Method for catalyzing preparation of adiponitrile from cyclohexanone by phosphorus-nitrogen co-doped porous carbon / co-p composite material

Abstract

The present application relates to a method for catalyzing cyclohexanone to prepare adiponitrile by phosphorus-nitrogen co-doped porous carbon / CoP composite material. The phosphorus-nitrogen co-doped porous carbon / CoP nanoparticle composite material is synthesized by a simple and easy-to-operate molten salt method, using cobalt chloride hexahydrate as a cobalt precursor and a molten salt, and glucose, melamine and diammonium hydrogen phosphate as precursors of carbon, nitrogen and phosphorus respectively. Under the conditions of using ammonia as a nitrogen source and oxygen as a terminal oxidant, cyclohexanone is ammoxidated to prepare adiponitrile, which is more environmentally friendly and safe. In addition, it is found that cyclic ketones with different carbon numbers and substituent groups can be converted into corresponding dinitrile products at high yield. Compared with the prior art, the technology involved in the present application is a new heterogeneous catalytic ammoxidation technology route, which uses a cheap heterogeneous catalyst and does not use hydrocyanic acid, and has the advantages of simple operation, low cost, high product yield, green environmental protection and the like.

Description

Technical Field

[0001] This invention belongs to the field of selective ammonia oxidation catalyst preparation and application technology, specifically involving a method for preparing adiponitrile from cyclohexanone catalyzed by phosphorus and nitrogen co-doped porous carbon / CoP composite materials. Background Technology

[0002] Adiponitrile, as an important chemical raw material, has broad applications in civilian clothing, special equipment, and new energy vehicles. It is mainly used in the production of nylon 66 salt, nylon fabric, engineering plastics, and as a stabilizer in the textile and paper industries. From 2005 to 2010, the global annual growth rate of adiponitrile was approximately 6.6%, with production reaching 1.18 million tons in 2010 and 1.41 million tons in 2018. In recent years, with the development of the nylon industry, global adiponitrile production capacity has reached 1.7 million tons per year, and global demand is projected to exceed 1.85 million tons by 2027.

[0003] The production methods differ in their characteristics. Acrylonitrile electrolysis can be completed in one step, producing high-quality products, but it involves complex reaction conditions and high process risks. It has stringent operational requirements, high energy consumption, and acrylonitrile is highly toxic and corrosive. Butadiene cyanation, with its low raw material cost, low energy consumption, short process route, and high-quality products, is a relatively ideal industrial production route suitable for large-scale industrial production. However, it requires a large initial investment, has high technical barriers, is difficult to catalyze, and the raw material, hydrogen cyanide, is highly toxic, necessitating stringent safety management. Adipic acid ammoniation has a simple production process and low equipment investment, but it involves numerous side reactions, leading to difficulties in product separation, poor product quality, limited capacity of a single unit, and low raw material utilization efficiency. As the adipic acid process matures and costs decrease, the economic benefits of the adipic acid method are beginning to change.

[0004] Against this backdrop, this technology utilizes cyclohexanone as a raw material and employs a phosphorus-nitrogen co-doped porous carbon / CoP composite material as a catalyst to synthesize adiponitrile in a one-step process under an ammonia and oxygen atmosphere, achieving a yield of 85.8%. Compared to traditional processes, this method offers significant advantages: the use of inexpensive and recyclable catalysts, mild reaction conditions, avoidance of highly toxic raw materials, and absence of iodine pollution. These characteristics demonstrate its great potential for industrial applications and provide a new solution for adiponitrile technology. Summary of the Invention

[0005] This invention provides a method for catalyzing the ammoxidation of cyclohexanone to synthesize adiponitrile using a phosphorus-nitrogen co-doped porous carbon / CoP composite material.

[0006] The technical solution adopted in this invention is:

[0007] A method for catalyzing the preparation of adiponitrile from cyclohexanone using a phosphorus-nitrogen co-doped porous carbon / CoP composite material: The phosphorus-nitrogen co-doped porous carbon / CoP composite material is synthesized via a simple and easy-to-operate molten salt method using cobalt chloride hexahydrate as the cobalt precursor and molten salt, and glucose, melamine, and diammonium hydrogen phosphate as the carbon, nitrogen, and phosphorus precursors, respectively. Under conditions where ammonia is used as the nitrogen source and oxygen as the terminal oxidant, the preparation of adiponitrile from cyclohexanone is efficiently catalyzed, i.e., the ammoxidation of cyclohexanone to adiponitrile.

