A method for preparing cyclohexylamine using cyclohexanol as raw material

Abstract

The present invention belongs to the field of chemical industry, and specifically relates to a production method for preparing cyclohexylamine from cyclohexanol and a related catalyst. The present invention provides a catalyst for preparing cyclohexylamine, which is composed of an active component and a catalyst carrier: the active component is composed of 0.1-20% cobalt, 0.1-2% copper, 0.1-2% zinc, and 0.1-2% barium by weight of the catalyst; the catalyst carrier is the remainder. The present invention also provides a method for preparing cyclohexylamine using cyclohexanol as a raw material using the above catalyst, comprising the following steps: the catalyst is first activated with hydrogen, cyclohexanol, liquid ammonia, and hydrogen are pumped into a vaporizer, and after vaporization, a reactor is carried out, and an amination reaction is carried out under the action of the activated catalyst; the amination reaction product is cooled to form a liquid phase product and a gas phase product, and the liquid phase product contains cyclohexylamine. The present invention improves the selectivity of dicyclohexylamine by improving the performance of the catalyst.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, and specifically relates to a production method for preparing cyclohexylamine from cyclohexanol and a related catalyst. Background Art

[0002] Cyclohexylamine, also known as hexahydroaniline, is an important chemical organic intermediate. Cyclohexylamine is an organic compound, a colorless liquid with a strong ammonia smell and strong organic base properties. The application areas of cyclohexylamine mainly include the following four aspects:

[0003] 1. The main use of cyclohexylamine is to make rubber accelerator CBS. Rubber accelerator can significantly improve the processing performance of rubber, improve the aging resistance, oxidation resistance and vulcanization resistance of rubber, and make rubber products more durable and environmentally friendly.

[0004] 2. Another important use of cyclohexylamine is as a raw material for making cyclamate. Cyclamate is widely used in food and beverage companies because of its good thermal stability and pure taste.

[0005] 3. Cyclohexylamine can be used as a PH value regulator for boiler feed water. Cyclohexylamine is a volatile substance. After adding cyclohexylamine, it is easy to diffuse into the entire system and is used as a boiler water treatment agent and corrosion inhibitor, rubber accelerator, and organic synthesis intermediate.

[0006] 4. Cyclohexylamine is a good solvent and can be used in resins, coatings, fats, paraffin oils, and can also be used to make desulfurizers, chemical additives for plastics and textiles, metal corrosion inhibitors, emulsifiers, preservatives, antistatic agents, latex coagulants, petroleum additives, fungicides, pesticides and dye intermediates. Cyclohexylamine sulfonates can be used as artificial sweeteners in food, beverages and medicines.

[0007] Among them, the main uses of cyclohexylamine are concentrated in two aspects: rubber accelerator and sodium cyclamate. In recent years, thanks to the rapid development of downstream product markets such as rubber accelerator CBS and sodium cyclamate, the market demand for cyclohexylamine in my country has grown steadily.

[0008] The existing methods for preparing cyclohexylamine mainly include catalytic hydrogenation of aniline, catalytic amination of cyclohexanol, hydrogenation amination of cyclohexanone, catalytic hydrogenation of nitrobenzene, and reduction amination of phenols.

[0009] The details are as follows:

[0010] 1. At present, the domestic industrial production methods all adopt the catalytic hydrogenation of aniline to prepare cyclohexylamine, using cobalt or nickel catalysts. This method has easy-to-obtain raw materials, high safety, and high atomic utilization rate.

[0011] 2. The one-pot catalytic production of cyclohexylamine from nitrobenzene is economical and simple, but the raw materials are not easy to obtain and do not meet the conditions for industrialization. Its research mainly focuses on precious metal Ru and Ni-based catalysts.

[0012] 3. The cyclohexanone hydrogenation amination method is divided into two steps, first generating imine, and then reacting with hydrogen to generate cyclohexylamine. Cyclohexanone raw materials are easy to obtain, but the homogeneous catalyst system in this process has problems such as difficult catalyst recovery and harsh reaction conditions (4.0-4.5MPa); and for heterogeneous catalysts, Ru, Co, Cu, Ni and other catalysts have been studied, but there are some catalyst stability problems, so the production cost is relatively high, and it is rarely used in industrial equipment.

