A denitrification method, an environmental protection treatment method for waste, and a preparation method of a compound

Abstract

The present application discloses a denitrogenation method and various applications thereof. The denitrogenation method comprises: reacting a nitrogen-containing heteroaromatic compound, a hydrogen donor, a catalyst and a solvent in an oxygen-free environment to generate a nitrogen-containing inorganic compound and an organic compound without nitrogen-containing heteroatoms, wherein the hydrogen donor is not hydrogen.

Description

Technical Field

[0001] This application relates to the field of chemical engineering, and more specifically, to a denitrification method, an environmentally friendly waste treatment method, and a method for preparing compounds. Background Technology

[0002] With the expansion of industrial scale, the denitrification and resource utilization of nitrogen-containing organic matter has attracted widespread attention from researchers. Current processes typically involve adding hydrogen gas to obtain downstream chemical raw materials and industrial solvents.

[0003] Chinese patent CN103980100A discloses a denitrification method, specifically a method for the direct synthesis of cyclohexanone by hydrogenation of aniline. This method mainly involves introducing hydrogen gas to obtain an organic phase containing cyclohexanone.

[0004] Chinese patent CN104003858A discloses a denitrification method, specifically a method for directly synthesizing cyclohexanone from nitrobenzene by hydrogenation. This method mainly involves introducing hydrogen gas to obtain an organic phase containing cyclohexanone.

[0005] However, hydrogenation methods suffer from high energy consumption, low conversion rates, harsh reaction conditions, and environmental pollution. In particular, the use of gaseous hydrogen poses significant safety risks, and hydrogen is expensive. Therefore, overcoming the technological bias that hydrogen must be used in denitrification methods and ultimately eliminating the use of gaseous hydrogen has become a key technical problem that needs to be solved in this field. Summary of the Invention

[0006] In view of this, this application proposes a solution for denitrification treatment that overcomes the technical bias that hydrogen must be used in denitrification treatment without the need for hydrogen.

[0007] According to one aspect of this application, a denitrification method is provided, comprising: reacting a nitrogen-containing heteroatom aromatic compound, a hydrogen donor, a catalyst, and a solvent in an oxygen-free environment to generate a nitrogen-containing inorganic compound and an organic compound without nitrogen heteroatoms, wherein the hydrogen donor is not hydrogen gas.

[0008] According to another aspect of this application, an environmentally friendly waste treatment method is also provided, which includes the above-described denitrification method.

[0009] Compared with the prior art, the advantage of this application is that it does not use gaseous H2, which is not easy to store and transport, but uses nitrogen-containing heteroatom aromatic compounds as raw materials, adds hydrogen donors, and performs denitrification treatment, and the denitrification conversion rate of raw materials and the yield of denitrification products are both high. Attached Figure Description

[0010] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application, and the illustrative embodiments and descriptions thereof are used to explain this application. In the drawings:

[0011] Figure 1 This is a comparison chromatogram of gas chromatography (GC) analysis before and after the reaction in Example 1 of this application;

[0012] Figure 2 This is the mass spectrum of cyclohexanone, the product of Example 1 of this application, obtained by gas chromatography-mass spectrometry (GC-MS). Detailed Implementation

[0013] The technical solution of this application will now be described in detail with reference to the accompanying drawings and embodiments.

[0014] The denitrification method provided in this application includes: reacting a nitrogen-containing heteroatom aromatic compound, a hydrogen donor, a catalyst, and a solvent in an oxygen-free environment to generate a nitrogen-containing inorganic compound and an organic compound without nitrogen heteroatoms, wherein the hydrogen donor is not hydrogen gas.

[0015] The above-described denitrification method can be implemented in various reactor dishes or equipment, such as reaction vessels, reaction flasks, and reaction containers. In these reactor dishes or equipment, an oxygen-free environment can be created. For example, the oxygen-free environment can be a vacuum environment with a vacuum degree of 0–0.02 MPa; or, the oxygen-free environment can be a protective gas environment with a pressure of 0.05–1 MPa, preferably 0.1–0.5 MPa, and even more preferably 0.1–0.12 MPa. The protective gas can be various inert gases or gases that do not participate in the reaction, including but not limited to argon, nitrogen, neon, and helium.

