylmorpholine according to the "Method for synthesizing methylmorpholine by using methanol and morpholine reaction" of Example 1, and the conversion rate of morpholine is 86% and the yield of methylmorpholine is 84%.

[0109] Comparative Example 5, instead of using Co(NO3)2·6H2O in Example 1, i.e., the mixed metal salt is composed of Cu(NO3)2·3H2O, Ni(NO3)2·6H2O and Zn(NO3)2·6H2O with a molar ratio of 1:0.4:0.15; the remaining is the same as the "Preparation method of catalyst for alcohol and amine reaction" of Example 1. The obtained catalyst is used to synthesize methylmorpholine according to the "Method for synthesizing methylmorpholine by using methanol and morpholine reaction" of Example 1, and the obtained results are: the conversion rate of morpholine is 85% and the yield of methylmorpholine is 83%.

[0110] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a catalyst for alcohol amination reaction, characterized in that: Fluorine-doped silicon dioxide is used as a catalyst carrier to load metal active components to be activated, and the metal active components are copper, nickel, cobalt and zinc.

2. The method for preparing a catalyst for alcohol amination according to claim 1, wherein: The following steps are involved: 1) Add tetraethoxysilane and fluorosilane to the solvent at room temperature, slowly add deionized water while stirring, and then adjust the pH to 2-4 with acid to obtain a sol; The mass ratio of tetraethoxysilane to fluorosilane is 2 to 6:1; Deionized water: solvent = 1: (15 ± 5) volume ratio; Tetraethoxysilane: solvent = 1g: (15±5)ml material-liquid ratio; 2) Stirring at room temperature to allow the sol to gradually form a gel; then allowing the gel to stand at room temperature for 24 to 36 hours and then drying to obtain a xerogel; Dispersing the dry gel in deionized water to prepare a slurry with a solid content of 20-40%; Solid content = weight ratio of xerogel / (xerogel + deionized water); 3) spray drying the slurry obtained in step 2) to form fluorine-doped porous silica microspheres; 4) Dissolving the modified silane in a solvent to obtain a modified silane solution with a concentration of 1 to 3 M; The fluorine-doped porous silica microspheres obtained in step 3) are immersed in a modified silane solution for 3 to 5 hours, and then taken out, dried, and then calcined at 350±20°C for 2±0.2 hours. The calcined product is used as a catalyst support; 5) dissolving a mixed metal salt consisting of a soluble copper salt, a soluble nickel salt, a soluble cobalt salt, and a soluble zinc salt in deionized water at a molar ratio of soluble copper salt: soluble nickel salt: soluble cobalt salt: soluble zinc salt = 0.8-1.2: 0.2-0.4: 0.1-0.3: 0.1-0.3, and controlling the total concentration of metal ions in the mixed metal salt to be 0.2-1 M; and then adding urea to obtain a metal precursor solution; Urea: metal salt = 2±0.1:1 mass ratio; 6) Immersing the catalyst support in the metal precursor solution, stirring after ultrasonic dispersion until the metal precursor solution is completely absorbed by the catalyst support; obtaining the impregnated catalyst support; 7) The impregnated catalyst carrier is dried first, and then calcined in an inert atmosphere at 300-500° C. for 3-6 hours to obtain a catalyst loaded with the metal active component to be activated.

3. The method for preparing a catalyst for alcohol amination according to claim 2, wherein: The fluorosilane in step 1) is 4-fluorophenyltriethoxysilane, trifluoropropyltrimethoxysilane, or perfluorooctylethyltrichlorosilane.

4. The method for preparing a catalyst for alcohol amination according to claim 3, wherein: The modified silane in step 4) is methyltriethoxysilane, octadecyltriethoxysilane, or phenyltriethoxysilane.

5. The method for preparing a catalyst for alcohol amination according to claim 4, wherein: In the step 5): The soluble copper salt is: Cu(NO3)2·3H2O, the soluble nickel salt is: Ni(NO3)2·6H2O, the soluble cobalt salt is: Co(NO3)2·6H2O, and the soluble zinc salt is: Zn(NO3)2·6H2O.

6. The method for preparing a catalyst for alcohol amination according to claim 5, wherein: In step 6), the catalyst support: metal precursor solution = solid-liquid ratio of 1g:5-15ml, ultrasonic dispersion for 30-60min; The drying step 2) is as follows: drying at 60-80° C. for 12-24 hours; In the spray drying step 3), the air inlet temperature is controlled at 160-180°C, the air outlet temperature is controlled at 90-100°C, the nozzle diameter is 0.7-2 mm, and the nozzle pressure of the spray drying is 0.15-0.3 MPa; The drying step 4) is as follows: drying at 120±20°C for 1 to 2 hours; The drying in step 7) is performed at 60-120° C. for 12-24 hours.

7. The method for preparing a catalyst for alcohol amination according to any one of claims 1 to 6, characterized in that: The solvent is ethanol.

8. A method for efficiently catalyzing the reaction of alcohols and organic amines, characterized in that: The catalyst to be activated is prepared by the method according to any one of claims 1 to 7, comprising the following steps: 1) The activated catalyst particles are ground and loaded into a fixed bed reactor for activation using H2 to serve as a catalyst layer; After activation is completed, an inert gas is introduced to flush the fixed bed reactor, and the fixed bed reactor is set to the reaction temperature and reaction pressure; 2) The alcohol and amine to be reacted are mixed in a molar ratio of 1.1 to 1.3:1 and then enter the gasification chamber as raw materials for gasification. The gasified raw materials enter the fixed bed reactor and react at a temperature of 200 to 400°C and a reaction pressure of 0.1 to 3 MPa. The residence time of the gasified raw materials in the catalyst layer is 10 to 30 minutes; The reaction product is cooled in a condenser to form a liquid phase, which is separated by distillation to obtain the product; The alcohol is The amine is 9. The method for efficiently catalyzing the reaction of alcohols and organic amines according to claim 8, characterized in that: R1 and R3 are substituted heteroaryl or substituted alkyl; The substituted heteroaryl group is furan, thiophene, pyridine, morpholine, piperidine, pyrrolidine, and the substituted alkyl group is an alkyl group substituted with carbon chain length and branching; The R2 is hydrogen.

10. The method for efficiently catalyzing the reaction of alcohol and organic amine according to claim 8 or 9, characterized in that: Step 1) Catalyst activation: first, introduce inert gas to purge, then heat the fixed bed reactor to 300±30°C, and introduce a H2 / N2 mixed gas with a H2 content of 4-6% to perform reduction activation of the catalyst.

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