[0013] 4. The raw materials for the phenol reduction amination method are easily available, but this method has a long reaction time, an unsatisfactory catalytic effect, and is prone to produce a variety of by-products.

[0014] 5. The advantages of cyclohexene direct amination are abundant raw material sources, short process, and easy refining and separation. However, the cyclohexene direct amination method has disadvantages such as low conversion rate, low equipment utilization rate, and high requirements for reaction conditions. The process has harsh reaction conditions and low yield, and currently does not have the conditions for industrialization.

[0015] 6. The catalytic ammonolysis of chlorocyclohexane has a long process route and contains hydrogen chloride in the product, which places high demands on equipment and does not meet the conditions for industrialization.

[0016] 7. The catalytic amination of cyclohexanol has been reported abroad, using Cu-Zn or Ni-Co as catalyst, introducing cyclohexanol and ammonia under pressure, and the reaction temperature is 160℃~180℃, generating cyclohexylamine and dicyclohexylamine in a ratio of 3:1. The reaction conversion rate is low, only 70%~80%.

[0017] In recent years, the following technical solutions have also been disclosed:

[0018] 1) Ni / Al was used in the literature ACS Catalysis, 2013, 3(1): 112-117 2 O 3 The catalyst reacts at 160°C for 28 hours without an external hydrogen source, with a cyclohexanol conversion rate of 96% and a cyclohexylamine selectivity of nearly 100%. However, toxic and high-boiling-point (144°C) o-xylene is used as a solvent, which is not environmentally friendly.

[0019] 2) The literature Catalysts, 2016, 6(5): 1-10. studied the amination reaction of cyclohexanol in water and low-boiling point solvents using three catalysts: Raney Ni, Ni / Al2O3, and Ni / C, and obtained a cyclohexanol conversion rate of more than 85% and a cyclohexylamine selectivity of more than 90%.

[0020] 3) In the literature, Journal of Catalysis, 2019, 378: 392-401., a 1% (w) Pt-1% (w) Co / CeO2 catalyst was prepared for the hydrogen amination of alcohols. The reaction was carried out at 180°C for 8 hours, and the cyclohexanol conversion rate was greater than 99%, and the cyclohexylamine yield was 73.1%.

[0021] 4) A hydrotalcite-derived NiCu / MgAlO alloy catalyst was prepared in ACS Sustainable Chemistry & Engineering, 2022, 10(40): 13367-13379, and the reaction was carried out in a fixed bed reactor at a reaction temperature of 170°C, a cyclohexanol conversion rate of more than 98%, and a cyclohexylamine selectivity of 95%.

[0022] 5) Patent CN114805088A uses Co, Ni, Mg, Cu, and Zn metal-supported catalysts, and uses cyclohexanol and cyclohexanone as raw materials to react in a fixed bed reactor. The raw material conversion rate is over 96%, and the product ratio of cyclohexylamine and dicyclohexylamine is adjusted by adjusting the ratio of ammonia and hydrogen. The selectivity of cyclohexylamine and dicyclohexylamine is over 96%. However, the cost of preparing the catalyst is very high and the economic benefit is low.

[0023] The ratio of cyclohexylamine to dicyclohexylamine in the product is adjusted by controlling the ratio of ammonia to hydrogen; when the molar ratio of ammonia to hydrogen is 1:2.5-4.0, the product is mainly dicyclohexylamine; when the molar ratio of ammonia to hydrogen is 1.5-4.5:1, the product is mainly cyclohexylamine.

[0024] Co 0-50wt%, Ni 0-55wt%, Mg 0-35wt%, Cu 0-60wt%, Zn 0-45wt% and a carrier, wherein the carrier comprises alumina, silica or a combination thereof. Preferably, the catalyst comprises: Co 0-40wt%, Ni 5-50wt%, Mg 3-21wt%, Cu 5-30wt% and Zn 5-40wt%.