[0016] In the denitrification method provided in this application, the solvent can be water, an alcohol-water mixture, a ketone-water mixture, an organic acid-water mixture, or an alkane-water mixture. The ketone may include at least one of acetone, butanone, and cyclohexanone; the acid may include at least one of formic acid, acetic acid, and oxalic acid; and the alkane may include cyclohexane.

[0017] The nitrogen-containing heteroatom aromatic compound used as a precursor may include at least one of nitrobenzene, aniline, azobenzene, azobenzene oxide, phenylhydroxylamine, hydrogenated azobenzene, nitrochlorobenzene, nitrobobromobenzene, nitroboiodobenzene, nitrobenzene, aminophenol, and haloaniline. Preferably, the nitrogen-containing heteroatom aromatic compound may include at least one of nitrobenzene, aniline, nitrosobenzene, phenylhydroxylamine, azobenzene, azobenzene oxide, and hydrogenated azobenzene.

[0018] The hydrogen donor is not hydrogen gas, but may include at least one of formic acid, oxalic acid, acetic acid and methanol.

[0019] The catalyst is a transition metal supported catalyst. Preferably, the transition metal includes at least one selected from Ru, Rh, Pd, Pt, Au, Ag, Ni, Co, and Fe. The catalyst support includes at least one selected from activated carbon, carbon nanotubes, ZrO2, TiO2, SiO2, Al2O3, molecular sieves, g-C3N4, BiVO4, WO3, ZnO2, CdS, and CuO. Preferably, the loading of the transition metal component is 0.1% to 10%, more preferably 0.5% to 5%, and even more preferably 1% to 2%.

[0020] A nitrogen-containing heteroatom aromatic compound, a hydrogen donor, and a catalyst are placed in a solvent within a reaction apparatus or reactor vessel to allow them to react, thereby generating nitrogen-containing inorganic compounds and organic compounds without nitrogen heteroatoms. In other words, nitrogen is converted from an organic form to an inorganic form, achieving denitrification.

[0021] For example, the denitrification method includes: preparing a nitrogen-containing heteroatom aromatic hydrocarbon raw material, or a raw material containing a nitrogen-containing heteroatom aromatic hydrocarbon (such as wastewater, waste liquid, waste residue, etc.); preparing the above-mentioned hydrogen donor; preparing the above-mentioned catalyst; and simultaneously or separately feeding the solvent continuously or intermittently.

[0022] The molar ratio of the nitrogen-containing heteroatom aromatic compound raw material to the hydrogen donor is 1:1 to 1:100, preferably 1:5 to 1:15, and even more preferably 1:8 to 1:10.

[0023] The molar ratio of the solvent to the hydrogen donor is greater than 1:1, preferably 50:1 to 2000:1.

[0024] The reaction temperature of the above-mentioned denitrification method is 10–110°C, preferably 10–90°C, more preferably 20–70°C, and even more preferably 20–50°C. The reaction time of the denitrification method is 0.25–3.0 hours, preferably 0.5–2 hours, more preferably 0.6–1.5 hours, and even more preferably 0.8–1.2 hours.

[0025] The denitrification method may preferably include phototreatment. The light intensity of the phototreatment may be 50–5000 mW / cm². 2 The preferred value is 100–2000 mW / cm². 2 The optimal value is 100–1000 mW / cm². 2 The optimal value is 100–400 mW / cm². 2 The illumination treatment is performed by natural sunlight and / or by artificial light sources.

[0026] According to the technical solution of this application, the organic compound that does not contain nitrogen heteroatoms may include at least one of cyclohexanone, cyclohexanol, benzene, and cyclohexane. The nitrogen-containing inorganic compound may include at least one of NH3, NH3·H2O, and ammonium salts.

[0027] According to a preferred embodiment of this application, the solvent is water, the nitrogen-containing inorganic compound is ammonia, and the nitrogen-free heteroatom-free organic compound is cyclohexanone.

