CN118079905A - Preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine - Google Patents

Abstract

The present invention discloses the preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine. Heterogeneous chemical catalysis of lysine decarboxylation to produce pentamethylenediamine has attracted much attention. The reported molecular sieve confined catalyst has a high selectivity for pentamethylenediamine, but the catalyst activity is poor and cannot be used industrially; the carbon-based ruthenium catalyst has a relatively stable structure, but its activity is still low. The present invention modifies the carbon-based ruthenium catalyst by rare earth metals and high-temperature calcination to prepare a carbon-based ruthenium catalyst with excellent performance. In the reaction of lysine decarboxylation to produce pentamethylenediamine, compared with the unmodified carbon-based ruthenium catalyst, the selectivity of the modified carbon-based ruthenium catalyst for pentamethylenediamine is significantly improved. This provides a new industrialization opportunity for the chemical decarboxylation of lysine to produce pentamethylenediamine, and has good industrial application prospects.

Description

Preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine

Technical Field

The invention relates to the field of chemical synthesis, and in particular to the preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine.

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 absorption and perspiration rate, good air permeability, softness and good dyeing performance, etc. It is also wear-resistant, chemical-resistant, flame-retardant and easy to process, and has a strong competitive advantage in the nylon material series. The most reported production method of 1,5-pentanediamine is biological fermentation. Nanjing University of Technology uses soybean dregs hydrolyzate to ferment and produce pentamethylenediamine (CN201810954086.X), but pentamethylenediamine is toxic to microorganisms and affects production efficiency. Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. has applied for multiple patents for pentamethylenediamine biofermentation methods (CN201811506539.9, CN201710453415.8, CN201710011198.7, etc.). The patent content points out that the seed liquid of lysine decarboxylase strains is introduced into the lysine fermentation process, which effectively improves the toxicity of pentamethylenediamine to the strain. However, the biofermentation method still has great difficulties, such as low lysine decarboxylase activity, poor toxicity resistance, low product concentration, and high separation cost.

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, the currently reported chemical method for preparing pentamethylenediamine has the problem of low and unstable catalyst activity. Chinese patent application No. 202110938327.3 discloses a molecular sieve confined metal oxide catalyst, preparation method and application. The invention adopts an in-situ synthesis method to prepare a molecular sieve confined metal catalyst, the metal active components of the catalyst are effectively immobilized, the active components are avoided from agglomerating, and the catalyst structure is well maintained; the use of the catalyst for the decarboxylation reaction of lysine effectively increases the production rate of pentamethylenediamine and shortens the reaction process time, but the selectivity needs to be improved.

The Chinese patent application No. 202211265811.5 discloses a metal ion modified molecular sieve confined transition metal nanoparticle and a method for catalytically synthesizing pentamethylenediamine. A series of molecular sieve-loaded or confined ruthenium catalysts are prepared for the decarboxylation of L-lysine to prepare pentamethylenediamine. By changing the alkalinity of the catalyst surface, the directional adsorption of carboxyl groups is promoted, thereby inhibiting the production of by-products, improving selectivity, and efficiently synthesizing pentamethylenediamine. By changing the alkalinity of the catalyst surface, the directional adsorption of lysine carboxyl groups is effectively improved, and the occurrence of side reactions is inhibited from the source, thereby strengthening the direct decarboxylation of lysine to produce pentamethylenediamine. The selectivity of pentamethylenediamine is greatly improved. The selectivity of pentamethylenediamine is as high as 77.4% using metal ion modified molecular sieve confined transition metal nanoparticles as catalysts, which is currently at the international leading level. However, the lysine decarboxylation reaction is carried out under high temperature, high pressure, and acidic conditions, and the poor stability of the catalyst is still the biggest problem restricting industrial production. For example, the carbon in the traditional Ru/C catalyst undergoes methanation reaction, the catalyst structure collapses, and the catalyst is deactivated. Catalysts based on molecular sieves also suffer from the phenomenon of catalyst deactivation after the reaction. The aluminum in the molecular sieve falls off, causing the molecular sieve structure to collapse. Therefore, it is extremely important to prepare a catalyst that has both pentamethylenediamine selectivity and stability for the decarboxylation of lysine to prepare pentamethylenediamine.

Carbon-based materials are used as carriers for catalysts for the decarboxylation of lysine to produce pentamethylenediamine due to their good high temperature resistance, acid resistance and large specific surface area. In 2017, Ru/C was reported as a catalyst for the decarboxylation of L-lysine, with a pentamethylenediamine selectivity of 32%. The selectivity of pentamethylenediamine is still relatively low. Therefore, the preparation of carbon-based ruthenium catalysts with excellent activity is extremely important for the decarboxylation of lysine to produce pentamethylenediamine.