[0025] The above-mentioned several cyclohexanol processes for preparing cyclohexylamine are currently only laboratory research and have not been industrialized. Summary of the invention

[0026] The technical problem to be solved by the present invention is to provide a production method for preparing cyclohexylamine by taking cyclohexanol as raw material.

[0027] In order to solve the above technical problems, the present invention provides a catalyst (supported metal catalyst) for preparing cyclohexylamine, which is composed of an active component and a catalyst carrier: the active component is composed of 0.1-20% cobalt, 0.1-2% copper, 0.1-2% zinc and 0.1-2% barium, which accounts for 0.1-20% of the weight of the catalyst; and the catalyst carrier is the remainder.

[0028] As an improvement of the catalyst for preparing cyclohexylamine of the present invention: the active ingredient consists of 15% to 19.5% cobalt, 0.5% to 1.5% copper, 0.5% to 1.5% zinc and 1% to 1.5% barium, which account for 15% to 19.5% of the catalyst weight.

[0029] As a further improvement of the catalyst for preparing cyclohexylamine of the present invention: the active ingredient consists of 19.5% cobalt, 1.5% copper, 0.5% zinc and 1.0% barium, which account for the weight of the catalyst.

[0030] The present invention also provides a method for preparing a catalyst for preparing cyclohexylamine, comprising the following steps:

[0031] ①, after uniformly mixing pseudo-boehmite, sesbania powder, deionized water and nitric acid, extruding and molding, drying and then calcining, to obtain a catalyst carrier;

[0032] The weight ratio of the pseudo-boehmite: sesbania powder: deionized water: nitric acid = 100: (5±0.5): (150±20): (3±0.3);

[0033] ②, prepare a mixed solution composed of nitrates of active ingredients, pour it into the catalyst carrier obtained in step ①, perform impregnation-calcination, and obtain a supported catalyst;

[0034] Note: The water absorption rate of the catalyst carrier can be measured in a conventional manner. The prepared mixed solution of nitrate must be completely absorbed by the catalyst carrier. In addition, due to calcination, metal oxides are attached to the supported catalyst.

[0035] ③. The supported catalyst obtained in step ② is reduced with hydrogen at high temperature to obtain a supported metal catalyst.

[0036] Description: Metal oxides are reduced with hydrogen at high temperatures to form the corresponding metals.

[0037] As an improvement of the preparation method of the catalyst for preparing cyclohexylamine of the present invention, in the step ①:

[0038] The drying step is: drying at 100-120° C. for 3±0.5 h;

[0039] The calcination is as follows: firstly heating the temperature to 280±30°C, calcining for 2±0.5 hours, and then heating the temperature to 400±50°C and calcining for 10±1 hours.

[0040] As a further improvement of the preparation method of the catalyst for preparing cyclohexylamine of the present invention, in step ②: the number of impregnation-roasting is 2 times (using double impregnation and double roasting);

[0041] Each impregnation-calcination process is as follows: first, the impregnation time is 2±0.5 hours, then the impregnated catalyst carrier is dried (dried until no water drips), placed in an oven at 110±20°C for 3±0.5 hours, and then calcined at 425±50°C for 5±0.5 hours.

[0042] As a further improvement of the preparation method of the catalyst for preparing cyclohexylamine of the present invention, in step ③, the high temperature hydrogen reduction is: hydrogen pressure 0.05MPa, temperature 450-480°C, space velocity 1000h -1 Reduction for 10 to 12 hours.

[0043] The present invention also provides a method for preparing cyclohexylamine using cyclohexanol as a raw material using the above catalyst, comprising the following steps:

[0044] 1) Loading the prepared supported metal catalyst into a reactor, and first activating it with hydrogen to obtain an activated catalyst;

[0045] 2) Cyclohexanol, liquid ammonia and hydrogen are pumped into the vaporizer, and after being vaporized, they are fed into the reactor to undergo amination reaction under the action of the activated catalyst;

[0046] The molar ratio of ammonia: hydrogen: cyclohexanol is 2-10:5:1; the reaction temperature is 160-200°C (preferably 160-180°C); the reaction pressure is 0.8-1.5Mpa (preferably 1.0-1.3Mpa); the reaction space velocity (liquid volume space velocity) is 0.2-0.6h -1 (Preferably 0.25 to 0.6 hours -1 );

[0047] Note: The feed ratio is controlled by the cyclohexanol metering pump, liquid ammonia metering pump and hydrogen flow meter; the system pressure is regulated and controlled by the back pressure valve on the vent line.

