CN113318767B - Catalyst for preparing amino acid by ammoniating carbonyl acid and preparation method and application thereof - Google Patents
Catalyst for preparing amino acid by ammoniating carbonyl acid and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing amino acid by ammoniating carbonyl acid, which is characterized in that the catalyst is coated on SiO 2 Nitrogen-doped carbon on the surface is used as a carrier, and a loaded transition metal is used as an active component; the transition metal accounts for 1.0-3.0% of the total mass of the catalyst. The method for preparing amino acid by ammoniating carbonyl acid by using the obtained catalyst does not use a highly toxic compound as a raw material, and has the characteristics of simple post-treatment, small environmental pollution and high product yield. The active components of the catalyst are non-noble metals, the catalyst is low in cost, good in catalytic performance and stable in activity, after 10 times of recycling, the yield and the purity are still in a very satisfactory degree, the catalyst can be recycled, and the catalyst has the advantage of cost in industry.
Description
Technical Field
The invention relates to the technical field of catalytic reaction, in particular to a catalyst for preparing amino acid by ammoniating carbonyl acid, a preparation method and application thereof.
Background
Amino acids are the basic units that constitute proteins and play a key role in the life processes of humans and other animals, and thus, the demand for food and feed additives is increasing day by day. In recent years, amino acids have also been used in the preparation of biodegradable plastic products. In addition, in the aspect of drug synthesis, amino groups of amino acids are easy to modify, and carboxyl groups are easy to combine with other chiral centers, so that the amino acids are not only basic building blocks of the current small-molecule drug chemistry, but also only building units of synthetic peptide drugs.
At present, the production of amino acid, especially small variety of amino acid, mainly depends on biological fermentation, but the culture conditions of biological bacteria are harsh, and the fermentation process is usually carried out in a dilute aqueous medium, so that the production efficiency is low, and the separation process is complicated, thereby promoting people to develop an efficient chemical synthesis method for producing amino acid and derivatives thereof. Currently, the general process routes developed for large-scale chemical production of amino acids are the Strecker route and the Bucherer-Bergs route. However, the above-mentioned processes have problems of serious environmental pollution and use of highly toxic hydrocyanic acid or its salt as a raw material.
Bucherer-Bergs route to amino acids
Therefore, in order to solve the above problems, there is a need to develop a new method for synthesizing amino acids, which is more green and environmentally friendly.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a catalyst for preparing amino acid by ammoniating carbonyl acid, a preparation method thereof and a method for preparing amino acid.
The invention provides the following technical scheme:
a catalyst for preparing amino acid by ammoniating carbonyl acid is coated on SiO 2 Nitrogen-doped carbon on the surface is used as a carrier, and a loaded transition metal is used as an active component; the transition metal accounts for 1.0-3.0% of the total mass of the catalyst.
The transition metal is at least one of Ni, Co, Fe, Mn and Ti.
Preferably, the transition metal is a complex of Ni and Co.
Further, the mass ratio of Ni to Co is 1-5.5: 1; preferably, the mass ratio of Ni to Co is 2.1-5.3: 1.
the inventor unexpectedly finds that when the catalytic active components are Ni and Co which are compounded according to a certain proportion, the catalytic activity is obviously improved, and the yield of the product amino acid is improved to more than 90%.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(S1) taking monomer aqueous solution of nitrogen carbon source, adjusting the pH value to 3-6, adding catalyst carrier precursor H 2 SiO 3 Particle, initiating monomer to polymerize in situ on the surface of the catalyst carrier precursor, adding transition metal salt in inert atmosphere, heating and stirring, filtering, washing and vacuum drying the catalyst precursor;
(S2) carrying out high-temperature heat treatment on the obtained catalyst precursor in an inert atmosphere to obtain the catalyst.
The catalyst support precursor H 2 SiO 3 The preparation method of the granules isThe sodium silicate is prepared by adjusting the sodium silicate to weak acid by acid, precipitating, filtering, washing and drying at high temperature, which is well known in the field.
Preferably, the nitrogen carbon source is one or more monomers containing nitrogen and carbon, and the nitrogen carbon source-coated catalyst carrier precursor particles are obtained by in-situ polymerization on the surface of the catalyst carrier precursor.
