Method for preparing N, N-bis (aminopropyl) cyclohexylamine based on cyclohexylamine

Abstract

The invention belongs to the technical field of polymer synthesis, and particularly relates to a method for preparing N, N-bis (aminopropyl) cyclohexylamine based on cyclohexylamine, which comprises the following steps: (1) mixing cyclohexylamine with water, and adding part of acrylonitrile to react; adding a catalyst and adding the rest acrylonitrile to continue the reaction; the obtained solution is subjected to filtration, adsorption and rotary evaporation, and N, N-dicyanoethyl cyclohexylamine is prepared; and (2) mixing the N, N-dicyanoethyl cyclohexylamine, the cobalt-based powder catalyst, ammonia water, EDTA (Ethylene Diamine Tetraacetic Acid) and a solvent, introducing hydrogen, and carrying out hydrogenation reaction to prepare the N, N-bis (aminopropyl) cyclohexylamine. The reaction conditions are mild, the process is simple, the cost is low, the catalyst is stable, the conversion rate of N, N-dicyanoethyl cyclohexylamine is larger than or equal to 99.9%, the selectivity of N, N-bis (aminopropyl) cyclohexylamine is larger than or equal to 96%, the total amount of monoaminopropyl cyclohexylamine is smaller than or equal to 3%, and the amount of condensed macromolecular by-products is smaller than or equal to 0.2%.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer synthesis, and particularly relates to a method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine. Background Art

[0002] As a polyamino functional compound, N,N-bisaminopropylcyclohexylamine has shown significant application potential in the field of epoxy resin curing agents due to its unique molecular structure. Epoxy resin, as a type of high-performance thermosetting material, is widely used in electronic packaging, aerospace, coatings and composite materials, but its final performance is highly dependent on the choice of curing agent. Although traditional amine curing agents such as aliphatic amines and aromatic amines can provide good cross-linking effects, they still face problems such as high toxicity, strong volatility, insufficient heat resistance or poor toughness. Therefore, the development of new, efficient, environmentally friendly and multifunctional curing agents has become a research hotspot, among which the research on the synthesis of N,N-bisaminopropylcyclohexylamine is of top priority.

[0003] Chinese patent CN115677509A discloses a method for preparing N,N-bisaminopropylcyclohexylamine, comprising the following steps: 1) mixing N,N-biscyanoethylcyclohexylamine and solvent A to prepare a solution; 2) mixing a Raney catalyst, solvent B and water, adding an alkaline buffer solution and a salt solution, introducing hydrogen to adjust the system to the reaction pressure, and heating to the reaction temperature, and then adding the solution prepared in step 1) under a hydrogen atmosphere to carry out a hydrogenation reaction to obtain N,N-bisaminopropylcyclohexylamine. The higher the pressure of the reaction process, the higher the requirements for the environment of the reaction equipment, but increasing the reaction pressure cannot improve the selectivity of the catalyst for the reaction product, and cannot effectively improve the yield of N,N-bisaminopropylcyclohexylamine.

[0004] Chinese patent CN118307416A discloses a one-step method for synthesizing special amine compounds. Special amine compounds for curing agents are produced in one step from acrylonitrile, amine compounds and hydrogen under the action of a catalyst. The special amine compounds include at least one of N-(3-aminopropyl)cyclohexylamine, N,N'-bis(3-aminopropyl)cyclohexylamine, N-(2-aminoethyl)-1,6-hexanediamine, N,N'-bis(2-aminoethyl)-1,6-hexanediamine, N-(3-aminopropyl)-2-methylcyclohexylamine and N-(3-aminopropyl)-4-methylcyclohexylamine. The yield of the target product of the method reaches 95%, and more monoaminopropylcyclohexylamine is synthesized during the reaction, and the synthesis selectivity of the special amine compounds for curing agents is low.

[0005] Chinese patent CN114907216A discloses a method for hydrogenating dicyanoethyl tertiary amine. The method comprises: using a free amine adsorbent, a hydrogenation catalyst and an organic solvent as a base, introducing H2, and carrying out a hydrogenation reaction using dicyanoethyl tertiary amine that has been pretreated and deacidified as a raw material; switching to dicyanoethyl tertiary amine that has not been pretreated and deacidified as a raw material to continue the hydrogenation reaction; and distilling and purifying the reaction mother liquor to obtain the target product. The reaction process is uncontrollable, the product yield is low, and multiple reactions and purifications are required, resulting in higher production costs and lower efficiency.