[0008] The preparation method of the phosphorus-nitrogen co-doped porous carbon / CoP composite material is as follows: Glucose, melamine, cobalt chloride hexahydrate, and diammonium hydrogen phosphate are mixed in a certain proportion and then ground in a mortar for 20-30 min. The ground material is placed in a tube furnace and heated at 1-20°C under a nitrogen atmosphere. o C / min (preferably 2-5) o Heating at a heating rate of C / min to 600-1000 o C (preferably 700-900) o C, more preferably 800-900 o C), calcined for 2-4 h (preferably 3-4 h). The obtained intermediate was washed several times with 1-2 mol / L sulfuric acid solution, then washed with water, and the washed sample was collected by filtration to obtain a black powder. Then, the final product was heated at 50-100... o The phosphorus and nitrogen co-doped porous carbon / CoP composite material GxMyCoz is obtained by vacuum drying at C for 12-24 h, where x, y, and z represent the amounts of glucose, melamine, and cobalt chloride hexahydrate. The ratio of the amounts of glucose, melamine, and cobalt chloride hexahydrate added, x, y, and z, is (1-10) g:(1-3) g:(4-6) g, preferably (2-8) g:(1.6-2.6) g:(4.6-5.6) g, more preferably (4-6) g:(1.8-2.2) g:(4.8-5.2) g. The molar ratio of cobalt chloride hexahydrate to diammonium hydrogen phosphate is 1:0.9-1.1, preferably 1:0.95-1.05, more preferably 1:0.98-1.02, and most preferably 1:1.

[0009] The preferred method for preparing the phosphorus-nitrogen co-doped porous carbon / CoP composite material is as follows: glucose, melamine, cobalt chloride hexahydrate, and diammonium hydrogen phosphate are mixed in a certain proportion, and then ground in a mortar for 25-30 min. The ground material is then placed in a tube furnace and heated at 2-30°C under a nitrogen atmosphere. o Heating rate of C / min to 800-900 oCalcination at C for 2.5-3.5 h. The obtained intermediate is washed several times with 1.3-1.8 mol / L sulfuric acid solution, then washed with water, and the washed sample is collected by filtration to obtain a black powder. The final product is then heated at 50-80 °C. o The phosphorus and nitrogen co-doped porous carbon / CoP composite material GxMyCoz was obtained by vacuum drying at C for 12-16 h, where x, y and z represent the amounts of glucose, melamine and cobalt chloride hexahydrate, and the molar ratio of cobalt chloride hexahydrate to diammonium hydrogen phosphate was always fixed at 1:1.

[0010] The preferred method for preparing the phosphorus-nitrogen co-doped porous carbon / CoP composite material is as follows: glucose, melamine, cobalt chloride hexahydrate, and diammonium hydrogen phosphate are mixed in a certain proportion and then ground in a mortar for 30 min. The ground material is then placed in a tube furnace and heated under a nitrogen atmosphere at 2... o Heating rate of C / min to 800 o C, calcined for 3 h. The obtained intermediate was washed several times with 1.5 mol / L sulfuric acid solution, then washed with water, and the washed sample was collected by filtration to obtain a black powder. Then, the final product was heated at 60 °C. o The phosphorus and nitrogen co-doped porous carbon / CoP composite material GxMyCoz was obtained by vacuum drying at C for 12 h, where x, y and z represent the amounts of glucose, melamine and cobalt chloride hexahydrate, and the molar ratio of cobalt chloride hexahydrate to diammonium hydrogen phosphate was always fixed at 1:1.

[0011] Furthermore, the ratio of the amounts of glucose, melamine, and cobalt chloride hexahydrate added, x, y, and z, is (1-10)g: (1-3)g: (4-6)g, preferably (2-8)g: (1.6-2.6)g: (4.6-5.6)g, more preferably (4-6)g: (1.8-2.2)g: (4.8-5.2)g, and most preferably 6g: 2g: 5g.

[0012] The reaction procedure for the ammoxidation of cyclohexanone to prepare adiponitrile is as follows: The catalyst, 25-28 wt% ammonia, solvent, and cyclohexanone are added to the reaction vessel at a ratio of (10-40) mg: (141-564) mg: (2-4) mL: 1 mmol. After sealing the reaction vessel, an oxygen source gas of 0.5-1.0 MPa is introduced, and the reaction is carried out at a temperature of 80-140°C. o The product adiponitrile was obtained by reacting under C conditions for 3-12 h.

