CN113731423A

CN113731423A - Application of carbon material coated nickel nanoparticle catalyst in synthesis of p-aminophenylacetic acid by hydrogenation of p-nitroacetophenone

Info

Publication number: CN113731423A
Application number: CN202111015801.1A
Authority: CN
Inventors: 卢春山; 杨园园; 李小年; 张群峰; 丰枫
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2021-08-31
Filing date: 2021-08-31
Publication date: 2021-12-03
Anticipated expiration: 2041-08-31
Also published as: CN113731423B

Abstract

The invention discloses application of a carbon material coated nickel nanoparticle catalyst in synthesizing p-aminophenylacetic acid by hydrogenating p-nitroacetoacetic acid. The carbon material coated nickel nanoparticle catalyst has 100% of conversion rate, high selectivity, good stability and long service life in the application of synthesizing p-aminophenylacetic acid by hydrogenating p-nitroacetoacetic acid.

Description

Application of carbon material coated nickel nanoparticle catalyst in synthesis of p-aminophenylacetic acid by hydrogenation of p-nitroacetophenone

Technical Field

The invention belongs to the field of catalyst preparation technology and application, and relates to application of a carbon material coated nickel nanoparticle catalyst in synthesizing p-aminophenylacetic acid by hydrogenating p-nitroacetoacetic acid.

Background

The nickel nano particles have great application value in the fields of catalysis, lithium batteries, sensors and the like. As a catalyst, the nano-sized nickel particles have better catalytic activity than bulk or flake, but due to higher surface energy, the nano-sized nickel particles are easily agglomerated to limit their advantages. When exposed to air, the metal nano particles are easily oxidized into metal oxide, and the carbon material layer is wrapped outside the metal nano particles to prevent the metal nano particles from being oxidized. The structure of the carbon layer coated metal has the characteristics of no toxicity, high thermal stability and low price, and simultaneously has the characteristics of graphene, rich pore channel structures in the structure can be regulated and controlled, surface groups are easy to modify, and the excellent physical and chemical properties enable the structure to be widely applied to the research and production fields of battery electrode materials, water treatment, catalysis, energy storage and the like.

The p-aminophenylacetic acid is an important chemical intermediate, is widely applied to medicine production and organic synthesis raw material production, and can be used for synthesizing antirheumatic (aclitar), non-steroidal anti-inflammatory drug (atenolol), cardiovascular and cerebrovascular drug (atenolol) and the like. Therefore, the preparation research of the p-aminophenylacetic acid has important application value. Aromatic amines are usually prepared by reduction of aromatic nitro compounds. The method for reducing the aromatic nitro compound mainly comprises the following steps: catalytic hydrogenation reduction, such as patent CN 109232283A; reducing sodium sulfide; ③ reducing iron powder in acid, alkaline and neutral system; hydrazine hydrate reduction, as in patent CN 106083631. However, the above methods have many disadvantages: the method is characterized in that Pd/C catalyst is used in the prior art, and the noble metal catalyst has high manufacturing cost and is not easy to recover; the method discharges a large amount of sulfur-containing wastewater, causes serious harm to the ecological environment, has large treatment investment of three wastes and does not conform to the green chemical concept; the method third produces a large amount of iron mud, the purity of the product cannot be guaranteed, the reduction product cannot be directly used for drug synthesis, and the catalyst cannot be reused. Fourthly, hydrazine hydrate has high toxicity, and the recovery and treatment of the waste liquid in the later period are complicated.

The nickel nanoparticle catalyst provided by the invention has the advantages of uniform size, high dispersity, high metal utilization rate, simple, green and efficient preparation method, and high activity, high selectivity and high stability in the reaction of catalyzing the hydrogenation synthesis of p-aminophenylacetic acid from p-nitrophenylacetic acid.

Disclosure of Invention

The first purpose of the invention is to provide a preparation method of a carbon material coated nickel nanoparticle catalyst.

It is a second object of the present invention to provide a carbon material coated nickel nanoparticle catalyst.

The third purpose of the invention is to provide the application of the carbon material coated nickel nanoparticle catalyst in the synthesis of halogenated aniline through catalytic hydrogenation of halogenated nitrobenzene.

The fourth purpose of the invention is to provide the application of the carbon material coated nickel nanoparticle catalyst in the synthesis of p-aminophenylacetic acid by the hydrogenation of p-nitroacetoacetic acid.

The fifth purpose of the invention is to provide the application of the carbon material coated nickel nanoparticle catalyst in the synthesis of m-aminobenzene sulfonic acid by hydrogenation of m-nitrobenzenesulfonic acid sodium salt.

The sixth purpose of the invention is to provide the application of the carbon material coated nickel nanoparticle catalyst in the synthesis of 4 ', 4-diaminodiphenyl ether by hydrogenation of 4', 4-dinitrodiphenyl ether.

