Catalyst for preparing nitrile through aerobic dehydrogenation of primary amine as well as preparation method and application of catalyst

Abstract

The invention relates to the technical field of catalysts, in particular to a catalyst for preparing nitrile through aerobic dehydrogenation of primary amine and a preparation method and application of the catalyst. According to the invention, oxygen in air is taken as an oxidant, and electron-rich oxygen in a NaKETS-10 skeleton can be selectively coordinated with electron-deficient amino hydrogen, so that adsorption and activation processes of primary amine are realized; the reaction for promoting dehydrogenation of primary amine to prepare nitrile is completed under mild conditions without any additives and ligands. The prepared catalyst is high in catalytic activity and excellent in product selectivity, use of additional additives and chemical oxidants in primary amine aerobic dehydrogenation reaction is avoided, a reaction system for preparing nitrile through primary amine dehydrogenation is clean and green, and product purification is simple; meanwhile, the catalytic system avoids poisoning inactivation of heteroatoms to a metal center, is suitable for a primary amine substrate containing heteroatoms, and widens the substrate range of the reaction.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly relates to a catalyst for aerobic dehydrogenation of primary amines to prepare nitriles, a preparation method thereof, and an application thereof. Background Art

[0002] Aerobic dehydrogenation of primary amines is a direct and effective method for preparing high-value-added nitrile derivatives. Although the currently used metal-organic catalysts can realize the dehydrogenation reaction of some primary amines to prepare nitriles, the reaction conditions are harsh, the substrate scope is limited, and it is easy to produce various unavoidable by-products. Ru carbonyl clusters can realize the dehydrogenation reaction of primary amines. A large amount of base and chemical oxidant are required in the reaction. The use of base inevitably leads to the formation of imine by-products (Dalton Trans., 2020, 49, 3480). Ru hydrides can also realize the dehydrogenation reaction of primary amines. Although the use of base is avoided, additional oxidant is still required, and a long reaction time (20 h; Chem. Commun., 2017, 53, 4006) is needed. In addition, a common problem faced by metal-organic compounds is that heteroatom substrates will cause the metal center to be poisoned and lose catalytic activity, resulting in a limited substrate scope (Chem. Commun., 2017, 53, 4006). Summary of the Invention

[0003] The purpose of the present invention is to propose a catalyst for aerobic dehydrogenation of primary amines to prepare nitriles, a preparation method thereof, and an application thereof, aiming at the above-mentioned deficiencies of the prior art.

[0004] The first object of the present invention is to provide a preparation method of a catalyst for aerobic dehydrogenation of primary amines to prepare nitriles, including the following steps:

[0005] S1. Prepare NaKETS-10 material by hydrothermal synthesis method;

[0006] Mix and stir an aqueous NaOH solution and water glass, then sequentially stir and add an aqueous KF solution and a hydrochloric acid solution of TiCl3 to form a mixed gel solution. Perform hydrothermal reaction crystallization on the gel solution. After the crystallization is completed, take out the autoclave, wash, filter by suction, dry, and calcine for the first time to obtain a sample. Wash the sample with deionized water again, filter, dry, and calcine for the second time to obtain the catalyst support NaKETS-10;

[0007] S2. Ultrasonically disperse the support in deionized water to obtain a suspension;

[0008] S3. Ultrasonically disperse a cobalt metal salt in the suspension obtained in step S2;

[0009] S4. Centrifuge the suspension in step S3 to obtain a catalyst precursor, and obtain the Co@NaKETS-10 catalyst through drying and calcination.

[0010] Further, in step S1, the first calcination is carried out at 325 - 355 °C in air for 3 - 4 h; the mass ratio of NaOH, sodium silicate, KF to the hydrochloric acid solution of TiCl₃ is 5.02:7.14:3.8:1, and the concentration of the hydrochloric acid solution of TiCl₃ is 17.5%.

[0011] Further, in step S1, when the sample is washed again with deionized water, the mass ratio of the sample to deionized water is 0.02 - 0.05; the filtration process is carried out under atmospheric pressure; the drying temperature is 90 - 110 °C and the drying time is 8 - 10 h; in step S1, the second calcination is carried out at 235 - 255 °C in air for 3.5 - 4.5 h.

[0012] Further, in step S2, the mass ratio of the carrier to deionized water is 0.5 - 1; the ultrasonic time is 0.5 - 1 h; in step S3, ultrasonic treatment is carried out at a temperature of 35 - 45 °C for 8 - 10 h.