The monomer is selected from o-phenylenediamine and/or dopamine. The initiating means is light irradiation (such as blue light irradiation) or an external initiator (such as ammonium persulfate).
Further, the mass ratio of the nitrogen-carbon source monomer, the catalyst carrier precursor and the transition metal salt is 4-10: 15-30: 2-5, preferably 4-7: 20-25: 3-4.
The transition metal salt is nitrate and chloride of Ni, Co, Fe, Mn and Ti.
The transition metal salt is preferably a compound of nickel salt and cobalt salt according to the mass ratio of 1-5:1, and is preferably a compound of nickel nitrate and cobalt nitrate according to the mass ratio of 2-5: 1, compounding.
Preferably, the high temperature heat treatment in the step (S2) is performed at a heating rate of 10-15 ℃/min and at a temperature of 600-800 ℃ for 3-5 h.
The metal ions in the metal nitrate and the coated o-phenylenediamine polymer form a complex; and then the inert gas is reduced into a metal simple substance in the process of being burnt.
More preferably, the high temperature heat treatment of step (S2) is performed according to the following temperature program: slowly heating to 300-.
The heating rate of the slow heating is 3-5 ℃/min, the heating rate of the fast heating is 8-10 ℃/min, and the rate of the slow cooling is-5 to-2 ℃/min.
A second object of the present invention is to provide a process for the preparation of amino acids by ammoniation starting from carbonyl acids, characterized in that the above-mentioned catalyst is used in an amount of 1-10 wt.%, preferably 6-10 wt.%, relative to the carbonyl acid.
The route for the preparation of the amino acids is shown below:
r is H, alkyl, aryl or aralkyl, the number of carbon atoms of the alkyl is an integer of 1-6, and the number of carbon atoms of the aryl is an integer of 6-10.
Examples of said alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, butyl; the aryl is selected from phenyl and naphthyl; the aralkyl group is selected from benzyl.
The H atoms on the alkyl, aryl and aralkyl are optionally substituted by 1 to 3 substituents selected from hydroxyl, sulfydryl, amino, amido, carboxyl and aldehyde groups. For example, R is selected from-CH 2 -Ph-OH、-(CH 2 ) n -COOH、-(CH 2 ) n -CONH 2 、-(CH 2 ) n -NH 2 、-(CH 2 ) n -S-CH 3 、-(CH 2 ) n -SH, wherein Ph is phenylene and n is an integer between 1 and 4, such as 1, 2, 3, 4.
The reaction condition is that ammonia water or ammonia gas, hydrogen and carbonyl acid are used as raw materials, and the amino acid is prepared at 80-150 ℃ under the hydrogen pressure of 1-5 MPa.
The method has the characteristics of no use of highly toxic compounds as raw materials, simple post-treatment, little environmental pollution and high product yield. And the active component of the catalyst is non-noble metal, the catalyst has low cost, good catalytic performance and stable activity, can be recycled, and has the advantage of cost in industry.
Drawings
FIG. 1 is the Ni-Co @ NC @ SiO prepared in example 4 2 XRD pattern of catalyst.
FIG. 2 Ni-Co @ NC @ SiO obtained in example 4 2 TEM image of the catalyst.
FIG. 3 is the respective Ni-Co @ NC @ SiO films obtained in example 9 2 TEM image of the catalyst.
Detailed Description
The invention is further illustrated by the following examples:
preparation example 1:
50.0g of Na was weighed 2 SiO 3 ·9H 2 Dissolving O in 200mL of deionized water, uniformly stirring, heating to 40 ℃, dropwise adding 30% dilute nitric acid to adjust the pH value of the solution to be 4.5, and continuously stirring for reaction for 1 hour. Filtering after the reaction is finished, washing a filter cake to be neutral by using deionized water, and drying at 110 ℃ to obtain a catalyst carrier precursor which is mainly H 2 SiO 3 。
Example 1: ni @ NC @ SiO 2 Preparation of the catalyst
6.0g of o-phenylenediamine was weighed out and dissolved in 50mL of deionized water, and 6N hydrochloric acid was added to adjust the pH to 4.0, and then 20.0g of the catalyst support precursor obtained in preparation example 1 was added thereto and stirred at room temperature. Starting a 15w blue light lamp for irradiation, initiating the polymerization reaction of o-phenylenediamine, reacting at room temperature for 8h, uniformly coating the polymer on the surface of the catalyst carrier precursor, filtering after the reaction is finished, washing a filter cake with 1N diluted hydrochloric acid, and drying in vacuum at 50 ℃ for 5 h.