[0006] At present, the reaction conditions for synthesizing N,N-bisaminopropylcyclohexylamine are relatively harsh, so the cost of large-scale production will increase and the yield and purity of the product will be affected. Summary of the invention

[0007] In view of the above deficiencies in the prior art, the technical problem to be solved by the present invention is to provide a method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine, wherein a cobalt-based powder catalyst is added for catalysis during the reaction, and ammonia water and EDTA are added as auxiliary agents, which can maintain the activity and selectivity of the catalyst and synthesize N,N-bisaminopropylcyclohexylamine with a high yield under relatively mild conditions.

[0008] The technical solution adopted by the present invention to solve its technical problem is: The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine of the present invention comprises the following steps: (1) Mix cyclohexylamine and water, add part of acrylonitrile to react, then add a catalyst and add the remaining acrylonitrile to continue the reaction; filter, adsorb and rotary evaporate the obtained solution to obtain N,N-biscyanoethylcyclohexylamine; (2) N,N-biscyanoethylcyclohexylamine, a cobalt-based powder catalyst, aqueous ammonia, EDTA and a solvent are mixed, and hydrogen is introduced to carry out a hydrogenation reaction to obtain N,N-bisaminopropylcyclohexylamine.

[0009] in: The preparation process of the cobalt-based powder catalyst is as follows: A1. Mix cobalt nitrate hexahydrate, sodium silicate nonahydrate and urea, add deionized water and mix evenly, and then precipitate to obtain a suspension containing a precipitate; A2. Filter the precipitate in the suspension and wash it to neutrality to obtain a precipitate, then disperse the precipitate in a dispersant to prepare a dispersion, spray granulate the dispersion to obtain a cobalt-based powder catalyst precursor, calcine the cobalt-based powder catalyst precursor, and then perform a reduction reaction to obtain a cobalt-based powder catalyst.

[0010] In the step A1, the mass ratio of cobalt nitrate hexahydrate, sodium silicate nonahydrate and urea is 1:(0.5-0.8):(0.8-1.2), the mass ratio of deionized water to cobalt nitrate hexahydrate is 10-30:1, the precipitation temperature is 70-90°C, and the precipitation time is 15-36h.

[0011] In the step A2, the dispersant is deionized water, the spray granulation pressure is 0.2-0.3MPa, the spray granulation temperature is 120-180°C, the calcination temperature is 450-600°C, the calcination time is 3-4h, the reduction reaction is carried out in a hydrogen atmosphere, the reduction reaction temperature is 400-500°C, and the reduction reaction time is 3-4h.

[0012] In the step (1), the mass ratio of cyclohexylamine to water is 11-22:1, the catalyst is AlCl3, and the mass ratio of the catalyst to cyclohexylamine is 0.03-0.06:1.

[0013] In the step (1), the mass ratio of part of the acrylonitrile to the cyclohexylamine is 0.5-1:1, the mass ratio of the remaining acrylonitrile to the cyclohexylamine is 0.6-1:1, and the mass ratio of part of the acrylonitrile to the remaining acrylonitrile is 1:1.05-1.15.

[0014] In the step (1), the reaction temperature is 40-60°C, the reaction time is 2-3h, the continued reaction temperature is 80-100°C, and the continued reaction time is 10-30h.

[0015] The adsorption in step (1) is carried out by mixing and stirring with clay, the mass ratio of clay to cyclohexylamine is 1:40-60, the stirring adsorption temperature is 80-100°C, and the rotary evaporation temperature is 80-100°C.

[0016] In the step (2), the mass ratio of the cobalt-based powder catalyst to N,N-bis-cyanoethylcyclohexylamine is 0.08-0.12:1, and the solvent is one of methanol, ethanol, isopropanol or 1,4-epoxyhexacyclohexylamine; the mass ratio of N,N-bis-cyanoethylcyclohexylamine, ammonia water, EDTA and solvent is 1:(0.1-0.125):(0.09-0.11):(4-5).

[0017] In the step (2), the hydrogenation reaction temperature is 80-90°C, the hydrogenation reaction pressure is 0.4-0.6MPa, and the hydrogenation reaction time is 6-8h.

