Hydrogen extraction catalyst and hydrogen extraction method based on partial oxidation of ammonia

Abstract

A hydrogen extraction catalyst based on the partial oxidation of ammonia, a method for producing the same, and a hydrogen extraction method using the above catalyst are disclosed. The hydrogen extraction catalyst based on the partial oxidation of ammonia comprises a support and ruthenium (Ru) supported on the support, and the hydrogen extraction method using the above catalyst maintains a high internal temperature of the reactor without an external heat source, solves the problem of reduced thermal efficiency due to long reaction times, and yields a high ammonia conversion rate.

Description

[Technical Field]

[0001] The present invention relates to a hydrogen extraction catalyst based on the partial oxidation of ammonia, a method for producing the same, and a hydrogen extraction method using the above catalyst. [Background technology]

[0002] Due to the depletion and environmental pollution caused by the indiscriminate use of fossil fuels, various studies are being conducted on new renewable alternative energy sources that can replace fossil fuels, particularly hydrogen production and utilization. Among the various hydrogen production methods, the method of extracting hydrogen by decomposing ammonia has a high hydrogen storage capacity (approximately 17.6 wt% H2) relative to the weight of ammonia, and an energy density (approximately 12.8 GJ / m³) relative to the volume. 3 , 120 kg-H2 / m 3 It has advantages such as ease of liquefaction (0.8 MPa, 20°C or 0.1 MPa, -33°C) and the fact that CO2 is not released after decomposition as a hydrogen carrier. For reference, the ammonia decomposition reaction is as follows: [Reaction Equation 1] NH3(g)→0.5N2(g)+1.5H2(g)(H=+46KJ / mol)

[0003] However, the above reaction is an endothermic reaction, and its activation energy is approximately ΔH = +117 kJ / mol, making external heat supply essential. Therefore, the combustion heat of carbon-based fuels such as natural gas is used to raise the internal temperature of the reactor to above 500°C, but this process of using carbon-based fuels to maintain a temperature above 500°C reduces the overall thermal efficiency of the system.

[0004] Therefore, it is considered important to develop a new ammonia decomposition hydrogen extraction system that does not require an external heat source, has a long reaction time, and can maintain a high internal temperature in the reactor, as well as catalysts that make this possible. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] An object of the present invention is to provide a hydrogen extraction catalyst and a system based on the partial oxidation of ammonia that do not require an external heat source.

[0006] Another object of the present invention is to provide a hydrogen extraction catalyst and a system based on the partial oxidation of ammonia that have a long reaction time, maintain a high internal temperature of the reactor, and solve the problem of reduced thermal efficiency.

[0007] Yet another object of the present invention is to provide a method for producing the above hydrogen extraction catalyst based on the partial oxidation of ammonia.

Means for Solving the Problems

[0008] According to one aspect of the present invention, there is provided a catalyst comprising a carrier containing a compound represented by the following Chemical Formula 1; and ruthenium (Ru) supported on the carrier. [Chemical Formula 1] Ce 1-x M x O 2-δ

[0009] In the above Chemical Formula 1, x is 0 < x < 1, M is a lanthanide metal or a transition metal, and δ can be 0 < δ ≦ 0.5.

[0010] Also, the lanthanide metal can include one or more selected from the group consisting of lanthanum (La), samarium (Sm), ytterbium (Yb), gadolinium (Gd), and lutetium (Lu).

[0011] Also, the lanthanide metal can include lanthanum (La).

[0012] Also, the lanthanide metal includes lanthanum (La), and x can be 0.05 ≦ x ≦ 0.8, preferably 0.1 ≦ x ≦ 0.7, more preferably 0.3 ≦ x ≦ 0.6.

[0013] Furthermore, the transition metal may include one or more selected from the group consisting of zirconium (Zr), yttrium (Y), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), and osmium (Os).

[0014] Furthermore, the above transition metal may include zirconium (Zr).

[0015] Furthermore, the transition metal may include zirconium (Zr), and x may be 0.05 ≤ x ≤ 0.5, preferably 0.1 ≤ x ≤ 0.4.

[0016] Furthermore, the catalyst may contain 1 to 3% by weight, preferably 1.3 to 2.0% by weight, of the ruthenium. Here, if the amount of ruthenium is less than 1% by weight, hydrogen extraction based on partial oxidation of ammonia may not occur, which is undesirable, and if it exceeds 3% by weight, the ammonia decomposition efficiency decreases, which is also undesirable.

[0017] Furthermore, the catalyst may be one that decomposes ammonia to extract hydrogen.

[0018] Another aspect of the present invention provides a method for producing a catalyst, comprising: (a) the step of producing a precursor solution containing one or more metals selected from the group consisting of lanthanide metal precursors and transition metal precursors, a cerium precursor, and water; (b) the step of coprecipitation of the precursors in the precursor solution to synthesize a coprecipitate containing one or more metals selected from the group consisting of lanthanide metals and transition metals, and cerium; (c) the step of heat-treating the coprecipitate to produce a carrier; and (d) the step of stirring the carrier solution containing the carrier, a ruthenium precursor, and water to produce a catalyst containing a carrier on which ruthenium is supported.

[0019] Furthermore, the catalyst may include a support containing a compound represented by the following chemical formula 1, and ruthenium (Ru) supported on the support. [Chemical formula 1] Ce 1-x M x O 2-δ

[0020] In the above Chemical Formula 1, x satisfies 0 < x < 1, M is a lanthanide metal or a transition metal, and δ can satisfy 0 < δ ≤ 0.5.

[0021] Furthermore, the pH of the precursor solution in step (a) can be 8 - 11, preferably 9 - 10.

[0022] Also, the lanthanide metal precursor can contain lanthanum nitrate hexahydrate, the transition metal precursor can contain Zirconium nitrate hexahydrate, and the cerium precursor can contain Cerium nitrate hexahydrate.

[0023] Also, the heat treatment in step (c) can be carried out in air.

[0024] Also, the heat treatment in step (c) can be carried out at 400 - 600 °C, preferably 450 - 550 °C.

[0025] According to still another aspect of the present invention, there is provided a hydrogen extraction method including step (1) of subjecting ammonia to a partial oxidation reaction in the presence of the above catalyst and oxygen to extract hydrogen.

[0026] Also, the partial oxidation reaction can include an ammonia decomposition reaction and an ammonia oxidation reaction.

[0027] Also, the partial oxidation reaction can be carried out by the reaction of the following Reaction Formula 1. [Reaction Formula 1: Partial oxidation reaction of ammonia (conversion from endothermic to exothermic reaction by injecting a small amount of oxygen)] NH3(g) + xO2(g) → 0.5N2(g) + 2xH2O(g) + (1.5 - 2x)H2(g) H = 46 - 484x kJ mol -1

[0028] In the above Reaction Formula 1, x satisfies 0 < x < 0.75, and preferably can satisfy 0.15 < x < 0.65.

[0029] The reaction of reaction formula 1 may also be carried out using the reaction heat from one or more exothermic reactions selected from the group consisting of reaction formulas 2 and 3 below, and a portion of an external heat source. [Reaction Equation 2: Ammonia thermal decomposition reaction (endothermic)] NH3(g)→0.5N2(g)+1.5H2(g) ΔH=45.9 kJ mol -1 [Reaction Equation 3: Complete combustion of ammonia (no hydrogen production; ammonia burns completely, forming only nitrogen and water vapor)] NH3(g)+0.75O2(g)→0.5N2(g)+1.5H2O(g) ΔH=-317 kJ mol -1

[0030] Furthermore, the endothermic reaction described in reaction equation 2 can be carried out using the reaction heat from one or more exothermic reactions selected from the group consisting of reaction equation 3.

[0031] Furthermore, step (1) above can be carried out without heat being supplied from the outside, or it can be carried out using some external heat source.