The seventh purpose of the invention is to provide the application of the carbon material coated nickel nanoparticle catalyst in the hydrogenation synthesis of 1-aminoanthraquinone from 1-nitroanthraquinone.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a method for preparing a carbon-coated nickel nanoparticle catalyst, wherein the carbon-coated nickel nanoparticle catalyst is prepared according to the following steps:

(1) weighing a certain mass of nickel salt and an organic ligand, pouring the nickel salt and the organic ligand into an alcohol solvent for dissolving, and stirring for 3-24 hours at 0-50 ℃ to obtain a mixed solution;

(2) dropwise adding alkali liquor into the mixed solution in batches, and adjusting the pH value of the solution in three stages, wherein the pH value is as follows: A) firstly, adjusting the pH value to 4.0-5.5 by using 0.1-5 mol/L sodium hydroxide aqueous solution, and keeping for 0.5-3 hours; B) then regulating the pH value to 6.5-7.5 by using 80-99% triethanolamine water solution, and keeping for 1-5 hours; C) finally, adjusting the pH value to 8.5-9.5 by using 25-28% ammonia water, and keeping for 1-3 hours; the mixed liquid is always in a stirring state in the adjusting process; the step is to adjust pH by stages to enable the complexing process of metal ions and ligands and control the growth of crystals so as to control the appearance of the formed crystals;

(3) sealing the slurry obtained in the step (2), placing the slurry on a vibration platform for crystallization, precipitation and aging, then filtering and washing, and carrying out vacuum drying to obtain a metal organic framework precursor; wherein the shaking program is set as: firstly, vibrating for 1-5 minutes at a vibration frequency of 10-20 Hz; secondly, vibrating for 1-5 minutes at the vibration frequency of 20-40 Hz; thirdly, vibrating for 1-5 minutes with the vibration frequency of 40-55Hz and the horizontal amplitude; running the program I-III to form a vibration period; the whole crystallization, precipitation and aging process is 10-20 hours, and a vibration period is operated at intervals of 1-2 hours; the step further controls the appearance of the crystal, namely the growth and development of the crystal are influenced through a vibration process to obtain a quasi-spherical precursor with uniform particle size;

(4) placing the precursor in an agate mortar for crushing and grinding, roasting at 300-800 ℃ for 5-24 hours, cooling to room temperature, and grinding to obtain a carbon material coated nickel nanoparticle catalyst; the roasting atmosphere is inert atmosphere or inert atmosphere containing carbon dioxide or carbon dioxide atmosphere.

The carbon material prepared by the preparation method disclosed by the invention covers the nickel nanoparticle catalyst, wherein the amount of the retained metal (namely the percentage of the metal contained in the catalyst to the metal input amount) reaches more than 90%.

Further, in the step (1), the nickel salt is at least one of nickel chloride, nickel carbonate, nickel nitrate and nickel acetate, preferably nickel nitrate or nickel acetate. The alcohol solvent is preferably methanol or ethanol, the volume concentration of the alcohol solvent is more than 95%, and absolute ethanol is preferably used. The organic ligand is at least one of benzoic acid, terephthalic acid, urea, ethylene diamine tetraacetic acid, 4-picolinic acid, 2' -bipyridyl, triphenylphosphine, oxalic acid and glycine, and 4-picolinic acid is preferred. The molar ratio of nickel in the nickel salt to the organic ligand is 1: 1-1: 8, preferably 1: 2-1: 6; the mass ratio of nickel in the nickel salt to the alcohol solvent is 1: 50-1: 1000, preferably 1: 100-1: 500.

further, in the step (1), the stirring temperature is 0-50 ℃, and preferably 20-50 ℃; the stirring time is 3 to 24 hours, preferably 6 to 15 hours.

And (3) further, filtering and washing the precipitate with ethanol after aging, putting the precipitate into a vacuum oven, drying the precipitate for 2 to 15 hours at the temperature of between 50 and 120 ℃, and taking the precipitate out.

Further, in the step (4), the roasting temperature is 300-800 ℃, and preferably 400-600 ℃; the calcination time is 5 to 24 hours, preferably 5 to 10 hours. The inert atmosphere is nitrogen or argon, the volume fraction of carbon dioxide in the roasting atmosphere is not less than 10%, and the most preferable roasting atmosphere is carbon dioxide atmosphere; the total flow rate of the gas is 5-50 mL/min.

In a second aspect, the present invention provides a carbon material coated nickel nanoparticle catalyst prepared by the above method. The catalyst consists of nickel nano particles and a graphene layer completely wrapping the nickel nano particles, wherein the size distribution range of the carbon material wrapping the nickel nano particles is 2-20 nm, and the thickness of the graphene layer is

The number of corresponding carbon layers is 1-6, and the carbon layers have pore channels; the catalyst is also characterized in that the catalyst is subjected to 0.1-5 mol/L of H₂SO₄Or H₃PO₄Metal loss after sufficient washing (preferably 4-24h washing time), drying (drying temperature is room temperature-80 ℃) is less than 1 wt% (i.e. the amount of metal lost by sulfuric acid washing is percentage of the amount of metal in the catalyst before acid washing), and the carbon material is coated with the nickel nanoparticle catalyst; after the catalyst is fully washed by 0.1-5 mol/LHCl or HF (preferably, the washing time is 4-24h) and dried (the drying temperature is room temperature to 80 ℃), the amount of the metal retained in the catalyst is below 20 wt% (namely, the metal contained in the washed catalyst accounts for the percentage of the metal input).

The innovation of the invention is that: the preparation method of the invention effectively controls the shape of the precursor on the basis of improving the utilization rate of the metal (the utilization rate of the metal can reach 100 percent, namely 100 percent of nickel is coated in the carbon layer), thereby obtaining the catalyst with a specific microstructure (the carbon layer has a specific thickness and the carbon layer has a pore channel with a specific size), and solving the problems that the size of nickel nano particles is not small enough and the metal nickel is easy to be oxidized when exposed in the air. More importantly, the pore channel with a specific size formed by the graphene carbon layer has differential mass transfer influence on organic reactants and hydrogen molecules, namely hydrogen can be allowed to enter, but large molecules of a substrate are intercepted due to large volume, and hydrogen is not excessive relative to the substrate, so that excessive hydrogenation is avoided, side reactions are avoided, and the selectivity of the catalyst is effectively improved.

