CN113070087A - Non-noble metal catalyst and preparation method and application thereof - Google Patents
Non-noble metal catalyst and preparation method and application thereof Download PDFInfo
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- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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Abstract
The invention belongs to the technical field of catalyst preparation, and provides a non-noble metal catalyst and a preparation method and application thereof. The non-noble metal catalyst provided by the invention replaces expensive noble metal with a nickel metal simple substance, so that the cost is saved; in addition, the non-noble metal catalyst takes a metal nickel unit as an active center, and the carbon nitride well wraps a nickel simple substance, so that the stability of the catalyst is improved, and the catalytic activity of the catalyst is further improved. The preparation method of the non-noble metal catalyst provided by the invention has the advantages of wide source of raw materials, low cost, simple preparation method and easy industrialization. When the non-noble metal catalyst is used for catalytic hydrogenation of p-chloronitrobenzene, the reaction condition is mild and easy to control. The data of the examples show that: the catalyst provided by the invention has the conversion rate of p-chloronitrobenzene of 36.8-98.9% and the selectivity of p-chloroaniline of 58.4-98.3% under the conditions of 10MPa and 60 ℃.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a non-noble metal catalyst and a preparation method and application thereof.
Background
Chloroaniline obtained by selective hydrogenation of Chloronitrobenzene (CNBs) has wide application in the dye, medicine and pesticide industries. The traditional process for producing chloroaniline by using corresponding CNBs as raw materials and adopting Fe/HCl or sulfide reduction method has many routes and producesToxic waste, non-ideal yield and the like. Some studies have subsequently emerged involving the use of sodium borohydride (NaBH)4) Or hydrazine hydrate directly reduces the chloronitrobenzene into the corresponding chloroaniline. Although sodium borohydride or hydrazine hydrate catalytic systems have superior catalytic performance, they typically produce large amounts of by-products and environmental stress.
Researchers have increasingly focused on the production of chloroaniline by the liquid phase hydrogenation of non-noble metal catalysts and noble metal catalysts. Noble metal catalysts Pt, Ru, Pd and Au are applied to the preparation of chloroaniline by the hydrogenation of chloronitrobenzene and show excellent catalytic performance; but the cost is high, the resource is scarce, and the wide application of the noble metal in the industry is greatly limited. In recent years, many non-noble metal catalysts such as Ni, Ni-B, Co-B and Co-Mo-S have been developed for the hydrogenation of chloronitrobenzene; however, these catalytic systems still require harsh reaction conditions. The non-noble metal magnetic nanoparticles have unique catalytic properties due to their small particle size, but are extremely prone to agglomeration. Leaching or sintering of the non-noble metal nanoparticles can lead to irreversible deactivation of the non-noble metal catalyst.
Therefore, it is urgently needed to design a non-noble metal catalyst with high catalytic performance to improve the conversion rate of chloronitrobenzene and the selectivity of chloroaniline.
Disclosure of Invention
In view of the above, the present invention provides a non-noble metal catalyst, and a preparation method and an application thereof. The non-noble metal catalyst provided by the invention does not use expensive noble metal, but has higher conversion rate on p-chloronitrobenzene and higher selectivity on p-chloroaniline.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a non-noble metal catalyst, which comprises carbon nitride and a nickel simple substance, wherein the carbon nitride wraps the nickel simple substance; the mass ratio of the carbon nitride to the nickel simple substance is 1: (0.1-0.5).
The invention also provides a preparation method of the non-noble metal catalyst in the technical scheme, which comprises the following steps:
mixing a nickel precursor and a carbon nitrogen organic compound, and calcining to obtain the non-noble metal catalyst;
the mass ratio of the nickel precursor to the carbon nitrogen organic matter is (0.5-3): 1.
preferably, the nickel precursor is nickel acetate, nickel nitrate, nickel sulfate, nickel chloride or nickel acetylacetonate.
Preferably, the carbon nitrogen organic compound comprises one or more of dicyandiamide, cyanamide, urea and melamine.
Preferably, the calcining temperature is 300-600 ℃, the calcining time is 0.5-6 h, and the atmosphere is protective gas.
Preferably, the calcination is finished, and the method further comprises the steps of sequentially carrying out acid treatment, filtration and drying on the obtained calcination product.
Preferably, the acid-treating agent is an inorganic acid; the concentration of the inorganic acid is 0.2-3 mol/L; the dosage ratio of the acid-treated reagent to the calcined product is 50 mL: (0.2-1) g; the acid treatment time is 2-8 h.
