CN117085727A - Double-layer coated metal particle catalyst, preparation method and application of catalyst in catalytic synthesis of pentanediamine - Google Patents

Abstract

The invention discloses a double-layer wrapped metal particle catalyst, a preparation method and an application in catalytically synthesizing pentanediamine. Transition metal nanoparticles are the active sites of the decarboxylation reaction and serve as the core of the catalyst. First, the rich pore structure of the molecular sieve is used to confine the metal nanoparticles to obtain highly dispersed metal nanoparticles with a size of ~1.5 nm to prevent the metal nanoparticles from agglomeration during the reaction; secondly, a hydrothermal synthesis crystallization method is used to grow an acid-resistant silicon shell in situ on the outer layer of the molecular sieve to prevent corrosion by inorganic acids in the reaction solution. Compared with the single-layer wrapped catalyst, the double-layer wrapped catalyst of the present invention significantly improves the stability of the catalyst. After the catalyst is circulated 5 times, the lysine conversion rate is 80% and the pentanediamine selectivity is 60%. The invention provides a new industrialization opportunity for the chemical decarboxylation of lysine to produce pentamethylenediamine, and has good industrial application prospects.

Description

Double-layer wrapped metal particle catalyst, preparation method and catalytic synthesis of pentanediamine application

Technical field

The invention relates to the field of chemical synthesis, and specifically relates to a double-layer wrapped metal particle catalyst, a preparation method and an application in catalytically synthesizing pentanediamine.

Background technique

1,5-pentanediamine, also known as cadaverine, can be polymerized with adipic acid to produce nylon 56 material. Nylon 56 material has good comprehensive properties, such as high moisture wicking rate, good air permeability, softness and good dyeing performance. It is also wear-resistant, chemical-resistant, flame-retardant and easy to process. Among the nylon material series Have a strong competitive advantage. The most reported production method for 1,5-pentanediamine is biological fermentation. Nanjing University of Technology uses bean dregs hydrolyzate to ferment to produce pentanediamine (CN201810954086.X). However, pentanediamine is toxic to microorganisms and affects production efficiency. Shanghai Kaiser Biotechnology R&D Center Co., Ltd. has applied for multiple patents for the pentamethylenediamine biological fermentation method (CN201811506539.9, CN201710453415.8, CN201710011198.7, etc.). The patent content points out that lysine is inserted into the lysine fermentation process. The seed liquid of the acid decarboxylase strain effectively improves the toxicity of pentylenediamine to the strain. However, biological fermentation methods still have major difficulties, such as low lysine decarboxylase activity, poor toxicity resistance, low product concentration, and high separation costs.

Compared with the biological fermentation decarboxylation method, the chemical decarboxylation method has obvious advantages, such as the catalyst activity is not affected by the toxicity of pentamethylenediamine and the product is easy to separate. However, there are two main problems in the currently reported chemical methods for preparing pentanediamine. The formation rate of monopentanediamine is low. The main reason is that the catalyst performance is low. The currently reported catalysts for the decarboxylation of lysine to produce pentanediamine are mainly based on Supported ruthenium catalysts are mainly used. In 2017, the use of Ru/C as a catalyst for L-lysine decarboxylation reaction was reported for the first time, with a selectivity of 32% for pentanediamine.

Chinese patent application number 202110938327.3 discloses a molecular sieve-confined metal oxide catalyst, preparation method and application. This invention uses an in-situ synthesis method to prepare a molecular sieve-confined metal catalyst. The metal active component of the catalyst is effectively immobilized, avoiding the agglomeration of the active component, and the catalyst structure is maintained well; the catalyst is used for lysine decarboxylation reaction The production rate of pentanediamine is effectively increased and the reaction process time is shortened, but the selectivity needs to be improved.