[0048] Note: Reaction space velocity is the amount of cyclohexanol passing through a unit catalyst per unit time.

[0049] 3) The amination reaction product is cooled to form a liquid product and a gas product, wherein the liquid product contains cyclohexylamine.

[0050] The details are as follows:

[0051] A vent line is provided on the top of the crude product tank, and the vent line is connected to the water absorption system. The vent line is divided into two paths, one is a vent valve, and the other is provided with a back pressure valve, and the back pressure valve is used to adjust the reaction pressure in the reactor; the uncondensed gas after the gas-liquid condensation is discharged through the vent valve, and the uncondensed gas includes hydrogen, etc.;

[0052] The amination reaction product is cooled to form a liquid product and a gas product which enter the crude product tank. The liquid product is stored in the crude product tank, and the gas product is discharged to the water absorption system through the vent line at the top of the crude product tank.

[0053] As an improvement of the method for preparing cyclohexylamine from cyclohexanol as raw material of the present invention: the vaporization temperature in the vaporizer is 160~180 ℃.

[0054] The crude product of the invention is subjected to gas chromatography and internal standard analysis, so that the conversion rate of cyclohexanol can be as high as over 98%, and the total selectivity of cyclohexylamine and dicyclohexylamine can be as high as over 99.5%.

[0055] Cyclohexanol conversion rate = (total cyclohexanol concentration - residual cyclohexanol concentration) / total cyclohexanol concentration * 100%;

[0056] Total selectivity of cyclohexylamine and dicyclohexylamine=(cyclohexylamine concentration+dicyclohexylamine concentration) / total cyclohexanol concentration-residual cyclohexanol concentration*100%.

[0057] Reaction equation:

[0058]

[0059] The beneficial effects of the present invention are mainly reflected in:

[0060] 1. In this experiment, Co / Cu / Zn / Ba metal-supported catalyst was used to prepare cyclohexylamine. The reaction conditions of cyclohexylamine were mild, the catalyst preparation process was simple, and it had good catalytic performance.

[0061] 2. The catalyst prepared by the present invention is suitable for preparing cyclohexylamine from cyclohexanol, and has high conversion rate, high catalyst activity and long service life.

[0062] In addition, by improving the performance of the catalyst, the selectivity of dicyclohexylamine is increased and the cost of preparing the catalyst is reduced.

[0063] 3. Cyclohexylamine and dicyclohexylamine were produced through catalyst preparation and cyclohexanol process.

[0064] 4. Additives (barium) can make the catalyst disperse evenly, improve the activity and stability of the catalyst, and thus improve the catalytic performance. They interact with the oxides and can change the structural state and distribution form of the oxides, allowing the catalyst to exist in a highly dispersed form. Research results show that additives such as barium metal also have a certain effect on improving the performance of the catalyst.

[0065] 5. The catalyst prepared by the present invention is suitable for preparing cyclohexylamine from cyclohexanol, and has high conversion rate, high catalyst activity and long service life. In addition, by improving the catalyst performance, the selectivity of dicyclohexylamine is increased and the cost of preparing the catalyst is reduced.

[0066] The cyclohexanol conversion rate is higher than 98%, and the selectivity of cyclohexylamine and dicyclohexylamine is higher than 99%.