The invention also provides the application of the non-noble metal catalyst in the technical scheme or the non-noble metal catalyst obtained by the preparation method in the technical scheme in the p-chloronitrobenzene hydrogenation reaction.
Preferably, the p-chloronitrobenzene hydrogenation comprises the following steps:
mixing a non-noble metal catalyst, p-chloronitrobenzene and an alcohol solvent, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain p-chloroaniline;
the mass ratio of the non-noble metal catalyst to the p-chloronitrobenzene is 10: (50-150).
Preferably, the temperature of the hydrogenation reaction is 40-100 ℃, and the pressure is 0.1-2 MPa.
The invention provides a non-noble metal catalyst, which comprises carbon nitride and a nickel simple substance, wherein the carbon nitride wraps the nickel simple substance; the mass ratio of the carbon nitride to the nickel simple substance is 1: (0.1-0.5). The non-noble metal catalyst provided by the invention replaces expensive noble metal with a nickel metal simple substance, so that the cost is saved; the non-noble metal catalyst takes a metal nickel unit as an active center, and the carbon nitride well wraps a nickel simple substance, so that the stability of the catalyst is improved; meanwhile, nitrogen element or carbon element coated by the carbon nitride can be well combined with the nickel elementary substance serving as the active component, so that the electronic structure of metal is changed, the adsorption and reaction of the non-noble metal catalyst on reactants are promoted, and the catalytic activity of the catalyst is improved.
The invention also provides a preparation method of the non-noble metal catalyst, which comprises the following steps of mixing a nickel precursor and a carbon nitrogen organic compound, and calcining to obtain the non-noble metal catalyst. The preparation method provided by the invention has the advantages of wide source of used raw materials, low cost, simple preparation method and easy industrialization.
The invention also provides the application of the non-noble metal catalyst in the technical scheme in the p-chloronitrobenzene hydrogenation reaction. When the non-noble metal catalyst is used for catalytic hydrogenation of p-chloronitrobenzene, the reaction condition is mild and easy to control.
The data of the examples show that: the catalyst provided by the invention has the conversion rate of p-chloronitrobenzene of 36.8-98.9% and the selectivity of p-chloroaniline of 58.4-98.3% under the conditions of 10MPa and 60 ℃.
Drawings
FIG. 1 is a transmission electron micrograph of a non-noble metal catalyst obtained in example 1;
FIG. 2 is a TEM image of the non-noble metal catalyst obtained in example 2;
FIG. 3 is a TEM image of the non-noble metal catalyst obtained in example 3.
Detailed Description
The invention provides a non-noble metal catalyst, which comprises carbon nitride and a nickel simple substance, wherein the carbon nitride wraps the nickel simple substance; the mass ratio of the carbon nitride to the nickel simple substance is 1: (0.1-0.5).
The non-noble metal catalyst provided by the invention comprises a nickel simple substance, wherein the particle size of the nickel simple substance is 5-30 nm; the elementary nickel is wrapped in the form of clusters. The non-noble metal catalyst provided by the invention comprises carbon nitride. In the invention, the mass ratio of the carbon nitride to the nickel simple substance is 1: (0.1 to 0.5), preferably 1: (0.2 to 0.4), and more preferably 1: (0.22-0.3).
The invention also provides a preparation method of the non-noble metal in the technical scheme, which comprises the following steps:
and mixing the nickel precursor with a carbon nitrogen organic compound, and calcining to obtain the non-noble metal catalyst.
In the present invention, the nickel precursor is preferably nickel acetate, nickel nitrate, nickel sulfate, nickel chloride, or nickel acetylacetonate, and more preferably nickel acetate. In the present invention, the carbon nitrogen organic compound preferably includes one or more of dicyandiamide, cyanamide, urea and melamine, and more preferably dicyandiamide. In the invention, the mass ratio of the nickel precursor to the organic carbon-nitrogen is (0.5-3): 1, preferably (0.8-1.2): 1, more preferably 1: 1. in the invention, the mixing mode is preferably grinding, and the rotation speed of the grinding is preferably 400-700 rpm, and more preferably 500-600 rpm; the time is preferably 5-8 h.
In the invention, the calcination temperature is preferably 300-600 ℃, and more preferably 450-550 ℃; the rate of raising the temperature from room temperature to the calcining temperature is preferably 2-4 ℃/min, and more preferably 3 ℃/min; the time is preferably 0.5-6 h, and more preferably 2-4 h; the atmosphere of the calcination is preferably a protective gas, which is preferably nitrogen. In the present invention, the calcination is preferably carried out in a tube furnace.