[0018] The present invention allows cyclohexylamine to react with a portion of acrylonitrile; then adds a catalyst and continues to react with another portion of acrylonitrile, thereby improving the reaction efficiency of cyclohexylamine and acrylonitrile and the yield of N,N-biscyanoethylcyclohexylamine; the obtained N,N-biscyanoethylcyclohexylamine, cobalt-based powder catalyst, ammonia water, EDTA and solvent are mixed and hydrogenated to obtain N,N-bisaminopropylcyclohexylamine. The present invention allows acrylonitrile to be added in stages for reaction, thereby effectively improving the reaction efficiency and reducing the occurrence of side reactions; the solvent can disperse N,N-biscyanoethylcyclohexylamine and the catalyst, allowing ammonia water and EDTA to fully function; and the hydrogenation reaction on this basis can allow the adsorbed ammonia molecules and -COO - The cobalt-based powder catalyst is fully mixed with N,N-biscyanoethylcyclohexylamine to promote the conversion of N,N-biscyanoethylcyclohexylamine.

[0019] The beneficial effects of the present invention are: (1) The present invention uses a cobalt-based powder catalyst as the main catalyst, and introduces ammonia and EDTA as auxiliary agents. On the one hand, EDTA is adsorbed on the active metal surface of the cobalt-based catalyst by physical adsorption or weak chemical adsorption. The strongly electronegative group -COO in EDTA - The electrons on the Co surface are attracted by the "inductive effect", resulting in a local decrease in the surface electron density. The ammonia molecules in the ammonia water form weak adsorption with the active metal Co surface through the lone pair of electrons, and feed back electrons to the Co surface as an electron donor, partially offsetting the electron-pulling effect of EDTA. EDTA and ammonia water form a "pull-push" balance on the electron density on the active metal Co surface through adsorption, optimize the surface electron distribution, and optimize the Co surface's regulation of the polarization and breakage of the C≡N bond of N,N-biscyanoethylcyclohexylamine. This balance enables the active metal Co surface in the cobalt-based powder catalyst to have both high catalytic activity and anti-deactivation ability, so that it can react at lower temperature and pressure, and make the cobalt-based powder catalyst have higher stability; on the other hand, ammonia water can activate hydrogen species to generate NH 2- , NH 2- It preferentially attacks the carbon atom in the cyano group rather than the nitrogen atom, which can promote N,N-biscyanoethylcyclohexylamine to generate N,N-bisaminopropylcyclohexylamine with -CH-NH2. The obtained N,N-bisaminopropylcyclohexylamine will not continue to hydrogenate to generate other impurities. The addition of EDTA can make the cyano group mainly adsorbed in the terminal form, avoiding the CN stretching and breaking to cause cyclization reaction, and converting the cyano group to the amino group, thereby inhibiting the shedding of the propylamine group to generate the by-product monoaminopropylcyclohexylamine.

[0020] (2) The reaction conditions of the present invention are relatively mild, the process is simple, the cost is low, the catalyst is stable, the conversion rate of N,N-biscyanoethylcyclohexylamine is ≥99.9%, the selectivity of N,N-bisaminopropylcyclohexylamine is ≥96%, the total amount of monoaminopropylcyclohexylamine is ≤3%, and the amount of condensation macromolecular by-products is ≤0.2%. DETAILED DESCRIPTION

[0021] The present invention is further described below with reference to the embodiments.

[0022] Example 1 The preparation process of cobalt-based powder catalyst is as follows: A1. Mix 9.9 g of cobalt nitrate hexahydrate, 6.07 g of sodium silicate nonahydrate and 10 g of urea, add 300 ml of deionized water and mix well, and precipitate at 90° C. for 24 h to obtain a suspension containing a precipitate; A2. Filter the precipitate in the suspension and wash it to neutrality to obtain a precipitate, then add the precipitate into deionized water to prepare a dispersion, spray granulate the dispersion at a pressure of 0.2 MPa and a temperature of 150°C to obtain a cobalt-based powder catalyst precursor, calcine the cobalt-based powder catalyst precursor at 600°C for 4 hours, and finally reduce it in a rotary tube furnace at 400°C for 4 hours in a hydrogen atmosphere to obtain a cobalt-based powder catalyst.

[0023] The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine comprises the following steps: (1) 19.8 g of cyclohexylamine was mixed with 1.8 g of water, 11.66 g of acrylonitrile was added dropwise at 50°C, the mixture was reacted for 2 h, the temperature was raised to 90°C, 1 g of AlCl3 was added, and 12.72 g of acrylonitrile was added dropwise again and the reaction was continued for 10 h; the obtained solution was filtered and mixed with 0.5 g of white clay, stirred and adsorbed at 90°C, the white clay was filtered, and the obtained solution was rotary evaporated at 90°C to obtain N,N-biscyanoethylcyclohexylamine; (2) 2 g of N,N-bis(cyanoethyl)cyclohexylamine, 0.24 g of a cobalt-based powder catalyst, 0.2 g of aqueous ammonia, 0.2 g of EDTA and 10 g of methanol were mixed and added to a reactor, and then hydrogen was introduced to 0.5 MPa. The mixture was heated to 80°C and hydrogenated for 8 h to obtain N,N-bis(aminopropyl)cyclohexylamine.