Chinese patent application number 202211265811.5 discloses a metal ion-modified molecular sieve-confined transition metal nanoparticle and its catalytic method for synthesizing pentanediamine. By changing the alkalinity of the catalyst surface, it promotes the directional adsorption of carboxyl groups, thereby inhibiting the production of by-products. , improve selectivity and efficiently synthesize pentanediamine. By changing the surface alkalinity of the catalyst, it effectively improves the directional adsorption of lysine carboxyl groups, inhibits the occurrence of side reactions from the source, and then strengthens the direct decarboxylation of lysine to generate pentanediamine. , greatly improving the selectivity of pentanediamine, using metal ion modified molecular sieve-confined transition metal nanoparticles as catalysts to catalyze the synthesis of pentanediamine with a selectivity as high as 77.4%, which is currently at the international leading level. However, the lysine decarboxylation reaction proceeds under high temperature, high pressure, and acidic conditions, and poor catalyst stability is still the biggest problem restricting industrial production. For example, when the carbon in the traditional Ru/C catalyst undergoes a methanation reaction, the catalyst structure collapses and the catalyst becomes deactivated. Catalysts using molecular sieves as carriers also suffer from catalyst deactivation after the reaction. The aluminum in the molecular sieves falls off, causing the molecular sieve structure to collapse. Therefore, a catalyst with both selectivity and stability for pentamethylenediamine is prepared. For the preparation of lysine decarboxylation Pentylenediamine is extremely important.

In view of this, the present invention is proposed.

Contents of the invention

In view of the problems existing in the prior art, the present invention provides a double-layer wrapped metal particle catalyst and a preparation method thereof, and uses the catalyst for the chemical decarboxylation of lysine to prepare pentamethylene diamine. The catalyst is used in the decarboxylation reaction of lysine. Among them, it has high selectivity to pentanediamine, good catalyst stability, and good industrial application prospects.

In order to solve the above technical problems, the present invention adopts the following technical solutions:

Preparation of a double-layer wrapped metal particle catalyst and a method for catalytically synthesizing pentanediamine. The preparation method of the double-layer wrapped metal particle catalyst is to use the rich pore structure of molecular sieves (ZEO) to limit metal nanoparticles (M). Domain wrapping to form M@ZEO; then adding directing agent and silicon source for the second wrapping, crystallization at a certain temperature and time, washing and drying, and then calcination to form a double-layer wrapping structure catalyst with metal nanoparticles as the core. .

In a preferred embodiment, the M@ZEO includes any one of Ru@MFI, Ru@GIS, Ru@FAU, and Ru@LTA. The M@ZEO, that is, the metal particle-wrapped catalyst accounts for 50% of the catalyst. The mass fraction is 1~80%.

In a preferred embodiment, the structure directing agent is one or more of tetrapropylammonium hydroxide, sodium hydroxide, and BMP.

In a preferred embodiment, after adding the structure directing agent, water, silicon source and metal particle-wrapped catalyst, stir at room temperature for 1-20 h at a stirring rate of 50-1000 rpm. After stirring, put it into the reaction kettle and wait until the temperature After rising to 80-350°C, the crystallization reaction takes place for 5-72 hours and then taken out. Preferably, the stirring time is 2-10h, the crystallization temperature is 100-300°C, and the crystallization time is 12-48h.

In a preferred embodiment, the mass ratio of M@ZEO, directing agent and silicon source is 1:1:1~1:10:10.

In a preferred embodiment, the calcination temperature is 300-600°C and the calcination time is 2-8h.

The double-layer wrapped metal particle catalyst of the present invention is used to catalyze the synthesis of pentanediamine. The method is as follows: placing lysine or lysine salt, water and catalyst in a high-pressure reaction kettle, and reacting to obtain an aqueous solution containing pentanediamine.

In a preferred embodiment, the lysine is L-lysine, and the lysine salt is lysine hydrochloride, lysine sulfate, lysine acetate, or lysine phosphate. any kind.

In a preferred embodiment, the molar ratio of the catalyst to lysine or lysine salt is 1: (0.1~10).

In a preferred embodiment, the autoclave reaction conditions are reaction temperature 120~250°C, pressure 1~3Mpa, lysine or lysine salt concentration 0.01~3 M, lysine or lysine salt solution The pH value is between 1 and 5, the reaction time is between 0 and 600 min, and the reaction atmosphere is any one of nitrogen, hydrogen, argon, helium or carbon monoxide.