In N 2 Under protection, 50mL of deionized water, 50mL of methanol and the previously prepared poly-o-phenylenediamine-coated catalyst support precursor microspheres were added to a reaction flask, stirred at room temperature for 30min, and then 2.0g of Ni (NO) was added 3 ) 2 ·6H 2 O (10mL of deionized water) solution, heating to 50 ℃, and stirring for reaction for 10 h. After the reaction, filtering, washing the filter cake 3 times by using 50mL of methanol and water mixed solvent (volume ratio is 1:1), and vacuum drying at 50 ℃ for 5h to obtain the catalyst precursor.
The dried catalyst precursor was pyrolyzed in a tube furnace under argon protection. The temperature-raising program is: heating to 700 ℃ at the speed of 10 ℃/min, and preserving the heat for 3 hours to obtain the catalyst Ni @ NC @ SiO 2 The Ni content in the catalyst was 1.28 wt% (ICP analysis).
Example 2: co @ NC @ SiO 2 Preparation of the catalyst
7.0g of o-phenylenediamine was weighed and dissolved in 50mL of deionized water, and 6N hydrochloric acid was added to adjust the pH to 4.0, and then 20.0g of the catalyst support precursor obtained in preparation example 1 was added thereto and stirred at room temperature. Starting a 15w blue light lamp for irradiation, initiating the polymerization reaction of o-phenylenediamine, reacting for 8 hours at room temperature, filtering after the reaction is finished, washing a filter cake with 1N diluted hydrochloric acid, and drying for 5 hours in vacuum at 50 ℃.
In N 2 Under protection, 50mL of deionized water, 50mL of methanol and the prepared poly-o-phenylenediamine-coated catalyst support precursor microspheres were added to a reaction flask, stirred at room temperature for 30min, and then 3.0g of Co (NO) was added 3 ) 2 ·6H 2 O (10mL of deionized water) solution, heating to 50 ℃, and stirring for reaction for 10 h. After the reaction, filtering, washing the filter cake 3 times by using 50mL of methanol and water mixed solvent (volume ratio is 1:1), and vacuum drying at 50 ℃ for 5h to obtain the catalyst precursor.
The dried catalyst precursor was pyrolyzed in a tube furnace under argon protection. The temperature rising procedure is as follows: heating to 700 ℃ at the speed of 10 ℃/min, and preserving the heat for 3 hours to obtain the catalyst Co @ NC @ SiO 2 The Co content in the catalyst was 1.72 wt% (ICP analysis).
Example 3: fe @ NC @ SiO 2 Preparation of the catalyst
4.5g of o-phenylenediamine was dissolved in 50mL of deionized water, and 6N hydrochloric acid was added to adjust the pH to 4.0, and then 20.0g of the catalyst support precursor obtained in preparation example 1 was added thereto and stirred at room temperature. Starting a 15w blue light lamp for irradiation, initiating the polymerization reaction of o-phenylenediamine, reacting for 8 hours at room temperature, filtering after the reaction is finished, washing a filter cake with 1N diluted hydrochloric acid, and drying for 5 hours in vacuum at 50 ℃.
In N 2 Under protection, 50mL of deionized water, 50mL of methanol and the prepared poly-o-phenylenediamine-coated catalyst support precursor microspheres were added to a reaction flask, stirred at room temperature for 30min, and then 3.0g of Fe (NO) was added 3 ) 3 ·9H 2 O (10mL of deionized water) solution, heating to 50 ℃, and stirring for reaction for 10 h. After the reaction, filtering, washing the filter cake 3 times by using 50mL of methanol and water mixed solvent (volume ratio is 1:1), and vacuum drying at 50 ℃ for 5h to obtain the catalyst precursor.