In a third aspect, the invention provides an application of the carbon material coated nickel nanoparticle catalyst in the synthesis of halogenated aniline represented by a formula II through catalytic hydrogenation of halogenated nitrobenzene represented by the formula I, wherein a dehalogenation inhibitor is not required to be added in the application;

in formula I or formula II, R_nRepresents n substituents on the phenyl ring, wherein n is 0, 1, 2, 3 or 4, each substituent R is independently C1-C3 alkyl, and X is_mRepresents m halogen substituents on the benzene ring, wherein m is 1-5, and each halogen substituent is independent; m + n is less than or equal to 5.

Further, n is 0.

Further, the application process is as follows: putting a carbon material coated nickel nanoparticle catalyst and halogenated nitrobenzene into a high-pressure reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, heating materials in the kettle, starting stirring, and carrying out liquid-phase catalytic hydrogenation reaction at the temperature of 30-150 ℃ and the pressure of 0.5-5 MPa to obtain halogenated aniline, wherein the liquid-phase catalytic hydrogenation reaction is carried out under the solvent-free condition or in absolute ethyl alcohol, methanol or water.

Preferably, the mass ratio of the carbon material coated nickel nanoparticle catalyst to the halogenated nitrobenzene is 1:10 to 50, more preferably 1: 20.

preferably, the reaction temperature is 100 ℃ and the hydrogen pressure is 1.0 MPa.

Preferably, the stirring rate is 1500-.

In a fourth aspect, the invention provides an application of the carbon material coated nickel nanoparticle catalyst in the synthesis of p-aminophenylacetic acid by the hydrogenation of p-nitroacetoacetic acid.

Further, the application process is as follows: putting a catalyst, paranitroacetophenone and methanol into a high-pressure reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, starting stirring, reacting for a period of time at the temperature of 50-100 ℃ and the hydrogen pressure of 0.5-1 MPa, opening the reaction kettle, filtering, taking filtrate, and evaporating 60-80% of methanol solvent; cooling, crystallizing, filtering and drying to obtain a crude product; recrystallizing the crude product with ethanol, and decolorizing with active carbon to obtain light white crystalline p-aminophenylacetic acid.

Preferably, the feeding ratio of the nickel nanoparticle catalyst coated with the paranitroacetic acid, the methanol and the carbon material is 1 g: 10-40 mL: 0.01 to 0.10g, more preferably 1: 20mL of: 0.05 g.

Preferably, the stirring rate is 1000-.

Preferably, the reaction time is 1 to 2 hours.

Preferably, the reaction temperature is 60 ℃ and the hydrogen pressure is 0.6 MPa.

In a fifth aspect, the invention provides an application of the carbon material coated nickel nanoparticle catalyst in the synthesis of m-aminobenzene sulfonic acid by hydrogenation of m-nitrobenzenesulfonic acid sodium salt.

Further, the application process is as follows:

(1) adding water into the sodium m-nitrobenzenesulfonate, heating to dissolve the sodium m-nitrobenzenesulfonate, adding activated carbon to boil, carrying out heat filtration, and adjusting the pH value of the obtained filtrate to 7.5-8.5 by using sodium hydroxide to obtain a treated sodium m-nitrobenzenesulfonate solution;

(2) adding a treated sodium m-nitrobenzenesulfonate solution and the carbon material into an autoclave, coating a nickel nanoparticle catalyst, sealing the autoclave, replacing air with nitrogen, replacing nitrogen with hydrogen, heating the autoclave, starting stirring, reacting at 50-80 ℃ and 0.5-1.5 MPa of hydrogen pressure until no hydrogen is consumed (namely, the hydrogen pressure does not decrease within 10 min), stopping stirring, cooling to room temperature, filtering, adjusting the pH value of the obtained filtrate to 1.5-2.5 with sulfuric acid, and separating out a white precipitate, namely m-aminobenzenesulfonic acid. The product was analyzed by liquid chromatography.

Preferably, the mass ratio of the nickel nanoparticle catalyst coated by the carbon material to the raw material sodium m-nitrobenzenesulfonate is 1: 10-50, and more preferably 1: 50.

Preferably, in the step (2), the stirring speed is 800-12000 r/min, and more preferably 1000 r/min.

Preferably, in the step (2), the reaction temperature is 60 ℃ and the hydrogen pressure is 1.0 MPa.

In a sixth aspect, the invention provides an application of the carbon material coated nickel nanoparticle catalyst in the synthesis of 4,4 '-diaminodiphenyl ether by hydrogenation of 4, 4' -dinitrodiphenyl ether.

Further, the application process is as follows: putting a carbon material coated with a nickel nanoparticle catalyst, 4 '-dinitrodiphenyl ether and DMF (dimethyl formamide) into a high-pressure reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing the nitrogen with hydrogen, heating, starting stirring, reacting at 30-80 ℃ and 0.3-0.6 MPa of hydrogen pressure until hydrogen is not absorbed any more, stopping stirring, and filtering the catalyst after the temperature is reduced to room temperature to obtain the 4, 4' -diaminodiphenyl ether.