[0067] The amination process of cyclohexanol is green and environmentally friendly, with good atom economy and theoretically no water as a by-product. In particular, it does not rely on an external hydrogen source, so the development of a high-conversion, high-selectivity process route and a highly stable catalyst is of great value and can be applied to large-scale industrial production. DETAILED DESCRIPTION

[0068] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0069] Catalyst Example 1:

[0070] 1) Weigh 100g of pseudo-boehmite and 5g of sesbania powder and mix them evenly, then weigh 150g of deionized water, add 3g of nitric acid into the water, mix evenly, extrude into a strip using an extruder, dry it at 110°C for 3h, then heat it to 280°C in a muffle furnace, roast it for 2h, then heat it to 400°C and roast it for 10h to obtain a catalyst carrier;

[0071] 2) The catalyst composition is set to be 19.5% Co, 1.5% Cu, 0.5% Zn, 1% Ba, and the remainder is the catalyst carrier; the above % is mass %;

[0072] According to the ratio of the above active components and the water absorption rate of the catalyst carrier, a nitrate mixed solution consisting of cobalt nitrate, copper nitrate, zinc nitrate, barium nitrate and water is prepared; the amount of water used must ensure that the nitrate mixed solution can be completely absorbed by the catalyst carrier.

[0073] The nitrate mixed solution is poured into the catalyst carrier obtained in step 1) for impregnation, and double impregnation and double calcination are adopted. The impregnation time of each time is 2 hours, and then the impregnated catalyst is dried (dried until no water drips), placed in an oven at 110°C for 3 hours, and calcined at 425°C for 5 hours, and then the above impregnation-calcination is repeated to obtain a supported catalyst cat.1.

[0074] Due to the calcination, the metal oxide is attached to the supported catalyst.

[0075] 3) The supported catalyst obtained in step 2) was loaded into a reactor with an inner diameter of 5.6 cm and a height of 12 cm, with the amount of supported metal catalyst being about 250 ml, and subjected to hydrogen reduction: the reduction conditions were hydrogen pressure of 0.05 MPa, temperature of 450°C, and space velocity of 1000 h -1 The reduced reaction was carried out under the following conditions for 12 hours to obtain a supported metal catalyst.

[0076] Description: Metal oxides are reduced with hydrogen at high temperatures to form the corresponding metals.

[0077] Catalyst Example 2-1: The active components of Catalyst Example 1 were changed from "19.5% cobalt, 1.5% copper, 0.5% zinc and 1% barium" to "15% cobalt, 0.5% copper, 1.5% zinc and 1.5% barium", and the rest were the same as Catalyst Example 1. The supported catalyst cat.2 was obtained.

[0078] Catalyst Example 2-2: The active components of Example 1 were changed from "19.5% cobalt, 1.5% copper, 0.5% zinc and 1% barium" to "19.5% cobalt, 1% copper, 1% zinc and 1% barium", and the rest were the same as Catalyst Example 1. Supported catalyst cat.3 was obtained.

[0079] The process of preparing cyclohexylamine from cyclohexanol as raw material of the present invention is as follows: loading a catalyst in a reactor, the raw material cyclohexanol is metered and pressurized by a horizontal flow pump, and then enters a vaporizer together with liquid ammonia from a double plunger pump metering pump and hydrogen from a steel cylinder, and then enters a reactor after being heated to 160-180°C and gasified, and an amination reaction occurs in the catalyst bed. Therefore, the feed ratio is controlled by a cyclohexanol metering pump, a liquid ammonia metering pump and a hydrogen flowmeter. The product obtained by the amination reaction is cooled to form a liquid phase product and a gas phase product and enter a crude product tank. A vent line is provided at the top of the crude product tank, and the vent line is connected to a water absorption system. A vent valve and a back pressure valve are respectively provided on the vent line, and the back pressure valve is used to adjust the reaction pressure in the reactor. The uncondensed gas after gas-liquid condensation is discharged through the vent valve, and the uncondensed gas includes hydrogen and the like; another function of the vent valve is to vent and release the pressure when the pressure is abnormal.

