Catalyst, preparation method thereof and application of catalyst in preparation of nitrile compounds through ammoxidation of alcohol compounds

Abstract

The invention belongs to the technical field of catalysts, and particularly discloses a catalyst, a preparation method of the catalyst and application of the catalyst to preparation of nitrile compounds through ammoxidation of alcohol compounds. Manganese acetate is used as a manganese source, dicyanodiamine is used as a carbon source and a nitrogen source, the catalyst is obtained through high-temperature pyrolysis under the protection of nitrogen, a carbon-nitrogen material is used as a framework, and an active component MnNCN is loaded on the framework. The catalyst not only can be used for catalyzing monohydric alcohol ammoxidation to synthesize nitrile compounds under mild conditions, but also can be used for catalyzing aromatic dihydric alcohol C-C bond oxidative cracking to synthesize nitrile compounds. The preparation method of the catalyst is simple, the stability of the catalyst is relatively good, the catalyst can be recycled for more than 6 times, and the catalyst has a good industrial application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to a catalyst and a preparation method thereof, and application thereof in preparing nitrile compounds by ammoxidation of alcohol compounds. Background Art

[0002] Nitrile compounds are high-value chemicals with wide applications in pesticides, medicine, functional polymer materials, organic synthesis and other fields. The traditional synthesis of nitrile compounds is achieved through nucleophilic substitution reactions of halides or CH bonds with metal cyanides or organic cyanides, or hydrocyanation reactions of C=C bonds with HCN or HCN donors, which involve highly toxic cyanides. The green synthesis of nitrile compounds is achieved through ammoxidation reactions of alcohols, aldehydes, ketones, etc., avoiding the use of toxic cyanides.

[0003] At present, heterogeneous catalytic systems for the ammoxidation of alcohol compounds to synthesize nitrile compounds have been widely studied, but these catalytic systems have low universality for alcohol compounds. For example, Matthias Beller et al. used a single-atom Fe catalyst (Fe1-NC) with oxygen and ammonia as the oxidant and nitrogen source, respectively, to catalyze the ammoxidation of alcohol compounds to synthesize nitrile compounds. This catalytic system is limited to monohydric alcohols and has excellent catalytic activity for aromatic monohydric alcohol compounds, but for aliphatic monohydric alcohols, higher reaction temperatures and oxygen pressures are required to obtain a considerable nitrile yield [Nature Communications [J], 2022, 13, 1848.]. Our research group has previously developed a single-atom Fe catalyst (Fe-N3 / NC-1100) that can efficiently catalyze the ammoxidation of aromatic monohydric alcohols and aromatic vicinal diols to synthesize nitrile compounds, but has no catalytic activity for aliphatic alcohols [Science Advances [J], 8, eadd1267.].

[0004] In summary, the methods for preparing nitrile compounds by ammoxidation of alcohol compounds disclosed in the prior art have great limitations on the substrates of alcohol compounds, and therefore it is necessary to develop a catalyst that can be widely applied to the ammoxidation reaction of various alcohol compounds to synthesize nitrile compounds. Summary of the invention

[0005] According to the deficiencies in the prior art, the object of the present invention is to provide a catalyst and a preparation method thereof and an application thereof in preparing nitrile compounds by ammoxidation of alcohol compounds. Specifically, a carbon-nitrogen material-supported MnNCN catalyst (denoted as MnNCN / NC) having an active component of MnNCN is provided, and an application thereof in catalyzing the ammoxidation of alcohol compounds to synthesize nitrile compounds. The catalyst preparation method is simple, and the raw materials are cheap and readily available, and can be applied to large-scale industrial production. The catalyst MnNCN / NC is used for catalyzing the ammoxidation of alcohol compounds to synthesize nitrile compounds, and not only the reaction conditions are mild, the product selectivity is high, but also the substrate range is very wide.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] One of the technical solutions is a carbon-nitrogen material-supported MnNCN catalyst, denoted as MnNCN / NC, with a carbon-nitrogen material as a skeleton, and an active component MnNCN is supported on the skeleton. The mass content of the Mn element in the carbon-nitrogen material-supported MnNCN catalyst is 25wt.%-27wt.%, more preferably 25.8wt.%-26.2wt.%, and more preferably 26wt.%. The specific surface area of ​​the carbon-nitrogen material-supported MnNCN catalyst is 80m 2 / g-100m 2 / g, preferably 90m 2 / g-100m 2 / g, more preferably 95m 2 / g-100m 2 The carbon-nitrogen material-loaded MnNCN catalyst uses manganese acetate as a manganese source and dicyandiamide as a carbon source and a nitrogen source, and is obtained by high-temperature pyrolysis under nitrogen protection.