[0013] Further, in step S3, the cobalt metal salt is one of cobalt nitrate, cobalt carbonate, and cobalt acetate; in step S3, the mass ratio of the cobalt metal salt to the carrier used in step S2 is 0.01 - 0.05.

[0014] Further, in step S4, the centrifugation rate is 5000 - 10000 rpm and the centrifugation time is 3 - 5 min; in step S4, the drying temperature is 80 - 100 °C and the drying time is 8 - 10 h;

[0015] Further, in step S4, the calcination temperature is 235 - 255 °C and the calcination time is 3.5 - 4.5 h; in step S4, the calcination atmosphere is nitrogen, and the nitrogen flow rate is 150 - 250 mL / min.

[0016] The second object of the present invention is to provide a catalyst for aerobic dehydrogenation of primary amines to prepare nitriles prepared by the above - mentioned preparation method.

[0017] The second object of the present invention is to provide a method for aerobic dehydrogenation of primary amines to prepare nitriles. Using the catalyst for aerobic dehydrogenation of primary amines to prepare nitriles as described above, with primary amines as raw materials, in a reaction solvent, under an aerobic atmosphere, heating and reacting to prepare nitriles.

[0018] Further, the heating reaction temperature is 80 - 100 °C; the reaction time is 2 - 5 h; the ratio of primary amine to catalyst is 0.3 - 0.5 mmol:5 - 15 mg; the reaction solvent is cyclohexane, and the ratio of primary amine to reaction solvent is 0.3 - 0.5 mmol:1.2 - 1.5 mL.

[0019] The present invention uses NaKETS-10 as a carrier to prepare a catalyst Co@NaKETS-10 for aerobic dehydrogenation of primary amines to nitriles. Using oxygen in the air as an oxidant, the electron-rich oxygen in the NaKETS-10 framework can selectively coordinate with the electron-deficient amino hydrogen, thereby realizing the adsorption and activation process of primary amines, and promoting the reaction of dehydrogenating primary amines to nitriles to be completed under mild conditions without any additives and ligands.

[0020] The present invention first washed the prepared NaKETS-10 with deionized water to remove impurity ions that may be introduced during the synthesis process. Therefore, only the equilibrium cations Na + , K + ions and the active metal Co oxide exist on the surface of the prepared Co@NaKETS-10 catalyst. The influence of other cations on the catalytic activity of the catalyst is avoided.

[0021] The present invention loads metal cobalt onto the surface of the carrier NaKETS-10 by ultrasonic method, so that the Co metal is evenly dispersed on the surface of the carrier, forming small nanoparticles and improving the catalytic activity.

[0022] The catalyst prepared by the present invention by ultrasonic impregnation method has the property of dual active sites. The electron-rich oxygen with electron transport property in the NaKETS-10 framework and the Co metal clusters loaded on it synergistically catalyze the two-step oxidative dehydrogenation reaction of primary amines. The selective coordination between the electron-rich oxygen in the catalyst and the electron-deficient amino hydrogen in the primary amine and the highly active Co metal sites are the essential reasons for the occurrence of this reaction under mild and clean conditions.

[0023] The Co@NaKETS-10 catalyst prepared by the present invention has high catalytic activity and excellent product selectivity. By using the prepared Co@NaKETS-10 catalyst, the use of additional additives and chemical oxidants in the aerobic dehydrogenation reaction of primary amines is avoided, and the generation of imine by-products is avoided from the source, making the reaction system for dehydrogenating primary amines to nitriles clean and green, and the product purification is simple; at the same time, this catalytic system avoids the poisoning and inactivation of the metal center by heteroatoms, is applicable to primary amine substrates containing heteroatoms, and broadens the substrate scope of the reaction. Description of the Drawings

[0024] Figure 1 It is the X-ray diffraction pattern of the carrier NaKETS-10 used in the present invention;

[0025] Figure 2 It is the X-ray diffraction pattern of the Co@NaKETS-10 prepared by the present invention;

[0026] Figure 3 It is the nitrogen adsorption and desorption diagram of the Co@NaKETS-10 prepared by the present invention;

[0027] Figure 4 Spherical aberration electron microscopy image of Co@NaKETS-10 prepared according to the present invention;

[0028] Figure 5 For the product of Example 1 of the present invention 1 1H NMR spectrum;

[0029] Figure 6 For the product of Example 1 of the present invention 1 1H NMR spectrum;

[0030] Figure 7 For the product of Example 1 of the present invention 1 1H NMR spectrum;

[0031] Figure 8 For the product of Example 1 of the present invention 1 1H NMR spectrum;

[0032] Figure 9 For the product of Example 1 of the present invention 1 1H NMR spectrum. Detailed implementation manners

[0033] The following are specific examples of the present invention and, in conjunction with the accompanying drawings, the technical solutions of the present invention are further described, but the present invention is not limited to these examples.