Preferably, the carbon material is coated with the nickel nanoparticle catalyst, 4' -dinitrodiphenyl ether and DMF, and the feeding ratio is 0.1 g: 1-10 g: 15-30mL, more preferably 0.1 g: 5 g: 20 mL.

Preferably, the stirring rate is 500-.

Preferably, the reaction temperature is 50 ℃ and the hydrogen pressure is 0.4 MPa.

In a seventh aspect, the invention provides an application of the carbon material coated nickel nanoparticle catalyst in the hydrogenation synthesis of 1-aminoanthraquinone from 1-nitroanthraquinone;

further, the application process specifically comprises: putting the carbon material coated with the nickel nanoparticles, 1-nitroanthraquinone and absolute ethyl alcohol into a high-pressure reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, starting stirring, reacting at 30-90 ℃ under the condition of hydrogen pressure of 0.5-2 MPa until hydrogen is not absorbed, stopping stirring, cooling to room temperature, and carrying out aftertreatment on the obtained reaction mixture to obtain the 1-aminoanthraquinone.

Preferably, the carbon material is coated with the nickel nanoparticle catalyst, 1-nitroanthraquinone and absolute ethyl alcohol at a feeding ratio of 0.1 g: 1-10 g: 20-50mL, more preferably 0.1 g: 4 g: 40 mL.

Preferably, the stirring rate is 500-.

Preferably, the reaction temperature is 70 ℃ and the hydrogen pressure is 1.0 MPa.

Preferably, the post-treatment is as follows: and filtering out the catalyst, putting the filtrate into a three-neck flask, starting stirring, and oxidizing in the air for 10-24 hours.

Compared with the prior art, the invention has the following advantages:

(1) the preparation method of the catalyst is simple, green and efficient, is easy to operate, has mild conditions, cheap raw materials, 100% utilization rate of metal atoms and low production cost.

(2) The nickel nano particles are small, the particle size distribution is uniform, the dispersion degree is high, the graphene layer is thin, the nickel is not removed by acid washing, and the wrapping efficiency is up to 100 percent, so that a uniform and stable catalyst and more reaction active sites are obtained, and the catalytic activity is greatly improved; the carbon layer pore passage can allow hydrogen to enter, but substrate molecules are intercepted due to large volume, so that differential mass transfer is realized, and the catalytic selectivity is greatly improved.

(3) The catalyst has single metal component and is easy to separate and recycle.

(4) In the application of synthesizing halogenated aniline by hydrogenating halogenated nitrobenzene, the conversion rate is high, the selectivity is high, the dechlorination phenomenon is avoided, the stability is good, and the service life is long.

(5) In the application of 1-nitroanthraquinone hydrogenation to synthesize halogenated aniline, the conversion rate is high, the selectivity is high, the stability is good, and the service life is long.

(6) In the application of synthesizing p-aminophenylacetic acid by hydrogenating p-nitroacetoacetic acid, the conversion rate is high, the selectivity is high, the stability is good, and the service life is long.

(7) In the application of synthesizing m-aminobenzene sulfonic acid by hydrogenation, the conversion rate is high, the selectivity is high, the stability is good, and the service life is long.

(8) In the application of 4,4 '-diaminodiphenyl ether synthesized by hydrogenating 4, 4' -dinitrodiphenyl ether, the conversion rate is high, the selectivity is high, the stability is good, and the service life is long.

Drawings

FIG. 1, FIG. 2, and FIG. 3 are SEM images of three stages of precursors regulated by different alkali solutions in example 5. Thus, the crystal grows along a certain direction along with the increase of pH in the process of staged regulation.

FIG. 4 is a TEM image of the carbon material coated nickel nanoparticle catalyst prepared in example 5. As can be seen in the figure, the nickel nano particles wrapped by the carbon material are small and have high dispersity, and the thickness of the graphene layer is

The graphene layer is 1-4 layers.

Fig. 5 is a particle size distribution diagram corresponding to a TEM image of the carbon material coated nickel nanoparticle catalyst prepared in example 5, and it can be seen from the diagram that the particle size of the carbon material coated nickel nanoparticle is intensively distributed around 4.8 nm.

FIG. 6 is a TEM image of the carbon material coated nickel nanoparticle catalyst prepared in example 10, in which the carbon layer spacing can be seen

Is typically a layer of graphene having a thickness of

The number of layers is 2-5.

FIG. 7 is a TEM image of the nickel nanoparticle catalyst obtained in comparative example 12, and it can be seen that the number of carbon layers is 6 to 15.

Fig. 8 is a carbon layer pore size distribution diagram of the nickel nanoparticle catalyst prepared in example 9. The pore diameter of the catalyst carbon layer is uniform in distribution and concentrated at about 0.5 nm.

FIG. 9 (a) is an XRD pattern of the nickel nanoparticle catalyst prepared in example 9; (b) is the XRD pattern of the catalyst after the catalytic hydrogenation reaction is mechanically applied for ten times. XRD images before and after application have no obvious change, which shows that the catalyst has good stability when being applied to hydrogenation reaction of halogenated nitrobenzene.

Detailed Description

The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.