[0008] Technical solution 2, the preparation method of the above-mentioned carbon-nitrogen material-supported MnNCN catalyst (MnNCN / NC) comprises the following steps:

[0009] (1) fully grinding manganese acetate and dicyandiamide and mixing them uniformly;

[0010] (2) The mixture obtained in step (1) is pyrolyzed at high temperature under nitrogen protection, the pyrolysis temperature is 580-650° C., and the pyrolysis time is 1.5-2.5 h, thereby obtaining the carbon-nitrogen material-loaded MnNCN catalyst.

[0011] Furthermore, in the step (1), the mass ratio of manganese acetate to dicyandiamide is 3:10.

[0012] Furthermore, in the step (2), the pyrolysis temperature is 590-620°C; preferably, the pyrolysis temperature is 595-605°C; more preferably, the pyrolysis temperature is 600°C and the pyrolysis time is 2h.

[0013] The third technical solution is the use of the above-mentioned carbon-nitrogen material-loaded MnNCN catalyst or the carbon-nitrogen material-loaded MnNCN catalyst prepared by the above-mentioned method in the preparation of nitrile compounds by ammoxidation of alcohol compounds, the steps of which are: adding the carbon-nitrogen material-loaded MnNCN catalyst, an organic solvent, an alcohol compound and aqueous ammonia into a high-pressure reactor, sealing it and filling it with 7.5-15 bar of oxidizing gas, and then conducting an ammoxidation reaction at 80-150°C under constant stirring to obtain nitrile compounds.

[0014] Furthermore, the solvent is 1,4-dioxane.

[0015] Furthermore, the concentration of the aqueous ammonia is 25.0wt.%-28.0wt.%.

[0016] Furthermore, the ratio of the carbon-nitrogen material loaded with MnNCN catalyst, organic solvent, alcohol compound and ammonia water is 20 mg: 10 mL: 0.5 mmol: 100-300 μL, preferably 20 mg: 10 mL: 0.5 mmol: 150-250 μL, and further preferably 20 mg: 10 mL: 0.5 mmol: 195-205 μL.

[0017] Furthermore, the oxidizing gas is air or oxygen.

[0018] Furthermore, the pressure of the oxidizing gas charged is 7.5-10 bar, and then the ammoxidation reaction is carried out at 110-150° C. with constant stirring.

[0019] Furthermore, the alcohol compound is any one of an aromatic monohydric alcohol, an aliphatic monohydric alcohol, an aromatic vicinal diol, an aliphatic vicinal diol, and a long-chain end diol; further,

[0020] The aromatic monohydric alcohol is any one of the following structural formulas: n is a natural number from 1 to 3, n is a natural number from 1 to 2, n is a natural number from 1 to 2, n is a natural number from 1 to 2,

[0021] Aliphatic monohydric alcohols are C3-C8 monohydric alcohols, such as heptanol, cyclohexylmethanol, etc.;

[0022] The aromatic vicinal diol is any one of the following structural formulas:

[0023] Aliphatic vicinal diols are C3-C8 vicinal diols, such as 1,2-propylene glycol and 1,2-hexanediol;

[0024] The long chain end diol is a C3-C8 end diol, such as 1,6-hexanediol or

[0025] in:

[0026] R1 is monosubstituted or polysubstituted, R1 is ortho, meta and / or para, and R1 is independently selected from the following groups: H, C1-C4 alkyl, hydroxyl, vinyl, methoxy, methylthio, phenyl, amino, halogen (F, Cl, Br, I), trifluoromethyl, nitro, etc.;

[0027] R2 is monosubstituted, R2 is ortho, meta or para, and is selected from the following groups: H, methyl, halogen (F, Cl, Br, I), trifluoromethyl, phenyl, etc.;

[0028] R3 is selected from the following groups: C1-C3 alkyl, etc.;

[0029] R4 is monosubstituted, R4 is ortho, meta or para, and R4 is selected from the following groups: H, halogen (F, Cl, Br, I), methyl, methoxy, nitro, trifluoromethyl, etc.;

[0030] R5 is monosubstituted, R5 is ortho, meta or para, and R5 is selected from the following groups: H, halogen (F, Cl, Br, I), methyl, methoxy, etc.;

[0031] R6 is selected from the following groups: H, methyl, phenyl, substituted phenyl (the substituents are: halogen (F, Cl, Br, I), methyl, methoxy).

[0032] Compared with the prior art, the advantages and beneficial effects of the catalyst of the present invention and its application are:

[0033] Compared with other non-precious metal catalysts, such as single-atom Fe catalysts, the preparation method of this catalyst is simple and the raw materials are cheap and easily available.

[0034] The catalyst of the invention has high activity, can realize the ammoxidation of aromatic vicinal diols at low temperature (80° C.), and can efficiently synthesize nitrile compounds.

[0035] The catalyst of the present invention has high universality for alcohol compounds, and can catalyze the ammoxidation of aromatic monohydric alcohols, aliphatic monohydric alcohols, aromatic vicinal diols, aliphatic vicinal diols, terminal phenyl-substituted fatty alcohols and long-chain terminal diols, and can synthesize nitrile compounds with high efficiency and selectivity.

[0036] The catalyst of the present invention has good stability, can be recycled more than 6 times, and has good industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 X-ray diffraction (XRD) patterns of Mn / NC-500, MnNCN / NC-600 and MnNCN / NC-700 catalysts.

[0038] Figure 2 (a), (b), and (c) are high-resolution transmission electron microscopy (HR-TEM) images of Mn / NC-500, MnNCN / NC-600, and MnNCN / NC-700 catalysts, respectively.

[0039] Figure 3 Mn 2p XPS patterns of Mn / NC-500, MnNCN / NC-600 and MnNCN / NC-700 catalysts.

[0040] Figure 4 N2 physical adsorption-desorption isotherms of Mn / NC-500, MnNCN / NC-600 and MnNCN / NC-700 catalysts. DETAILED DESCRIPTION

[0041] Some specific embodiments are listed below to further illustrate the present invention, but are not intended to limit the scope of protection requested by the claims of the present invention.

[0042] Embodiment 1:

[0043] 0.6g of manganese acetate and 2.0g of dicyandiamide were fully ground and mixed. The obtained mixture was pyrolyzed at high temperature under nitrogen protection, and the temperature was raised from room temperature to 600°C at a heating rate of 2°C / min, and kept at 600°C for 2h to obtain MnNCN / NC-600 catalyst. The active component was MnNCN, and the mass content of Mn element in the catalyst was 26% as determined by plasma resonance technology (ICP-AES).

[0044] Embodiment 2:

[0045] The operation and steps were the same as those in Example 1, except that the pyrolysis temperature was changed to 500° C. The obtained catalyst was recorded as Mn / NC-500, wherein the mass content of Mn element was 21%.

[0046] Embodiment 3:

[0047] The operation and steps are the same as those in Example 1, except that the pyrolysis temperature is changed to 700° C., and the catalyst having the active component of MnNCN is recorded as MnNCN / NC-700, wherein the active component is MnNCN and the mass content of Mn element is 37%.

