A graphitized activated carbon-supported ruthenium catalyst for ammonia synthesis

Abstract

The application discloses a graphitized activated carbon supported ruthenium catalyst for synthesizing ammonia, which is prepared by the following steps: high-temperature heat treatment of activated carbon in an inert atmosphere, then reaming treatment in a mixed gas containing water vapor, obtaining graphitized activated carbon, then impregnation of a ruthenium precursor solution to introduce a ruthenium component, reduction, then introduction of a cerium compound in a solution, then introduction of carbon-containing organic matter, then impregnation of a barium salt solution, and reduction to obtain an ammonia synthesis catalyst with the graphitized activated carbon as a carrier, the ruthenium as an active component, and barium and cerium as additives. Compared with the graphitized carbon supported ruthenium catalyst prepared by the prior art, the catalyst prepared by the application has higher ammonia synthesis activity and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ammonia synthesis catalysts, and particularly relates to a graphitized activated carbon supported ruthenium catalyst for synthesizing ammonia and a preparation method thereof. BACKGROUND

[0002] Ammonia is one of the largest chemical products, and the annual ammonia production in the world exceeds 170 million tons, of which about 80% of ammonia products are used for producing chemical fertilizers, and are also widely used in the fields of medicines, explosives, plastics and the like. Recently, it is found that ammonia is an ideal hydrogen storage material and a carbon-free energy source. Therefore, the demand for ammonia is increasing, and the importance of the catalytic synthesis process of ammonia is increasing.

[0003] The traditional industrial ammonia synthesis process uses nitrogen and hydrogen as raw materials, and uses an iron catalyst to complete under high temperature and high pressure conditions (15-30 MPa, 450-510 ℃), and the reaction energy consumption is high. Replacing the iron catalyst with a ruthenium catalyst can significantly reduce the operating conditions (380-440 ℃, 10-11.0 MPa) of the ammonia synthesis process, and achieve energy saving and emission reduction of the ammonia synthesis industry. At present, the graphitized carbon supported ruthenium catalyst is the only ruthenium-based ammonia synthesis catalyst that can be industrialized. However, the price of ruthenium metal is high, and the cost of the catalyst is high, and it is urgent to further improve the performance of the catalyst to increase its economy. In view of the problem, the application introduces a high-dispersed cerium element to optimize the performance of the catalyst and significantly improve the ammonia synthesis activity of the catalyst by taking graphitized activated carbon as the carrier. SUMMARY

[0004] The application provides a graphitized carbon supported catalyst for synthesizing ammonia and a preparation method thereof.

[0005] To achieve the above object, the application adopts the following technical scheme.

[0006] A graphitized activated carbon supported ruthenium catalyst for synthesizing ammonia is prepared by taking graphitized activated carbon as a carrier, ruthenium metal as an active component, and barium and cerium as additives; wherein the mass ratio of ruthenium to the graphitized activated carbon is 0.03:1-0.2:1, the mass ratio of barium to the graphitized activated carbon is 0.01:1-0.12:1, and the mass ratio of cerium to the graphitized activated carbon is 0.005:1-0.05:1.

[0007] The preparation method of the graphitized activated carbon supported iron-cobalt bimetallic catalyst comprises the following steps:

[0008] 1) After the activated carbon is heat treated in an inert atmosphere and cooled to room temperature, the activated carbon is subjected to a pore expansion treatment in a water vapor mixed gas to obtain graphitized activated carbon;

[0009] 2) The above graphitized active carbon is impregnated with a ruthenium precursor solution to introduce the ruthenium component, and then reduced to obtain a graphitized carbon supported ruthenium catalyst;

[0010] 3) The catalyst obtained in step 2) is put into deionized water, and a certain amount of cerium salt is added under stirring, and then ammonia water is added to obtain a sample containing cerium;

[0011] 4) The sample obtained in step 3) is impregnated with a carbon-containing organic solution;

[0012] 5) The sample obtained in step 4) is impregnated with a barium salt solution, dried, and then reduced to obtain a graphitized active carbon supported ruthenium catalyst.