[0013] The preferred reaction procedure for the ammoxidation of cyclohexanone to prepare adiponitrile is as follows: Phosphorus and nitrogen co-doped porous carbon / CoP composite material, 25-28 wt% ammonia, solvent, and cyclohexanone are added to a reaction vessel at a mass ratio of (25-40) mg:(282-564) mg:(2.5-4) mL:1 mmol. After sealing the reaction vessel, an oxygen source gas of 0.8-1.0 MPa is introduced, and the reaction is carried out at a temperature of 90-130°C. o The product adiponitrile was obtained by reacting under C conditions for 4-10 h.

[0014] A more preferred reaction procedure for the ammoxidation of cyclohexanone to prepare adiponitrile is as follows: Phosphorus and nitrogen co-doped porous carbon / CoP composite material, 25-28 wt% ammonia, solvent, and cyclohexanone are added to a reaction vessel at a mass ratio of (30-40) mg:(423-564) mg:(3-4) mL:1 mmol. After sealing the reaction vessel, an oxygen source gas of 0.9-1.0 MPa is introduced, and the reaction is carried out at a temperature of 110-120 °C. o The product adiponitrile was obtained by reacting under C conditions for 5-8 h.

[0015] The optimal reaction procedure for the ammoxidation of cyclohexanone to prepare adiponitrile is as follows: Phosphorus and nitrogen co-doped porous carbon / CoP composite material, 25-28 wt% ammonia, solvent, and cyclohexanone are added to a reaction vessel at a mass ratio of 40 mg: 564 mg: 4 mL: 1 mmol. After sealing the reaction vessel, an oxygen source gas of 1.0 MPa is introduced, and the reaction is carried out at a temperature of 110 °C. o The product adiponitrile was obtained by reacting under C conditions for 6 hours.

[0016] Furthermore, the reaction solvent is one or more selected from 1,4-dioxane, acetonitrile, tert-amyl alcohol, 1,2-dichloroethane, dimethyl sulfoxide, N,N-dimethylformamide, n-heptane, and tetrahydrofuran, with acetonitrile being the most preferred.

[0017] Furthermore, the oxygen source is either pure oxygen or air, with oxygen being the most preferred.

[0018] Furthermore, in the method for preparing adiponitrile from cyclohexanone catalyzed by the phosphorus-nitrogen co-doped porous carbon / CoP composite material, the cyclohexanone can be prepared using cycloketones with different carbon numbers. , Or cyclohexanone with different substituents R = one or more of 2-Me, 3-Me, 3-Et, and 3-Pr.

[0019] Compared with existing technologies, this invention has significant technical advantages and practical value, mainly reflected in the following two aspects: Regarding the catalyst system, the phosphorus-nitrogen co-doped porous carbon / CoP composite catalyst used is not only readily available and inexpensive, but also has a simple and controllable preparation process, making it very suitable for large-scale production. Particularly noteworthy is the catalyst's excellent recyclability; it can be reused with simple filtration and maintains stable catalytic activity and selectivity over a long period, providing a reliable guarantee for controlling production costs. Regarding the process route, this invention innovatively develops a completely new synthetic route. This route features simplified reaction steps, the use of a recyclable and inexpensive heterogeneous catalyst system, and complete avoidance of the use of highly toxic hydrogen cyanide. It also boasts advantages such as ease of operation and environmental friendliness, demonstrating broad prospects for industrial application and potentially becoming a new generation of green adiponitrile production technology.

[0020] The catalyst used in this method exhibits excellent recyclability and can be reused simply by separation after the reaction. Experiments show that the catalyst maintains stable catalytic activity after 20 cycles without significant decline.

[0021] This method has good potential for scale-up production. In kilogram-scale experiments, the selectivity for adiponitrile reached 85.8% after 6 hours of standard reaction conditions. This result indicates that the catalytic system has excellent prospects for industrial application and can meet the needs of large-scale production. Detailed Implementation

[0022] The following examples will help to understand the present invention, but the scope of the present invention is not limited thereto.