[0048] Embodiment 4:

[0049] The catalysts prepared in Examples 1 to 3 were subjected to X-ray diffraction pattern analysis. By conducting an X-ray diffraction test on the material and analyzing its diffraction pattern, information such as the structure or morphology of atoms or molecules inside the material can be obtained. Figure 1 The XRD pattern of the Mn / NC-500 catalyst only shows a broad diffraction peak at 2θ=27.8°, which is attributed to the (002) crystal plane of the g-C3N4 structure. As the calcination temperature increases, the g-C3N4 structure gradually collapses (MnNCN / NC-600) and disappears (MnNCN / NC-700). In addition, the characteristic peaks of MnNCN (corresponding to PDF: 01-073-3162) at 2θ=18.5°, 31.4°, 33.2°, 37.6°, 39.9°, 44.3°, 54.6°, 58.2°, 65.61°, and 68.38° were detected in the spectra of the MnNCN / NC-600 and MnNCN / NC-700 catalysts, indicating that the MnNCN structure exists in both the MnNCN / NC-600 and MnNCN / NC-700 catalysts.

[0050] Embodiment 5:

[0051] The catalysts prepared in Examples 1 to 3 were subjected to HR-TEM analysis, and information such as the material morphology and crystal structure was obtained based on the HR-TEM images of the materials. Figure 2 No crystal diffraction fringes were observed in the HT-TEM image of the Mn / NC-500 catalyst. Characteristic crystal planes with interplanar spacings of 0.17 nm, 0.27 nm, and 0.48 nm were observed in the HR-TEM images of the MnNCN / NC-600 and MnNCN / NC-700 catalysts, corresponding to the (110), (012), and (003) crystal planes of the MnNCN structure, respectively. This phenomenon is consistent with the results of the XRD spectrum in Example 4.

[0052] Embodiment 6:

[0053] The catalysts prepared in Examples 1-3 were subjected to X-ray photoelectron spectroscopy analysis. Based on the XPS graph of the material, information such as the valence state of the elements on the surface of the material was obtained. Figure 3 As shown in the figure, in the Mn / NC-500 catalyst, Mn2p 3 / 2 The orbital energy is fitted into three peaks with binding energies of 640.8eV, 642.9eV and 646.3eV, which are attributed to the Mn coordinated with the N atom in the triazine ring of g-C3N4. The binding energy of divalent Mn in MnNCN / NC-600 and MnNCN / NC-700 catalysts is shifted to the low binding energy direction compared with that of Mn / NC-500 catalyst. This is because the high spin divalent manganese containing 5 unpaired electrons is bound to the linear [N=C=N] 2-The unit coordination forms the octahedral structure of MnNCN.

[0054] Embodiment 7:

[0055] The catalysts prepared in Examples 1-3 were subjected to N2 physical adsorption-desorption isotherm analysis. According to the N2 physical adsorption-desorption isotherm of the material, the texture property information of the material was obtained. Figure 4 As shown in Figure 2, with the increase of calcination temperature, the specific surface area of ​​the catalyst increases first and then decreases. The MnNCN / NC-600 catalyst has the largest specific surface area of ​​98.9 m 2 / g, the minimum specific surface area of ​​MnNCN / NC-700 catalyst is 24.5m 2 / g, the specific surface area of ​​Mn / NC-500 catalyst is 31.7m 2 / g. Since the large specific surface area and rich pore structure are conducive to mass transfer, the specific surface area is one of the factors affecting the efficiency of the catalytic reaction for the solid-liquid reaction system. The MnNCN / NC-700 catalyst exhibits poor catalytic activity due to its small specific surface area (see Example 9 for specific data).