[0032] Furthermore, in step (1) above, the gas space velocity (Gas Hour Space Velocity, GHSV, L / (g)) of ammonia and oxygen is measured. cat The ratio of -h)) may be 2:1 to 6:1, preferably 3:1 to 5:1, and more preferably 3.5:1 to 4.5:1. Here, in step (1) above, the gas space velocity of ammonia and oxygen (Gas Hour Space Velocity, GHSV, L / (g) cat If the ratio of -h)) is less than 6:1 (e.g., 6.5:1 or 7:1), it is difficult to supply enough heat for the ammonia endothermic reaction to occur. If it is greater than 2:1 (e.g., 2.5:1 or 1:1), the reaction approaches complete combustion due to the injection of excess oxygen, and as it approaches combustion, the amount of hydrogen produced decreases, which is undesirable.

[0033] Furthermore, step (1) above can be carried out at 450 to 700°C, preferably 500 to 650°C. [Effects of the Invention]

[0034] The objective of the present invention is to provide a hydrogen extraction system based on the partial oxidation of ammonia that does not require an external heat source.

[0035] Another object of the present invention is to provide a hydrogen extraction system based on the partial oxidation of ammonia, which has a long reaction time and solves the problem of reduced thermal efficiency by maintaining a high internal temperature of the reactor.

[0036] Another object of the present invention is to provide a highly functional ammonia partial oxidation-based hydrogen extraction catalyst for use in the above-described system, and a method for producing the same. [Brief explanation of the drawing]

[0037] These drawings are for reference in describing exemplary embodiments of the present invention and should not be construed as limiting the technical concept of the present invention to these drawings. [Figure 1] This is a schematic diagram illustrating a method for producing a carrier containing a lanthanide metal or transition metal and a catalyst containing ruthenium supported on the carrier according to embodiments of the present invention. [Figure 2a] This graph shows the reaction temperature range when using the Ru / Ce0.9Zr0.1O2-δ catalyst from Example 2-3 and the Ru / Ce0.9Y0.1O2-δ catalyst from Example 4-1. [Figure 2b] This graph shows the ammonia conversion rate and hydrogen production amount using the Ru / Ce0.9Zr0.1O2-δ catalyst from Example 2-3 and the Ru / Ce0.9Y0.1O2-δ catalyst from Example 4-1. [Figure 3a]This graph shows the reaction temperature range when using the Ru / Ce0.9La0.1O2-δ catalyst from Example 1-4, the Ru / Ce0.9Sm0.1O2-δ catalyst from Example 3-1, and the Ru / Ce0.9Yb0.1O2-δ catalyst from Example 3-2. [Figure 3b] This graph shows the ammonia conversion rate and hydrogen production amount using the Ru / Ce0.9La0.1O2-δ catalyst from Example 1-4, the Ru / Ce0.9Sm0.1O2-δ catalyst from Example 3-1, and the Ru / Ce0.9Yb0.1O2-δ catalyst from Example 3-2. [Figure 4a] This graph shows the reaction temperature range when using the Ru / Ce0.9Fe0.1O2-δ catalyst from Example 4-2, the Ru / Ce0.9Cu0.1O2-δ catalyst from Example 4-3, the Ru / Ce0.9Ni0.1O2-δ catalyst from Example 4-4, and the Ru / Ce0.9Co0.1O2-δ catalyst from Example 4-5. [Figure 4b] This graph shows the ammonia conversion rate and hydrogen production amount using the Ru / Ce0.9Fe0.1O2-δ catalyst from Example 4-2, the Ru / Ce0.9Cu0.1O2-δ catalyst from Example 4-3, the Ru / Ce0.9Ni0.1O2-δ catalyst from Example 4-4, and the Ru / Ce0.9Co0.1O2-δ catalyst from Example 4-5. [Figure 5a] This graph shows the reaction temperatures for different x values ​​using the zirconium-containing Ru / Ce1-xZrxO2-δ catalyst according to Examples 2-1 to 2-4. [Figure 5b] This graph shows the ammonia conversion rate data for different x values ​​using the zirconium-containing Ru / Ce1-xZrxO2-δ catalyst according to Examples 2-1 to 2-4. [Figure 6a] This graph shows the reaction temperatures for different x values ​​using the Ru / Ce1-xLaxO2-δ catalyst containing lanthanum, as described in Examples 1-1 to 1-5 and Comparative Example 1-1. [Figure 6b] This graph shows the ammonia conversion rate data for different x values ​​using a Ru / Ce1-xLaxO2-δ catalyst containing lanthanum, as described in Examples 1-1 to 1-5 and Comparative Example 1-1. [Figure 7a]This graph shows the ammonia conversion rate and chemical formula coefficient data obtained by analyzing the detailed gas concentrations of the Ru / Ce0.5La0.5O2-δ catalysts according to Examples 1-2. [Figure 7b] This graph shows the ammonia conversion rate and chemical formula coefficient data obtained by analyzing the detailed gas concentrations of the Ru / Ce0.7La0.3O2-δ catalysts according to Examples 1-3. [Figure 8] This graph shows the evaluation protocols (AOR:NH3 / O2 ratio, varied from 4 to 6) for the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. The reaction was carried out for 2 hours and 30 minutes under each condition. [Figure 9] This graph shows the temperature data for different time intervals for the Ru(3wt%) / Ce1-xLaxO2-δ catalysts used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. [Figure 10a] This graph shows the ammonia conversion rate data over time when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalysts used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 4 to 5. [Figure 10b] This graph shows the ammonia conversion rate data depending on the lanthanum (La) content when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 4 to 5. [Figure 11a] This graph shows the ammonia conversion rate data over time when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 5 to 6. [Figure 11b] This graph shows the ammonia conversion rate data depending on the lanthanum (La) content when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 5 to 6. [Figure 12a]This graph shows the ammonia conversion rate data over time when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 5 to 6. [Figure 12b] This graph shows the ammonia conversion rate data depending on the lanthanum (La) content when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 5 to 6. [Figure 13a] This graph shows the ammonia conversion rate data over time when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalysts used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 6 to 7. [Figure 13b] This graph shows the ammonia conversion rate data depending on the lanthanum (La) content when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 6 to 7. [Figure 14a] This graph shows the ammonia conversion rate data over time when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalysts used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 6 to 7. [Figure 14b] This graph shows the ammonia conversion rate data depending on the lanthanum (La) content when the AOR (NH3 / O2 ratio) of the Ru(3wt%) / Ce1-xLaxO2-δ catalyst used in Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 is 6 to 7.

[0038] The 2wt% shown in Figures 2a to 6b above means that the amount of ruthenium precursor used during catalyst synthesis corresponds to a stoichiometric ruthenium (Ru) content of 2 wt% of the catalyst, and the 3wt% shown in Figures 8 to 14b above means that the amount of ruthenium precursor used during catalyst synthesis corresponds to a stoichiometric ruthenium (Ru) content of 3 wt% of the catalyst. [Modes for carrying out the invention]

[0039] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that they can be easily implemented by persons with ordinary skill in the art to which the present invention pertains.

[0040] However, the following description is not intended to limit the present invention to any particular embodiment, and if a specific description of the prior art related to the present invention is deemed to obscure the gist of the invention, such detailed description will be omitted.

[0041] The terms used in this application are used solely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “includes” or “having” specify the existence of features, figures, stages, actions, components, or combinations thereof described in the specification, and should be understood not to preclude the existence or possibility of adding one or more other features, figures, stages, actions, components, or combinations thereof.

[0042] Furthermore, while terms including ordinal numbers such as "first," "second," etc., used below may be used to describe various components, the above components are not limited by such terms. The above terms are used solely for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be named the second component, and similarly, the second component may be named the first component.

[0043] Furthermore, when one component is referred to as being "formed" or "laminated" on another component, it should be understood that it may be formed by being directly attached to or laminated on all or one surface of the other component, but there may also be other components in between.

[0044] Hereinafter, the present invention will be described in detail with respect to a hydrogen extraction catalyst based on the partial oxidation of ammonia, a method for producing the same, and a hydrogen extraction method using the above catalyst. However, this is presented as an example and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims described below.