In view of this, the present invention is proposed.

Summary of the invention

In view of the problems existing in the prior art, the present invention provides a preparation method of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine. The catalyst has high selectivity for pentamethylenediamine in the decarboxylation reaction of lysine, and the catalyst has good stability and good industrial application prospects.

A method for preparing a modified carbon-supported ruthenium-based catalyst comprises the following steps: adding a ruthenium precursor and a rare earth metal precursor to an aqueous dispersion of a carbon material in sequence, stirring the mixture at a certain temperature, and then drying the mixture. After drying, the mixture is calcined at a certain atmosphere and temperature to obtain a modified carbon-supported ruthenium-based catalyst.

In a preferred embodiment, the ruthenium precursor is any one of ruthenium chloride, ruthenium dodecacarbonyl, and ruthenium hexaamine, and the mass fraction of ruthenium in the modified carbon-supported ruthenium-based catalyst is 0.01 to 50%, preferably 0.1 to 10%.

In a preferred embodiment, the rare earth metal is one or more of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), and samarium (Sm), and the mass fraction of the rare earth metal in the modified carbon-supported ruthenium-based catalyst is 0.01 to 50%, preferably 0.1 to 5%.

In a preferred embodiment, the carbon material is one of activated carbon, graphene and carbon nanotubes.

In a preferred embodiment, the stirring temperature is 30-80°C, the calcination atmosphere is one of nitrogen, hydrogen, argon and helium, and the calcination temperature is 30-1000°C.

The present invention also provides a modified carbon-supported ruthenium-based catalyst prepared by the preparation method of the modified carbon-supported ruthenium-based catalyst.

The present invention also provides the use of the modified carbon-supported ruthenium-based catalyst in the decarboxylation of lysine to prepare pentamethylenediamine: the decarboxylation of lysine to synthesize pentamethylenediamine is carried out in a high-pressure reactor, lysine or lysine salt, deionized water, phosphoric acid and the modified carbon-supported ruthenium-based catalyst are added into the high-pressure reactor, and the pentamethylenediamine aqueous solution is obtained by reaction.

In a preferred embodiment, the autoclave reaction conditions are as follows: reaction temperature is 120-250° C., pressure is 0.5-6 MPa, concentration of lysine or lysine salt in the reaction solution is 0.01-3 M, molar ratio of catalyst to lysine or lysine salt is 1:(0.1-10), phosphoric acid is used to adjust pH value of the reaction solution to 1-8, preferably 1-5, reaction time is 0-3 h, reaction atmosphere is any one of nitrogen, hydrogen, argon, helium or carbon monoxide, lysine is L-lysine, lysine salt is any one of lysine hydrochloride and lysine sulfate.

Compared with the prior art, the present invention has the following beneficial effects: the present invention uses rare earth metals as electronic additives and structural additives, and dopes with a variety of rare earth additives to improve the activity and structural stability of the catalyst. The rare earth-modified catalyst is used in the decarboxylation reaction of lysine, has a high selectivity for pentamethylenediamine, good catalyst stability, and good industrial application prospects.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows XRD patterns of the catalysts of Comparative Example 1-2 and Example 1-2.

FIG2 is an XRD diagram of the catalyst of Example 2 before and after reaction.

FIG3 is an XRD diagram of the catalyst of Example 4 before and after reaction.

FIG4 is an XRD diagram of the catalyst of Example 5 before and after reaction.

Detailed ways

The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Comparative Example 1 (Unmodified Ru/C Catalyst)

Comparative Example 1 is a method for preparing a 5% Ru/C catalyst, and the steps are as follows:

0.02 g of ruthenium trichloride was added to 20 g of deionized water and mixed evenly, and 1 g of activated carbon was added, and magnetic stirring was performed at room temperature for 12 h. Then, the water was evaporated at 105° C., and further dehydrated by drying at 100° C. for 4 h to obtain comparative catalyst 1.

The 5% Ru/C catalyst (Comparative Catalyst 1) prepared in Comparative Example 1 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It was found that the lysine conversion rate reached 70% when the reaction was 2.5h. The selectivity of pentamethylenediamine was 30%.