The dried catalyst precursor was pyrolyzed in a tube furnace under argon protection. The temperature rising procedure is as follows: raising the temperature to 700 ℃ at a speed of 10 ℃/min, and preserving the temperature for 3h to obtain the catalyst Fe @ NC @ SiO 2 The Fe content in the catalyst was 1.66 wt% (ICP analysis).
Example 4: Ni-Co @ NC @ SiO 2 Preparation of the catalyst
6.0g of o-phenylenediamine was weighed out and dissolved in 50mL of deionized water, and 6N hydrochloric acid was added to adjust the pH to 4.0, and then 20.0g of the catalyst support precursor obtained in preparation example 1 was added thereto and stirred at room temperature. Starting a 15w blue light lamp for irradiation, initiating the polymerization reaction of o-phenylenediamine, reacting for 8 hours at room temperature, filtering after the reaction is finished, washing a filter cake with 1N diluted hydrochloric acid, and drying for 5 hours in vacuum at 50 ℃.
In N 2 Under protection, 50mL of deionized water, 50mL of methanol and the previously prepared poly-o-phenylenediamine-coated catalyst support precursor microspheres were added to a reaction flask, stirred at room temperature for 30min, and then 2.5g of Ni (NO) was added 3 ) 2 ·6H 2 O and 0.5g Co (NO) 3 ) 2 ·6H 2 O (10mL of deionized water) solution, heating to 50 ℃, and stirring for reaction for 10 h. After the reaction, filtering, washing the filter cake 3 times by using 50mL of methanol and water mixed solvent (volume ratio is 1:1), and vacuum drying at 50 ℃ for 5h to obtain the catalyst precursor.
The dried catalyst precursor was pyrolyzed in a tube furnace under argon protection. The temperature rising procedure is as follows: heating to 700 ℃ at the speed of 10 ℃/min, and preserving the heat for 3 hours to obtain the catalyst Ni-Co @ NC @ SiO 2 The catalyst contained Ni in an amount of 1.57 wt% and Co in an amount of 0.30 wt% (ICP analysis), and the mass ratio of Ni to Co was 5.23.
Example 4 preparation of Ni-Co @ NC @ SiO 2 The XRD pattern of the catalyst is shown in figure 1. As can be seen, Ni-Co @ NC @ SiO 2 Compared with NC @ SiO 2 And a new obvious XRD peak does not appear, which indicates that the catalytic active components Ni and Co are uniformly dispersed.
Example 5: Ni-Co @ NC @ SiO 2 Preparation of the catalyst
Other conditions and operations were the same as in example 4 except that Ni (NO) 3 ) 2 ·6H 2 The amount of O is 2g, Co (NO) 3 ) 2 ·6H 2 The dosage of O is 1g, and finally the catalyst Ni-Co @ NC @ SiO is obtained 2 The catalyst contained 1.26 wt% of Ni and 0.58 wt% of Co (ICP analysis), and the mass ratio of Ni to Co was 2.17.
Example 6: Ni-Co @ NC @ SiO 2 Preparation of the catalyst
Other conditions and operations were the same as in example 4 except that Ni (NO) 3 ) 2 ·6H 2 The amount of O is 1.5g, Co (NO) 3 ) 2 ·6H 2 The dosage of O is 1.5g, and the catalyst Ni-Co @ NC @ SiO is finally obtained 2 The catalyst contained Ni in an amount of 0.91 wt% and Co in an amount of 0.87 wt% (ICP analysis), and the mass ratio of Ni to Co was 1.04.
Example 7: Ni-Co @ NC @ SiO 2 Preparation of the catalyst
Other conditions and operations were the same as in example 4 except that Ni (NO) 3 ) 2 ·6H 2 The amount of O is 0.5g, Co (NO) 3 ) 2 ·6H 2 The dosage of O is 2.5g, and the catalyst Ni-Co @ NC @ SiO is finally obtained 2 The catalyst contained Ni in an amount of 0.33 wt% and Co in an amount of 1.44 wt% (ICP analysis), and the mass ratio of Ni to Co was 0.23.