[0024] The obtained N,N-bisaminopropylcyclohexylamine was collected for gas chromatography test: the experimental equipment was Agilent gas chromatograph, the chromatographic column was HP-5, the injection port temperature was 280°C, the FID detector temperature was 240°C, the column flow rate was 1ml / min, the hydrogen flow rate was 30ml / min, the air flow rate was 400ml / min, and the program temperature was: 80°C for 2min, then heated to 240°C at 20°C / min and kept for 15min. The gas chromatography test results of 10 cycles are shown in Table 1. As can be seen from Table 1, after 10 cycles, the conversion rate of N,N-biscyanoethylcyclohexylamine and the selectivity of N,N-bisaminopropylcyclohexylamine were maintained at a high level, and only a small part of the condensed macromolecules were generated, indicating that the cobalt-based powder catalyst has high stability and selectivity under the synergistic effect of EDTA and ammonia water.

[0025]

[0026] Example 2 The preparation process of cobalt-based powder catalyst is as follows: A1. Mix 9.9 g of cobalt nitrate hexahydrate, 5.01 g of sodium silicate nonahydrate and 11.5 g of urea, add 100 ml of deionized water and mix well, and precipitate at 80° C. for 15 h to obtain a suspension containing a precipitate; A2. Filter the precipitate in the suspension and wash it to neutrality to obtain a precipitate, then add the precipitate into deionized water to prepare a dispersion, spray granulate the dispersion at a pressure of 0.3 MPa and a temperature of 180°C to obtain a cobalt-based powder catalyst precursor, calcine the cobalt-based powder catalyst precursor at 450°C for 3 hours, and finally reduce it in a rotary tube furnace at 450°C for 3 hours in a hydrogen atmosphere to obtain a cobalt-based powder catalyst.

[0027] The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine comprises the following steps: (1) 19.8 g of cyclohexylamine was mixed with 0.9 g of water, 14.66 g of acrylonitrile was added dropwise at 60 °C, the reaction was continued for 3 h, the temperature was raised to 100 °C, 0.6 g of AlCl3 was added, and 16.72 g of acrylonitrile was added dropwise again and the reaction was continued for 30 h; the obtained solution was filtered and mixed with 0.3 g of white clay, stirred and adsorbed at 80 °C, the white clay was filtered, and the obtained solution was rotary evaporated at 80 °C to obtain N,N-biscyanoethylcyclohexylamine; (2) 2 g of N,N-bis(cyanoethyl)cyclohexylamine, 0.16 g of a cobalt-based powder catalyst, 0.25 g of aqueous ammonia, 0.22 g of EDTA and 8 g of ethanol were added to a reactor, and then hydrogen was introduced to 0.4 MPa, heated to 90°C, and hydrogenation reaction was carried out for 6 hours to obtain N,N-bis(aminopropyl)cyclohexylamine.

[0028] The obtained N,N-bisaminopropylcyclohexylamine was collected for gas chromatography test: the experimental equipment was Agilent gas chromatograph, the chromatographic column was HP-5, the injection port temperature was 280°C, the FID detector temperature was 240°C, the column flow rate was 1ml / min, the hydrogen flow rate was 30ml / min, the air flow rate was 400ml / min, and the programmed temperature was: 80°C for 2min, then heated to 240°C at 20°C / min, and kept for 15min. The gas chromatography test results of 10 cycles are shown in Table 2.

[0029]

[0030] Example 3 The preparation process of cobalt-based powder catalyst is as follows: A1. Mix 9.9 g of cobalt nitrate hexahydrate, 8.3 g of sodium silicate nonahydrate and 8.46 g of urea, add 200 ml of deionized water and mix well, and precipitate at 70° C. for 36 hours to obtain a suspension containing a precipitate; A2. Filter the precipitate in the suspension and wash it to neutrality to obtain a precipitate, then add the precipitate into deionized water to prepare a dispersion, spray granulate the dispersion at a pressure of 0.25 MPa and a temperature of 120°C to obtain a cobalt-based powder catalyst precursor, calcine the cobalt-based powder catalyst precursor at 550°C for 3 hours, and finally reduce it at 500°C for 4 hours in a rotary tube furnace under a hydrogen atmosphere to obtain a cobalt-based powder catalyst.