[0023] The preparation method of phosphorus-nitrogen co-doped porous carbon / CoP composite materials used in the following examples is as follows:

[0024] Mix 6 g glucose, 2 g melamine, 5.0 g cobalt chloride hexahydrate, and 2.8 g diammonium hydrogen phosphate in the specified proportions, and then grind them in a mortar for 30 min. Place the ground mixture in a tube furnace and heat it under a nitrogen atmosphere at 2... o Heating rates from room temperature to 800 °C / min o C, calcined for 3 h. The obtained intermediate was washed twice with 1.5 mol / L sulfuric acid solution (10 min each time, 100 mL of sulfuric acid solution), then washed twice with water, and the washed sample was collected by filtration to obtain a black powder. Then, the final product was heated at 60 °C. oAfter vacuum drying at C for 12 h, a phosphorus-nitrogen co-doped porous carbon / CoP nanoparticle composite material G6M2Co5 was obtained. The Co content was 1.9 wt%, the P content was 2.5 wt%, the N content was 3.2 wt%, the pore size distribution range was 2-5 nm, and the CoP nanoparticle size was 5-50 nm.

[0025] As a comparative experiment, the same process (procedure and conditions) as the preparation of the G6M2Co5 catalyst were used, except that the amount of glucose added was changed (2 g, 4 g, and 8 g, respectively), to prepare phosphorus and nitrogen co-doped porous carbon / CoP nanoparticle composites G2M2Co5, G4M2Co5, and G8M2Co5, respectively. Specifically, G2M2Co5 had a Co content of 2.2 wt%, a P content of 2.0 wt%, a N content of 2.9 wt%, a pore size distribution of 2-5 nm, and CoP nanoparticle size of 7-56 nm. G4M2Co5 had a Co content of 2.0 wt%, a P content of 2.6 wt%, a N content of 3.3 wt%, a pore size distribution of 2-5 nm, and CoP nanoparticle size of 5-52 nm. G8M2Co5 had a Co content of 1.7 wt%, a P content of 2.3 wt%, a N content of 2.9 wt%, a pore size distribution of 2-5 nm, and CoP nanoparticle size of 5-70 nm.

[0026] Using the same process flow (process and conditions) as the preparation of the G6M2Co5 catalyst, the only difference being the amount of melamine added (0 g, 1 g, and 3 g, respectively), phosphorus and nitrogen co-doped porous carbon / CoP nanoparticle composites G6M0Co5, G6M1Co5, and G6M3Co5 were prepared. Specifically, G6M0Co5 had a Co content of 2.5 wt%, a P content of 3.8 wt%, and a N content of 0.1 wt%, with a pore size distribution of 5-10 nm and CoP nanoparticle size of 8-60 nm; G6M1Co5 had a Co content of 2.6 wt%, a P content of 2.7 wt%, and a N content of 2.5 wt%, with a pore size distribution of 2-5 nm and CoP nanoparticle size of 5-55 nm; and G6M3Co5 had a Co content of 1.8 wt%, a P content of 2.0 wt%, and a N content of 4.1 wt%, with a pore size distribution of 2-5 nm and CoP nanoparticle size of 5-45 nm.

[0027] Example 1

[0028] G6M2Co5 (40 mg), 25-28 wt% ammonia (564 mg), cyclohexanone (1 mmol), and acetonitrile (4 mL, solvent) were added to a reaction vessel. After sealing the vessel, the internal atmosphere was replaced with oxygen, and then 1.0 MPa of oxygen was introduced. The reaction was carried out at a temperature of 110°C.o The reaction was carried out at C for 6 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The pressure was slowly released to atmospheric pressure, the reactor was opened, 20 mg of naphthalene was added as an internal standard, and then 2 mL of acetonitrile was added for dilution. The mixture was stirred and centrifuged to separate the solid and liquid (the solid was the catalyst). The supernatant was taken for GC and GC-MS analysis.

[0029] Examples 2-7

[0030] Except for changing the type of catalyst, all other procedures and steps are the same as in Example 1, as shown in Table 1:

[0031] Table 1. Catalytic performance of different catalysts in the ammoxidation of cyclohexanone to adiponitrile

[0032]

[0033] Reaction conditions: Cyclohexanone (1 mmol), GxMyCoz (40 mg), 25-28 wt% ammonia (564 mg), acetonitrile (4 mL), 1.0 MPa oxygen, 110 o C, 6 h.

[0034]

[0035] Examples 8-14

[0036] Except for changing the type of solvent, all other procedures and steps are the same as those in Example 1, as shown in Table 2:

[0037] Table 2. Effect of different solvents on the G6M2Co5-catalyzed reaction of cyclohexanone to adiponitrile

[0038]

[0039] Reaction conditions: Cyclohexanone (1 mmol), G6M2Co5 (40 mg), 25-28 wt% ammonia (564 mg), solvent (4 mL), 1.0 MPa O2, 110 o C, 6 h.