[0028] According to the technical solution of this application, the conversion rate of raw materials after reaction can reach up to 100%, and the yield of denitrification products is 30% to 100%.

[0029] This application also provides an environmentally friendly waste treatment method, wherein the method includes the above-mentioned denitrification method.

[0030] This application also provides a method for preparing a compound comprising cyclohexanone, cyclohexanol, cyclohexane, adipic acid, caprolactam, nylon 6, nylon 66, ammonia, ammonium carbonate, or ammonium nitrate, wherein the preparation method includes the denitrification method described above. In other words, the denitrification method of this application can be used in the preparation of various downstream compounds.

[0031] According to a preferred embodiment of this application, cyclohexanone is synthesized using nitrobenzene as a raw material, formic acid or oxalic acid as a hydrogen donor, and a Pd-supported catalyst under light irradiation. Quantitative analysis by GC and qualitative analysis by GC-MS show that, under the reaction conditions described in the example, the conversion rate of nitrobenzene can reach 100%, and the yield of cyclohexanone can reach 98%.

[0032] The method specifically includes the following steps:

[0033] (1) Mix nitrobenzene, hydrogen donor, catalyst and water. The molar ratio of nitrobenzene to hydrogen donor is 1:5 to 1:15, and the amount of catalyst is 0.1 to 100 g / L.

[0034] (2) Under light irradiation, with protective gas, reaction temperature 10-99℃, stirring for 0.25-1.0h, nitrobenzene can be completely hydrogenated and denitrogenated to produce cyclohexanone.

[0035] The nitrobenzene mentioned in step (1) may also include aniline obtained by reducing nitrobenzene. The hydrogen donor mentioned in step (1) is formic acid or oxalic acid or a mixture of the two. The catalyst mentioned in step (1) can be a Pd-supported catalyst, including but not limited to Pd / TiO2, Pd / g-C3N4, Pd / BiVO4, Pd / WO3, Pd / ZnO2, Pd / CdS, Pd / CuO, Pd / C, Pd / Al2O3, etc., with a Pd loading of 0.1% to 10%. The solvent mentioned in step (1) is water. The protective gas mentioned in step (2) includes but is not limited to argon, nitrogen, neon, helium, etc., and mixtures of them in any proportion. The reaction temperature mentioned in step (2) is 10 to 90°C, and no additional heat source is required. The light source used for illumination in step (2) is sunlight or artificial light source, including but not limited to sunlight, xenon lamps, high-pressure mercury lamps, LED lamps, etc. The reaction time range for step (2) is 0.25 to 1.0 h, and the optimal light reaction time is 0.5 h.

[0036] In this preferred embodiment, the reaction formula for the above-mentioned denitrification method is:

[0037]

[0038] This application provides a non-hydrogen hydrodenitrification method, which can be used for the denitrification and resource recovery of waste containing nitrobenzene or nitroaromatic hydrocarbons (such as wastewater), and can also be used for the synthesis of cyclohexanone from nitrobenzene. According to one application scenario, the crude cyclohexanone obtained from denitrification of nitrobenzene-containing wastewater can be directly used as an energy source for combustion, and further distillation into cyclohexanone chemicals can be sold commercially. Cyclohexanone is an important intermediate in the manufacture of caprolactam and adipic acid, used in the production of polycaprolactam, polyhexamethylene adipamide (nylon 66), etc.; it can also be used as an industrial solvent and pharmaceutical intermediate. This method uses nitrobenzene as a raw material, formic acid or oxalic acid as a hydrogen donor, employs a metal-supported catalyst, and under inert gas protection, uses light irradiation to promote complete denitrification of nitrobenzene and highly selectively produce cyclohexanone. The raw materials used in this application, nitrobenzene and its derivatives, can be contained in wastewater or waste residue, or can be directly fed into industrial products.

[0039] The technical solutions of this application are further described below with reference to various embodiments.