[0080] The crude product (liquid product) comprises components such as cyclohexylamine, dicyclohexylamine, cyclohexanol, and liquid ammonia, and can be subjected to the following conventional aftertreatment: a small amount of liquid ammonia is evaporated off by an ammonia tower, a fraction at 130 to 134° C. is collected by a rectifying tower to obtain the cyclohexylamine product, and a fraction at 150 to 152° C. is collected by a vacuum distillation tower (-0.09MPa) to obtain the dicyclohexylamine product, thereby obtaining purified (purity ≥ 99.5%) cyclohexylamine and (purity ≥ 99.5%) dicyclohexylamine.

[0081] The gas phase products are mainly composed of the following components: liquid ammonia, methane, and hydrogen; therefore, they form an alkaline solution after entering the water absorption system, and the others that are insoluble in water are discharged into the atmosphere.

[0082] See the following examples for details.

[0083] Embodiment 1:

[0084] The reactor was loaded with 250 ml of the supported metal catalyst cat.1 prepared in Catalyst Example 1. The raw materials ammonia, hydrogen and cyclohexanol were introduced into the vaporizer at a molar ratio of 8:5:1. After being heated and vaporized, they were introduced into the reactor and heated at 160°C, 1.3 MPa, and 0.25 h. -1 Amination reaction occurs at a space velocity of 2.5 %.

[0085] The liquid product and gaseous product formed after condensation and cooling of the amination reaction product enter the crude product tank, the liquid product is stored in the crude product tank, and the gaseous product is discharged to the water absorption system through the vent line at the top of the crude product tank.

[0086] The liquid phase product is a crude cyclohexylamine product. Using gas chromatography and internal standard analysis, the cyclohexanol conversion rate is 98.3%, the cyclohexylamine selectivity is 99.59%, and the dicyclohexylamine selectivity is 0.24%.

[0087] Example 2-1: The "supported metal catalyst cat.1 prepared by loading catalyst example 1" in Example 1 was changed to "supported metal catalyst cat.2 prepared by loading catalyst example 2-1", and the dosage remained unchanged, still 250 ml, and the rest was the same as Example 1. The cyclohexanol conversion rate was 96.5%, and the cyclohexylamine selectivity was 98.52%.

[0088] Example 2-2: The "supported metal catalyst cat.1 prepared by loading catalyst example 1" in Example 1 was replaced by "supported metal catalyst cat.3 prepared by loading catalyst example 2-2", and the dosage remained unchanged at 250 ml, and the rest was the same as Example 1. The cyclohexanol conversion rate was 97.6%, and the cyclohexylamine selectivity was 94.81%.

[0089] In Examples 3 to 6, the "molar ratio of ammonia: hydrogen: cyclohexanol", "reaction temperature" and "reaction pressure" are changed to those described in Table 1 below, and the rest are the same as in Example 1.

[0090] Table 1

[0091]

[0092] In Examples 7 and 8, the "reaction space velocity" is changed to that described in Table 2 below, and the rest is the same as in Example 1.

[0093] Table 2

[0094] Reaction space velocity Cyclohexanol conversion Cyclohexylamine selectivity Example 1 <![CDATA[0.25h -1 ]]> 98.3％ 99.59％ Example 7 <![CDATA[0.4h -1 ]]> 98.1％ 99.73％ Example 8 <![CDATA[0.6h -1 ]]> 96.4％ 99.67％

[0095] Comparative Examples 1-1 to 1-4: The active ingredients in Example 1 are changed to those described in Table 3 below, and the rest are the same as in Example 1.

[0096] The comparison of the obtained results with those of the present invention is shown in Table 3 below.

[0097] Table 3

[0098]

[0099] Example 9: Continuous operation of the catalyst

[0100] The supported metal catalyst cat.1 after the reaction in Example 1 was used to continue the reaction according to the method described in Example 1, and the rest was the same as Example 1. The continuous operation days and the corresponding results are shown in Table 4 below.

[0101] Table 4

[0102]

[0103]

[0104] Embodiment 10:

[0105] The fixed bed reactor was loaded with 15.16 tons of catalyst cat.1, the liquid mass space velocity was 0.25 h-1, the molar ratio of ammonia to hydrogen alcohol was 5:5:1, the reactor temperature was 170°C, the synthesis pressure was 1.2 MPa, the cyclohexanol conversion rate was 98.15%, the selectivity of cyclohexylamine was 93.09%, and the selectivity of dicyclohexylamine was 6.19%.