[0040]

[0041] Examples 15-18

[0042] Except for changing the oxygen pressure, all other operations and steps are the same as in Example 1, as shown in Table 3:

[0043] Table 3. Effect of different oxygen pressures on the G6M2Co5-catalyzed reaction of cyclohexanone to adiponitrile

[0044]

[0045] Reaction conditions: Cyclohexanone (1 mmol), G6M2Co5 (40 mg), 25-28 wt% ammonia (564 mg), acetonitrile (4 mL), O2, 110 o C, 6 h.

[0046]

[0047] Examples 19-22

[0048] Except for the change in reaction temperature, all other procedures and steps are the same as in Example 1, as shown in Table 4:

[0049] Table 4. Effect of different reaction temperatures on the G6M2Co5-catalyzed reaction of cyclohexanone to adiponitrile

[0050]

[0051] Reaction conditions: Cyclohexanone (1 mmol), G6M2Co5 (40 mg), 25-28 wt% ammonia (564 mg), solvent (4 mL), 1.0 MPa O2, 6 h.

[0052]

[0053] Examples 23-26

[0054] Except for the change in reaction time, all other procedures and steps are the same as in Example 1, as shown in Table 5:

[0055] Table 5. Effect of different reaction times on the G6M2Co5-catalyzed reaction of cyclohexanone to adiponitrile

[0056]

[0057] Reaction conditions: Cyclohexanone (1 mmol), G6M2Co5 (40 mg), 25-28 wt% ammonia (564 mg), solvent (4 mL), 1.0 MPa O2, 110 o C.

[0058]

[0059] Examples 27-46

[0060] The catalyst used in Example 1 was collected and reused in the reaction. The reaction was carried out under the same procedures and conditions as in Example 1. The difference between Examples 27-47 is that the number of cycles of the G6M2Co5 catalyst was changed. As shown in Table 6, it can be seen that G6M2Co5 can be recycled at least 20 times with its activity remaining basically unchanged, indicating that the catalyst has good cycle stability.

[0061] Table 6. Cyclic experiments of selective ammoxidation of cyclohexanone to adiponitrile

[0062]

[0063] Reaction conditions: Cyclohexanone (1 mmol), G6M2Co5 (40 mg), 25-28 wt% ammonia (564 mg), acetonitrile (4 mL), 1.0 MPa O2, 110 o C, 6 h.

[0064]

[0065] Examples 47-54

[0066] Except for changing the substrate, the other processes and conditions are the same as those in Example 1, as shown in Table 7. Cyclic ketones with different carbon numbers and substituents can be converted into the corresponding dinitrile products in high yield, demonstrating the universality of the method.

[0067] Table 7. Effect of different carbon numbers and substituents on product yield of cyclic ketones

[0068]

[0069] Reaction conditions: substrate (1 mmol), G6M2Co5 (40 mg), 25-28 wt% ammonia (564 mg), acetonitrile (4 mL), 1.0 MPa O2, 110 o C, 6 h.

[0070] In summary, the cyclohexanone ammoxidation process developed in this invention has significant comprehensive advantages: it adopts an innovative and reliable process route, features low production costs, environmental friendliness, and catalyst recyclability, while simultaneously yielding high-yield adiponitrile products. These technical characteristics make this process a promising breakthrough in my country's adiponitrile production technology research and development, fully demonstrating its enormous potential for industrial application.