Compared with the existing technology, the beneficial effects of the present invention are: the present invention provides a double-layer wrapped metal particle catalyst. Transition metal nanoparticles are the active sites for the decarboxylation reaction. They are used as the core of the catalyst. First, molecular sieves are used to enrich the pore structure. The metal nanoparticles are confined to obtain highly dispersed metal nanoparticles with a size of ~1.5 nm to prevent the metal nanoparticles from agglomerating during the reaction; secondly, a hydrothermal synthesis crystallization method is used to grow an acid-resistant silicon shell in situ on the outer layer of the molecular sieve. Prevent corrosion by inorganic acids in the reaction solution. The present invention significantly improves the stability of the catalyst. The double-layer wrapped metal particle catalyst is used for the chemical decarboxylation of lysine to prepare pentanediamine. The catalyst has high selectivity for pentanediamine in the lysine decarboxylation reaction. At the same time, the catalyst has good stability and good industrial application prospects.

Description of the drawings

Figure 1 XRD patterns of the catalysts in Examples 1-3 and Comparative Example 1;

Figure 2 XRD patterns of the catalyst before and after the catalyst reaction in Example 1;

Figure 3 XRD patterns of the catalyst before and after the catalyst reaction in Example 2;

Figure 4 XRD patterns of the catalyst before and after the catalyst reaction in Example 3;

Figure 5 XRD patterns of the catalyst before and after the catalyst reaction in Comparative Example 1.

Detailed ways

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without exerting creative efforts shall fall within the scope of protection of the present invention.

Example 1

The synthesis method of the double-layer wrapped metal particle catalyst in this embodiment is as follows:

(1) Synthesis of Ru@FAU: Put 2.8 g of sodium hydroxide into 25 ml of deionized water and stir to dissolve, then add 0.3375 g of sodium metaaluminate and stir until clear; slowly add 12.68g of silica sol dropwise, after the dropwise addition is completed Add 0.34g ruthenium chloride and stir at room temperature 600rpm for 4h. The resulting solution was moved into a stainless steel hydrothermal synthesis kettle and crystallized at 100°C for 12 h. After the hydrothermal synthesis kettle is completely cooled, wash it with deionized water until the pH value of the filtrate becomes neutral. Dry at 100°C overnight to obtain the Ru@FAU catalyst;

(2) Mix 5.084g tetrapropylammonium hydroxide and 39.2g deionized water to stir the solution until uniform. Slowly add 1g Ru@FAU catalyst during the stirring process, and then add 5.208g ethyl orthosilicate to the above solution. Stir magnetically at room temperature for 6 hours. The solution obtained after stirring is put into a stainless steel high-pressure reaction kettle, heated and crystallized using a drying oven, and crystallized at 180°C for 12 hours; after the crystallization is completed, wait for the reaction kettle to cool to room temperature, take out the reaction solution, and analyze the reaction solution. Carry out centrifugation and washing operations until the pH value of the centrifuged solution reaches neutral; dry the solid after centrifugation and washing at 100°C and calcine at 550°C for 6 hours to obtain catalyst 1.

The XRD characterization results of the prepared catalyst are shown in Figure 1. In the figure, 6.09°, 15.4°, and 23.31° belong to the diffraction peaks of the core FAU, and 7.89°, 8.85°, and 23.21° belong to the diffraction peaks of the outer shell S-1. This indicates that S-1 was successfully wrapped on Ru@FAU.