[0045] According to one aspect of the present invention, there is provided a catalyst comprising: a carrier containing a compound represented by the following Chemical Formula 1; and ruthenium (Ru) supported on the above carrier. [Chemical Formula 1] Ce 1-x M x O 2-δ

[0046] In the above Chemical Formula 1, x satisfies 0 < x < 1, M is a lanthanide metal or a transition metal, and δ can satisfy 0 < δ ≦ 0.5.

[0047] Further, the above lanthanide metal can include one or more selected from the group consisting of lanthanum (La), samarium (Sm), ytterbium (Yb), gadolinium (Gd), and lutetium (Lu).

[0048] Further, the above lanthanide metal can include lanthanum (La).

[0049] Further, the above lanthanide metal includes lanthanum (La), and x can satisfy 0.05 ≦ x ≦ 0.8, preferably 0.1 ≦ x ≦ 0.7, more preferably 0.3 ≦ x ≦ 0.6. Here, if the range of x is less than 0.05, the reaction does not occur and ammonia decomposition does not occur, which is not preferable. If it exceeds 0.8, the specific surface area of the carrier decreases rapidly, which is not preferable.

[0050] Further, the above transition metal can include one or more selected from the group consisting of zirconium (Zr), yttrium (Y), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), and osmium (Os).

[0051] Furthermore, the above transition metal may include zirconium (Zr).

[0052] Furthermore, the transition metal may include zirconium (Zr), and x may be between 0.05 ≤ x ≤ 0.5, preferably 0.1 ≤ x ≤ 0.4. Here, if the range of x is less than 0.05, the exothermic reaction will not occur, which is undesirable, and if it exceeds 0.5, ammonia decomposition will not occur, which is also undesirable.

[0053] Furthermore, the catalyst may contain 1 to 3% by weight, preferably 1.3 to 2.0% by weight, of the ruthenium. Here, if the amount of ruthenium is less than 1% by weight, hydrogen extraction based on partial oxidation of ammonia may not occur, which is undesirable, and if it exceeds 3% by weight, the ammonia decomposition efficiency decreases, which is also undesirable.

[0054] Furthermore, the catalyst described above may be used to decompose ammonia and extract hydrogen.

[0055] Another aspect of the present invention provides a method for producing a catalyst, comprising: (a) the step of producing a precursor solution containing one or more metals selected from the group consisting of lanthanide metal precursors and transition metal precursors, a cerium precursor, and water; (b) the step of coprecipitation of the precursors in the precursor solution to synthesize a coprecipitate containing one or more metals selected from the group consisting of lanthanide metals and transition metals, and cerium; (c) the step of heat-treating the coprecipitate to produce a carrier; and (d) the step of stirring the carrier solution containing the carrier, a ruthenium precursor, and water to produce a catalyst containing a carrier on which ruthenium is supported.

[0056] Furthermore, the catalyst may include a support containing a compound represented by the following chemical formula 1, and ruthenium (Ru) supported on the support. [Chemical formula 1] Ce 1-x M x O 2-δ

[0057] In the above Chemical Formula 1, x satisfies 0 < x < 1, M is a lanthanide metal or a transition metal, and δ can satisfy 0 < δ ≤ 0.5.

[0058] First, a precursor solution containing at least one selected from the group consisting of a lanthanide metal precursor and a transition metal precursor, a cerium precursor, and water is prepared (step a).

[0059] The pH of the precursor solution in step (a) can be 8 - 11, preferably 9 - 10. Here, when the pH of the precursor solution is 8 or higher, the separation of Ce 3+ , M 3+ in the precursor in the basic solution is easy, and it is preferable that the metal cations easily form precipitates in the aqueous solution. When the pH exceeds 11, the solubility of the metal precursor decreases, making it difficult to form precipitates, which is not preferable.

[0060] Also, the lanthanide metal precursor can contain lanthanum nitrate hexahydrate, the transition metal precursor can contain zirconium nitrate hexahydrate, and the cerium precursor can contain cerium nitrate hexahydrate.

[0061] The precursors in the precursor solution are co-precipitated to synthesize a co-precipitate containing at least one selected from the group consisting of a lanthanide metal and a transition metal and cerium (step b).

[0062] The co-precipitate is heat-treated to produce a support (step c).

[0063] The heat treatment in step (c) can be carried out in air.

[0064] Further, the heat treatment in step (c) can be carried out at 400 to 600 °C, preferably 450 to 550 °C. Here, in the case of high-temperature air heat treatment, it is preferable to remove impurities or adsorbed substances on the carrier surface and improve the crystallinity of the carrier. At this time, if the heat treatment temperature is less than 400 °C, it is highly likely that the above-mentioned preferable expected effects will not appear, which is not preferable. If it is carried out above 600 °C, a phase with low density or specific surface area may appear during the carrier crystallization process at high temperature, which is not preferable.

[0065] Finally, a catalyst containing a carrier on which ruthenium is supported is produced by stirring a carrier solution containing the above carrier, a ruthenium precursor, and water (step d).

[0066] According to still another aspect of the present invention, there is provided a hydrogen extraction method including step (1) of subjecting ammonia to a partial oxidation reaction in the presence of the above catalyst and oxygen to extract hydrogen.

[0067] Further, the partial oxidation reaction may include an ammonia decomposition reaction and an ammonia oxidation reaction.

[0068] Further, the partial oxidation reaction can be carried out by the reaction of the following Reaction Formula 1. [Reaction Formula 1: Partial oxidation reaction of ammonia (conversion from endothermic to exothermic reaction by injecting a small amount of oxygen)] NH3(g)+xO2(g)→0.5N2(g)+2xH2O(g)+(1.5-2x)H2(g) H=46-484x kJ mol -1

[0069] In the above Reaction Formula 1, x is 0 <x <0.75, preferably 0.15 <x <0.65.

[0070] The reaction of the above Reaction Formula 1 can be carried out using the reaction heat of one or more exothermic reactions selected from the group consisting of the following Reaction Formula 2 and Reaction Formula 3 and a part of an external heat source. [Reaction Formula 2: Ammonia thermal decomposition reaction (endothermic)] NH3(g)→0.5N2(g)+1.5H2(g) ΔH=45.9 kJ mol -1 [Reaction Equation 3: Complete combustion of ammonia (no hydrogen production; ammonia burns completely, forming only nitrogen and water vapor)] NH3(g)+0.75O2(g)→0.5N2(g)+1.5H2O(g) ΔH=-317 kJ mol -1

[0071] Furthermore, the endothermic reaction described in reaction equation 2 can be carried out using the reaction heat from one or more exothermic reactions selected from the group consisting of reaction equation 3.

[0072] Ammonia is partially oxidized in the presence of the above catalyst and oxygen to extract hydrogen (Step 1).

[0073] Furthermore, step (1) above can be carried out without the supply of heat from the outside, or with the use of some external heat sources.

[0074] Furthermore, in step (1) above, the gas space velocity of ammonia and oxygen (GHSV, L / (g) cat -h)) ratio may be 2:1 to 6:1, preferably 3:1 to 5:1, more preferably 3.5:1 to 4.5:1. Here, in step (1) above, the gas space velocity of ammonia and oxygen (GHSV, L / (g) cat If the ratio of -h)) is less than 6:1 (e.g., 6.5:1 or 7:1), it is difficult to supply enough heat for the ammonia endothermic reaction to occur. If it is greater than 2:1 (e.g., 2.5:1 or 1:1), the reaction approaches complete combustion due to excessive oxygen injection, and as it approaches combustion, the amount of hydrogen produced decreases, which is undesirable.

[0075] Furthermore, step (1) above can be carried out at 450 to 700°C, preferably 500 to 650°C. In step (1) above, this corresponds to ammonia thermal decomposition. In the case of ammonia thermal decomposition reactions, if carried out at a temperature below 450°C, the ammonia conversion rate is low and undesirable. If carried out at a temperature above 700°C, a large amount of combustion heat is required to maintain the ultra-high temperature, which is undesirable because it affects the overall decrease in thermal efficiency. [Examples]

[0076] [Examples] The present invention will be described in more detail below with reference to examples. However, these are illustrative and do not limit the scope of the present invention.