Example 8: Ni-Fe @ NC @ SiO 2 Preparation of the catalyst
6.0g of o-phenylenediamine was weighed out and dissolved in 50mL of deionized water, and 6N hydrochloric acid was added to adjust the pH to 4.0, and then 20.0g of the catalyst support precursor was added thereto and stirred at room temperature. Starting a 15w blue light lamp for irradiation, initiating the polymerization reaction of o-phenylenediamine, reacting for 8 hours at room temperature, filtering after the reaction is finished, washing a filter cake with 1N diluted hydrochloric acid, and drying for 5 hours in vacuum at 50 ℃.
In N 2 Under protection, 50mL of deionized water, 50mL of methanol and the previously prepared poly-o-phenylenediamine-coated catalyst support precursor microspheres were added to a reaction flask, stirred at room temperature for 30min, and then 2.4g of Ni (NO) was added 3 ) 2 ·6H 2 O and 0.6g Fe (NO) 3 ) 3 ·9H 2 O (10mL of deionized water) solution, heating to 50 ℃, and stirring for reaction for 10 h. After the reaction, filtering, washing the filter cake 3 times by using 50mL of methanol and water mixed solvent (volume ratio is 1:1), and vacuum drying at 50 ℃ for 5h to obtain the catalyst precursor.
The dried catalyst precursor was pyrolyzed in a tube furnace under argon protection. The temperature rising procedure is as follows: heating to 700 ℃ at the speed of 10 ℃/min, and preserving the heat for 3h to obtain the catalyst Ni-Fe @ NC @ SiO 2 The catalyst contained 1.57% of Ni and 0.32% of Fe (ICP analysis), and the mass ratio of Ni to Fe was 4.91.
Example 9:Ni-Co@NC@SiO 2 preparation of the catalyst
The other conditions and operations were the same as in example 4 except that the difference was that. The temperature rising procedure is as follows: heating to 300 deg.C at 4 deg.C/min, maintaining for 1h, heating to 700 deg.C at 10 deg.C/min, maintaining for 3h, slowly cooling to 200 deg.C at a cooling rate of 2-3 deg.C/min, maintaining for 1h, and naturally cooling to obtain Ni-Co @ NC @ SiO 2 A catalyst. The catalyst had an Ni content of 1.58 wt% and a Co content of 0.30 wt% (ICP analysis). FIGS. 2 and 3 are Ni-Co @ NC @ SiO prepared in examples 4 and 9, respectively 2 TEM image of the catalyst. It can be seen that the Ni and Co in example 4 still have a certain degree of agglomeration, and the catalyst of example 9 undergoes a specific temperature-raising procedure of rapid temperature-300 ℃, temperature-holding, slow temperature-raising by 700 ℃, temperature-holding, slow temperature-lowering by 200 ℃, and temperature-holding, so that the Ni and Co in the obtained catalyst are dispersed more uniformly, and have better catalytic activity, and the stability and the service life of the catalyst are obviously improved.
Example 10
6.06g of tris (hydroxymethyl) aminomethane, 80ml of a 1N aqueous hydrochloric acid solution and 120ml of deionized water were weighed, dissolved and clarified, and then the pH was adjusted to 8.5 with a 4% aqueous sodium hydroxide solution, 10.0g of dopamine hydrochloride was added thereto, and after stirring the mixture uniformly, 20.0g of the catalyst support precursor obtained in preparation example 1 was added thereto, and the mixture was stirred uniformly at room temperature. Introducing oxygen at the speed of 10.0ml/min, reacting at room temperature for 24h, filtering after the reaction is finished, washing a filter cake by deionized water, and drying in vacuum at 50 ℃ for 5 h.
At N 2 Under protection, 50mL of deionized water, 50mL of methanol and the previously prepared polydopamine-coated catalyst support precursor microspheres were added to a reaction flask, stirred at room temperature for 30min, and then 2.5g of Ni (NO) was added 3 ) 2 ·6H 2 O and 0.5g Co (NO) 3 ) 2 ·6H 2 O (10mL of deionized water) solution, heating to 50 ℃, and stirring for reaction for 10 h. After the reaction, filtering, washing the filter cake 3 times by using 50mL of methanol and water mixed solvent (volume ratio is 1:1), and vacuum drying at 50 ℃ for 5h to obtain the catalyst precursor.