The double-layer wrapped metal particle catalyst prepared in Example 1 is used to catalyze the synthesis of pentanediamine. The method is as follows:

Take 0.1826 g of lysine hydrochloride and put it into the lining of a 25 ml reaction kettle. Add 10 ml of water to dissolve it. Then add 0.101g of catalyst and stir until completely mixed. Use phosphoric acid to adjust the pH of the mixed solution to 2.0; install the reaction kettle. , replace the air in the kettle with nitrogen, and then replace the nitrogen with hydrogen. After the replacement is completed, the pressure is increased to 2 MPa; the reaction kettle is opened and the reaction is carried out at 200°C and a stirring speed of 800 r/min. Reactions were carried out at various times of 0-3 hours. After derivatization of the reaction solution, liquid chromatography was used to detect the concentrations of lysine and pentanediamine in the solution after the reaction. It was found that when the reaction was 2.5 h, the lysine conversion rate reached 71.1%. Pentylenediamine selectivity reaches 70.1%.

The XRD characterization results of the reacted catalyst 1 are shown in Figure 2. It can be seen that the diffraction peak of the shell S-1 in the catalyst has not been significantly weakened, and the catalyst structure is good.

Example 2

The synthesis method of the double-layer wrapped metal particle catalyst in this embodiment is as follows:

(1) The synthesis of Ru@FAU is the same as in Example 1;

(2) Mix 5.084g tetrapropylammonium hydroxide and 39.2g deionized water to stir the solution until uniform. Slowly add 1g Ru@FAU catalyst during the stirring process, and then add 5.208g ethyl orthosilicate to the above solution. Stir magnetically at room temperature for 6 hours. The solution obtained after stirring is put into a stainless steel high-pressure reaction kettle, heated and crystallized using a drying oven, and crystallized at 180°C for 36 hours; after the crystallization is completed, wait for the reaction kettle to cool to room temperature, take out the reaction solution, and analyze the reaction solution. Carry out centrifugation and washing operations until the pH value of the centrifuged solution reaches neutral; dry the solid after centrifugation and washing at 100°C and calcine at 550°C for 6 hours to obtain catalyst 2.

The XRD characterization results of the prepared catalyst are shown in Figure 1. In the figure, 6.09°, 15.4°, and 23.31° belong to the diffraction peaks of the core FAU, and 7.89°, 8.85°, and 23.21° belong to the diffraction peaks of the outer shell S-1. This indicates that S-1 was successfully wrapped on Ru@FAU.

The double-layer wrapped metal particle catalyst prepared in Example 2 is used to catalyze the synthesis of pentanediamine. The method is as follows:

Take 0.1826 g of lysine hydrochloride and put it into the lining of a 25 ml reaction kettle. Add 10 ml of water to dissolve it. Then add 0.101g of catalyst and stir until completely mixed. Use phosphoric acid to adjust the pH of the mixed solution to 2.0; install the reaction kettle. , replace the air in the kettle with nitrogen, and then replace the nitrogen with hydrogen. After the replacement is completed, the pressure is increased to 2 MPa; the reaction kettle is opened and the reaction is carried out at 200°C and a stirring speed of 800 r/min. Reactions were carried out at various times of 0-3 hours. After derivatization of the reaction solution, liquid chromatography was used to detect the concentrations of lysine and pentanediamine in the solution after the reaction. It was found that when the reaction was 2.5 h, the lysine conversion rate reached 71.9%. Pentylenediamine selectivity reaches 64.5%.

The XRD characterization results of the reacted catalyst 2 are shown in Figure 3. It can be seen that the diffraction peak of the shell S-1 in the catalyst has not been significantly weakened, and the catalyst structure is good.

Example 3

The synthesis method of the double-layer wrapped metal particle catalyst in this embodiment is as follows:

(1) The synthesis of Ru@FAU is the same as in Example 1;

(2) Mix 5.084g tetrapropylammonium hydroxide and 39.2g deionized water to stir the solution until uniform. Slowly add 1g Ru@FAU catalyst during the stirring process, and then add 5.208g ethyl orthosilicate to the above solution. Stir magnetically at room temperature for 6 hours. The solution obtained after stirring is put into a stainless steel high-pressure reaction kettle, heated and crystallized in a drying box, and crystallized at 180°C for 24 hours; after the crystallization is completed, wait for the reaction kettle to cool to room temperature, take out the reaction solution, and analyze the reaction solution. Carry out centrifugation and washing operations until the pH value of the centrifuged solution reaches neutral; dry the solid after centrifugation and washing at 100°C and calcine at 550°C for 6 hours to obtain catalyst 3.