[0040] Example 1

[0041] 50 mL of nitrobenzene-water solution (125 mg / L) and 22 μL of formic acid were measured into a stoppered reactor. 50 mg of Pd / TiO2 was added, and Ar was bubbled through for 5 min to displace the air in the reactor. The reactor was then sealed and irradiated with a 300 W xenon lamp at 66 °C for 0.25 h with stirring to obtain cyclohexanone. The nitrobenzene conversion rate was 100%, and the cyclohexanone yield was 97%. Quantitative analysis by GC and qualitative analysis by GC-MS were performed, such as... Figure 1 and Figure 2 As shown, the results indicate that the reaction from nitrobenzene to cyclohexanone occurred under the example conditions, and the only product was cyclohexanone. Specific methods for GC quantitative analysis: An Agilent 8860 gas chromatograph was used, with an HP-5MS column (30m × 250μm × 0.25μm), an FID detector, and N2 as the carrier gas. The column oven temperature was programmed, with an initial temperature of 40℃, a holding time of 2 min, and then increased at 4℃·min. -1 The temperature is increased to 100℃ at a rate of [temperature value missing], held at that temperature for 3 minutes, and then increased at a rate of 10℃ / min. -1 The temperature is increased to 200℃ at a rate of 20℃·min. -1 The temperature was increased to 300℃ at a rapid rate; the split ratio at the injection port was 40:1. Specific methods for GC-MS qualitative analysis: An Agilent 5977B-7890B GC-MS system was used for qualitative analysis of the material. The chromatographic column was a DB-Wax (30m × 250μm × 0.25μm), the carrier gas was He, and the outlet pressure was 0.5MPa; the GC injection port temperature was 270℃, the split ratio was 5:1, and the split flow rate was 5mL·min. -1 Column flow rate: 5 mL / min -1 The GC column oven temperature was programmed, with an initial temperature of 40℃, held for 3 minutes, and then increased at 7℃·min. -1 Heat to 180℃, then increase the temperature by 10℃·min. -1 Heat to 250℃ and hold for 10 min; ion source temperature at the mass spectrometer end: 230℃; quadrupole temperature: 150℃; solvent delay: 2 min; scan range: 50–300 m / z; scan rate: 781 u·s. -1 Step size 0.1 m / z. Mass spectrometry reference library: NIST08.L.

[0042] The quantitative GC analysis and qualitative GC-MS analysis in Examples 2-19 are performed using the same methods as in Example 1.

[0043] Example 2:

[0044] Measure 50 mL of nitrobenzene-water solution (125 mg / L), weigh 69.3 mg of oxalic acid dihydrate into a stoppered reactor, add 50 mg of Pd / TiO2, purge with Ar for 5 min to replace the air in the reactor, seal the reactor, irradiate with a 300 W xenon lamp, maintain the reaction temperature at 66 °C, and stir for 1 h to obtain cyclohexanone. The nitrobenzene conversion rate is 100%, and the cyclohexanone yield is 96%.

[0045] Example 3:

[0046] Measure 50 mL of nitrobenzene-water solution (125 mg / L) and 22 μL of formic acid into a stoppered reactor, add 50 mg of Pd / g-C3N4, purge with Ar for 5 min to replace the air in the reactor, seal the reactor, irradiate with a 300 W xenon lamp, maintain the reaction temperature at 66 °C, and stir for 1 h to obtain cyclohexanone. The nitrobenzene conversion rate is 100%, and the cyclohexanone yield is 98%.

[0047] Example 4:

[0048] Measure 50 mL of nitrobenzene-water solution (125 mg / L) and 22 μL of formic acid into a stoppered reactor, add 25 mg of Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. The reaction temperature is 66 °C, and the mixture is stirred for 1 h to obtain cyclohexanone. The nitrobenzene conversion rate is 100%, and the cyclohexanone yield is 98%.

[0049] Example 5:

[0050] Measure 50 mL of nitrobenzene-water solution (125 mg / L) and 22 μL of formic acid into a stoppered reactor, add 50 mg of Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Seal the reactor, expose it to sunlight, and stir for 1 h at a maximum reaction temperature of about 40 °C to obtain cyclohexanone. The nitrobenzene conversion rate is 100% and the cyclohexanone yield is 98%.