In the invention, the calcination can decompose carbon nitrogen organic matter into ammonia gas and form a carbon nitride carrier, the carbon nitride takes a nickel precursor as a center, the nickel precursor is reduced into a nickel simple substance by generated reducing gases (such as ammonia gas and carbon monoxide), and the formed carbon nitride carrier wraps the nickel simple substance.
After the calcination, the invention preferably further comprises the steps of sequentially carrying out acid treatment, filtration and drying on the obtained calcination product. In the invention, the acid treatment reagent is preferably an inorganic acid, and the concentration of the inorganic acid is preferably 0.2-3 mol/L, more preferably 0.8-1.2 mol/L, and more preferably 1.0 mol/L; the inorganic acid preferably comprises sulfuric acid, nitric acid or hydrochloric acid, and further preferably sulfuric acid; the ratio of the amount of the acid-treated reagent to the calcined product is preferably 50 mL: (0.2-1) g; the time for the acid treatment is preferably 2 to 8 hours, more preferably 5 to 7 hours, and even more preferably 6 hours.
In the present invention, the acid treatment can remove metal ions that have not been reduced; by controlling the acid treatment conditions, the loss of stable nickel simple substances is reduced.
In the invention, the drying temperature is preferably 40-100 ℃, more preferably 70-90 ℃, and more preferably 80 ℃; the time is preferably 3-8 h, and further preferably 5-7 h; the drying is preferably carried out in a vacuum drying oven.
The invention also provides the application of the non-noble metal catalyst in the technical scheme or the non-noble metal catalyst obtained by the preparation method in the technical scheme in the p-chloronitrobenzene hydrogenation reaction.
In the invention, the p-chloronitrobenzene hydrogenation reaction comprises the following steps:
mixing a non-noble metal catalyst, p-chloronitrobenzene and an alcohol solvent, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain p-chloroaniline.
In the invention, the mass ratio of the non-noble metal catalyst to the p-chloronitrobenzene is 10: (50 to 150), more preferably 10: (60 to 130), more preferably 10: 79; the dosage ratio of the alcohol solvent to the p-chloronitrobenzene is preferably 1 mL: 79 mg; the alcohol solvent is preferably ethanol. In the invention, the temperature of the hydrogenation reaction is preferably 40-100 ℃, and more preferably 60 ℃; the pressure is preferably 0.1-2 MPa, and more preferably 1 MPa; the time is preferably 0.5 to 3 hours, and more preferably 1 hour.
The non-noble metal catalyst provided by the invention is used for catalyzing the hydrogenation reaction of p-chloronitrobenzene, the reaction condition is mild, the conversion rate of the p-chloronitrobenzene is high, and the selectivity of the p-chloroaniline is high.
The non-noble metal catalysts provided by the present invention, and the preparation method and application thereof, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 1.5g of nickel acetate and 1.5g of dicyandiamide, grinding for 6h at 500rpm, putting the ground materials into a quartz boat, putting the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then, putting 1g of the calcined product into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, filtering, drying the obtained solid in a vacuum drying oven at 80 ℃ for 8h to obtain a non-noble metal catalyst, and measuring the content of the obtained non-noble metal catalyst by adopting an ICP (inductively coupled plasma) method, wherein the result is as follows: the mass ratio of the carbon nitride to the nickel simple substance is 1: 0.15.
fig. 1 is a transmission electron micrograph of the non-noble metal catalyst obtained in this example, and it can be seen from fig. 1 that: the metallic nickel simple substance is well wrapped in the carbon nitride.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion rate of p-chloronitrobenzene is 98.9 percent, and the selectivity of p-chloroaniline is 98.3 percent.
Example 2
Weighing 1.2g of nickel acetate and 1.5g of dicyandiamide, grinding for 6h at 500rpm, putting the ground materials into a quartz boat, putting the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then, putting 1g of calcined product into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, filtering, drying the obtained solid in a vacuum drying oven at 80 ℃ for 8h to obtain a non-noble metal catalyst, and measuring the content of the non-noble metal catalyst by adopting an ICP (inductively coupled plasma) method, wherein the result is as follows: the mass ratio of the carbon nitride to the nickel simple substance is 1: 0.1.
fig. 2 is a transmission electron micrograph of the non-noble metal catalyst obtained in this example, and it can be seen from fig. 2 that: the metallic nickel simple substance is well wrapped in the carbon nitride material, and the particle size of the nickel simple substance is relatively large.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion rate of p-chloronitrobenzene is 65.3 percent, and the selectivity of p-chloroaniline is 89.2 percent.