[0013] Further, in step 1), the inert atmosphere is one or more of nitrogen, a group 0 gas; the temperature of the heat treatment is 1500-2000 DEG C, and the time is 2-10 hours; the temperature of the hole expansion treatment is 300-600 DEG C, and the time is 3-28 hours; the water vapor containing gas is a mixed gas composed of one or more of water vapor and nitrogen or a group 0 gas, wherein the volume content of water vapor is 10-80 vol%.

[0014] Further, in step 2), the ruthenium precursor solution is one of a ruthenium nitrosyl nitrate aqueous solution or a ruthenium chloride aqueous solution; the reduction is a treatment in a hydrogen-containing gas at 200-600 DEG C for 0.2-24 hours, and the hydrogen-containing gas is a mixed gas of hydrogen and nitrogen or a group 0 gas.

[0015] Further, in step 3), the cerium salt is cerium nitrate or cerium chloride, and the molar ratio of ammonium to cerium salt in the ammonia water is 2:1-15:1.

[0016] Further, in step 4), the carbon-containing organic matter is any one of melamine, glucose and sucrose, and the mass ratio of the amount to the graphitized active carbon is 0.01:1-0.05:1.

[0017] Further, in step 5), the barium salt solution is a barium nitrate or barium oxalate aqueous solution; the reduction is a treatment in a hydrogen-containing gas at 200-600 DEG C for 0.2-48 hours, and the hydrogen-containing gas is a mixed gas of hydrogen and nitrogen or a group 0 gas.

[0018] The application provides a graphitized active carbon supported ruthenium catalyst for synthesizing ammonia and a preparation method thereof, which uses graphitized active carbon as a carrier, introduces a ruthenium precursor, and then introduces cerium, carbon-containing organic matter and barium in sequence, and then performs reduction treatment, so that the obtained catalyst has a wide ruthenium particle distribution and a large average particle size, and the barium additive is uniformly distributed. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 Ru and Ba element distribution maps of the 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Example 1 and the 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Comparative Example 4. imp

[0020] Figure 2 Ru and Ba element distribution maps of the 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Example 1 and the 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Comparative Example 4. imp DETAILED DESCRIPTION

[0021] A graphitization activated carbon supported ruthenium catalyst for synthesizing ammonia, the preparation comprising the following steps:

[0022] 1) heat treating the activated carbon in an inert atmosphere at 1500-2000 ℃ for 2-10 hours, cooling to room temperature, and then treating the pores in a water vapor mixed gas at 300-600 ℃ for 3-28 hours to obtain graphitized activated carbon;

[0023] 2) impregnating a ruthenium precursor solution into the above graphitized activated carbon to introduce a ruthenium component, and reducing to obtain a graphitized carbon supported ruthenium catalyst;

[0024] 3) putting the catalyst obtained in step 2) into deionized water, stirring to add a certain amount of cerium salt, and then adding ammonia water to obtain a cerium-containing sample;

[0025] 4) impregnating the sample obtained in step 3) with a carbon-containing organic solution;

[0026] 5) impregnating the sample obtained in step 4) with a barium salt solution, drying, and then reducing to obtain a graphitized activated carbon supported ruthenium catalyst;

[0027] In step 1), the inert atmosphere is one or more of nitrogen, a group 0 gas, and the water vapor mixed gas is a mixed gas composed of water vapor and one or more of nitrogen or a group 0 gas, wherein the volume content of water vapor is 10-80 vol%, and the gas flow rate is 20-1000 mL / min.

[0028] In step 2), the ruthenium precursor solution is one of a ruthenium nitrosyl nitrate aqueous solution or a ruthenium chloride aqueous solution; the reduction is treating in a hydrogen-containing gas at 200-600 ℃ for 0.2-24 hours, and the hydrogen-containing gas is a mixed gas of hydrogen and nitrogen or a group 0 gas.