[0031] The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine comprises the following steps: (1) 19.8 g of cyclohexylamine was mixed with 1.2 g of water, 18.66 g of acrylonitrile was added dropwise at 40°C, the reaction was continued for 2 h, the temperature was raised to 80°C, 1.18 g of AlCl3 was added, and 19.72 g of acrylonitrile was added dropwise again to continue the reaction for 20 h; the obtained solution was filtered and mixed with 0.4 g of white clay, stirred and adsorbed at 100°C, the white clay was filtered, and the obtained solution was rotary evaporated at 100°C to obtain N,N-biscyanoethylcyclohexylamine; (2) 2 g of N,N-bis(cyanoethyl)cyclohexylamine, 0.18 g of a cobalt-based powder catalyst, 0.22 g of aqueous ammonia, 0.185 g of EDTA and 8 g of isopropanol were added to a reactor, and then hydrogen was introduced to 0.6 MPa. The mixture was heated to 85°C and hydrogenated for 6 h to obtain N,N-bis(aminopropyl)cyclohexylamine.

[0032] The obtained N,N-bisaminopropylcyclohexylamine was collected for gas chromatography test: the experimental equipment was Agilent gas chromatograph, the chromatographic column was HP-5, the injection port temperature was 280°C, the FID detector temperature was 240°C, the column flow rate was 1ml / min, the hydrogen flow rate was 30ml / min, the air flow rate was 400ml / min, and the programmed temperature was: 80°C for 2min, then heated to 240°C at 20°C / min, and maintained for 15min. The gas chromatography test results of 10 cycles are shown in Table 3.

[0033]

[0034] Comparative Example 1 In step A1, cobalt nitrate hexahydrate is replaced with nickel nitrate hexahydrate to prepare a nickel-based powder catalyst, and the cobalt-based powder catalyst in step (2) is replaced with a nickel-based powder catalyst. The remaining operations are the same as in Example 1, and the hydrogenated product is collected for gas chromatography test. The gas chromatography test results of 10 cycles of reaction are shown in Table 4. The product prepared using the nickel-based powder catalyst has a higher selectivity for monoaminopropylcyclohexylamine and a lower selectivity for N,N-bisaminopropylcyclohexylamine, and the content of by-products increases, indicating that the nickel-based powder catalyst has a poor selectivity for N,N-bisaminopropylcyclohexylamine in the system.

[0035]

[0036] Comparative Example 2 In step (2), no ammonia water was added, and the remaining operations were the same as in Example 1. The hydrogenated product was collected for gas chromatography test, and the gas chromatography test results of 10 cycles of reaction were shown in Table 5. Compared with Example 1, the conversion rate of N, N-bis-cyanoethylcyclohexylamine in Comparative Example 2 was lower, indicating that the stability of the cobalt-based powder catalyst was poor without the synergistic effect of ammonia water and EDTA. The selectivity of N, N-bis-aminopropylcyclohexylamine in Comparative Example 2 was lower than that in Example 1, indicating that ammonia water played a vital role in the system.

[0037]

[0038] Comparative Example 3 No EDTA was added in step (2), and the remaining operations were the same as in Example 1. The hydrogenated product was collected for gas chromatography test, and the gas chromatography test results of 10 cycles of reaction were shown in Table 6. Compared with Example 1, the conversion rate of N,N-biscyanoethylcyclohexylamine in Comparative Example 3 was lower and gradually decreased, and the selectivity of N,N-bisaminopropylcyclohexylamine in Comparative Example 3 was lower than that in Example 1, indicating that EDTA plays a vital role in the system.

[0039]

[0040] Comparative Example 4 In step (2), EDTA was replaced with citric acid, and the remaining operations were the same as in Example 1. The hydrogenated product was collected for gas chromatography test, and the gas chromatography test results of 10 cycles of reaction were shown in Table 7. Compared with Example 1, the conversion rate of N,N-biscyanoethylcyclohexylamine in Comparative Example 4 was lower, indicating that the stability of the cobalt-based powder catalyst was poor without the synergistic effect of EDTA and ammonia water. The selectivity of N,N-bisaminopropylcyclohexylamine in Comparative Example 4 was lower than that in Example 1, indicating that the role of EDTA in the system was irreplaceable by citric acid.