Example 1

Weighing a certain amount of nickel nitrate hexahydrate and 4-picolinic acid, dissolving in a certain amount of absolute ethanol, wherein the molar ratio of nickel to organic ligand is 1: 2; the mass ratio of the nickel to the alcoholic solution is 1: 100. Heating and stirring at 25 ℃ for 6 hours, dropwise adding 1.0mol/L sodium hydroxide aqueous solution into the mixed solution, adjusting the pH of the solution to 4.0, and keeping for 1 hour; dripping 98% triethanolamine solution, adjusting pH to 6.5, and keeping for 2 hours; and (3) dropwise adding 25-28% ammonia water, adjusting the pH to 8.5, and keeping for 2 hours. The obtained slurry is sealed and then placed on a vibration table, and the vibration program is set as follows: 1) the vibration frequency is 10Hz, and the banner vibrates for 2 minutes; 2) the vibration frequency is 30Hz, and the banner vibrates for 5 minutes; 3) the vibration frequency is 40Hz, and the banner vibrates for 1 minute; 4) running programs 1) -3) for one vibration period; the whole crystallization, precipitation and aging process was 12 hours, during which the shaking period was set to be once at 1 hour intervals. And filtering and washing the precipitate by using ethanol after aging, putting the precipitate into a vacuum oven, drying the precipitate for 10 hours at 85 ℃, and taking the precipitate out to obtain the nickel nanoparticle catalyst precursor. And (3) placing the precursor in an agate mortar for crushing and grinding, roasting at 400 ℃ for 10 hours in a carbon dioxide atmosphere with the flow rate of 10mL/min, cooling to room temperature, and grinding to obtain the carbon material coated nickel nanoparticle catalyst. In the catalyst, the size distribution range of nickel nano particles is 4-6 nm, and the thickness of a graphene layer is

The number of carbon layers is 1-3, the carbon layers have pore channels, and the pore size is 0-1 nm. The amount of metal retained in the catalyst was 95 wt% based on the metal charge. The catalysisThe agent is subjected to 0.5mol of H₂SO₄After washing for 5h and drying at 50 ℃, the metal loss is measured to be 0.5 wt%; after the catalyst is washed by 0.5mol/LHCl for 5h and dried at 50 ℃, the amount of the metal retained in the catalyst is 20wt percent of the metal input amount.

The specific parameters of the catalysts prepared according to the preparation process of example 1 in examples 2 to 15 are shown in Table 1.

Comparative example 1

Based on the preparation process and parameters of example 1, the pH was adjusted to 7.0 with 98% triethanolamine solution without stepwise adjustment, and the solution was kept for 6 hours, and the other steps were the same as in example 1. The amount of metal retained in the catalyst was 30 wt% based on the metal charge, 0.5mol/LH₂SO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was determined to be 8 wt%.

Comparative example 2

Based on the preparation process and parameters of example 1, the pH was adjusted to 10.0 with ammonia without stepwise adjustment, and the rest steps were the same as in example 1. With the continuous addition of ammonia, the precipitate gradually dissolved until the precipitate completely disappeared, because nickel dissolved in the solvent in the form of complex ions. Therefore, the precipitation cannot be completely precipitated by directly adjusting the pH with ammonia water.

Comparative example 3

Based on the preparation process and parameters of example 1, the pH was adjusted to 9.0 with sodium hydroxide solution without stepwise adjustment, and the solution was kept for 8 hours, and the nickel hydroxide precipitate was obtained in the same manner as in example 1. The amount of metal retained in the catalyst was 56 wt% based on the metal charge, 0.5mol/LH₂SO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 8 wt%.

Comparative example 4

Based on the preparation process and parameters of example 1, stepwise adjustment was used for pH adjustment, but only the second and third steps were used, and the rest of the procedure was the same as in example 1. The amount of metal retained in the catalyst was 33 wt% based on the metal charge, calculated as 0.5mol/LH₂SO₄Washing for 5h, drying at 50 deg.C, catalyzingThe amount of metal retained in the agent was 15 wt%.

Comparative example 5

Based on the preparation process and parameters of example 1, stepwise adjustment was used for pH adjustment, but only the first and third steps were used, and the rest of the procedure was the same as in example 1. The amount of metal retained in the catalyst was 52 wt% based on the metal charge, 0.5mol/LH₂SO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 11 wt%.

Comparative example 6

Based on the preparation process and parameters of example 1, stepwise adjustment was used for pH adjustment, but only the first and second steps were used, and the rest of the procedure was the same as in example 1. The amount of metal retained in the catalyst was 60 wt% based on the metal charge, 0.5mol/LH₂SO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 13 wt%.

Comparative example 7

Based on the preparation process and parameters of example 1, the pH was adjusted in a stepwise manner, but the steps were the same as in example 1 except that 1mol/L sodium carbonate was used in the first step, 1mol/L sodium bicarbonate was used in the second step, and 1mol/L sodium hydroxide was used in the third step. The amount of metal retained in the catalyst was 37 wt% based on the metal charge, 0.5mol/LH₂SO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 5 wt%.

Comparative example 8

Based on the preparation process and parameters of example 1, the shaking procedure was set as: 1) and 2), i.e., 1) and 2) is a shaking period, and the rest of the steps are the same as those of embodiment 1. The amount of metal retained in the catalyst was 64 wt% based on the metal charge, 0.5mol/LH₂SO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 25 wt%.

Comparative example 9

Based on the preparation process and parameters of example 1, the shaking procedure was set as: 1) and 3), i.e., 1) and 3) is a shaking period, and the rest of the steps are the same as those of embodiment 1. The amount of metal retained in the catalyst was 71 wt% based on the metal charge, calculated as 0.5mol/LH₃PO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 30 wt%.