[0029] In step 3), the cerium salt is cerium nitrate or cerium chloride, and the molar ratio of ammonium to cerium salt in the added ammonia water is 2:1-15:1. ​​

[0030] Step 4) the carbon-containing organic matter is any one of melamine, glucose and sucrose, and the mass ratio of the carbon-containing organic matter to the graphitized activated carbon is 0.01:1-0.05:1;

[0031] In step 5), the barium salt solution is an aqueous solution of barium nitrate or barium oxalate; and the reduction is carried out in a hydrogen-containing gas at 200-600° C. for 0.2-48 hours, wherein the hydrogen-containing gas is a mixture of hydrogen and nitrogen or a Group 0 gas.

[0032] In the obtained catalyst, the mass ratio of ruthenium to graphitized activated carbon is 0.03:1-0.2:1, the mass ratio of barium to graphitized activated carbon is 0.01:1-0.12:1, and the mass ratio of cerium to graphitized activated carbon is 0.005:1-0.05:1.

[0033] In order to make the contents of the present invention easier to understand, the technical solutions of the present invention are further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0034] Example 1:

[0035] 1) The activated carbon was heat treated at 1900 °C for 2 h in nitrogen (1000 mL / min), cooled to room temperature, and then oxidized and expanded at 450 °C for 24 h in a mixture of 75% water vapor and nitrogen at 300 mL / min to obtain graphitized activated carbon.

[0036] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and then reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0037] 3) Place the sample obtained in step 2) in 200 mL of deionized water, add 0.03 g of cerium nitrate with stirring, then add 0.15 mL of 28 wt% concentrated ammonia water and continue stirring for 10 minutes;

[0038] 4) immersing the sample obtained in step 3) in a 3 wt % melamine aqueous solution, wherein the mass ratio of melamine to graphitized activated carbon is 0.04:1;

[0039] 5) The sample obtained in step 4) was impregnated with a 0.3 mol / L aqueous solution of barium nitrate, dried, and reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized activated carbon-supported ruthenium catalyst 9Ba-4Mel-2Ce-15Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon was 0.15:1, the mass ratio of barium to graphitized activated carbon was 0.09:1, and the mass ratio of cerium to graphitized activated carbon was 0.02:1.

[0040] Example 2:

[0041] 1) The activated carbon was heat treated at 1550 °C for 9 hours in helium (600 mL / min), cooled to room temperature, and then oxidized and expanded at 550 °C for 3 hours in a mixture of 25% water vapor and nitrogen at 300 mL / min to obtain graphitized activated carbon.

[0042] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and then reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0043] 3) Place the sample obtained in step 2) in 200 mL of deionized water, add 0.045 g of cerium nitrate with stirring, then add 0.25 mL of 28 wt% concentrated ammonia water and continue stirring for 10 minutes;

[0044] 4) immersing the sample obtained in step 3) in a 3 wt % glucose aqueous solution, wherein the mass ratio of glucose to graphitized activated carbon is 0.03:1;

[0045] 5) The sample obtained in step 4) was impregnated with a 0.3 mol / L aqueous solution of barium oxalate, dried, and reduced in pure hydrogen at 550°C for 10 hours to obtain a graphitized activated carbon-supported ruthenium catalyst 6Ba-3Glu-4Ce-20Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon was 0.2:1, the mass ratio of barium to graphitized activated carbon was 0.06:1, and the mass ratio of cerium to graphitized activated carbon was 0.04:1.

[0046] Example 3:

[0047] 1) The activated carbon was heat treated at 1600°C in a mixture of 20% He and 80% N2 (1000 mL / min) for 5 hours, then cooled to room temperature, and then oxidized and expanded in a mixture of 60% water vapor and nitrogen (100 mL / min) at 400°C for 20 hours to obtain graphitized activated carbon.