[0051] Example 6:

[0052] Measure 5 μL of aniline, add 50 mL of aqueous solution, stir well, add 22 μL of formic acid to a stoppered reactor, add 25 mg of Pd / TiO2, purge with N2 for 5 min to replace the air in the reactor, seal the reactor, irradiate with a 300 W xenon lamp, the reaction temperature is 66 °C, stir for 1 h, and cyclohexanone can be obtained with a 100% conversion of nitrobenzene and a 98% yield of cyclohexanone.

[0053] Example 7:

[0054] Measure 50 mL of nitrobenzene-water solution (125 mg / L) and 22 μL of formic acid into a stoppered reactor, add 25 mg of Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Then place it in a dark room, heat it in a water bath at a constant temperature of 30 °C, and stir for 1 h to obtain cyclohexanone. The nitrobenzene conversion rate is 100% and the cyclohexanone yield is 27%.

[0055] Example 8:

[0056] Measure 50 mL of nitrobenzene-water solution (125 mg / L) and 22 μL of formic acid into a stoppered reactor, add 25 mg of Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Then place it in a dark room, heat it in a water bath, keep the temperature at 110 °C, and stir for 1 h to obtain cyclohexanone. The nitrobenzene conversion rate is 100% and the cyclohexanone yield is 34%.

[0057] Example 9:

[0058] Measure 40 μL of nitrobenzene, add 100 mL of 60 vol.% methanol aqueous solution and 100 mg Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Heat the reactor and keep it at 200 °C for 12 h. The conversion rate of nitrobenzene is 100% and the yield of cyclohexanone is 2%.

[0059] Example 10:

[0060] Measure 5 μL of nitrobenzene, add 50 mL of tetrahydrofuran (anhydrous organic solvent), 22 μL of formic acid, and 50 mg of Pd / TiO2. Purge with Ar for 5 min to replace the air in the reactor. Irradiate with a 300 W xenon lamp source. The reaction temperature is 66 °C. Stir for 1 h. The conversion rate of nitrobenzene is 100%, and the yield of cyclohexanone is 0.

[0061] Implementation Example 11:

[0062] Measure 5 μL of nitrobenzene, add 50 mL of water and 50 mg of Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. The reaction temperature is 68 °C and the reaction time is 1 h. The conversion rate of nitrobenzene is 46% and the yield of cyclohexanone is 0.

[0063] Implementation Example Twelve:

[0064] Measure 5 μL of nitrobenzene, add 50 mL of water and 22 μL of formic acid, and purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. The reaction temperature is 72 °C and the reaction time is 1 h. The conversion rate of nitrobenzene is 7% and the yield of cyclohexanone is 0%.

[0065] Implementation Example Thirteen:

[0066] Measure 5 μL of nitrobenzene, add 50 mL of water, add 25 mg of Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Then purge with H2 for 5 min, using H2 as the hydrogen source. Seal the reactor and irradiate with a 300 W xenon lamp. The reaction temperature is 60 °C and the reaction time is 3 h. The conversion rate of nitrobenzene is 100% and the yield of cyclohexanone is 72%.

[0067] Implementation Example Fourteen:

[0068] Measure 5 μL of nitrobenzene, add 50 mL of water, 259 μL of formic acid, and 25 mg of Pd / TiO2. Purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. The reaction temperature is 70 °C and the reaction time is 1 h. The conversion rate of nitrobenzene is 100% and the yield of cyclohexanone is 14%.

[0069] Implementation Example 15:

[0070] Measure 5 μL of nitrobenzene, add 50 mL of water, 25.9 μL of formic acid, and 50 mg of recovered Pd / TiO2. Purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. The reaction temperature is 70 °C and the reaction time is 1 h. The conversion rate of nitrobenzene is 100% and the yield of cyclohexanone is 81%.

[0071] Example 16:

[0072] Dissolve 10 mg of azobenzene in 50 mL of water and stir well. Add 25 μL of formic acid and 50 mg of Pd / TiO2. Purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. Stir at 66 °C for 1 h to obtain cyclohexanone with a yield of 98%.