The dried catalyst precursor was pyrolyzed in a tube furnace under argon protection. The temperature rising procedure is as follows: heating to 350 deg.C at 3 deg.C/min for 1 hr, heating to 800 deg.C at 15 deg.C/minThe temperature is 3h, then the temperature is slowly reduced to 250 ℃ at the rate of 2-3 ℃/min, and the temperature is kept for 1h, thus obtaining the catalyst Ni-Co @ NC @ SiO 2 The catalyst contained 1.55 wt% of Ni and 0.29 wt% of Co (ICP analysis), and the mass ratio of Ni to Co was 5.34.
Comparative example 1: ni @ SiO 2 Preparation of the catalyst
2.0g of Ni (NO) was weighed 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and then 20.0g of the catalyst support precursor obtained in preparation example 1 was added thereto, and the mixture was stirred at 30 ℃ for 10 hours. Then, the deionized water was distilled off, dried at 120 ℃ for 2 hours, and calcined in a muffle furnace. The temperature rising procedure is as follows: raising the temperature to 700 ℃ at the speed of 5 ℃/min, preserving the heat for 3 hours, and then reducing the temperature to room temperature to obtain the catalyst Ni @ SiO 2 The Ni content in the catalyst was 1.32% (ICP analysis).
Comparative example 2: Ni-Co @ NC @ SiO 2 Preparation of the catalyst
The other operation was the same as in example 4 except that irradiation with a blue light lamp, that is, polymerization of o-phenylenediamine was not carried out. Finally obtaining the catalyst Ni-Co @ NC @ SiO 2 The catalyst contained 1.52 wt% of Ni and 0.29 wt% of Co (ICP analysis), and the mass ratio of Ni to Co was 5.24.
Comparative example 3
A commercial Pd/C catalyst was used, purchased from Beijing Mino sincerity technologies, Inc., with a Pd loading of about 2.1%.
Application example 1
3.0g of the catalyst prepared in the example 1, 50.0g of pyruvic acid, 50g of 25% ammonia water, 200ml of deionized water, 3 times of nitrogen replacement and 3 times of hydrogen replacement are added into a 500ml high-pressure reaction kettle, hydrogen is filled into the reaction kettle to the pressure of 1.0MPa, the temperature is raised to 120 ℃, the hydrogen pressure is kept at 1.0MPa, the reaction is carried out for 3 hours, the temperature is reduced, the catalyst is removed by filtration, the reduced pressure evaporation is carried out, the remainder is recrystallized by absolute ethyl alcohol to obtain 42.94g of the product DL-alanine, the yield is 83.9%, and the purity is 98.8% through HPLC verification. Purity was measured by HPLC.
The results for each example catalyst are shown in table 1 below:
TABLE 1
Application example 2:
the commercial palladium on carbon catalysts of examples 4 and 9 and comparative example 3 were reused by filtration after the reaction under the reaction conditions of application example 1, and the number of times of recycling of the catalyst and the degree of deterioration of the catalytic performance were examined, and the results are shown in Table 2.
Table 2: experimental results of catalyst recycling
It can be seen from the data in table 2 that the catalyst prepared by the present invention can be repeatedly used for more than 10 times when used for catalyzing the amination of carbonyl acid to synthesize amino acid, and the yield and purity are still kept at satisfactory levels, and particularly, the catalyst of example 9 has a significantly improved service life through a specific heat treatment process, i.e., a slow temperature rise-fast temperature rise-slow temperature fall procedure of three stages of 300 ℃ to 700 ℃ to 200 ℃. After 10 recycles, the yield and purity are still at a very satisfactory level. The catalyst prepared by the invention has the advantages of cheap and easily available raw materials, simple preparation method, equivalent catalytic performance to that of a commercial Pd/C catalyst, far lower price than that of a noble metal Pd catalyst, obviously longer service life than that of the commercial Pd/C catalyst, and strong industrial application prospect in amino acid synthesis.