[0077] Manufacturing Example 1: Ce based on lantern composition ratio 1-x La x O 2-δ Synthesis of carriers Manufacturing Example 1-1: Ce 0.3 La 0.7 O 2-δ Carrier A carrier solution was prepared by stirring 2.60532g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 6.06214g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, in 200ml of distilled water at 1000-1500 rpm for approximately 1 hour. The pH of the carrier solution was adjusted to approximately 9-10 using ammonia water. The carrier solution was then dried in an oven at 100°C for approximately 12 hours to produce the carrier. The prepared carrier was separated from the distilled water by centrifugation and washed. The carrier separated from the distilled water was further dried in an oven at 120°C for approximately 12 hours. After that, the carrier was subjected to a heat treatment reaction at 500°C for 3 hours in an air atmosphere to produce Ce. 0.3 La 0.7 O 2-δA support material was manufactured. The subscript "2-δ" next to oxygen (O) in the chemical formula of the above support material indicates that an oxygen deficiency site was formed by adding a metal to the support material. Measuring or specifying the exact value of δ at this time would not have a meaningful effect on the results of the experimental example below, so it is estimated to be a value in the range of approximately 0 to 0.05.

[0078] Manufacturing Example 1-2: Ce 0.5 La 0.5 O 2-δ Carrier Except for using 2.60532g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 6.06214g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, instead using 4.3422g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 4.3301g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, the same method as in Production Example 1-1 is used to produce Ce. 0.5 La 0.5 O 2-δ We manufactured the carrier material.

[0079] Manufacturing example 1-3: Ce 0.7 La 0.3 O 2-δ Carrier Except for using 2.60532g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 6.06214g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, the same method as in Preparation Example 1-1 is used to produce Ce. 0.7 La 0.3 O 2-δ We manufactured the carrier material.

[0080] Manufacturing Example 1-4: Ce 0.9 La 0.1 O 2-δ Carrier Except for using 2.60532g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 6.06214g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, instead using 7.816g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 0.86602g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, the same method as in Production Example 1-1 is used to produce Ce. 0.9 La 0.1 O 2-δ We manufactured the carrier material.

[0081] Manufacturing Examples 1-5: Ce 0.95 La 0.05 O 2-δ Carrier Except for using 2.60532g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 6.06214g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, the same method as in Production Example 1-1 is used to produce Ce. 0.95 La 0.05 O 2-δ We manufactured the carrier material.

[0082] Comparative manufacturing example 1-1: La2O3 carrier A La2O3 support was prepared in the same manner as in Production Example 1-1, except that instead of using 2.60532 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 6.06214 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, 0 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 8.6602 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, a La2O3 support was used.

[0083] Comparative manufacturing example 1-2: CeO2 carrier A CeO2 support was prepared in the same manner as in Production Example 1-1, except that instead of using 2.60532 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 6.06214 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, 8.6844 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 0 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), a metal precursor, was used.

[0084] Manufacturing Example 2: Ce by Zirconium Composition Ratio 1-x Zr x O 2-δ Synthesis of carriers Manufacturing Example 2-1: Ce 0.5 Zr 0.5 O 2-δ Carrier A support solution was prepared by stirring 4.3422g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 3.8301g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, in 200ml of distilled water at 1000-1500rpm for approximately 1 hour. The pH of the support solution was adjusted to approximately 9-10. The support solution was then dried in an oven at 100°C for approximately 12 hours to produce the support. The prepared support was washed using centrifugation, further dried in an oven at 120°C for approximately 12 hours, and then subjected to a heat treatment reaction at 500°C for 3 hours in an air atmosphere to produce Ce. 0.5 Zr 0.5 O 2-δA support material was manufactured. The subscript "2-δ" next to oxygen (O) in the chemical formula of the support material indicates that an oxygen deficiency site was formed by adding metal to the support material. Measuring or identifying the exact value of δ at this time would not have a meaningful effect on the results of the experimental example below, so it is estimated to be a value in the range of approximately 0 to 0.05.

[0085] Manufacturing Example 2-2: Ce 0.7 Zr 0.3 O 2-δ Carrier Except for using 4.3422g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 3.8301g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, instead using 6.08g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 2.30g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, the same method as in Production Example 2-1 is used to produce Ce. 0.7 Zr 0.3 O 2-δ We manufactured the carrier material.

[0086] Manufacturing Example 2-3: Ce 0.9 Zr 0.1 O 2-δ Carrier Instead of using 4.3422 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), which is a cerium (Ce) precursor, and 3.8301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), which is a metal precursor, 7.816 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), which is a cerium (Ce) precursor, and 0.76602 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), which is a metal precursor were used. Except for this, Ce was prepared in the same manner as in Production Example 2-1. 0.9 Zr 0.1 O 2-δ A carrier was produced.

[0087] Production Example 2-4: Ce 0.95 Zr 0.05 O 2-δ Carrier Instead of using 4.3422 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), which is a cerium (Ce) precursor, and 3.8301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), which is a metal precursor, 8.25 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), which is a cerium (Ce) precursor, and 0.38301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), which is a metal precursor were used. Except for this, Ce was prepared in the same manner as in Production Example 2-1. 0.95 Zr 0.05 O 2-δ A carrier was produced.

[0088] Production Example 3: Ce with different lanthanide metal species (M) 1-x M x O 2-δ Synthesis of carrier Production Example 3-1: Ce 0.9Sm 0.1 O 2-δ Support 7.816 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), which is a cerium (Ce) precursor, and 0.88894 g of samarium nitrate hexahydrate (Sm(NO3)3·6H2O), which is a lanthanide metal precursor, were stirred in 200 ml of distilled water at about 1000 - 1500 rpm for about 1 hour to produce a support solution, and the pH of the support solution was adjusted to about 9 - 10. Thereafter, the support solution was dried in an oven at a temperature of 100 °C for about 12 hours to produce a support. The produced support was washed using a centrifugation method and further dried in an oven at a temperature of 120 °C for about 12 hours. Thereafter, the support was heat-treated at a temperature of 500 °C for 3 hours in an air atmosphere to produce Ce 0.9 Sm 0.1 O 2-δ Support was produced. The subscript "2-δ" of oxygen (O) in the chemical formula of the support means that oxygen deficiency points were formed by adding metal to the support. At this time, since accurately measuring or specifying the exact value of δ has no meaningful influence on the results of the following experimental examples, it is estimated to be a value within the range of approximately 0 - 0.05.

[0089] Production Example 3-2: Ce 0.9 Yb 0.1 O 2-δ Support Ce 0.9 Yb 0.1 O 2-δ Support was produced in the same manner as in Production Example 3-1, except that 0.89826 g of ytterbium nitrate hexahydrate (Yb(NO3)3·6H2O) was used instead of 0.88894 g of samarium nitrate hexahydrate (Sm(NO3)3·6H2O), which is a lanthanide metal precursor.

[0090] Production Example 4: Ce by transition metal type (M) 1-x M x O 2-δ Synthesis of support Manufacturing Example 4-1: Ce 0.9 Y 0.1 O 2-δ Carrier A support solution was prepared by stirring 7.816 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 0.76602 g of yttrium(III) nitrate hexahydrate (Y(NO3)3·6H2O), a transition metal precursor, in 200 ml of distilled water at 1000-1500 rpm for approximately 1 hour. The pH of the support solution was adjusted to approximately 9-10. The support solution was then dried in an oven at 100°C for approximately 12 hours to produce the support. The prepared support was washed using centrifugation, further dried in an oven at 120°C for approximately 12 hours, and then subjected to a heat treatment reaction at 500°C for 3 hours in an air atmosphere to produce Ce. 0.9 Y 0.1 O 2-δ A support material was manufactured. The subscript "2-δ" next to oxygen (O) in the chemical formula of the support material indicates that an oxygen deficiency site was formed by adding metal to the support material. Measuring or identifying the exact value of δ at this time would not have a meaningful effect on the results of the experimental example below, so it is estimated to be a value in the range of approximately 0 to 0.05.