Example 3
Weighing 1.8g of nickel acetate and 1.5g of dicyandiamide, grinding for 6h at 600rpm, putting the ground materials into a quartz boat, putting the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then, putting 1g of calcined product into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, filtering, drying the obtained solid in a vacuum drying oven at 80 ℃ for 8h to obtain a non-noble metal catalyst, and measuring the content of the non-noble metal catalyst by adopting an ICP (inductively coupled plasma) method, wherein the result is as follows: the mass ratio of the carbon nitride to the nickel simple substance is 1: 0.23.
fig. 3 is a transmission electron micrograph of the non-noble metal catalyst obtained in this example, and it can be seen from fig. 3 that: the metal nickel simple substance is well wrapped in the carbon nitride material, and the particle size of the nickel metal simple substance is large; meanwhile, compared with the non-noble metal catalysts of examples 1 and 2, the non-noble metal catalyst obtained in this example has a higher elemental nickel content.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion of p-chloronitrobenzene was 74.7% and the selectivity to chloroaniline was 58.8%.
Example 4
Weighing 1.5g of nickel acetate and 1.5g of dicyandiamide, grinding for 6h at 600rpm, putting the ground materials into a quartz boat, putting the quartz boat into a tube furnace, heating to 450 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then, putting 1g of calcined product into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, filtering, drying the obtained solid in a vacuum drying oven at 80 ℃ for 8h to obtain a non-noble metal catalyst, and measuring the content of the non-noble metal catalyst by adopting an ICP (inductively coupled plasma) method, wherein the result is as follows: the mass ratio of the carbon nitride to the nickel simple substance is 1: 0.17.
10mg of the non-noble metal catalyst, 1mL of methanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion rate of p-chloronitrobenzene is 36.8 percent, and the selectivity of p-chloroaniline is 58.4 percent.
Example 5
Weighing 1.5g of nickel acetate and 1.5g of dicyandiamide, grinding for 6h at 600rpm, putting the ground materials into a quartz boat, putting the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then, putting 1g of calcined product into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, filtering, drying the obtained solid in a vacuum drying oven at 80 ℃ for 8h to obtain a non-noble metal catalyst, and measuring the content of the non-noble metal catalyst by adopting an ICP (inductively coupled plasma) method, wherein the result is as follows: the mass ratio of the carbon nitride to the nickel simple substance is 1: 0.15.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h at the temperature of 60 ℃ and under the pressure of 0.5 MPa.
The results were: the conversion rate of p-chloronitrobenzene is 40.5 percent, and the selectivity of p-chloroaniline is 75.3 percent.
Example 6
Weighing 1.5g of nickel acetate and 1.5g of dicyandiamide, grinding for 6h at 600rpm, putting the ground materials into a quartz boat, putting the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then, putting 1g of calcined product into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, filtering, drying the obtained solid in a vacuum drying oven at 80 ℃ for 8h to obtain a non-noble metal catalyst, and measuring the content of the non-noble metal catalyst by adopting an ICP (inductively coupled plasma) method, wherein the result is as follows: the mass ratio of the carbon nitride to the nickel simple substance is 1: 0.15.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are subjected to hydrogenation reaction for 1h under the pressure of 1MPa and the temperature of 80 ℃.
The results were: the conversion of p-chloronitrobenzene was 94.2% and the selectivity to chloroaniline was 68.5%.
Comparative example 1
Grinding 1.5g of dicyandiamide at 600rpm, placing the ground dicyandiamide in a quartz boat, placing the quartz boat in a tube furnace, heating the quartz boat to 550 ℃ at the speed of 3 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a calcined product; and then 0.3g of calcined product is put into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, and the calcined product is filtered, and dried in a vacuum drying oven at 80 ℃ for 8h to obtain the non-noble metal catalyst.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion rate of p-chloronitrobenzene is 3.1 percent, and the selectivity of p-chloroaniline is 8.6 percent.