Claims (16)
1. A catalyst for preparing amino acid by aminating carbonyl acid is characterized by being coated on SiO 2 Nitrogen-doped carbon on the surface is used as a carrier, and a loaded transition metal is used as an active component; the transition metal accounts for 1.0-3.0% of the total mass of the catalyst; the transition metal is Ni and/or Co;
the catalyst is obtained by a preparation method comprising the following steps:
(S1) taking the water solution of the nitrogen-carbon source monomer, adjusting the pH value to 3-6, adding the catalyst carrier precursor H 2 SiO 3 Particle, initiating monomer to polymerize in situ on the surface of the catalyst carrier precursor, adding transition metal salt in inert atmosphere, heating and stirring, filtering, washing, and vacuum drying the catalyst precursor; the monomer is selected from o-phenylenediamine and/or dopamine; the initiating polymerization mode is light irradiation or an external initiator;
(S2) carrying out high-temperature heat treatment on the obtained catalyst precursor in an inert atmosphere to obtain the catalyst.
2. The catalyst of claim 1 wherein the transition metal is a combination of Ni and Co.
3. The catalyst according to claim 2, wherein the mass ratio of Ni and Co is 1 to 5.5: 1.
4. the catalyst according to claim 3, wherein the mass ratio of Ni and Co is 2.1-5.3: 1.
5. the catalyst according to claim 1, wherein the mass ratio of the nitrogen-carbon source monomer, the catalyst support precursor and the salt of the transition metal is 4-10: 15-30: 2-5.
6. The catalyst according to claim 5, wherein the mass ratio of the nitrogen-carbon source monomer, the catalyst support precursor and the salt of the transition metal is 4-7: 20-25: 3-4.
7. The catalyst according to claim 1, wherein the salt of the transition metal is a nitrate, chloride of Ni and/or Co.
8. The catalyst according to claim 7, wherein the transition metal salt is a nickel salt and a cobalt salt compounded according to a mass ratio of 1-5: 1.
9. The catalyst according to claim 8, wherein the salt of the transition metal is nickel nitrate and cobalt nitrate in a mass ratio of 2-5: 1, compounding.
10. The catalyst as claimed in claim 1, wherein the step (S2) of high temperature heat treatment is performed by heat preservation at 600-800 ℃ for 3-5h at a temperature rising rate of 10-15 ℃/min.
11. The catalyst according to claim 10, wherein the high temperature heat treatment of step (S2) is performed according to the following temperature program: slowly heating to 300-.
12. The catalyst of claim 11, wherein the slow temperature rise rate is 3-5 ℃/min, the fast temperature rise rate is 8-10 ℃/min, and the slow temperature fall rate is-5 to-2 ℃/min.
13. A process for the preparation of amino acids by aminating carbonyl acids as starting material, characterized in that a catalyst according to any of claims 1 to 12 is used in an amount of 1 to 10% by weight of the carbonyl acid.
14. A process according to claim 13, characterised in that the catalyst is used in an amount of 6-10wt% of the carbonyl acid.
15. The method of claim 13, wherein the synthetic route is as follows:
r is H, alkyl, aryl or aralkyl, wherein the carbon atom number of the alkyl is an integer from 1 to 6, and the carbon atom number of the aryl is an integer from 6 to 10;
h atoms on the alkyl, aryl and aralkyl are optionally substituted by 1 to 3 substituents selected from hydroxyl, sulfydryl, amino, amido, carboxyl and aldehyde groups;
the reaction condition is that ammonia water or ammonia gas, hydrogen and carbonyl acid are used as raw materials, and the amino acid is prepared at 80-150 ℃ under the hydrogen pressure of 1-5 MPa.
16. The method of claim 15, wherein R is selected from-CH 2 -Ph-OH、-（CH 2 ） n -COOH、-（CH 2 ） n -CONH 2 、-（CH 2 ） n -NH 2 、-（CH 2 ） n -S-CH 3 、-（CH 2 ） n -SH, wherein Ph is phenylene and n is an integer between 1 and 4.
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