[0091] Manufacturing Example 4-2: Ce 0.9 Fe 0.1 O 2-δ Carrier The process is carried out in the same manner as in Preparation Example 4-1, except that 0.808 g of iron(III) nitrate nonahydrate (Fe(NO3)3·9H2O) is used instead of 0.76602 g of yttrium(III) nitrate hexahydrate (Y(NO3)3·6H2O), a transition metal precursor, and Ce is prepared in the same manner as in Preparation Example 4-1. 0.9 Fe 0.1 O 2-δ We manufactured the carrier material.

[0092] Manufacturing Example 4-3: Ce 0.9 Cu 0.1 O2-δ Carrier The preparation method is the same as in Preparation Example 4-1, except that 0.482 g of copper(II) nitrate trihydrate (Cu(NO3)3·3H2O) is used instead of 0.76602 g of yttrium(III) nitrate hexahydrate (Y(NO3)3·6H2O), a transition metal precursor. 0.9 Cu 0.1 O 2-δ We manufactured the carrier material.

[0093] Manufacturing Example 4-4: Ce 0.9 Ni 0.1 O 2-δ Carrier The process is carried out in the same manner as in Preparation Example 4-1, except that 0.76602 g of nickel(II) nitrate hexahydrate (Ni(NO3)3·6H2O) is used instead of 0.582 g of yttrium(III) nitrate hexahydrate (Y(NO3)3·6H2O), a transition metal precursor, and Ce is prepared in the same manner as in Preparation Example 4-1. 0.9 Ni 0.1 O 2-δ We manufactured the carrier material.

[0094] Manufacturing example 4-5: Ce 0.9 Co 0.1 O 2-δ Carrier The process is carried out in the same manner as in Preparation Example 4-1, except that 0.582 g of dicobalt nitrate hexahyrate (Co(NO3)3·6H2O) is used instead of 0.76602 g of yttrium(III) nitrate hexahydrate (Y(NO3)3·6H2O), a transition metal precursor, and Ce is prepared in the same manner as in Preparation Example 4-1. 0.9 Co 0.1 O 2-δ We manufactured the carrier material.

[0095] Example 1: Catalyst production by supporting ruthenium (Ru) on a lanthanum carrier. Example 1-1: Ru / Ce 0.3La 0.7 O 2-δ A ruthenium solution was prepared by diluting 1.026 g of ruthenium chloride hydrate (RuCl3·xH2O), a ruthenium precursor, in 50 ml of distilled water. Then, 2 ml (2 wt% Ru) of the above ruthenium solution and Ce according to the above preparation example 1-1 were mixed. 0.3 La 0.7 O 2-δ A catalyst solution was prepared by stirring 1 g of support in 100 ml of distilled water at 400 rpm for approximately 24 hours, and the pH of the catalyst solution was adjusted to approximately 9-10. After this, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed. The catalyst was then dried in an oven at 120°C for 12 hours, and the remaining distilled water was removed to obtain the Ru / Ce solution supported with ruthenium. 0.3 La 0.7 O 2-δ A catalyst was manufactured. The subscript "2-δ" around oxygen (O) in the catalyst's chemical formula indicates that an oxygen deficiency site was formed by adding a metal to the support. Measuring or identifying the exact value of δ would not significantly affect the results of the experimental example below; therefore, it is estimated to be within the range of approximately 0 to 0.05.

[0096] The 2 wt% mentioned in the examples means that the amount of ruthenium precursor used during catalyst synthesis corresponds to a stoichiometric ruthenium (Ru) content of 2 wt% of the catalyst.

[0097] Examples 1-2: Ru / Ce 0.5 La 0.5 O 2-δ Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ Instead of using a carrier, Ce produced in Manufacturing Example 1-2 0.5 La 0.5 O 2-δ Ruthenium is supported in the same manner as in Example 1-1, except that a support is used. 0.5 La 0.5 O 2-δ We manufactured a catalyst.

[0098] Examples 1-3: Ru / Ce 0.7 La 0.3 O 2-δ Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ Instead of using a carrier, Ce produced in Manufacturing Example 1-3 0.7 La 0.3 O 2-δ Ruthenium is supported in the same manner as in Example 1-1, except that a support is used. 0.7 La 0.3 O 2-δ We manufactured a catalyst.

[0099] Examples 1-4: Ru / Ce 0.9 La 0.1 O 2-δ Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ Instead of using a carrier, Ce produced in Manufacturing Example 1-4 0.9 La 0.1 O 2-δ Ruthenium is supported in the same manner as in Example 1-1, except that a support is used. 0.9 La 0.1 O 2-δ We manufactured a catalyst.

[0100] Examples 1-5: Ru / Ce 0.95 La 0.05 O 2-δ Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ Instead of using a carrier, Ce produced in Manufacturing Example 1-5 0.95 La 0.05 O 2-δ Ruthenium is supported in the same manner as in Example 1-1, except that a support is used. 0.95 La 0.05 O 2-δ We manufactured a catalyst.

[0101] Comparative example 1-1: Ru / La2O3 Ce according to manufacturing example 1-10.5 La 0.5 O 2-δ A ruthenium-supported Ru / La2O3 catalyst was prepared in the same manner as in Example 1-1, except that a La2O3 support according to Comparative Production Example 1-1 was used instead of a support.

[0102] Example 2: Catalyst production by supporting ruthenium (Ru) on a zirconium support. Example 2-1: Ru / Ce 0.5 Zr 0.5 O 2-δ A ruthenium solution was prepared by diluting 1.026 g of ruthenium chloride hydrate (RuCl3·xH2O), a ruthenium precursor, in 50 ml of distilled water. Then, 2 ml (2 wt% Ru) of the above ruthenium solution and Ce prepared according to the above preparation example 2-1 were mixed. 0.5 Zr 0.5 O 2-δ A catalyst solution was prepared by stirring 1 g of support in 100 ml of distilled water at 400 rpm for approximately 24 hours, and the pH of the catalyst solution was adjusted to approximately 9-10. After this, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed. The catalyst was then dried in an oven at 120°C for 12 hours, and the remaining distilled water was removed to obtain the Ru / Ce solution supported with ruthenium. 0.5 Zr 0.5 O 2-δ A catalyst was manufactured. The subscript "2-δ" around oxygen (O) in the catalyst's chemical formula indicates that an oxygen deficiency site was formed by adding a metal to the support. Measuring or identifying the exact value of δ would not significantly affect the results of the experimental example below; therefore, it is estimated to be within the range of approximately 0 to 0.05.

[0103] Example 2-2: Ru / Ce 0.7 Zr 0.3 O 2-δ Ce, a metal precursor produced in manufacturing example 2-1 0.5 Zr 0.5 O 2-δ Instead of using a carrier, Ce according to manufacturing example 2-2 0.7 Zr 0.3 O2-δ Ru / Ce on which ruthenium was supported in the same manner as in Example 2-1, except that a carrier was used 0.7 Zr 0.3 O 2-δ A catalyst was produced.

[0104] Example 2-3: Ru / Ce 0.9 Zr 0.1 O 2-δ Ce which is a metal precursor according to Production Example 2-1 0.5 Zr 0.5 O 2-δ Instead of using a carrier, Ce according to Production Example 2-3 0.9 Zr 0.1 O 2-δ Ru / Ce on which ruthenium was supported in the same manner as in Example 2-1, except that a carrier was used 0.9 Zr 0.1 O 2-δ A catalyst was produced.

[0105] Example 2-4: Ru / Ce 0.95 Zr 0.05 O 2-δ Ce which is a metal precursor according to Production Example 2-1 0.5 Zr 0.5 O 2-δ Instead of using a carrier, Ce according to Production Example 2-3 0.95 Zr 0.05 O 2-δ Ru / Ce on which ruthenium was supported in the same manner as in Example 2-1, except that a carrier was used 0.95 Zr 0.05 O 2-δ A catalyst was produced.