[0034] The NaKETS-10 material was prepared using the hydrothermal synthesis method.

[0035] The specific steps are as follows: Dissolve 1.6 g of NaOH in 6 mL of distilled water, stir until it cools to room temperature, and then add it to 9.7 mL of water glass and stir until it cools to room temperature. Dissolve 1.5 g of KF in 8.1 mL of distilled water, and after it dissolves and becomes clear, add it to the previously described solution and stir for 30 min. Then weigh 7 g of a hydrochloric acid solution of TiCl3 and slowly add it drop by drop to the previous solution. After all of it is added, stir for 4 h. The synthesis system of the mixed gel solution is TiO2 / 7.14SiO2 / 5.02Na2O / 3.8KF / 232.79H2O. After all of it is added, place it in a 50 mL polytetrafluoroethylene-lined autoclave and crystallize at 230 °C for 48 h. After the crystallization is completed, take out the autoclave, wash, filter, dry, and calcine at 475 °C for 4 h to obtain the sample.

[0036] The prepared sample was washed in deionized water until neutral, and after washing, it was filtered, dried, and calcined to obtain the catalyst support NaKETS-10.

[0037] See attached Figure 1 , which is the X-ray diffraction pattern of the carrier NaKETS-10 used in the present invention. The typical topological diffraction peaks of ETS-10 zeolite appear, indicating that the prepared NaKETS-10 has good crystallinity.

[0038] Example 1:

[0039] The specific preparation steps of Co@NaKETS-10 catalyst are as follows:

[0040] (1) Place 1.0 g of the prepared NaKETS-10 powder in 30 mL of deionized water and wash it until neutral. After washing, filter it under normal pressure, dry it at 100 °C for 9 h, and calcine it at 235 °C for 4 h to obtain the catalyst support;

[0041] (2) Place the support obtained in step 1 in 1.5 g of deionized water and ultrasonically disperse it for 0.5 h to make the white powder of NaKETS-10 uniformly suspended in deionized water;

[0042] (3) Weigh 0.039 g of cobalt nitrate and place it in the suspension in step 2, and ultrasonically treat it at 35 °C for 8 h;

[0043] (4) Centrifuge the suspension in step 3 to obtain the catalyst precursor, dry it at 80 °C for 9 h, and calcine it at 235 °C for 3.5 h to obtain the Co@NaKETS-10 catalyst.

[0044] Under the condition of thermal reflux, the catalytic activity of the catalyst for aerobic dehydrogenation to prepare nitrile was investigated. The reaction was carried out in a 10 mL glass tube for 2 h, the reaction temperature was 80 °C, the reaction solvent was 1.2 mL of cyclohexane, the catalyst was 5 mg, and benzylamine was 0.3 mmol. The GC conversion rate of benzylamine was close to 100%, and the GC yield of the corresponding nitrile was 100%, and no by-products were detected. Product characterization data: 1 HNMR(400MHz,CDCl3)δ:7.69~7.63(m,2H),7.63~7.57(m,1H),7.47(t,J=7.7Hz,2H);MS(70eV)m / z(%):103(M + ,100),104(35),77(26).

[0045] See Appendix Figure 2 , which is the X-ray diffraction pattern of Co@NaKETS-10 prepared by the present invention. By comparison Figure 1 it can be seen that the ultrasonic impregnation operation does not damage the topological structure of the zeolite. In addition, no diffraction peaks of Co metal were found, indicating that metallic Co is highly dispersed on the catalyst surface by ultrasonic impregnation, forming small nanoparticles (<5 nm);

[0046] See Appendix Figure 3, which is the nitrogen adsorption and desorption diagram of Co@NaKETS-10 prepared in the present invention. An obvious hysteresis loop appears in the range of relative pressure from 0.42 to 0.99 in the adsorption and desorption curve, indicating that the prepared catalyst structure contains obvious mesopores, and the mesopore aperture is concentrated at 10.3 nm. The existence of mesopores is beneficial to the diffusion process and mass transfer process of primary amine substrates and nitrile products;

[0047] See attached Figure 4 , which is the spherical aberration electron microscope image of Co@NaKETS-10 prepared in the present invention. It can be seen from the figure that metallic Co is highly dispersed on the catalyst surface, forming metal nanoparticles with a particle size of 1.5 - 3.5 nm;

[0048] See attached Figure 5 , which is the 1 1H NMR spectrum of the product in Example 1 of the present invention. It can be seen from the figure that the product is the target product and has a high purity (>99%).