Comparative Example 2 (without calcination)

A method for preparing a modified carbon-supported ruthenium-based catalyst, the method is as follows:

0.02g of ruthenium trichloride and 0.023g of cerium nitrate were added to 20g of deionized water and mixed evenly, and 1g of activated carbon was added, and magnetic stirring was performed at room temperature for 12h. Then, the water was evaporated at 105°C, and further dehydrated at 100°C for 4h to obtain a modified carbon-supported ruthenium-based catalyst 1% Ce-5% Ru/C, which was recorded as comparative catalyst 2.

The modified carbon-supported ruthenium-based catalyst 1% Ce-5% Ru/C (Comparative Catalyst 2) prepared in Comparative Example 2 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of comparative catalyst 2, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It was found that the lysine conversion rate reached 85% when the reaction was 1.5h. The selectivity of pentamethylenediamine reached 34.2%.

Comparative Example 3 (Increasing rare earth metal content)

A method for preparing a modified carbon-supported ruthenium-based catalyst 15% Ce-5% Ru/C, comprising the following steps:

0.02g of ruthenium trichloride and 0.345g of cerium nitrate were added to 20g of deionized water and mixed evenly, and 1g of activated carbon was added. The mixture was stirred magnetically for 12h at room temperature. The water was then evaporated at 105°C and further dehydrated at 100°C for 4h. The dried solid was then used to obtain comparative catalyst 3.

The modified carbon-supported ruthenium-based catalyst 15% Ce-5% Ru/C (comparative catalyst 3) prepared in Comparative Example 3 was used for decarboxylation of lysine to prepare pentamethylenediamine, and the method was as follows:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of comparative catalyst 3, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction was carried out within different 0-3 hours. After the reaction solution was derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction were detected by liquid chromatography. It was found that the lysine conversion rate reached 90% when the reaction was 1h. The selectivity of pentamethylenediamine was 25%.

Example 1

This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-5% Ru/C, the method is as follows:

0.02 g of ruthenium trichloride and 0.023 g of cerium nitrate were added to 20 g of deionized water and mixed evenly, and 1 g of activated carbon was added. The mixture was magnetically stirred at room temperature for 12 h, and then the water was evaporated at 105 ° C. and further dehydrated at 100 ° C. for 4 h. The dried solid was then calcined at 400 ° C. for 3 h in a nitrogen atmosphere to obtain catalyst 1.

The 1% Ce-5% Ru/C catalyst (catalyst 1) prepared in Example 1 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 1, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that the lysine conversion rate reaches 87% when the reaction is 1.5h. The selectivity of pentamethylenediamine reaches 40%.

Example 2

This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-5% Ru/C, the method is as follows:

0.02 g of ruthenium trichloride and 0.023 g of cerium nitrate were added to 20 g of deionized water and mixed evenly. 1 g of activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 ° C and further dehydrated at 100 ° C for 4 h. The dried solid was then calcined at 800 ° C for 3 h in a nitrogen atmosphere to obtain catalyst 2.

The 1% Ce-5% Ru/C catalyst (catalyst 2) prepared in Example 2 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 2, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 90%. The selectivity of pentamethylenediamine reaches 41.2%.

Example 3

This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% La-5% Ru/C, the method is as follows:

0.02 g of ruthenium trichloride and 0.017 g of lanthanum chloride were added to 20 g of deionized water and mixed evenly. 1 g of activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 ° C and further dehydrated at 100 ° C for 4 h. The dried solid was then calcined at 800 ° C for 3 h in a nitrogen atmosphere to obtain catalyst 3.

The 1% La-5% Ru/C catalyst (catalyst 3) prepared in Example 3 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 3, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 82%. The selectivity of pentamethylenediamine reaches 36.4%.

Example 4

This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Sm-5% Ru/C, the method is as follows:

0.02 g of ruthenium trichloride and 0.016 g of samarium chloride were added to 20 g of deionized water and mixed evenly. Activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 °C and further dehydrated at 100 °C for 4 h. The dried solid was then calcined at 800 °C for 3 h under a nitrogen atmosphere to obtain catalyst 4.

The 1% Sm-5% Ru/C catalyst (catalyst 4) prepared in Example 4 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 4, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 92.4%. The selectivity of pentamethylenediamine reaches 42.3%.

Example 5

This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-0.5% Sm-5% Ru/C, the method is as follows:

0.02 g of ruthenium trichloride, 0.008 g of samarium chloride and 0.023 g of cerium nitrate were added to 20 g of deionized water and mixed evenly. 1 g of activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 ° C and further dehydrated at 100 ° C for 4 h. The dried solid was then calcined at 800 ° C for 3 h in a nitrogen atmosphere to obtain catalyst 5.