[0073] Example 17:

[0074] Dissolve 10 mg of azobenzene in 50 mL of water and stir well. Add 22 μL of formic acid and 50 mg of Pd / TiO2. Purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. Stir at 66 °C for 1 h to obtain cyclohexanone with a yield of 97%.

[0075] Example 17:

[0076] Dissolve 6 mg of p-chloronitrobenzene in 50 mL of water and stir well. Add 30 μL of formic acid and 50 mg of Pd / TiO2. Purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. Stir at 66 °C for 1 h to obtain cyclohexanone with a yield of 93%.

[0077] Example 18:

[0078] Dissolve 10 mg of p-chloroaniline in 50 mL of water and stir well. Add 30 μL of formic acid and 50 mg of Pd / TiO2. Purge with Ar for 5 min to replace the air in the reactor. Seal the reactor and irradiate with a 300 W xenon lamp. Stir at 66 °C for 1 h to obtain cyclohexanone with a yield of 92%.

[0079] Example 19:

[0080] Take 3 μL of aniline and 3 μL of nitrobenzene, add 50 mL of water to dissolve, stir evenly, add 25 μL of formic acid and 50 mg of Pd / TiO2, and purge Ar for 5 min to replace the air in the reactor. Seal the reactor, irradiate with a 300 W xenon lamp, and stir at 66 °C for 1 h to obtain cyclohexanone with a yield of 96%.

[0081] Example 20:

[0082] Take 3 μL of nitrobenzene and 5 mg of azobenzene, add 50 mL of water to dissolve, stir evenly, add 22 μL of formic acid and 50 mg of Pd / TiO2, and purge Ar for 5 min to replace the air in the reactor. Seal the reactor, irradiate with a 300 W xenon lamp, and stir at 66 °C for 1 h to obtain cyclohexanone with a yield of 95%.

[0083] Example 21:

[0084] Take 3 μL of nitrobenzene and 5 mg of 4-bromo-nitrobenzene, dissolve them in 50 mL of water, stir well, add 30 μL of formic acid and 50 mg of Pd / TiO2, and purge with Ar for 5 min to replace the air in the reactor. Seal the reactor, irradiate with a 300 W xenon lamp, and stir for 1 h to obtain cyclohexanone with a yield of 96%.

[0085] The preferred embodiments of this application have been described in detail above. However, this application is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.

[0086] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this application will not describe the various possible combinations separately.

[0087] Furthermore, various different implementations of this application can be combined in any way, as long as they do not violate the spirit of this application, they should also be regarded as the content disclosed in this application.

Claims

1. A denitrogenation method, comprising: reacting a nitrogen-containing heteroaromatic compound, a hydrogen donor, a catalyst, and a solvent in an oxygen-free environment to produce a nitrogen-containing inorganic compound and a non-nitrogen-containing heteroatom organic compound, and the produced organic compound is only a non-nitrogen-containing organic compound, wherein: the hydrogen donor is not hydrogen; the denitrogenation method comprises a light treatment, and the light treatment is irradiated by natural sunlight and / or artificial light sources; the reaction temperature of the denitrogenation method is 10-110℃, and the reaction time is 0.25-3 hours; the molar ratio of the nitrogen-containing heteroaromatic compound to the hydrogen donor is 1:5-1:15; the solvent comprises at least one of water, an alcohol-water mixture, a ketone-water mixture, an organic acid-water mixture, and an alkane-water mixture; the nitrogen-containing inorganic compound comprises at least one of NH 3, NH 3·H 2O, and an ammonium salt; the non-nitrogen-containing heteroatom organic compound comprises cyclohexanone; the nitrogen-containing heteroaromatic compound comprises at least one of nitrobenzene, aniline, azobenzene, azoxybenzene, phenylhydroxylamine, hydrazobenzene, nitrochlorobenzene, nitro-bromobenzene, nitro-iodobenzene, nitrophenol, aminophenol, and halogenated aniline; the hydrogen donor comprises at least one of formic acid, oxalic acid, acetic acid, and methanol; the catalyst is a transition metal supported catalyst; the transition metal comprises at least one of Ru, Rh, Pd, Pt, Au, Ag, Ni, Co, and Fe.