[0049] Example 2:

[0050] In this example, a catalyst for aerobic dehydrogenation of primary amine to prepare nitrile is prepared. The specific preparation steps are as follows:

[0051] (1) Place 1.2 g of the prepared NaKETS-10 powder in 40 mL of deionized water and wash it to neutral. After washing, filter it under normal pressure, dry it at 110 °C for 9 h, and calcine it at 235 °C for 3 h to obtain a catalyst support;

[0052] (2) Place the support obtained in step 1 in 1.7 g of deionized water and ultrasonically disperse it for 0.5 h to make the white powder of NaKETS-10 evenly suspended in deionized water;

[0053] (3) Weigh 0.045 g of cobalt nitrate and place it in the suspension in step 2, and ultrasonically treat it at 35 °C for 9 h;

[0054] (4) Centrifuge the suspension in step 3 to obtain a catalyst precursor, dry it at 90 °C for 9 h, and calcine it at 245 °C for 3.5 h to obtain a Co@NaKETS-10 catalyst;

[0055] (5) Investigate the catalytic activity of the catalyst for aerobic dehydrogenation to prepare nitrile under thermal reflux conditions. The reaction is carried out in a 15 mL glass tube for 3 h, the reaction temperature is 90 °C, the catalyst is 8 mg, the reaction solvent is 1.0 mL of cyclohexane, and 2-methylbenzylamine is 0.3 mmol. The GC conversion rate of 2-methylbenzylamine is close to 100%, and the GC yield of the corresponding nitrile is 100%. No by-products are detected. Product characterization data: 11H NMR (300 MHz, CDCl3) δ: 7.51 (d, J = 7.7 Hz, 1H), 7.40 (t, J = 7.6 Hz, 1H), 7.30 - 7.12 (m, 2H), 2.47 (s, 3H); MS (70 eV) m / z (%): 117 (M + , 100), 118 (26), 92 (13).

[0056] See the appendix Figure 6 , which is the 1 1H NMR spectrum of the product in Example 2 of the present invention. It can be seen from the figure that the product is the target product and has a high purity (>99%).

[0057] Example 3:

[0058] In this example, a catalyst for aerobic dehydrogenation of primary amine to prepare nitrile is prepared. The specific preparation steps are as follows:

[0059] (1) Place 1.3 g of the prepared NaKETS-10 powder in 45 mL of deionized water and wash until neutral. After washing, filter at atmospheric pressure, dry at 110 °C for 8 h, and calcine at 255 °C for 4 h to obtain the catalyst support;

[0060] (2) Place the support obtained in step 1 in 1.6 g of deionized water and ultrasonically disperse for 1.0 h to make the white powder of NaKETS-10 evenly suspended in deionized water;

[0061] (3) Weigh 0.05 g of cobalt nitrate and place it in the suspension in step 2, and ultrasonically treat at 45 °C for 10 h;

[0062] (4) Centrifuge the suspension in step 3 to obtain the catalyst precursor, dry at 100 °C for 10 h, and calcine at 255 °C for 4.5 h to obtain the Co@NaKETS-10 catalyst;

[0063] (5) Investigate the catalytic activity of the catalyst for aerobic dehydrogenation to prepare nitrile under the condition of thermal reflux. The reaction is carried out in a 20 mL glass tube for 5 h, the reaction temperature is 100 °C, the catalyst is 10 mg, the reaction solvent is 1.5 mL of cyclohexane, and 2-furan benzylamine is 0.5 mmol. The GC conversion rate of 2-furan benzylamine is close to 100%, and the GC yield of the corresponding nitrile is 100%. No by-products are detected. Product characterization data: 1 1H NMR (300 MHz, CDCl3) δ: 7.52 (d, J = 1.7 Hz, 1H), 7.04 (d, J = 3.6 Hz, 1H), 6.56 - 6.39 (m, 1H); MS (70 eV) m / z (%): 93 (M + , 100), 94 (37), 67 (36).