[0106] Example 3: Production of a catalyst by supporting ruthenium (Ru) on a carrier containing a lanthanide-based metal Example 3-1: Ru / Ce 0.9 Sm 0.1 O 2-δ A ruthenium solution was prepared by diluting 1.026 g of ruthenium chloride hydrate (RuCl3·xH2O), a ruthenium precursor, in 50 ml of distilled water. Then, 2 ml (2 wt% Ru) of the above ruthenium solution was mixed with Ce according to the above preparation example 3-1. 0.9 Sm 0.1 O 2-δ A catalyst solution was prepared by stirring 1 g of support in 100 ml of distilled water at 400 rpm for approximately 24 hours, and the pH of the catalyst solution was adjusted to approximately 9-10. After this, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed. The catalyst was then dried in an oven at 120°C for 12 hours, and the remaining distilled water was removed to obtain the Ru / Ce solution supported with ruthenium. 0.9 Sm 0.1 O 2-δ A catalyst was manufactured. The subscript "2-δ" around oxygen (O) in the catalyst's chemical formula indicates that an oxygen deficiency site was formed by adding a metal to the support. Measuring or identifying the exact value of δ would not significantly affect the results of the experimental example below; therefore, it is estimated to be within the range of approximately 0 to 0.05.

[0107] Example 3-2: Ru / Ce 0.9 Yb 0.1 O 2-δ Ce, a metal precursor produced in manufacturing example 3-1 0.9 Sm 0.1 O 2-δ Instead of using a carrier, Ce according to manufacturing example 3-2 0.9 Yb 0.1 O 2-δ Ruthenium is supported in the same manner as in Example 3-1, except that a support is used. 0.9 Yb 0.1 O 2-δ We manufactured a catalyst.

[0108] Example 4: Catalyst production by supporting ruthenium (Ru) on a transition metal-containing support. Example 4-1: Ru / Ce 0.9 Y 0.1 O 2-δ A ruthenium solution was prepared by diluting 1.026 g of ruthenium chloride hydrate (RuCl3·xH2O), a ruthenium precursor, in 50 ml of distilled water. Then, 2 ml (2 wt% Ru) of the above ruthenium solution and Ce according to the above production example 4-1 were mixed. 0.9 Y 0.1 O 2-δ A catalyst solution was prepared by stirring 1 g of support in 100 ml of distilled water at 400 rpm for approximately 24 hours, and the pH of the catalyst solution was adjusted to approximately 9-10. After this, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed. The catalyst was then dried in an oven at 120°C for 12 hours, and the remaining distilled water was removed to obtain the Ru / Ce solution supported with ruthenium. 0.9 Y 0.1 O 2-δ A catalyst was manufactured. The subscript "2-δ" around oxygen (O) in the catalyst's chemical formula indicates that an oxygen deficiency site was formed by adding a metal to the support. Measuring or identifying the exact value of δ would not significantly affect the results of the experimental example below; therefore, it is estimated to be within the range of approximately 0 to 0.05.

[0109] Example 4-2: Ru / Ce 0.9 Fe 0.1 O 2-δ Ce, a metal precursor produced in manufacturing example 4-1 0.9 Y 0.1 O 2-δ Instead of a carrier, Ce according to manufacturing example 4-2 0.9 Fe 0.1 O 2-δ Ruthenium was supported in the same manner as in Example 4-1, except that a support was used. 0.9 Fe 0.1 O 2-δ We manufactured a catalyst.

[0110] Example 4-3: Ru / Ce 0.9 Cu 0.1 O 2-δ Ce, a metal precursor produced in manufacturing example 4-1 0.9 Y 0.1 O 2-δInstead of using a carrier, Ce according to manufacturing example 4-3 0.9 Cu 0.1 O 2-δ Ruthenium was supported in the same manner as in Example 4-1, except that a support was used. 0.9 Cu 0.1 O 2-δ We manufactured a catalyst.

[0111] Example 4-4: Ru / Ce 0.9 Ni 0.1 O 2-δ Ce, a metal precursor produced in manufacturing example 4-1 0.9 Y 0.1 O 2-δ Instead of using a carrier, Ce according to manufacturing example 4-4 0.9 Ni 0.1 O 2-δ Ruthenium was supported in the same manner as in Example 4-1, except that a support was used. 0.9 Ni 0.1 O 2-δ We manufactured a catalyst.

[0112] Examples 4-5: Ru / Ce 0.9 Co 0.1 O 2-δ Ce, a metal precursor produced in manufacturing example 4-1 0.9 Y 0.1 O 2-δ Instead of using a carrier, Ce according to manufacturing example 4-5 0.9 Co 0.1 O 2-δ Ruthenium was supported in the same manner as in Example 4-1, except that a support was used. 0.9 Co 0.1 O 2-δ We manufactured a catalyst.

[0113] Example 5: Catalyst production by supporting 3 wt% ruthenium on a lanthanum carrier Example 5-1: Ru(3wt%) / Ce 0.3 La 0.7 O 2-δ A ruthenium solution was prepared by diluting 1.03 g of ruthenium chloride hydrate (RuCl3·xH2O), a ruthenium precursor, in 50 ml of distilled water. 3 ml (3 wt% Ru) of the above ruthenium solution was then mixed with Ce according to the above preparation example 1-1. 0.3 La 0.7 O 2-δ A catalyst solution was prepared by stirring 1 g of support in 100 ml of distilled water at 400 rpm for approximately 24 hours, and the pH of the catalyst solution was adjusted to approximately 9-10. After this, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed. The catalyst was then dried in an oven at 120°C for 12 hours, and the remaining distilled water was removed to obtain the Ru / Ce solution supported with ruthenium. 0.3 La 0.7 O 2-δ A catalyst was manufactured. The subscript "2-δ" around oxygen (O) in the catalyst's chemical formula indicates that an oxygen deficiency site was formed by adding a metal to the support. Measuring or identifying the exact value of δ would not significantly affect the results of the experimental example below; therefore, it is estimated to be within the range of approximately 0 to 0.05.

[0114] The 3 wt% mentioned in the examples means that the amount of ruthenium precursor used during catalyst synthesis corresponds to the stoichiometric ruthenium (Ru) content of 3 wt% of the catalyst.

[0115] Example 5-2: Ru(3wt%) / Ce 0.5 La 0.5 O 2-δ Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ Instead of using a carrier, Ce produced in Manufacturing Example 1-2 0.5 La 0.5 O 2-δ Ruthenium was supported in the same manner as in Example 5-1, except that a support was used. Ru(3wt%) / Ce 0.5 La 0.5 O 2-δ We manufactured a catalyst.

[0116] Example 5-3: Ru(3wt%) / Ce0.7 La 0.3 O 2-δ Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ Instead of using a carrier, Ce produced in Manufacturing Example 1-3 0.7 La 0.3 O 2-δ Ruthenium was supported in the same manner as in Example 5-1, except that a support was used. Ru(3wt%) / Ce 0.7 La 0.3 O 2-δ We manufactured a catalyst.

[0117] Example 5-4: Ru(3wt%) / Ce 0.9 La 0.1 O 2-δ Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ Instead of using a carrier, Ce produced in Manufacturing Example 1-4 0.9 La 0.1 O 2-δ Ruthenium was supported in the same manner as in Example 5-1, except that a support was used. Ru(3wt%) / Ce 0.9 La 0.1 O 2-δ We manufactured a catalyst.

[0118] Comparative example 2-1: Ru(3wt%) / La2O3 Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δ A ruthenium-supported Ru(3wt%) / La2O3 catalyst was prepared in the same manner as in Example 5-1, except that a La2O3 support according to Comparative Production Example 1-1 was used instead of a support.

[0119] Comparative example 2-2: Ru(3wt%) / CeO2 Ce according to manufacturing example 1-1 0.3 La 0.7 O 2-δA ruthenium-supported Ru(3wt%) / CeO2 catalyst was prepared in the same manner as in Example 5-1, except that a CeO2 support according to Comparative Production Example 1-2 was used instead of a support.

[0120] [Example Test] Evaluation of partial oxidation reaction gas concentration Catalyst Ru / Ce according to Examples 1-1 to 1-5 and Comparative Example 1-1 1-x La x O 2-δ The gas concentrations in the partial oxidation reaction were evaluated at (x=0.05, 0.1, 0.3, 0.5, 0.7, 1.0). Table 1 below shows the data calculated for the change in the gas coefficient due to the partial oxidation reaction of ammonia, and Table 2 below shows the formulas for calculating the gas generation and conversion indices in the partial oxidation reaction of ammonia.