The XRD characterization results of the prepared catalyst are shown in Figure 1. In the figure, 6.09°, 15.4°, and 23.31° belong to the diffraction peaks of the core FAU, and 7.89°, 8.85°, and 23.21° belong to the diffraction peaks of the outer shell S-1. This indicates that S-1 successfully produced packages on Ru@FAU.

The double-layer wrapped metal particle catalyst prepared in Example 2 is used to catalyze the synthesis of pentanediamine. The method is as follows:

Take 0.1826 g of lysine hydrochloride and put it into the lining of a 25 ml reaction kettle. Add 10 ml of water to dissolve it. Then add 0.101g of catalyst and stir until completely mixed. Use phosphoric acid to adjust the pH of the mixed solution to 2.0; install the reaction kettle. , replace the air in the kettle with nitrogen, and then replace the nitrogen with hydrogen. After the replacement is completed, the pressure is increased to 2 MPa; the reaction kettle is opened and the reaction is carried out at 200°C and a stirring speed of 800 r/min. Reactions were carried out at various times of 0-3 hours. After derivatization of the reaction solution, liquid chromatography was used to detect the concentrations of lysine and pentanediamine in the solution after the reaction. It was found that when the reaction lasted for 2.5 h, the lysine conversion rate reached 81.5%. Pentylenediamine selectivity reaches 65.8%.

The XRD characterization results of the reacted catalyst 3 are shown in Figure 4. It can be seen that the diffraction peak of the shell S-1 in the catalyst has not been significantly weakened, and the catalyst structure is good.

Repeated experiments were carried out on the double-layer wrapped metal particle catalyst 3. The method is as follows:

The catalyst after the lysine decarboxylation reaction was separated and centrifuged and washed three times with distilled water and added to the reactor. Then, 10 mL, 0.1 mol/L L-lysine solution was added, and the pH of the mixed solution was adjusted to 2 by adding phosphoric acid solution. The reactor was sealed at 200°C and 2MPa hydrogen for 1.5 hours. After this process was repeated five times, the catalyst activity could still reach 80% lysine conversion rate and 60% pentanediamine selectivity.

Comparative example 1

Mix 5.084g tetrapropylammonium hydroxide and 39.2g deionized water, stir the solution until uniform, slowly add 1g Ru@FAU catalyst during the stirring process, and stir magnetically at room temperature for 6 hours.

The solution obtained after stirring is put into a stainless steel high-pressure reaction kettle, heated and crystallized in a drying box, and crystallized at 180°C for 24 hours; after the crystallization is completed, wait for the reaction kettle to cool to room temperature, take out the reaction solution, and analyze the reaction solution. Carry out centrifugation and washing operations until the pH value of the centrifuged solution reaches neutral; dry the solid after centrifugation and washing at 100°C and calcine at 550°C for 6 hours to obtain catalyst 4.

The XRD characterization results of the prepared catalyst are shown in Figure 1. In the figure, only 6.09°, 15.4°, and 23.31° belong to the diffraction peaks of FAU, and there are no characteristic peaks of S-1, proving that no double-layer wrapped metal particle catalyst was synthesized.

The catalyst in this method is considered to be Ru@FAU. In order to compare the advantages and disadvantages of the core Ru@FAU and the synthesized silicon-wrapped core-shell catalyst in the synthesis of pentanediamine and catalyst stability, the catalyst prepared in this example was used to catalyze the synthesis of pentanediamine. Diamine, the method is as follows:

Take 0.1826 g of lysine hydrochloride and put it into the lining of a 25 ml reaction kettle. Add 10 ml of water to dissolve it. Then add 0.101g of catalyst and stir until completely mixed. Use phosphoric acid to adjust the pH of the mixed solution to 2.0; install the reaction kettle. , replace the air in the kettle with nitrogen, and then replace the nitrogen with hydrogen. After the replacement is completed, the pressure is increased to 2 MPa; the reaction kettle is opened and the reaction is carried out at 200°C and a stirring speed of 800 r/min. Reactions were carried out at various times of 0-3 hours. After derivatization of the reaction solution, liquid chromatography was used to detect the concentrations of lysine and pentanediamine in the solution after the reaction. It was found that the optimal reaction time was 1 h, with the lysine conversion rate reaching 46.9% and the pentanediamine selectivity reaching 80%.