Comparative example 10

Based on the preparation process and parameters of example 1, the shaking procedure was set as: 2) and 3), i.e., 2) and 3) is a shaking period, and the rest of the steps are the same as those of embodiment 1. The amount of metal retained in the catalyst was 69 wt% based on the metal charge, 0.5mol/LH₃PO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 26 wt%.

Comparative example 11

Based on the preparation process and parameters of example 1, no shaking procedure was used, and the rest of the procedure was the same as in example 1. The amount of metal retained in the catalyst was 20 wt%, based on the metal charge, via 0.5mol/L H₂SO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 4 wt%.

Comparative example 12

The firing was carried out in a closed atmosphere without flowing gas, as in example 1. The number of graphene carbon layers of the catalyst is 6-15. The amount of metal retained in the catalyst was 89 wt% based on the metal charge and 67 wt% after washing with 0.5mol/LHCl for 5h and drying at 50 ℃.

Comparative example 13

The air used during firing was the same as in example 1. The carbon material is burnt out, does not form a core-shell structure and is in a micron-millimeter level particle.

Comparative example 14

The procedure of example 1 was repeated except that Ar was used as an inert gas at a flow rate of 100ml/min for calcination. In the catalyst, the number of graphene carbon layers is 1-2, the carbon layers are porous, and the pore size is large. The amount of metal retained in the catalyst was 65 wt% based on the metal charge, 0.5mol/LH₃PO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 15 wt%.

Comparative example 15

The precursor is put into an agate mortar for crushing and grinding, then is roasted for 16 hours at 200 ℃ in inert atmosphere Ar, and the rest isThe same as in example 1. In the catalyst, nickel particles are distributed unevenly, a graphene carbon layer is not formed, and amorphous carbon is arranged around the graphene carbon layer. The amount of metal retained in the catalyst is less than 29 wt% based on the metal charge, 0.5mol/L H₃PO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 10 wt%.

Comparative example 16

The precursor was crushed and ground in an agate mortar and then calcined at 900 ℃ for 10 hours in an inert atmosphere Ar, as in example 1. In the catalyst, the size distribution range of nickel nano particles is 20-30 nm, the number of graphene carbon layers is 1-2, and the aperture size of the carbon layer is large. The amount of metal remaining in the catalyst was 73 wt%, based on the metal charge, 0.5mol/L H₃PO₄After washing for 5h and drying at 50 ℃, the amount of metal retained in the catalyst was 18 wt%.

Table 1 example 1 to example 15 catalyst preparation parameters

Table 2 characteristic parameters of the catalysts prepared in examples 1 to 15

Example 16

Example 16 the performance of the different nickel nanoparticle catalysts prepared in examples 1-15 and comparative examples 1-16 in the catalytic hydrogenation synthesis of haloaniline was investigated.

Adding 25ml of methanol, 1.0g of p-chloronitrobenzene and 0.05g of carbon material prepared in different examples or comparative examples to a 50ml stainless steel reaction kettle, covering a nickel nanoparticle catalyst, closing the reaction kettle, replacing the air in the reaction kettle by hydrogen for 10 times, raising the temperature to 100 ℃, and starting stirring at the hydrogen pressure of 1.0MPa, wherein the stirring speed is 1800r/min, and reacting for 40 min. Stopping the reaction, cooling the temperature to room temperature, taking supernatant of the reaction solution, filtering the catalyst, and analyzing the filtrate by gas chromatography. The results of the experiment are shown in table 3:

TABLE 3 Performance of different carbon materials coated with nickel nanoparticle catalysts in catalytic hydrogenation reactions for synthesis of haloanilines

Example 17

Example 17 examines the performance of the carbon-coated nickel nanoparticle catalyst prepared in example 2 for hydrogenation of various halonitrobenzenes to produce haloanilines.

In a 50ml stainless steel reaction kettle, 25ml methanol, 1.0g different halogenated nitrobenzene, 0.05g carbon material prepared in example 2 covered with nickel nanoparticle catalyst, closing the reaction kettle, replacing the air in the reaction kettle with hydrogen for 10 times, raising the temperature to 100 ℃, hydrogen pressure to 1.0MPa, starting stirring, the stirring speed is 1800r/min, and reacting for 1 h. Stopping the reaction, cooling the temperature to room temperature, taking supernatant of the reaction solution, filtering the catalyst, and analyzing the filtrate by gas chromatography. The results of the experiment are shown in table 4:

TABLE 4 reaction Performance of the carbon-coated nickel nanoparticle catalyst for hydrogenation of different halonitrobenzenes to haloanilines

Example 18

Example 18 examines the performance of the carbon-coated nickel nanoparticle catalyst prepared in example 5 in the reaction of hydrogenation of p-chloronitrobenzene to p-chloroaniline in example 16. The results of the experiment are shown in table 5:

TABLE 5 stability of nickel nanoparticle catalysts in the preparation of parachloroaniline by hydrogenation of parachlorohalonitrobenzene

Number of times of application	Conversion rate	Selectivity is
			1	100	99.71
2	100	99.59
			3	100	99.67
4	100	99.74
			5	100	99.93
6	100	99.85
			7	100	99.68
8	100	99.59
			9	100	99.84
10	100	99.62

Example 19

Example 19 the performance of the different nickel nanoparticle catalysts prepared in examples 1-15 and comparative examples 1-16 in the catalytic hydrogenation synthesis of p-aminophenylacetic acid was examined.