[0048] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and then reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0049] 3) Place the sample obtained in step 2) in 200 mL of deionized water, add 0.06 g of cerium nitrate with stirring, then add 0.08 mL of 28 wt% concentrated ammonia water and continue stirring for 10 minutes;

[0050] 4) immersing the sample obtained in step 3) in a 3 wt % melamine aqueous solution, wherein the mass ratio of melamine to graphitized activated carbon is 0.02:1;

[0051] 5) The sample obtained in step 4) was impregnated with a 0.3 mol / L aqueous solution of barium nitrate, dried, and reduced in pure hydrogen at 350°C for 12 hours to obtain a graphitized activated carbon-supported ruthenium catalyst 6Ba-2Mel-3Ce-10Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon was 0.10:1, the mass ratio of barium to graphitized activated carbon was 0.06:1, and the mass ratio of cerium to graphitized activated carbon was 0.03:1.

[0052] Comparative Example 1:

[0053] 1) The activated carbon was heat treated at 1900 °C for 2 h in nitrogen (1000 mL / min), cooled to room temperature, and then oxidized and expanded at 450 °C for 24 h in a mixture of 75% water vapor and nitrogen at 300 mL / min to obtain graphitized activated carbon.

[0054] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and then reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0055] 3) Place the sample obtained in step 2) in 200 mL of deionized water, add 0.013 g of cerium nitrate with stirring, then add 0.15 mL of 28 wt% concentrated ammonia water and continue stirring for 10 minutes;

[0056] 4) The sample obtained in step 3) was impregnated with a 0.3 mol / L aqueous solution of barium nitrate, dried, and reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized activated carbon-supported ruthenium catalyst 9Ba-2Ce-15Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon was 0.15:1, the mass ratio of barium to graphitized activated carbon was 0.09:1, and the mass ratio of cerium to graphitized activated carbon was 0.02:1.

[0057] Comparative Example 2:

[0058] 1) The activated carbon was heat treated at 1900 °C for 2 h in nitrogen (1000 mL / min), cooled to room temperature, and then oxidized and expanded at 450 °C for 24 h in a mixture of 75% water vapor and nitrogen at 300 mL / min to obtain graphitized activated carbon.

[0059] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and then reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0060] 3) immersing the sample obtained in step 2) in a 3 wt % melamine aqueous solution, wherein the mass ratio of melamine to graphitized activated carbon is 0.04:1;

[0061] 4) The sample obtained in step 3) was immersed in a 0.3 mol / L aqueous solution of barium nitrate, dried, and reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized activated carbon-supported ruthenium catalyst 9Ba-4Mel-15Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon was 0.15:1, and the mass ratio of barium to graphitized activated carbon was 0.09:1.

[0062] Comparative Example 3:

[0063] 1) The activated carbon was heat treated at 1900 °C for 2 h in nitrogen (1000 mL / min), cooled to room temperature, and then oxidized and expanded at 450 °C for 24 h in a mixture of 75% water vapor and nitrogen at 300 mL / min to obtain graphitized activated carbon.

[0064] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and reduced in pure hydrogen at 450 °C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0065] 3) The sample obtained in step 2) was impregnated with a 0.3 mol / L aqueous solution of barium nitrate, dried, and reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized activated carbon-supported ruthenium catalyst 9Ba-15Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon was 0.15:1, and the mass ratio of barium to graphitized activated carbon was 0.09:1.

[0066] Comparative Example 4:

[0067] 1) The activated carbon was heat treated at 1900 °C for 2 h in nitrogen (1000 mL / min), cooled to room temperature, and then oxidized and expanded at 450 °C for 24 h in a mixture of 75% water vapor and nitrogen at 300 mL / min to obtain graphitized activated carbon.