The XRD characterization results of the catalyst after the reaction are shown in Figure 5. It can be seen that as the reaction time prolongs, the diffraction peaks in the XRD gradually weaken and new diffraction peaks appear, which indicates that the structure of the catalyst gradually collapses during the reaction. Change.

Comparative example 2

Comparative Example 2 is the synthesis of a single-layer package, Ru@FAU. The method is as follows:

Put 2.8 g of sodium hydroxide into 25 ml of deionized water and stir to dissolve, then add 0.3375 g of sodium metaaluminate and stir until clear; slowly add 12.68g of silica sol dropwise, after the dropwise addition is complete, add 0.34g of ruthenium chloride, room temperature 600rpm Stir for 4 hours. The resulting solution was moved into a stainless steel hydrothermal synthesis kettle and crystallized at 100°C for 12 h. After the hydrothermal synthesis kettle is completely cooled, it is washed with deionized water until the pH value of the filtrate is neutral, and dried at 100°C overnight to obtain Ru@FAU.

The Ru@FAU prepared in Example 1 was used to catalyze the synthesis of pentanediamine as follows:

Take 0.1826 g of lysine hydrochloride and put it into the lining of a 25 ml reaction kettle. Add 10 ml of water to dissolve it. Then add 0.101g of catalyst and stir until completely mixed. Use phosphoric acid to adjust the pH of the mixed solution to 2.0; install the reaction kettle. , replace the air in the kettle with nitrogen, and then replace the nitrogen with hydrogen. After the replacement is completed, the pressure is increased to 2 MPa; the reaction kettle is opened and the reaction is carried out at 200°C and a stirring speed of 800 r/min. Reactions were carried out at various times of 0-3 hours. After derivatization of the reaction solution, liquid chromatography was used to detect the concentrations of lysine and pentylenediamine in the reaction solution. It was found that the lysine conversion rate reached 100% when the reaction lasted for 1 hour. Pentylenediamine selectivity reaches 32%.

Conduct repeated experiments on a single-layer package, Ru@FAU, as follows:

The catalyst after the lysine decarboxylation reaction was separated and centrifuged and washed three times with distilled water and added to the reactor. Then, 10 mL, 0.1 mol/L L-lysine solution was added, and the pH of the mixed solution was adjusted to 2 by adding phosphoric acid solution. The reactor was sealed at 200°C and 2MPa hydrogen for 1 hour. After this process was repeated five times, the catalyst activity could still reach a lysine conversion rate of 20% and a pentanediamine selectivity of 2%, but the catalyst performance dropped significantly.

Comparative example 3

Comparative Example 3 is the synthesis of single-layer wrapped Ru@S-1. The method is as follows:

Mix 5.084 g tetrapropylammonium hydroxide and 39.2 g deionized water and stir evenly, then add 0.34g ruthenium chloride and 5.208 g ethyl orthosilicate in sequence, and stir magnetically at room temperature for 6 hours.

The solution obtained after stirring is put into a stainless steel high-pressure reaction kettle, heated and crystallized using a drying oven, and crystallized at 180°C for 12 hours; after the crystallization is completed, wait for the reaction kettle to cool to room temperature, take out the reaction solution, and analyze the reaction solution. Centrifuge and wash until the pH value of the centrifuged solution reaches neutral; dry the solid after centrifugation and washing at 100°C and calcine at 550°C for 6 hours to obtain Ru@S-1.