[0056] Embodiment 8:

[0057] A method for synthesizing benzonitrile by catalyzing the ammoxidation of benzyl alcohol using the MnNCN / NC-600 catalyst prepared in Example 1, comprising the following steps:

[0058] In a typical reaction, benzyl alcohol (0.5 mmol), MnNCN / NC-600 (20 mg), ammonia (26.5 wt.%, 200 μL) and solvent 1,4-dioxane (10 mL) were added to an autoclave, and then the autoclave was purged with O2 for 5 times to completely remove the air therein. After the autoclave was sealed, 10 bar of O2 was added at room temperature, and then it was heated from room temperature to 130°C, and then reacted at 130°C with a mechanical stirring speed of 1000 rpm for 4 hours. After the reaction was completed, the catalyst was collected by centrifugation. The liquid phase product was quantitatively analyzed by gas chromatography, in which benzyl alcohol was completely converted, the selectivity of benzonitrile was 94%, and the selectivity of the intermediate product benzaldehyde was 6%.

[0059] Embodiment 9:

[0060] The operation method and steps are the same as those in Example 8, except that the added catalyst is changed. The products obtained are also benzaldehyde and benzonitrile, as shown in Table 1:

[0061] Table 1

[0062]

[0063]

[0064] Example 10: The operation method and steps are the same as those of Example 8, only the reaction temperature is changed, and the product distribution is shown in Table 2:

[0065] Table 2

[0066]

[0067] Example 11: The operation method and steps are the same as those of Example 8, except that the reaction temperature is changed to 110°C and the reaction solvent is changed. The product distribution is shown in Table 3. When hydrocarbons such as toluene and n-hexane are used as reaction solvents, the conversion rate of benzyl alcohol is low and the selectivity of benzonitrile is relatively low. This is because the solubility of ammonia water in these solvents is low. Ammonia water can promote the oxidation of benzyl alcohol and is also the raw material for the subsequent ammoxidation synthesis of nitrile.

[0068] Table 3

[0069]

[0070]

[0071] Example 12: The operation method and steps are the same as those of Example 8, except that the reaction temperature is changed to 110°C and the oxygen pressure is changed (in order to eliminate the influence of the system pressure, when the oxygen pressure is different, nitrogen gas is added as a protective gas to make the system pressure consistent). The product distribution is shown in Table 4:

[0072] Table 4

[0073]

[0074] Example 13: The operation method and steps are the same as those of Example 8, except that the reaction temperature is changed to 110°C and the amount of ammonia water is changed. The product distribution is shown in Table 5:

[0075] Table 5

[0076]

[0077] Example 14: The operation method and steps are the same as those of Example 8, except that the reaction temperature is changed to 110°C and the reaction time is changed. The product distribution is shown in Table 6:

[0078] Table 6

[0079]

[0080] Example 15: Synthesis of nitriles by ammoxidation reaction of different aromatic primary alcohol compounds.

[0081] Different alcohol compounds (0.5mmol), 1,4-dioxane (10mL), ammonia (26.5wt.%, 200μL) and MnNCN / NC-600 catalyst (20mg) prepared in Example 1 were added to a 40mL stainless steel reactor. After replacing the air with oxygen 5 times, the reactor was sealed, and 10bar oxygen was filled into the reactor. The reaction was carried out at 80°C with a magnetic stirring speed of 1000rpm for 13-36h. After the reaction was completed, the catalyst was collected by centrifugation. The liquid product was detected by gas chromatography, and the conversion rate of alcohol and the yield of nitrile compounds were calculated. The results are shown in Table 7 below:

[0082] Table 7

[0083]

[0084]

[0085]

[0086] Example 16: Synthesis of nitrile by ammoxidation reaction of terminal benzene ring substituted fatty alcohol.

[0087] Different alcohol compounds (0.5mmol), 1,4-dioxane (10mL), ammonia (26.5wt.%, 200μL) and MnNCN / NC-600 catalyst (20mg) prepared in Example 1 were added to a 40mL stainless steel reactor. After replacing the air with oxygen 5 times, the reactor was sealed, and 10bar oxygen was filled into the reactor. The reaction was carried out at 150°C with a magnetic stirring speed of 1000rpm for 15-26h. After the reaction was completed, the catalyst was collected by centrifugation. The liquid product was detected by gas chromatography, and the conversion rate of alcohol and the yield of nitrile compounds were calculated. The results are shown in Table 8 below:

[0088] Table 8

[0089]

[0090]

[0091] Example 17: Synthesis of nitrile by ammoxidation reaction of aromatic secondary alcohol compounds.