[0041]

[0042] Comparative Example 5 In step (2), the ammonia water is replaced with the NaOH aqueous solution, and the other operations are the same as those in Example 1. The hydrogenated product is collected for gas chromatography test, and the gas chromatography test results of 10 cycles of reaction are shown in Table 8. Compared with Example 1, the conversion rate of N, N-bis-cyanoethylcyclohexylamine in Comparative Example 5 is lower, indicating that the molecule in ammonia water that can play a synergistic role with EDTA and the cobalt-based powder catalyst is ammonia molecule rather than hydroxide, and the cobalt-based powder catalyst has poor stability without the synergistic effect of ammonia molecules and EDTA. The selectivity of N, N-bis-aminopropylcyclohexylamine in Comparative Example 5 is lower than that in Example 1, indicating that the role of ammonia water in the system is irreplaceable by NaOH.

[0043]

Claims

1. A method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine, characterized in that: The following steps are involved: (1) Mix cyclohexylamine and water, add part of acrylonitrile to react, then add a catalyst and add the remaining acrylonitrile to continue the reaction; filter, adsorb and rotary evaporate the obtained solution to obtain N,N-biscyanoethylcyclohexylamine; (2) N,N-biscyanoethylcyclohexylamine, a cobalt-based powder catalyst, ammonia water, EDTA and a solvent are mixed, and hydrogen is introduced to carry out a hydrogenation reaction to obtain N,N-bisaminopropylcyclohexylamine.

2. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 1, characterized in that: The preparation process of cobalt-based powder catalyst is as follows: A1. Mix cobalt nitrate hexahydrate, sodium silicate nonahydrate and urea, add deionized water and mix evenly, and then precipitate to obtain a suspension containing a precipitate; A2. Filter the precipitate in the suspension and wash it to neutrality to obtain a precipitate, then disperse the precipitate in a dispersant to prepare a dispersion, spray granulate the dispersion to obtain a cobalt-based powder catalyst precursor, calcine the cobalt-based powder catalyst precursor, and then perform a reduction reaction to obtain a cobalt-based powder catalyst.

3. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 2, characterized in that: In step A1, the mass ratio of cobalt nitrate hexahydrate, sodium silicate nonahydrate and urea is 1:(0.5-0.8):(0.8-1.2), the mass ratio of deionized water to cobalt nitrate hexahydrate is 10-30:1, the precipitation temperature is 70-90° C., and the precipitation time is 15-36 hours.

4. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 2, characterized in that: In step A2, the dispersant is deionized water, the spray granulation pressure is 0.2-0.3 MPa, the spray granulation temperature is 120-180°C, the calcination temperature is 450-600°C, the calcination time is 3-4h, the reduction reaction is carried out under a hydrogen atmosphere, the reduction reaction temperature is 400-500°C, and the reduction reaction time is 3-4h.

5. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 1, characterized in that: In step (1), the mass ratio of cyclohexylamine to water is 11-22:1, the catalyst is AlCl3, and the mass ratio of the catalyst to cyclohexylamine is 0.03-0.06:

1.

6. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 1, characterized in that: In step (1), the mass ratio of part of acrylonitrile to cyclohexylamine is 0.5-1:1, the mass ratio of remaining acrylonitrile to cyclohexylamine is 0.6-1:1, and the mass ratio of part of acrylonitrile to remaining acrylonitrile is 1:1.05-1.

15.

7. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 1, characterized in that: In step (1), the reaction temperature is 40-60°C, the reaction time is 2-3h, the continued reaction temperature is 80-100°C, and the continued reaction time is 10-30h.

8. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 1, characterized in that: In step (1), the adsorption is carried out by mixing and stirring with kaolin, the mass ratio of kaolin to cyclohexylamine is 1:40-60, the stirring adsorption temperature is 80-100°C, and the rotary evaporation temperature is 80-100°C.

9. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 1, characterized in that: In step (2), the mass ratio of the cobalt-based powder catalyst to N,N-bis-cyanoethylcyclohexylamine is 0.08-0.12:1, and the solvent is one of methanol, ethanol, isopropanol or 1,4-epoxyhexacyclohexylamine; the mass ratio of N,N-bis-cyanoethylcyclohexylamine, ammonia water, EDTA and solvent is 1:(0.1-0.125):(0.09-0.11):(4-5).

10. The method for preparing N,N-bisaminopropylcyclohexylamine based on cyclohexylamine according to claim 1, characterized in that: In step (2), the hydrogenation reaction temperature is 80-90°C, the hydrogenation reaction pressure is 0.4-0.6MPa, and the hydrogenation reaction time is 6-8h.

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