[0121] [Table 1]

[0122] [Table 2]

[0123] The value of α in Table 2 above can be expressed by the following formula 1. [Formula 1]

number

[0124] In Equation 1 above, the x value is determined, and the coefficient values ​​(a, b, c, d) corresponding to each gas are determined. Using these coefficient values, the detailed gas concentrations can be analyzed by applying them to Equation 2 below, and the catalyst evaluation results can be shown. [Formula 2] NH3(g)+0.25 O2(g)→aN2(g)+bH2(g)+cNH3(g)+0.5 H2O(g)

[0125] Test Example 1: Evaluation of Inductively Coupled Plasma (ICP) Mass Spectrometry Inductively coupled plasma (ICP) mass spectrometry was used to evaluate the carriers produced in Production Examples 1-1 to 1-5, 2-1 to 2-4, 3-1, 3-2, 4-1 to 4-5, and Comparative Production Example 1-1, as well as the catalysts produced in Examples 1-2 and 1-3. Table 3 below shows the metal content data obtained by inductively coupled plasma (ICP) mass spectrometry for the carriers produced in Production Examples 1-1 to 1-5, 2-1 to 2-4, 3-1, 3-2, 4-1 to 4-5, and Comparative Production Examples 1-1 to 1-2. Table 4 below shows the metal content data obtained by inductively coupled plasma (ICP) mass spectrometry for the catalysts produced in Examples 1 to 5 and Comparative Examples 1 to 2.

[0126] [Table 3]

[0127] In Table 3 above, the metal content of manufacturing examples 3-2 and 4-2 to 4-5, for which the metal content is not listed, could not be measured by inductively coupled plasma (ICP) mass spectrometry.

[0128] [Table 4]

[0129] In Table 4 above, in Examples 1-1 to 1-5, 2-1 to 2-4, 3-1, 3-2, and 4-1 to 4-5, a ruthenium precursor was used after calculations to ensure a stoichiometric ruthenium (Ru) content of the catalyst of 2 wt%, but the final ruthenium (Ru) content of the synthesized catalyst was confirmed to be 0.7 to 2.02 wt%. In Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2, a ruthenium precursor was used after calculations to ensure a stoichiometric ruthenium (Ru) content of the catalyst of 3 wt%, but the final ruthenium (Ru) content of the synthesized catalyst was confirmed to be 2.7 to 3.09 wt%. Furthermore, in Comparative Example 1-1, where the metal content is not listed, it was not possible to measure the metal content by inductively coupled plasma (ICP) mass spectrometry.

[0130] The following test examples 2-5 were conducted through the following stages (1)-(3).

[0131] First, 0.2 g of catalyst was injected into the reactor, and the catalyst was pretreated at 500°C in a hydrogen atmosphere for 90 minutes (Step 1).

[0132] After this, the temperature was cooled to room temperature, and the injection of an external heat source into the furnace was stopped (Stage 2).

[0133] Finally, the reaction was evaluated using 120 ml / min of ammonia, 30 ml of oxygen, total GHSV, and a gas hourly space velocity of 45,000 ml / g. cat -h was used for evaluation (level 3).

[0134] Test Example 2: Reaction temperature, ammonia conversion rate, and hydrogen production amount depending on the type of lanthanide metal. Test Example 2-1: Lanthanum (La), Samarium (Sm), and Ytterbium (Yb) Figure 3a shows the Ru / Ce method according to Examples 1-4. 0.9 La 0.1 O 2-δ Catalyst, Ru / Ce according to Example 3-1 0.9 Sm 0.1 O 2-δ Catalyst and Ru / Ce according to Example 3-2 0.9 Yb 0.1O 2-δ This graph shows the reaction temperature range when using the catalyst, and Figure 3b shows the Ru / Ce reaction according to Examples 1-4. 0.9 La 0.1 O 2-δ Catalyst, Ru / Ce according to Example 3-1 0.9 Sm 0.1 O 2-δ Catalyst and Ru / Ce according to Example 3-2 0.9 Yb 0.1 O 2-δ The graph shows the ammonia conversion rate and hydrogen production using the catalyst. Table 5 below shows the reaction temperature, ammonia conversion rate, and hydrogen production using the catalysts in Examples 1-5 and Comparative Examples 1-2 of the present invention. The catalysts were calcined at 300°C before use.

[0135] Referring to Figures 3a, 3b and Table 5, Ru / Ce containing samarium (Sm) according to Example 3-1 0.9 Sm 0.1 O 2-δ Catalyst and Ru / Ce containing ytterbium (Yb) according to Example 3-2 0.9 Yb 0.1 O 2-δ Although the ammonia decomposition reaction did not occur when the catalyst was used, the Ru / Ce mixture containing lanthanum (La) according to Examples 1-4 did not decompose. 0.9 La 0.1 O 2-δ The reaction temperature during catalyst use was maintained at over 500°C, and the ammonia conversion rate was approximately 67.3%, with a hydrogen production of 1.7 kgH2 / kg. cat -h and overall performance were confirmed to be excellent.

[0136] Test Example 2-2: Iron (Fe), Copper (Cu), Nickel (Ni), and Cobalt (Co) Figure 4a shows the Ru / Ce according to Example 4-2. 0.9 Fe 0.1 O 2-δ Catalyst, Ru / Ce according to Example 4-3 0.9 Cu 0.1 O 2-δ Catalyst, Ru / Ce according to Example 4-4 0.9 Ni 0.1 O 2-δCatalyst and Ru / Ce according to Examples 4-5 0.9 Co 0.1 O 2-δ This graph shows the reaction temperature range when using the catalyst, and Figure 4b shows the Ru / Ce reaction according to Example 4-2. 0.9 Fe 0.1 O 2-δ Catalyst, Ru / Ce according to Example 4-3 0.9 Cu 0.1 O 2-δ Catalyst, Ru / Ce according to Example 4-4 0.9 Ni 0.1 O 2-δ Catalyst and Ru / Ce according to Examples 4-5 0.9 Co 0.1 O 2-δ The graph shows the ammonia conversion rate and hydrogen production using the catalyst. Table 5 below shows the reaction temperature, ammonia conversion rate, and hydrogen production using the catalysts in Examples 1-5 and Comparative Examples 1-2 of the present invention. The catalysts were calcined at 300°C before use.

[0137] Referring to Figures 4a and 4b and Table 5, the Ru / Ce mixture containing copper according to Example 4-3 0.9 Cu 0.1 O 2-δ Catalyst and Nickel-containing Ru / Ce according to Example 4-4 0.9 Ni 0.1 O 2-δ The catalyst did not cause the ammonia decomposition reaction, but the Ru / Ce / Iron catalyst according to Example 4-2 did not cause the ammonia decomposition reaction. 0.9 Fe 0.1 O 2-δ The catalyst maintained the reaction temperature above 500°C, resulting in an ammonia conversion rate of approximately 49% and a hydrogen production of 0.78 kgH2 / kg. cat -h indicates Ru / Ce containing cobalt according to Examples 4-5 0.9 Co 0.1 O 2-δ The catalyst maintained the reaction temperature at approximately 440°C, resulting in an ammonia conversion rate of approximately 52% and a hydrogen production of 0.93 kgH2 / kg. cat It was confirmed that this is indicated by -h.

[0138] Test Example 3: Reaction temperature, ammonia conversion rate, and hydrogen production amount depending on the type of transition metal Test Example 3-1: Yttrium (Y) and Zirconium (Zr) Figure 2a shows the Ru / Ce mixture according to Example 2-3. 0.9 Zr 0.1 O 2-δ Catalyst and Ru / Ce by 4-1 0.9 Y 0.1 O 2-δ This graph shows the reaction temperature range when using the catalyst. Figure 2b shows the Ru / Ce reaction according to Example 2-3. 0.9 Zr 0.1 O 2-δ Catalyst and Ru / Ce by 4-1 0.9 Y 0.1 O 2-δ The graph shows the ammonia conversion rate and hydrogen production using the catalyst. Table 5 below shows the reaction temperature, ammonia conversion rate, and hydrogen production using the catalysts in Examples 1-5 and Comparative Examples 1-2 of the present invention. The catalysts were calcined at 300°C before use.