[0092] Different alcohol compounds (0.5mmol), 1,4-dioxane (10mL), ammonia (26.5wt.%, 200μL) and the MnNCN / NC-600 catalyst (20mg) prepared in Example 1 were added to a 40mL stainless steel reactor. After replacing the air with oxygen 5 times, the reactor was sealed, and 10bar oxygen was filled into the reactor. The reaction was carried out at 150°C with a magnetic stirring speed of 1000rpm for 18-24h. After the reaction was completed, the catalyst was collected by centrifugation. The liquid product was detected by gas chromatography, and the conversion rate of alcohol and the yield of nitrile compounds were calculated. The results are shown in Table 9 below:

[0093] Table 9

[0094]

[0095] Example 18: Synthesis of nitrile by ammoxidation reaction of aromatic vicinal diol compounds.

[0096] Different alcohol compounds (0.5mmol), 1,4-dioxane (10mL), ammonia (26.5wt.%, 200μL) and the MnNCN / NC-600 catalyst (20mg) prepared in Example 1 were added to a 40mL stainless steel reactor. After replacing the air with oxygen 5 times, the reactor was sealed, and 10bar oxygen was filled into the reactor. The reaction was carried out at 80°C with a magnetic stirring speed of 1000rpm for 8-14h. After the reaction was completed, the catalyst was collected by centrifugation. The liquid product was detected by gas chromatography, and the conversion rate of alcohol and the yield of nitrile compounds were calculated. The results are shown in Table 10 below:

[0097] Table 10

[0098]

[0099]

[0100] Example 19: Synthesis of nitrile by ammoxidation of fatty alcohols.

[0101] Different alcohol compounds (0.5mmol), 1,4-dioxane (10mL), ammonia (26.5wt.%, 200μL) and MnNCN / NC-600 catalyst (20mg) prepared in Example 1 were added to a 40mL stainless steel reactor. After replacing the air with oxygen 5 times, the reactor was sealed, and 10bar oxygen was filled into the reactor. The reaction was carried out at 150°C with a magnetic stirring speed of 1000rpm for 24-36h. After the reaction was completed, the catalyst was collected by centrifugation. The liquid product was detected by gas chromatography, and the conversion rate of alcohol and the yield of nitrile compounds were calculated. The results are shown in Table 11 below:

[0102] Table 11

[0103]

[0104]

[0105] Example 20: MnNCN / NC-600 Cycling Experiment

[0106] The operation method and steps were the same as those in Example 8, except that the reaction temperature was changed to 110°C. After the reaction was completed, the catalyst was centrifuged and washed 3 times with water and ethanol respectively, dried in vacuum at 40°C overnight, and reused after drying. The conversion rate and product distribution of each use are shown in Table 12 below:

[0107] Table 12

[0108]

Claims

1. A carbon-nitrogen material-supported MnNCN catalyst, denoted as MnNCN / NC, with a carbon-nitrogen material as a skeleton, and an active component MnNCN is supported on the skeleton. The mass content of the Mn element in the carbon-nitrogen material-supported MnNCN catalyst is 25wt.%-27wt.%, more preferably 25.8wt.%-26.2wt.%, and more preferably 26wt.%.

2. The carbon-nitrogen material-supported MnNCN catalyst according to claim 1, wherein the specific surface area of ​​the carbon-nitrogen material-supported MnNCN catalyst is 80 m 2 / g-100m 2 / g, preferably 90m 2 / g-100m 2 / g, more preferably 95m 2 / g-100m 2 / g; Preferably, the carbon-nitrogen material-loaded MnNCN catalyst uses manganese acetate as a manganese source and dicyandiamide as a carbon source and a nitrogen source, and is obtained by high-temperature pyrolysis under nitrogen protection.