Claims

1. A method for catalyzing cyclohexanone to prepare adiponitrile by using phosphorus-nitrogen co-doped porous carbon / CoP composite material, characterized in that: the phosphorus-nitrogen co-doped porous carbon / CoP composite material is used as a catalyst to catalyze cyclohexanone to prepare adiponitrile; the phosphorus-nitrogen co-doped porous carbon / CoP composite material is synthesized by using cobalt chloride hexahydrate as a cobalt precursor and molten salt, and glucose, melamine and diammonium hydrogen phosphate as precursors of carbon, nitrogen and phosphorus, respectively, through a molten salt method; cyclohexanone is ammonoxidated to prepare adiponitrile under the conditions of ammonia as a nitrogen source and 0.5-1.0 MPa oxygen source gas; the reaction solvent is one or more of 1,4-dioxane, acetonitrile, tertiary amyl alcohol, dimethyl sulfoxide DMSO, N,N-dimethylformamide DMF and tetrahydrofuran; and the oxygen source gas is one or both of pure oxygen and air. 2.The preparation process of the phosphorus-nitrogen co-doped porous carbon / CoP composite material is as follows: 1) mixing glucose, melamine, cobalt chloride hexahydrate and diammonium hydrogen phosphate; 2. The method for catalyzing the preparation of adiponitrile from cyclohexanone by using the phosphorus-nitrogen co-doped porous carbon / CoP composite material according to claim 1, characterized in that: 2) placing the mixed sample in a tube furnace, heating from room temperature to 600-1000 ℃ at a heating rate of 1-20 ℃ / min under a nitrogen atmosphere, and calcining for 2-4 h to obtain an intermediate; 3) soaking and cleaning the obtained intermediate with a 1-2 mol / L sulfuric acid solution, washing with water, then filtering to collect the cleaned solid sample to obtain a powder; 4) then, drying the powder obtained in step 3) to obtain the product phosphorus-nitrogen co-doped porous carbon / CoP composite material. 3.The method for catalyzing cyclohexanone to prepare adiponitrile by using the phosphorus-nitrogen co-doped porous carbon / CoP composite material according to claim 2, characterized in that: the phosphorus-nitrogen co-doped porous carbon / CoP composite material is simply written as GxMyCoz, wherein x, y and z respectively represent the added mass of glucose, melamine and cobalt chloride hexahydrate in step 1), and the added amount of the glucose, melamine and cobalt chloride hexahydrate x, y and z is in a ratio of (1-10) g :(1-3) g :(4-6) g; the molar ratio of cobalt chloride hexahydrate to diammonium hydrogen phosphate is 1:0.9-1.

1. 4.The method for catalyzing cyclohexanone to prepare adiponitrile by using the phosphorus-nitrogen co-doped porous carbon / CoP composite material according to claim 2, characterized in that: in step 4), the drying refers to vacuum drying at 60-100 ℃ for 12-24 h. 5.The method for catalyzing cyclohexanone to prepare adiponitrile by using the phosphorus-nitrogen co-doped porous carbon / CoP composite material according to claim 2, characterized in that: in step 1), the mixing is followed by grinding in a mortar for 20-30 min; in step 3), the sulfuric acid solution is soaked and cleaned for 1-4 times, each time for 2-30 min. The reaction operation process of cyclohexanone ammonoxidation to prepare adiponitrile is as follows: ​ 6. The method of claim 1-5, wherein the phosphorus and nitrogen co-doped porous carbon / CoP composite material catalyzes the preparation of adiponitrile from cyclohexanone. ​ The phosphorus-nitrogen co-doped porous carbon / CoP composite GxMyCoz, 25-28 wt% ammonia water, a reaction solvent and cyclohexanone are added into a reaction container in a ratio of 10-40 mg GxMyCoz: 141-564 mg 25-28 wt% ammonia water: 2-4 mL reaction solvent: 1 mmol cyclohexanone, oxygen source gas is filled into the sealed reaction container at 0.5-1.0 MPa, and the reaction is carried out at a temperature of 80-140°C for 3-12 h to obtain a dinitrile product.

7. A method for catalyzing the preparation of dinitrile from cyclic ketone by using a phosphorus-nitrogen co-doped porous carbon / CoP composite material, characterized in that: The reaction operation process of preparing dinitrile by cycloketone ammoxidation is as follows: The phosphorus-nitrogen co-doped porous carbon / CoP composite GxMyCoz, 25-28 wt% ammonia water, a reaction solvent and cyclohexanone are added into a reaction container in a ratio of 10-40 mg GxMyCoz: 141-564 mg 25-28 wt% ammonia water: 2-4 mL reaction solvent: 1 mmol cyclohexanone, oxygen source gas is filled into the sealed reaction container at 0.5-1.0 MPa, and the reaction is carried out at a temperature of 80-140°C for 3-12 h to obtain a dinitrile product, The cyclic ketone is a cyclic ketone with a different number of carbon atoms. , Or cyclic ketones with different substituents R = one or more of 2-Me, 3-Me, 3-Et, and 3-Pr; The phosphorus-nitrogen co-doped porous carbon / CoP composite is a phosphorus-nitrogen co-doped porous carbon / CoP nanoparticle composite material synthesized by a molten salt method, in which cobalt chloride hexahydrate is used as a cobalt precursor and a molten salt, and glucose, melamine and diammonium hydrogen phosphate are used as carbon, nitrogen and phosphorus precursors, respectively.

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