[0064] See the appendixFigure 7 , which is the 1 1H NMR spectrum of the product of Example 3 of the present invention. It can be seen from the figure that the product is the target product and has a high purity (>99%).

[0065] Example 4:

[0066] In this example, a catalyst for aerobic dehydrogenation of primary amines to prepare nitriles was prepared. The specific preparation steps are as follows:

[0067] (1) Place 1.5 g of the prepared NaKETS-10 powder in 55 mL of deionized water and wash it until neutral. After washing, filter it under normal pressure, dry it at 100 °C for 9 h, and calcine it at 255 °C for 4 h to obtain a catalyst support;

[0068] (2) Place the support obtained in step 1 in 1.7 g of deionized water and ultrasonically disperse it for 0.5 h to make the white powder of NaKETS-10 evenly suspended in deionized water;

[0069] (3) Weigh 0.065 g of cobalt nitrate and place it in the suspension in step 2, and ultrasonically treat it at 40 °C for 9 h;

[0070] (4) Centrifuge the suspension in step 3 to obtain a catalyst precursor, dry it at 100 °C for 9 h, and calcine it at 245 °C for 4.5 h to obtain a Co@NaKETS-10 catalyst;

[0071] (5) Under the condition of thermal reflux, the catalytic activity of the catalyst for aerobic dehydrogenation to prepare nitriles was investigated. The reaction was carried out in a 10 mL glass tube for 3 h, the reaction temperature was 90 °C, the catalyst was 10 mg, the reaction solvent was 1.2 mL of cyclohexane, and 2-thiophenebenzylamine was 0.5 mmol. The GC conversion rate of 2-thiophenebenzylamine was close to 100%, and the GC yield of the corresponding nitrile was 100%. No by-products were detected. Product characterization data: 1 1H NMR (400 MHz, CDCl3) δ: 7.57 (dd, J = 3.8, 1.2 Hz, 1H), 7.55 (dd, J = 5.1, 1.2 Hz, 1H), 7.07 (dd, J = 5.1, 3.8 Hz, 1H); MS (70 eV) m / z (%): 109 (M + , 100), 111 (41), 83 (39).

[0072] See the appendix Figure 8 , which is the 1 1H NMR spectrum of the product of Example 4 of the present invention. It can be seen from the figure that the product is the target product and has a high purity (>99%).

[0073] Example 5:

[0074] In this embodiment, a catalyst for the aerobic dehydrogenation of primary amines to prepare nitriles is prepared, and the specific preparation steps are as follows:

[0075] (1) Place 1.5 g of the prepared NaKETS-10 powder in 50 mL of deionized water and wash it until neutral. After washing, filter it under normal pressure, dry it at 90 °C for 10 h, and calcine it at 235 °C for 4 h to obtain a catalyst support;

[0076] (2) Place the support obtained in step 1 in 1.65 g of deionized water and ultrasonically disperse it for 0.5 h to make the white NaKETS-10 powder evenly suspended in the deionized water;

[0077] (3) Weigh 0.06 g of cobalt nitrate and place it in the suspension in step 2, and ultrasonically treat it at 40 °C for 10 h;

[0078] (4) Centrifuge the suspension in step 3 to obtain a catalyst precursor, dry it at 80 °C for 10 h, and calcine it at 235 °C for 3.5 h to obtain a Co@NaKETS-10 catalyst;

[0079] (5) Under the condition of thermal reflux, the catalytic activity of the catalyst for the aerobic dehydrogenation to prepare nitriles is investigated. The reaction is carried out in a 10 mL glass tube for 2 h, the reaction temperature is 90 °C, the catalyst is 10 mg, the reaction solvent is 1.4 mL of cyclohexane, and 1-decylamine is 0.5 mmol. The GC conversion rate of 1-decylamine is close to 100%, and the GC yield of the corresponding nitrile is 100%, and no by-products are detected. Product characterization data: 1 H NMR (400 MHz, CDCl3) δ: 2.33 (t, J = 7.2 Hz, 2H), 1.73~1.60 (m, 2H), 1.53~1.39 (m, 2H), 1.38~1.18 (m, 10H), δ: 0.88 (t, J = 6.8 Hz, 3H); MS (70 eV) m / z (%) : 153 (M + , 100), 154 (67), 155 (45).