Comparative example 2
Weighing 1.5g of cobalt acetate and 1.5g of dicyandiamide, grinding for 6h at 500rpm, putting the ground materials into a quartz boat, putting the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then 1g of calcined product is put into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, the calcined product is filtered, and the obtained solid is dried in a vacuum drying oven at the temperature of 80 ℃ for 8h to obtain the non-noble metal catalyst.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion rate of p-chloronitrobenzene was 38.9%, and the selectivity of p-chloroaniline was 78.3%.
Comparative example 3
Weighing 1.5g of nickel acetate and 1.5g of glucose, grinding for 6h at 500rpm, placing the mixture into a quartz boat, placing the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a calcined product; and then 1g of calcined product is put into 50mL of 1mol/L sulfuric acid for acid treatment for 6h, the calcined product is filtered, and the obtained solid is dried in a vacuum drying oven at the temperature of 80 ℃ for 8h to obtain the non-noble metal catalyst.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion rate of p-chloronitrobenzene was 64.5%, and the selectivity of p-chloroaniline was 86.4%.
Comparative example 4
Weighing 1.5g of cobalt acetate and 1.5g of dicyandiamide, grinding for 6h at 500rpm, putting into a quartz boat, putting the quartz boat into a tube furnace, heating to 550 ℃ at the rate of 3 ℃/min under the nitrogen atmosphere, and preserving heat for 2 h; obtaining the non-noble metal catalyst.
10mg of the non-noble metal catalyst, 1mL of ethanol and 79mg of p-chloronitrobenzene are put into a high-pressure reaction kettle and subjected to hydrogenation reaction for 1h under the pressure of 1MPa and at the temperature of 60 ℃.
The results were: the conversion of p-chloronitrobenzene was 74.2% and the selectivity to chloroaniline was 84.6%.
The embodiment shows that the non-noble metal provided by the invention does not use noble metal, is low in cost, and has high conversion rate on p-chloronitrobenzene and high selectivity on p-chloroaniline under the conditions that the temperature is 40-100 ℃ and the pressure is 0.1-2 MPa.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A non-noble metal catalyst is characterized by comprising carbon nitride and a nickel simple substance, wherein the carbon nitride wraps the nickel simple substance; the mass ratio of the carbon nitride to the nickel simple substance is 1: (0.1-0.5).
2. A method of preparing a non-noble metal catalyst as claimed in claim 1, characterized in that it comprises the following steps:
mixing a nickel precursor and a carbon nitrogen organic compound, and calcining to obtain the non-noble metal catalyst;
the mass ratio of the nickel precursor to the carbon nitrogen organic matter is (0.5-3): 1.
3. the method according to claim 2, wherein the nickel precursor is nickel acetate, nickel nitrate, nickel sulfate, nickel chloride, or nickel acetylacetonate.
4. The preparation method according to claim 2, wherein the organic carbon nitrogen compound comprises one or more of dicyandiamide, cyanamide, urea and melamine.
5. The preparation method according to claim 2, wherein the calcining temperature is 300-600 ℃, the calcining time is 0.5-6 h, and the atmosphere is protective gas.
6. The production method according to claim 2 or 5, wherein the calcination is completed, and further comprising subjecting the obtained calcined product to acid treatment, filtration and drying in this order.
7. The preparation method according to claim 6, wherein the acid treatment agent is an inorganic acid, and the concentration of the inorganic acid is 0.2-3 mol/L; the dosage ratio of the acid-treated reagent to the calcined product is 50 mL: (0.2-1) g; the acid treatment time is 2-8 h.
8. The non-noble metal catalyst of claim 1 or the non-noble metal catalyst obtained by the preparation method of any one of claims 2 to 7, for use in p-chloronitrobenzene hydrogenation.
9. The use according to claim 8, wherein the hydrogenation of p-chloronitrobenzene comprises the steps of:
mixing a non-noble metal catalyst, p-chloronitrobenzene and an alcohol solvent, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain p-chloroaniline;
the mass ratio of the non-noble metal catalyst to the p-chloronitrobenzene is 10: (50-150).
10. The use of claim 9, wherein the hydrogenation reaction is carried out at a temperature of 40 to 100 ℃ and a pressure of 0.1 to 2 MPa.
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| CN113070087B (en) | 2021-11-19 |
| NL2030698B1 (en) | 2022-10-17 |
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Denomination of invention: A non noble metal catalyst and its preparation method and application Effective date of registration: 20221017 Granted publication date: 20211119 Pledgee: Bank of Shaoxing Co.,Ltd. high tech Development Zone sub branch Pledgor: Shaoxing Lvyi Chemical Co.,Ltd. Registration number: Y2022980018575 |