3. A method for preparing a carbon-nitrogen material-supported MnNCN catalyst according to any one of claims 1 to 2, characterized in that: The following steps are involved: (1) fully grinding manganese acetate and dicyandiamide and mixing them uniformly; (2) The mixture obtained in step (1) is pyrolyzed at high temperature under nitrogen protection, the pyrolysis temperature is 580-650° C., and the pyrolysis time is 1.5-2.5 h, thereby obtaining the carbon-nitrogen material-loaded MnNCN catalyst.

4. The preparation method according to claim 3, characterized in that: In the step (1), the mass ratio of manganese acetate to dicyandiamide is 3:

10.

5. The preparation method according to claim 3, characterized in that: In the step (2), the pyrolysis temperature is 590-620°C; preferably, the pyrolysis temperature is 595-605°C; more preferably, the pyrolysis temperature is 600°C and the pyrolysis time is 2h.

6. Use of the carbon-nitrogen material-supported MnNCN catalyst according to any one of claims 1-2 or the carbon-nitrogen material-supported MnNCN catalyst prepared by the method according to any one of claims 3-5 in the preparation of nitrile compounds by ammoxidation of alcohol compounds, characterized in that: The steps are: The carbon-nitrogen material-loaded MnNCN catalyst, an organic solvent, an alcohol compound and aqueous ammonia are added into a high-pressure reactor, which is sealed and filled with 7.5-15 bar oxidizing gas, and then an ammoxidation reaction is carried out at 80-150° C. with constant stirring to obtain a nitrile compound.

7. The use according to claim 6, characterized in that: The solvent is 1,4-dioxane.

8. The use according to claim 6, characterized in that: The concentration of ammonia water is 25.0wt.%-28.0wt.%, and the ratio of the carbon nitrogen material loaded MnNCN catalyst, organic solvent, alcohol compound and ammonia water is 20mg:10mL:0.5mmol:100-300μL, preferably 20mg:10mL:0.5mmol:150-250μL, and further preferably 20mg:10mL:0.5mmol:195-205μL.

9. The use according to claim 6, characterized in that: The oxidizing gas is air or oxygen; preferably, the pressure of the oxidizing gas is 7.5-10 bar, and then the ammoxidation reaction is carried out at 110-150° C. with constant stirring.

10. The use according to claim 6, characterized in that: The alcohol compound is any one of an aromatic monohydric alcohol, an aliphatic monohydric alcohol, an aromatic vicinal diol, an aliphatic vicinal diol, and a long-chain end diol; Preferably, the aromatic monohydric alcohol is any one of the following structural formulas: n is a natural number from 1 to 3, n is a natural number from 1 to 2, n is a natural number from 1 to 2, n is a natural number from 1 to 2, The aliphatic monohydric alcohol is a C3-C8 monohydric alcohol, preferably heptanol or cyclohexylmethanol; The aromatic vicinal diol is any one of the following structural formulas: The aliphatic vicinal diol is a C3-C8 vicinal diol, preferably 1,2-propylene glycol or 1,2-hexanediol; The long chain end diol is a C3-C8 end diol, preferably 1,6-hexanediol or Preferably, wherein: R1 is monosubstituted or polysubstituted, R1 is ortho, meta and / or para, and R1 is independently selected from the following groups: H, C1-C4 alkyl, hydroxyl, vinyl, methoxy, methylthio, phenyl, amino, halogen, trifluoromethyl, nitro; R2 is monosubstituted, R2 is ortho, meta or para, selected from the following groups: H, methyl, halogen, trifluoromethyl, phenyl; R3 is selected from the following groups: C1-C3 alkyl; R4 is monosubstituted, R4 is ortho, meta or para, and R4 is selected from the following groups: H, halogen, methyl, methoxy, nitro, trifluoromethyl; R5 is monosubstituted, R5 is ortho, meta or para, and R5 is selected from the following groups: H, halogen, methyl, methoxy; R6 is selected from the following groups: H, methyl, phenyl, substituted phenyl, and the substituent on the substituted phenyl is halogen, methyl, or methoxy.

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