[0080] See the appendix Figure 9 , which is the 1 H NMR spectrum of the product in Example 5 of the present invention. It can be seen from the figure that the product is the target product and has a high purity (>99%).

[0081] For those not covered above, the prior art applies.

[0082] Although some specific embodiments of the present invention have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and not for limiting the scope of the present invention. Those skilled in the technical field to which the present invention pertains can make various modifications or supplements to the specific embodiments described or use similar means for substitution, but will not deviate from the direction of the present invention or exceed the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc. made to the above embodiments based on the technical essence of the present invention should all be included within the protection scope of the present invention.

Claims

1. A method for preparing a nitrile catalyst by aerobic dehydrogenation of primary amines, characterized in that: The following steps are involved: S1. Preparation of NaKETS-10 material using hydrothermal synthesis method; The NaOH aqueous solution and water glass are mixed and stirred, and then the KF aqueous solution and the TiCl3 hydrochloric acid solution are added in sequence to form a mixed gel solution, and the gel solution is subjected to hydrothermal reaction crystallization. After the crystallization is completed, the kettle is taken out, washed, filtered, dried, and calcined for the first time to obtain a sample, and the sample is washed again with deionized water, filtered, dried, and calcined for the second time to obtain the catalyst carrier NaKETS-10; S2, ultrasonically dispersing the carrier in deionized water to obtain a suspension; S3, ultrasonically dispersing the cobalt metal salt in the suspension of step S2; S4, centrifuging the suspension in step S3 to obtain a catalyst precursor, and drying and calcining under an inert gas atmosphere to obtain a Co@NaKETS-10 catalyst.

2. The preparation method according to claim 1, characterized in that: In step S1, the first calcination is calcined at 325-355° C. in air for 3-4 hours; the mass ratio of NaOH, water glass, KF and TiCl3 hydrochloric acid solution is 5.02:7.14:3.8:1, and the concentration of TiCl3 hydrochloric acid solution is 17.5%.

3. The preparation method according to claim 1, characterized in that: In step S1, when the sample is washed again with deionized water, the mass ratio of the sample to the deionized water is 0.02-0.05; the filtration process is carried out under normal pressure; the drying temperature is 90-110° C. and the drying time is 8-10 hours; in step S1, the second calcination is calcined at 235-255° C. in air for 3.5-4.5 hours.

4. The preparation method according to claim 1, characterized in that: In step S2, the mass ratio of the carrier to deionized water is 0.5-1; the ultrasonic time is 0.5-1h; in step S3, the ultrasonic treatment is performed at a temperature of 35-45°C for 8-10h.

5. The preparation method according to claim 1, characterized in that: In step S3, the cobalt metal salt is one of cobalt nitrate, cobalt carbonate and cobalt acetate; in step S3, the mass ratio of the cobalt metal salt to the carrier used in step S2 is 0.01 to 0.

05.

6. The preparation method according to claim 1, characterized in that: In step S4, the centrifugal speed is 5000-10000 rpm, and the centrifugal time is 3-5 min; in step S4, the drying temperature is 80-100° C., and the drying time is 8-10 h.

7. The preparation method according to claim 1, characterized in that: In step S4, the calcination temperature is 235-255° C., and the calcination time is 3.5-4.5 h; in step S4, the calcination atmosphere is nitrogen, and the nitrogen flow rate is 150-250 mL / min.

8. A catalyst for preparing nitrile by aerobic dehydrogenation of primary amines prepared by the preparation method according to any one of claims 1 to 8.

9. Use of the catalyst for preparing nitrile by aerobic dehydrogenation of primary amines as claimed in claim 8 in preparing nitrile by aerobic dehydrogenation of primary amines, characterized in that: The catalyst for preparing nitrile by aerobic dehydrogenation of primary amine as claimed in claim 8 is used, and primary amine is used as a raw material, and the nitrile is prepared by heating reaction in a reaction solvent under an oxygen atmosphere.

10. A method for preparing nitrile by aerobic dehydrogenation of primary amines as claimed in claim 9, characterized in that: The heating reaction temperature is 80-100° C.; the reaction time is 2-5 h; the ratio of primary amine to catalyst is 0.3-0.5 mmol: 5-15 mg; the reaction solvent is cyclohexane, and the ratio of primary amine to reaction solvent is 0.3-0.5 mmol: 1.2-1.5 mL.

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