The Ru@S-1 catalyst prepared in Example 3 was used to catalyze the synthesis of pentanediamine as follows:

Take 0.1826 g of lysine hydrochloride and put it into the lining of a 25 ml reaction kettle. Add 10 ml of water to dissolve it. Then add 0.101g of catalyst and stir until completely mixed. Use phosphoric acid to adjust the pH of the mixed solution to 2.0; install the reaction kettle. , replace the air in the kettle with nitrogen, and then replace the nitrogen with hydrogen. After the replacement is completed, the pressure is increased to 2 MPa; the reaction kettle is opened and the reaction is carried out at 200°C and a stirring speed of 800 r/min. Reactions were carried out at various times of 0-3 hours. After derivatization of the reaction solution, liquid chromatography was used to detect the concentrations of lysine and pentanediamine in the solution after the reaction. It was found that no pentanediamine was produced within 3 h of reaction.

The invention provides the preparation of a double-layer wrapped metal particle catalyst and a method for catalytically synthesizing pentanediamine. This method effectively improves the selectivity of pentanediamine in the reaction of decarboxylation of lysine to produce pentanediamine, solves the problem of structural instability of the catalyst in the decarboxylation reaction of lysine, and provides a method for chemical decarboxylation of lysine to produce pentanediamine. New industrialization opportunities with good industrial application prospects.

The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. Those skilled in the art understand that other changes and modifications can be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A preparation method of a double-layer coated metal particle catalyst is characterized by comprising the following steps of: firstly, carrying out limited-domain wrapping on metal nano particles M by utilizing a pore channel structure rich in molecular sieve ZEO to form M@ZEO; then adding a guiding agent and a silicon source, carrying out secondary coating, crystallizing at a certain temperature and for a certain time, washing, drying and calcining to form the double-layer coated metal particle catalyst taking the metal nano particles as cores.

2. The method for preparing the double-layer coated metal particle catalyst according to claim 1, wherein: m in the M@ZEO comprises any one or more of Pd, ru, pt, au, cu, ni.

3. The method for preparing the double-layer coated metal particle catalyst according to claim 1, wherein: the ZEO in the M@ZEO is any one or more of FAU, LTA, GIS.

4. The method for preparing the double-layer coated metal particle catalyst according to claim 1, wherein: the structure directing agent is one or more of tetrapropylammonium hydroxide, sodium hydroxide and BMP.

5. The method for preparing the double-layer coated metal particle catalyst according to claim 1, wherein: the silicon source is one or more of silica sol, tetraethoxysilane and sodium silicate.

6. The method for preparing the double-layer coated metal particle catalyst according to claim 1, wherein: the mass ratio of the M@ZEO, the guiding agent and the silicon source is 1:1:1-1:10:10.

7. The method for preparing the double-layer coated metal particle catalyst according to claim 1, wherein: the crystallization temperature is 80-350 ℃, the crystallization time is 5-72h, the calcination temperature is 300-600 ℃, and the calcination time is 2-8h.

8. A double-layered coated metal particle catalyst produced by the production method of any one of claims 1 to 7.

9. The use of the double-layer coated metal particle catalyst according to claim 8 in synthesizing pentylene diamine by decarboxylation of lysine, characterized by: the preparation method comprises the steps of performing decarboxylation of lysine to synthesize the pentanediamine in a high-pressure reaction kettle, adding lysine or lysine salt, an acid solution with a certain pH value and a double-layer coated metal particle catalyst into the high-pressure reaction kettle, and reacting to obtain the pentanediamine aqueous solution.

10. The use according to claim 9, characterized in that: the reaction temperature is 120-250 ℃, the pressure is 0.5-6 MPa, the concentration of lysine or lysine salt is 0.01-3M, the pH value of an acid solution is 1-8, the molar ratio of a double-layer coated metal particle catalyst to lysine or lysine salt is 1 (0.1-10), the reaction time is 0-3 h, the reaction atmosphere is any one of nitrogen, hydrogen, argon, helium or carbon monoxide, the lysine is L-lysine, and the lysine salt is any one of lysine hydrochloride and lysine sulfate.