20ml of methanol, 1.0g of p-nitrophenylacetic acid and 0.05g of carbon material prepared in different examples or comparative examples and coated with a nickel nanoparticle catalyst are added into a 50ml stainless steel reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by hydrogen and nitrogen for 5 times, the nitrogen is replaced by the hydrogen and nitrogen for 10 times, the temperature is raised to 60 ℃, the hydrogen pressure is 0.6MPa, stirring is started, the stirring speed is 1200r/min, and the reaction is carried out for 60 min. Stopping the reaction, cooling to room temperature, filtering, distilling 60-80% methanol from the filtrate, cooling, crystallizing, filtering, and drying to obtain crude product; recrystallizing the crude product with ethanol, and decolorizing with active carbon to obtain light white crystalline p-aminophenylacetic acid. The results of the experiment are shown in table 6:

TABLE 6 Performance of nickel nanoparticle catalyst coated with carbon materials in catalytic hydrogenation reaction for synthesizing p-aminophenylacetic acid

Example 20

Example 20 examines the performance of the carbon-coated nickel nanoparticle catalyst prepared in example 1 in the reaction of preparing p-aminophenylacetic acid by hydrogenating p-nitroacetoacetic acid in example 19. The results are shown in Table 7.

TABLE 7 stability of nickel nanoparticle catalyst in p-aminophenylacetic acid preparation reaction by hydrogenation of p-nitroacetophenone

Number of times of application	Conversion rate	Selectivity is
			1	100	99.89
2	100	99.46
			3	100	99.59
4	100	99.67
			5	100	99.97
6	100	99.61
			7	100	99.84
8	100	99.82
			9	100	99.79
10	100	99.63

Example 21

Example 21 the performance of the different nickel nanoparticle catalysts prepared in examples 1-15 and comparative examples 1-16 in the catalytic hydrogenation synthesis of metanilic acid was examined.

Adding 20mL of water into 5g of sodium m-nitrobenzenesulfonate, heating for dissolving, adding 0.5g of activated carbon, boiling, and carrying out hot filtration, wherein the pH value of the obtained filtrate is adjusted to about 8 by using 20% of sodium hydroxide. Adding the treated sodium m-nitrobenzenesulfonate solution into a 50ml stainless steel reaction kettle, covering 0.1g of carbon material with a nickel nanoparticle catalyst, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for 5 times, replacing nitrogen with hydrogen for 5 times, raising the temperature to 60 ℃, and starting stirring, wherein the hydrogen pressure is 1.0MPa, the stirring speed is 1000r/min, and the hydrogen absorption time is 45 min. After the temperature is reduced to room temperature, filtering, adjusting the pH value of the obtained filtrate to 2 by using 20% sulfuric acid, separating out white precipitate which is m-aminobenzenesulfonic acid, and analyzing by using liquid chromatography. The results of the experiment are shown in table 8:

TABLE 8 Performance of different carbon materials coated with nickel nanoparticle catalyst in catalytic hydrogenation for synthesis of metanilic acid

Example 22

Example 22 examines the applicability of the carbon-coated nickel nanoparticle catalyst prepared in example 2 in the reaction of hydrogenation of m-nitrobenzenesulfonic acid to prepare m-aminobenzenesulfonic acid in example 21. The results are shown in Table 9.

TABLE 9 stability of the catalyst in the hydrogenation of m-nitrobenzenesulfonic acid to m-aminobenzenesulfonic acid

Number of times of application	Conversion rate	Selectivity is
			1	100	99.63
2	100	99.54
			3	100	99.49
4	100	99.52
			5	100	99.67
6	100	99.71
			7	100	99.76
8	100	99.82
			9	100	99.69
10	100	99.80

Example 23

Example 23 the performance of different nickel nanoparticle catalysts prepared in examples 1-15 and comparative examples 1-16 in the catalytic hydrogenation synthesis of 4, 4' -diaminodiphenyl ether was examined.

20ml of DMF, 5g of 4, 4' -dinitrodiphenyl ether and 0.1g of carbon material prepared in different examples or comparative examples are added into a 50ml stainless steel reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by nitrogen for 3 times, the nitrogen is replaced by hydrogen for 5 times, the temperature is raised to 50 ℃, the hydrogen pressure is 0.4MPa, the stirring is started, the stirring speed is 800r/min, and the reaction is carried out for 30 min. The reaction was stopped, the temperature was reduced to room temperature, the catalyst was removed by filtration and the product was analyzed by liquid chromatography. The results of the experiment are shown in table 10:

TABLE 10 Performance of different catalysts in the catalytic hydrogenation synthesis of 4, 4' -diaminodiphenyl ether

Example 24

Example 24 examined the ability of the carbon-coated nickel nanoparticle catalyst prepared in example 8 to be used in the hydrogenation of 4,4 '-dinitrodiphenyl ether to prepare 4, 4' -diaminodiphenyl ether in example 23. The results are shown in Table 11.

TABLE 11 stability of catalyst in 4,4 '-diaminodiphenyl ether hydrogenation to 4, 4' -diaminodiphenyl ether

Number of times of application	Conversion rate	Selectivity is
			1	100	99.69
2	100	99.38
			3	100	99.91
4	100	99.57
			5	100	99.53
6	100	99.64
			7	100	99.72
8	100	99.83
			9	100	99.80
10	100	99.78

Example 25

Example 25 the performance of different nickel nanoparticle catalysts prepared in examples 1-15 and comparative examples 1-16 in the catalytic hydrogenation synthesis of 1-aminoanthraquinone was examined.