[0068] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and then reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0069] 3) Immersing the sample obtained in step 2) in a 0.2 mol / L cerium nitrate solution;

[0070] 4) immersing the sample obtained in step 3) in a 3 wt % melamine aqueous solution, wherein the mass ratio of melamine to graphitized activated carbon is 0.04:1;

[0071] 5) The sample obtained in step 4) was immersed in 0.3 mol / L barium nitrate aqueous solution, dried, and reduced in pure hydrogen at 450 °C for 6 hours to obtain graphitized activated carbon-supported ruthenium catalyst 9Ba-4Mel-2Ce imp -15Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon is 0.15:1, the mass ratio of barium to graphitized activated carbon is 0.09:1, and the mass ratio of cerium to graphitized activated carbon is 0.02:1.

[0072] Comparative Example 5:

[0073] 1) The activated carbon was heat treated at 1900 °C for 2 h in nitrogen (1000 mL / min), cooled to room temperature, and then oxidized and expanded at 450 °C for 24 h in a mixture of 75% water vapor and nitrogen at 300 mL / min to obtain graphitized activated carbon.

[0074] 2) The obtained graphitized activated carbon was impregnated with a 1.5 wt% aqueous solution of ruthenium nitrosyl nitrate, dried, and then reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized carbon-loaded ruthenium sample;

[0075] 3) immersing the sample obtained in step 2) in a 3 wt % melamine aqueous solution, wherein the mass ratio of melamine to graphitized activated carbon is 0.04:1;

[0076] 4) Immersing the sample obtained in step 3) in a 0.3 mol / L barium nitrate aqueous solution;

[0077] 5) The sample obtained in step 4) was placed in 200 mL of deionized water, stirred and added with cerium nitrate, and then 0.15 mL of 28 wt% of cerium was added and stirred for 10 minutes; after drying, the mixture was reduced in pure hydrogen at 450°C for 6 hours to obtain a graphitized activated carbon-supported ruthenium catalyst 2Ce-9Ba-4Mel-15Ru / C; wherein the mass ratio of ruthenium metal to graphitized activated carbon was 0.15:1, the mass ratio of barium to graphitized activated carbon was 0.09:1, and the mass ratio of cerium to graphitized activated carbon was 0.02:1.

[0078] Figure 1 The 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Example 1 and the 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Comparative Example 4 are shown in FIG. impDistribution diagram of Ru and Ba elements in the -15Ru / C catalyst. As can be seen from the figure, compared with Comparative Example 4, the Ba element in the catalyst prepared using the technology reported in Example 1 is more evenly distributed around the Ru element, which helps modify the Ru active component. However, the Ce element introduced by the traditional impregnation method is difficult to improve the distribution of the Ba element. The Ba element exists in the form of numerous clusters on the catalyst surface, resulting in insufficient Ba element around some Ru active components, which hinders their full performance. Therefore, the catalyst obtained in Comparative Example 4 has low ammonia synthesis activity.

[0079] Figure 2 The 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Example 1 and the 9Ba-4Mel-2Ce-15Ru / C catalyst obtained in Comparative Example 4 are shown in FIG. imp TEM image of the 9Ba-4Mel-2Ce-15Ru / C catalyst. As can be seen from the figure, the ruthenium particles in the 9Ba-4Mel-2Ce-15Ru / C catalyst are more widely distributed (2-6 nm) and have a larger average particle size (4.3 nm); imp -15Ru / C particles are primarily distributed between 1 and 3 nm, with a relatively low average particle size of 2.3 nm. Ruthenium particles of varying sizes can play a role in the activation and reaction of nitrogen and hydrogen, as well as in the desorption of ammonia, thereby enhancing the catalyst's ammonia synthesis activity.