The 1% Ce-0.5% Sm-5% Ru/C catalyst (catalyst 5) prepared in Example 5 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 5, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 91.24%. The selectivity of pentamethylenediamine reaches 61.3%.

Example 6

This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-0.5% La-5% Ru/C, the method is as follows:

0.02g of ruthenium trichloride, 0.023g of cerium nitrate and 0.017g of lanthanum chloride were added to 20g of deionized water and mixed evenly. Activated carbon was added with a solid-liquid ratio of 1:5, and magnetic stirring was performed at room temperature for 12h. After that, the water was evaporated at 105°C and further dehydrated at 100°C for 4h. The dried solid was then calcined at 800°C for 3h under a nitrogen atmosphere to obtain catalyst 6.

The 1% Ce-0.5% La-5% Ru/C catalyst (catalyst 6) prepared in Example 7 was used to catalyze the synthesis of pentamethylenediamine in the following manner:

Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 6, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 90%. The selectivity of pentamethylenediamine reaches 56.5%.

Example 7

XRD analysis was performed on the catalysts prepared in Comparative Example 1, Examples 1 and 2, and it was found that high temperature calcination had a significant effect on the catalyst structure. Ruthenium and cerium oxide were found to exist at 800°C (as shown in Figure 1). XRD analysis was performed on the catalysts of Examples 2, 4 and 5 before and after the reaction, and it was found that the catalyst structure remained stable before and after the reaction (as shown in Figures 2, 3 and 4).

Example 8

This example is a repeatability experiment of catalyst 5, and the method is as follows:

The catalyst after the lysine decarboxylation reaction was separated and washed three times by centrifugation with distilled water before being added to the reactor. Then, 10 mL of 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 and reacted at 200°C and 2 MPa of hydrogen for 2 hours. After the process was repeated for 5 times, the catalyst activity could still reach a lysine conversion rate of 90% and a pentamethylenediamine selectivity of 60%.

The present invention provides a method for preparing a rare earth metal modified ruthenium carbon catalyst and catalytically synthesizing pentamethylenediamine. The rare earth metal modified ruthenium carbon catalyst effectively improves the selectivity of pentamethylenediamine in the reaction of preparing pentamethylenediamine by decarboxylation of lysine, provides a new industrialization opportunity for the chemical decarboxylation of lysine to produce pentamethylenediamine, and has 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. It is understood by those skilled in the art that other changes and modifications may be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.

Claims (10)

1. A method for preparing a modified carbon-supported ruthenium-based catalyst, characterized in that: a ruthenium precursor and a rare earth metal precursor are sequentially added to an aqueous dispersion of a carbon material, stirred at a certain temperature, and then the mixture is dried, and after drying, calcined under a certain atmosphere and temperature to obtain a modified carbon-supported ruthenium-based catalyst. 2. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1 is characterized in that the ruthenium precursor is any one or more of ruthenium chloride, carbonyl ruthenium, and hexaamine ruthenium. 3. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, wherein the rare earth metal is one or more of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), and samarium (Sm). 4. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, wherein the carbon material is one of activated carbon, graphene, and carbon nanotubes. 5. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, characterized in that the mass fraction of ruthenium in the modified carbon-supported ruthenium-based catalyst is 0.01~50%, and the mass fraction of rare earth metal in the modified carbon-supported ruthenium-based catalyst is 0.01~50%. 6. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1 is characterized in that: the stirring temperature is 30-80°C, the calcination atmosphere is one of nitrogen, hydrogen, argon, and helium, and the calcination temperature is 30-1000°C. 7. A modified carbon-supported ruthenium-based catalyst prepared according to the method for preparing a modified carbon-supported ruthenium-based catalyst according to any one of claims 1 to 6. 8. Use of the modified carbon-supported ruthenium-based catalyst according to claim 7 in the decarboxylation of lysine to produce pentamethylenediamine. 9. The use according to claim 8, characterized in that: the synthesis of pentamethylenediamine by decarboxylation of lysine is carried out in a high-pressure reactor, lysine or lysine salt, deionized water, phosphoric acid and a modified carbon-supported ruthenium-based catalyst are added to the high-pressure reactor, and the pentamethylenediamine aqueous solution is obtained by reaction. 10. The method for catalytic synthesis of pentamethylenediamine according to claim 9, characterized in that: the reaction temperature is 120-250° C., the pressure is 0.5-6 MPa, the concentration of lysine or lysine salt in the reaction solution is 0.01-3 M, the molar ratio of the catalyst to lysine or lysine salt is 1:(0.1-10), phosphoric acid is used to adjust the pH value of the reaction solution to 1-8, 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.