2. The denitrification method of claim 1, wherein, the solvent is water, the nitrogen-containing inorganic compound is NH 3, and the non-nitrogen-containing heteroatom organic compound is cyclohexanone.

3. The denitrification method of claim 1, wherein, the nitrogen-containing heteroaromatic compound comprises at least one of nitrobenzene, aniline, phenylhydroxylamine, azobenzene, azoxybenzene, and hydrazobenzene.

4. The denitrating method according to claim 1, wherein, the reaction temperature of the denitrogenation method is 10-90℃.

5. The denitrating method according to claim 4, wherein, the reaction temperature of the denitrogenation method is 20-70℃.

6. The denitrating method according to claim 5, wherein, the reaction temperature of the denitrogenation method is 20-50℃.

7. The denitrating method according to claim 1, wherein, the oxygen-free environment is a vacuum environment, and the vacuum degree is 0-0.02 MPa.

8. The denitrating method according to claim 1, wherein, the oxygen-free environment is a protective gas protection environment, and the gas pressure in the protective gas protection environment is 0.05-1 MPa.

9. The denitrating method according to claim 8, wherein, the gas pressure in the protective gas protection environment is 0.1-0.5 MPa.

10. The denitrating method according to claim 9, wherein, the gas pressure in the protective gas protection environment is 0.1-0.12 MPa.

11. The denitrating method according to claim 1, wherein, the carrier of the catalyst comprises at least one of activated carbon, carbon nanotubes, ZrO 2, TiO 2, SiO 2, Al 2O 3, molecular sieves, g-C 3N 4, BiVO 4, WO 3, ZnO 2, CdS, and CuO.

12. The denitrating method of claim 1, wherein, the loading amount of the transition metal component is 0.1%-10%.

13. The denitrating method of claim 12, wherein, the loading amount of the transition metal component is 0.5%-5%.

14. The denitrating method of claim 13, wherein, the loading amount of the transition metal component is 1%-2%.

15. The denitrating method of claim 1, wherein, the reaction time of the denitrogenation method is 0.5-2 hours.

16. The denitrating method of claim 15, wherein, the reaction time of the denitrogenation method is 0.6-1.5 hours.

17. The denitrating method of claim 16, wherein, the reaction time of the denitrogenation method is 0.8-1.2 hours.

18. The denitrating method of claim 1, wherein, The light intensity of the light treatment is 50-5000 mW / cm 2 .

19. The denitrating method of claim 18, wherein, The light intensity of the light treatment is 100-2000 mW / cm 2 .

20. The denitrating method of claim 19, wherein, The light intensity of the light treatment is 100-1000 mW / cm 2 .

21. The denitrating method of claim 20, wherein, The light intensity of the light treatment is 100-400 mW / cm 2 .

22. The denitrating method of claim 1, wherein, the denitrogenation method comprises: Preparation of a nitrogen-containing heteroaromatic compound raw material, or a raw material containing a nitrogen-containing heteroaromatic compound; preparation of a hydrogen donor; Preparation of a catalyst; Simultaneously or separately, continuously or intermittently, feeding the solvent.

23. The denitrating method of claim 1, wherein, The molar ratio of the nitrogen-containing heteroaromatic compound to the hydrogen donor is 1:8 to 1:

10.

24. The denitrating method of claim 1, wherein, The molar ratio of the solvent to the hydrogen donor is greater than 1:

1.

25. The denitrating method of claim 24, wherein, The molar ratio of the solvent to the hydrogen donor is 50:1 to 2000:

1.

26. The denitrating method of claim 1, wherein, The conversion rate of the raw material after the reaction is 100%, and the yield of the denitrogenated product is 30% to 100%.

27. An environmentally friendly waste disposal method wherein, The method comprises the denitrogenation method of any one of claims 1 to 26.

28. A method for preparing a compound comprising cyclohexanone or adipic acid or caprolactam or nylon 6 or nylon 66 or ammonia gas or ammonium carbonate or ammonium nitrate, the method comprising the denitrogenation method of any one of claims 1 to 26.

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