[0080] The catalytic activity of the ammonia synthesis catalysts obtained in the examples and comparative examples was evaluated in a high-pressure activity test apparatus. During the test, 0.3 g of the catalyst was mixed with quartz sand and loaded into the isothermal zone of the reactor. The reaction gas was a nitrogen-hydrogen mixture obtained by high-temperature catalytic cracking of ammonia, with a hydrogen-nitrogen ratio of 3:1. The reaction conditions were: pressure of 1 MPa, reaction temperature of 400°C, and reaction space velocity of 3.6 × 10 4 cm 3 g -1 h -1 The results of catalytic activity determination are shown in Table 1.

[0081] Table 1

[0082]

[0083] As can be seen from Table 1, the ammonia synthesis rate of the catalysts prepared without introducing carbon-containing organic matter or adding cerium, introducing cerium by impregnation, or introducing cerium at the end is low. Under the same conditions, the ammonia synthesis rate of the graphitized activated carbon-supported ruthenium catalyst obtained in the example is significantly higher than that of the catalyst obtained in the comparative example, demonstrating that it has good catalytic activity for ammonia synthesis and has good application prospects.

[0084] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A graphitized activated carbon-supported ruthenium catalyst for synthesizing ammonia, characterized in that: The catalyst is composed of graphitized activated carbon as a carrier, ruthenium metal as an active component, and barium and cerium as additives; wherein the mass ratio of ruthenium to graphitized activated carbon is 0.03:1-0.2:1, the mass ratio of barium to graphitized activated carbon is 0.01:1-0.12:1, and the mass ratio of cerium to graphitized activated carbon is 0.005:1-0.05:1; The method for preparing a graphitized activated carbon-supported ruthenium catalyst for synthesizing ammonia comprises the following steps: 1) The activated carbon is heat-treated in an inert atmosphere and then cooled to room temperature, and then pore-expanded in a mixed gas containing water vapor to obtain graphitized activated carbon; 2) impregnating the graphitized activated carbon with a ruthenium precursor solution and reducing the resulting graphitized carbon-supported ruthenium catalyst; 3) placing the catalyst obtained in step 2) into deionized water, stirring, adding a certain amount of cerium salt, and then adding ammonia water to obtain a cerium-containing sample; 4) impregnating the sample obtained in step 3) with a carbon-containing organic solution, then with a barium salt solution, drying, and then reducing the sample to obtain a graphitized activated carbon-supported ruthenium catalyst; Step 3) The cerium salt is cerium nitrate or cerium chloride, and the molar ratio of ammonium ion to cerium salt in ammonia water is 2:1-15:

1.

2. The graphitized activated carbon-supported ruthenium catalyst for ammonia synthesis according to claim 1, characterized in that: In step 1), the inert atmosphere is one or more of nitrogen and group 0 gases; the heat treatment temperature is 1500-2000°C and the time is 2-10 hours; the pore expansion treatment temperature is 300-600°C and the time is 3-28 hours; the water vapor-containing mixed gas is a mixture of water vapor and one or more of nitrogen and group 0 gases, wherein the volume content of water vapor is 10-80 vol%.

3. The graphitized activated carbon-supported ruthenium catalyst for ammonia synthesis according to claim 1, wherein: The ruthenium precursor solution in step 2) is one of an aqueous solution of ruthenium nitrosyl nitrate or an aqueous solution of ruthenium chloride; the reduction is carried out in a hydrogen-containing gas at 200-600°C for 0.2-24 hours, wherein the hydrogen-containing gas is a mixture of hydrogen and nitrogen or a Group 0 gas.

4. The graphitized activated carbon-supported ruthenium catalyst for ammonia synthesis according to claim 1, wherein: In step 4), the carbon-containing organic matter is any one of melamine, glucose, and sucrose, and the mass ratio of the carbon-containing organic matter to the graphitized activated carbon is 0.01:1-0.05:1; the barium salt solution is an aqueous solution of barium nitrate or barium oxalate; and the reduction is carried out in a hydrogen-containing gas at 200-600°C for 0.2-48 hours, where the hydrogen-containing gas is a mixture of hydrogen and nitrogen or a Group 0 gas.

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