20mL of absolute ethyl alcohol, 2g of 1-nitroanthraquinone and 0.05g of carbon material prepared in different examples or comparative examples covering a nickel nanoparticle catalyst are added into a 50mL stainless steel reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by hydrogen for 5 times, the nitrogen is replaced by the hydrogen for 3 times, the temperature is raised to 70 ℃, the hydrogen pressure is 1.0MPa, stirring is started, the stirring speed is 1000r/min, and the reaction is carried out for 50 min. Stopping the reaction, cooling to room temperature, taking the supernatant of the reaction solution, filtering the catalyst, and taking the supernatant for gas chromatography analysis. The results of the experiment are shown in table 12:

TABLE 12 Performance of different carbon materials coated with nickel nanoparticle catalysts in the catalytic hydrogenation synthesis of 1-aminoanthraquinone

Example 26

Example 26 examined the applicability of the carbon-coated nickel nanoparticle catalyst prepared in example 9 in the hydrogenation of 1-nitroanthraquinone to 1-aminoanthraquinone reaction in example 25. The results are shown in Table 13.

TABLE 13 stability of catalyst in 1-nitroanthraquinone hydrogenation to 1-aminoanthraquinone reaction

Claims

1. The application of the carbon material coated nickel nanoparticle catalyst in the synthesis of p-aminophenylacetic acid by the hydrogenation of p-nitroacetoacetic acid is characterized in that: the carbon material coated nickel nanoparticle catalyst is prepared according to the following steps:

(2) dropwise adding alkali liquor into the mixed solution in batches, and adjusting the pH value of the solution in three stages, wherein the pH value is as follows: A) firstly, adjusting the pH value to 4.0-5.5 by using 0.1-5 mol/L sodium hydroxide aqueous solution, and keeping for 0.5-3 hours; B) then regulating the pH value to 6.5-7.5 by using 80-99% triethanolamine water solution, and keeping for 1-5 hours; C) finally, adjusting the pH value to 8.5-9.5 by using 25-28% ammonia water, and keeping for 1-3 hours; the mixed liquid is always in a stirring state in the adjusting process;

(3) sealing the slurry obtained in the step (2), placing the slurry on a vibration platform for crystallization, precipitation and aging, then filtering and washing, and carrying out vacuum drying to obtain a metal organic framework precursor; wherein the shaking program is set as: firstly, vibrating for 1-5 minutes at a vibration frequency of 10-20 Hz; secondly, vibrating for 1-5 minutes at the vibration frequency of 20-40 Hz; thirdly, vibrating for 1-5 minutes with the vibration frequency of 40-55Hz and the horizontal amplitude; running the program I-III to form a vibration period; the whole crystallization, precipitation and aging process is 10-20 hours, and a vibration period is operated at intervals of 1-2 hours;

2. The use of claim 1, wherein: the application process comprises the following steps: putting a carbon material coated with a nickel nanoparticle catalyst, paranitroacetic acid and methanol into a high-pressure reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, starting stirring, reacting for a period of time at the temperature of 50-100 ℃ and the hydrogen pressure of 0.5-1 MPa, opening the reaction kettle, filtering, taking filtrate, evaporating 60-80% of methanol solvent, cooling, crystallizing, filtering and drying to obtain a crude product; recrystallizing the crude product with ethanol, and decolorizing with active carbon to obtain light white crystalline p-aminophenylacetic acid.

3. Use according to claim 2, characterized in that: the feeding ratio of the nickel nanoparticle catalyst coated with the paranitroacetoacetic acid, the methanol and the carbon material is 1 g: 10-40 mL: 0.01 to 0.10 g.

4. Use according to one of claims 1 to 3, characterized in that: in the step (1), the nickel salt is at least one of nickel chloride, nickel carbonate, nickel nitrate and nickel acetate; the alcohol solvent methanol or absolute ethanol has the volume concentration of more than 95 percent; the organic ligand is at least one of benzoic acid, terephthalic acid, urea, ethylene diamine tetraacetic acid, 4-picolinic acid, 2' -bipyridyl, triphenylphosphine, oxalic acid and glycine.

5. Use according to one of claims 1 to 3, characterized in that: in the step (1), the molar ratio of nickel in the nickel salt to the organic ligand is 1: 1-1: 8, preferably 1: 2-1: 6; the mass ratio of nickel in the nickel salt to the alcohol solvent is 1: 50-1: 1000, preferably 1: 100-1: 500.

6. use according to one of claims 1 to 3, characterized in that: in the step (1), the stirring temperature is 0-50 ℃, and preferably 20-50 ℃; the stirring time is 3 to 24 hours, preferably 6 to 15 hours.

7. The method according to any one of claims 1 to 3, wherein: and (3) filtering and washing the precipitate with ethanol after aging, putting the precipitate into a vacuum oven, and drying the precipitate for 2 to 15 hours at the temperature of between 50 and 120 ℃ and taking the precipitate out.

8. Use according to one of claims 1 to 3, characterized in that: in the step (4), the roasting temperature is 300-800 ℃, and preferably 400-600 ℃; the calcination time is 5 to 24 hours, preferably 5 to 10 hours.

9. Use according to one of claims 1 to 3, characterized in that: in the step (4), the inert atmosphere is nitrogen or argon, the volume fraction of carbon dioxide in the roasting atmosphere is not less than 10%, and the most preferable roasting atmosphere is carbon dioxide atmosphere; the total flow rate of the gas is 5-50 mL/min.