[0106] Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and there are many variations. All variations that can be directly derived or associated with the content disclosed by a person skilled in the art should be considered as the protection scope of the present invention.

Claims

1. A catalyst for preparing cyclohexylamine, characterized in that Composed of active ingredients and catalyst carrier: The active components are composed of 0.1-20% cobalt, 0.1-2% copper, 0.1-2% zinc and 0.1-2% barium, accounting for 0.1-2% of the weight of the catalyst; the catalyst carrier is the balance.

2. The catalyst for preparing cyclohexylamine according to claim 1, characterized in that: The active component consists of 15% to 19.5% cobalt, 0.5% to 1.5% copper, 0.5% to 1.5% zinc and 1% to 1.5% barium, based on the weight of the catalyst.

3. The catalyst for preparing cyclohexylamine according to claim 2, characterized in that: The active ingredients consist of 19.5% cobalt, 1.5% copper, 0.5% zinc and 1.0% barium based on the weight of the catalyst.

4. The method for preparing a catalyst for preparing cyclohexylamine as claimed in any one of claims 1 to 3, characterized in that The following steps are involved: ①, after uniformly mixing pseudo-boehmite, sesbania powder, deionized water and nitric acid, extruding and molding, drying and then calcining, to obtain a catalyst carrier; The weight ratio of the pseudo-boehmite: sesbania powder: deionized water: nitric acid = 100: (5±0.5): (150±20): (3±0.3); ②, prepare a mixed solution composed of nitrates of active ingredients, pour it into the catalyst carrier obtained in step ①, perform impregnation-calcination, and obtain a supported catalyst; ③. The supported catalyst obtained in step ② is reduced with hydrogen at high temperature to obtain a supported metal catalyst.

5. The method for preparing a catalyst for preparing cyclohexylamine according to claim 4, characterized in that In step ①: The drying step is: drying at 100-120° C. for 3±0.5 h; The calcination is as follows: firstly heating the temperature to 280±30°C, calcining for 2±0.5 hours, and then heating the temperature to 400±50°C and calcining for 10±1 hours.

6. The method for preparing a catalyst for preparing cyclohexylamine according to claim 5, characterized in that In the step ②, the number of times of impregnation-roasting is 2 times; Each impregnation-calcination process is as follows: first, the impregnation time is 2±0.5 hours, then the impregnated catalyst carrier is dried in an oven at 110±20°C for 3±0.5 hours, and then calcined at 425±50°C for 5±0.5 hours.

7. The method for preparing a catalyst for preparing cyclohexylamine according to claim 6, characterized in that In step ③: Hydrogen reduction at high temperature: hydrogen pressure 0.05MPa, temperature 450-480℃, space velocity 1000h -1 Reduction for 10 to 12 hours.

8. A method for preparing cyclohexylamine using cyclohexanol as a raw material using a catalyst as described in any one of claims 1 to 3, characterized in that The following steps are involved: 1) Loading the prepared supported metal catalyst into a reactor, and first activating it with hydrogen to obtain an activated catalyst; 2) Cyclohexanol, liquid ammonia and hydrogen are pumped into the vaporizer, and after being vaporized, they are fed into the reactor to undergo amination reaction under the action of the activated catalyst; The molar ratio of ammonia: hydrogen: cyclohexanol is 2-10:5:1; the reaction temperature is 160-200°C; the reaction pressure is 0.8-1.5 MPa, and the reaction space velocity is 0.2-0.6 h -1 ; The reaction space velocity is the amount of cyclohexanol passing through a unit catalyst per unit time; the reaction space velocity is the liquid volume space velocity; 3) The amination reaction product is cooled to form a liquid product and a gas product, wherein the liquid product contains cyclohexylamine.

9. The method for preparing cyclohexylamine using cyclohexanol as raw material according to claim 8, characterized in that: The vaporization temperature in the vaporizer is 160-180°C.

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