[0139] Referring to Figures 2a and 2b and Table 5, Ru / Ce according to Example 2-3 0.9 Zr 0.1 O 2-δ Catalyst and Ru / Ce according to Example 4-1 0.9 Y 0.1 O 2-δ The catalysts maintain reaction temperatures of approximately 460°C and 440°C, respectively, and have similar temperature ranges. However, the Ru / Ce reaction according to Examples 2-3 0.9 Zr 0.1 O 2-δ The catalyst maintained an ammonia conversion rate of approximately 63%, and hydrogen production was 1.43 kgH2 / kg. cat -h indicates Ru / Ce according to Example 4-1 0.9 Y 0.1 O 2-δ The catalyst's ammonia conversion rate was sustained at approximately 52%, and hydrogen production was 0.93 kgH2 / kg. cat As indicated by -h, it was confirmed that the catalyst from Example 2-3 had superior ammonia conversion rate and hydrogen production compared to the catalyst from Example 4-1.

[0140] Test Example 4: Comparison of catalyst reaction temperature, ammonia conversion rate, and hydrogen production based on lanthanum (La) composition ratio. Figure 6a shows Ru / Ce containing lanthanum according to Examples 1-1 to 1-5 and Comparative Example 1-1. 1-x La x O 2-δ This graph shows the reaction temperature for different x values ​​using a catalyst. Figure 6b shows the Ru / Ce reaction containing lanthanum from Examples 1-1 to 1-5 and Comparative Example 1-1. 1-x La x O 2-δ The graph shows ammonia conversion rate data and hydrogen production amount for different x values ​​using the catalyst. Table 5 below shows the reaction temperature, ammonia conversion rate, and hydrogen production amount using the catalysts in Examples 1-5 and Comparative Examples 1-2 of the present invention. The catalysts were calcined at 300°C before use.

[0141] Referring to Figures 6a, 6b and Table 5, the lanthanum-containing catalysts of Examples 1-2 to 1-4 were shown to maintain a reaction temperature of 500°C or higher, but the lanthanum-containing catalyst of Example 1-5 did not react, and the Ru / Ce containing lanthanum of Example 1-2 0.5 La 0.5 O 2-δ The catalyst achieved the best ammonia conversion rate of 95%, and hydrogen production was 3.03 kgH2 / kg. cat -h was obtained. Therefore, it was confirmed that the lanthanum-containing catalyst according to Example 1 had significantly better ammonia conversion rate and hydrogen production than the zirconium-containing catalyst according to Example 2.

[0142] Furthermore, comparing the catalysts of Example 1 (Ru 2wt%) and Example 5 (Ru 3wt%), it was confirmed that when the ruthenium content increased from 2wt% to 3wt%, the injection gas flow rate increased significantly, leading to an improved ammonia conversion rate and even higher hydrogen production.

[0143] Furthermore, in Example 1-1 and Comparative Example 1-1, it was confirmed that the catalytic activity decreases as the composition ratio of lanthanum (La) increases.

[0144] Test Example 5: Comparison of Catalyst Reaction Temperature, Ammonia Conversion Rate, and Hydrogen Production Amount Based on Zirconium (Zr) Composition Ratio Figure 5a shows the Ru / Ce mixture containing zirconium according to Examples 2-1 to 2-4. 1-x Zr x O 2-δ This graph shows the reaction temperature for different x values ​​using a catalyst. Figure 5b shows the reaction temperature of Ru / Ce containing zirconium according to Examples 2-1 to 2-4. 1-x Zr x O 2-δ The graph shows ammonia conversion rate data and hydrogen production amount for different x values ​​using the catalyst. Table 5 below shows the reaction temperature, ammonia conversion rate, and hydrogen production amount using the catalysts in Examples 1-5 and Comparative Examples 1-2 of the present invention. The catalysts were calcined at 300°C before use.

[0145] Referring to Figures 5a, 5b and Table 5, the reaction temperatures of the catalysts with x values ​​of 0.3 and 0.1 in Examples 2-2 and 2-3 were excellent, at approximately 500°C or higher and approximately 460°C, respectively. In contrast, the zirconium-containing catalysts with x values ​​of 0.5 and 0.05 in Examples 2-1 and 2-4 showed poor results, with reaction temperatures below approximately 400°C. Furthermore, the ammonia conversion rates of the catalysts with x values ​​of 0.3 and 0.1 in Examples 2-2 and 2-3 were excellent, at 52.7% and 63%, respectively. In contrast, it was confirmed that the zirconium-containing catalysts with x values ​​of 0.5 and 0.05 in Examples 2-1 and 2-4 did not undergo the ammonia decomposition reaction. In Table 5 below, reaction X means that the ammonia decomposition reaction did not occur.

[0146] [Table 5]

[0147] In Table 5 above, for Examples 1-5, 3-1, 3-2, 4-3, 4-4, and Comparative Example 1-1, where the reaction temperature is not listed, the catalysts were not activated, and therefore the reaction temperature could not be measured.

[0148] Test Example 6: Analysis of detailed gas concentrations based on lanthanum (La) composition ratio Figure 7a shows the Ru / Ce method according to Example 1-2. 0.5La 0.5 O 2-δ Figure 7b shows the ammonia conversion rate and chemical formula coefficient data obtained by analyzing the detailed gas concentration of the catalyst. 0.7 La 0.3 O 2-δ This graph shows the ammonia conversion rate and chemical formula coefficient data obtained by analyzing the detailed gas concentrations of the catalyst. Table 1 shows the data calculated for the change in gas coefficient due to the partial oxidation reaction of ammonia, and Table 2 shows the calculation formulas for gas production and conversion indices in the partial oxidation reaction of ammonia. Using the above formula 1, the coefficient values ​​(a, b, c, d) corresponding to each gas were obtained and applied to the above formula 2, allowing for the analysis of detailed gas concentrations and the graphs in Figures 7a and 7b showing the catalyst evaluation results.

[0149] Referring to Figures 7a and 7b, Ru / Ce according to Example 1-2 0.5 La 0.5 O 2-δ The catalyst exhibited the best ammonia conversion rate at 95%, and it was confirmed that the reaction could be maintained for 2 hours, the longest retention time for a single reaction.

[0150] Test Example 7: Comparison of exothermic temperatures using the protocol (AOR:NH3 / O2 ratio) Figure 8 shows the Ru(3wt%) / Ce ratio for Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δThis graph shows the catalyst evaluation protocol (AOR:NH3 / O2 ratio), with each reaction performed for 2 hours and 30 minutes under different conditions. The AOR in Figure 8 is divided into sections (a) to (e). Specifically, section (a) has an AOR of 4 to 5 with NH3 flow rates of 200 to 300 ml / min, O2 flow rates of 40 to 75 ml / min, and N2 flow rates of 60 to 300 ml / min; section (b) has an AOR of 5 to 6 with NH3 flow rates of 200 to 300 ml / min, O2 flow rates of 32 to 60 ml / min, and N2 flow rates of 28 to 240 ml / min; and section (c) has an AOR of 300 to 400 ml / min. (d) is an AOR of 5-6 at flow rates of NH3 200-300 ml / min, O2 28-50 ml / min, and N2 112-200 ml / min, and (e) is an AOR of 6-7 at flow rates of NH3 300-400 ml / min, O2 42-67 ml / min, and N2 168-268 ml / min. Figure 9 shows Ru(3wt%) / Ce from Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This graph shows the temperature data for each section of the catalyst.

[0151] Referring to Figures 8 and 9, it can be seen that the exothermic temperature decreases as the oxygen ratio in the protocol decreases, and the exothermic temperature increases as the amount of gas injected into the protocol increases.

[0152] Test Example 8: Protocol (AOR:NH3 / O2 ratio) and Ru(3wt%) / Ce based on lanthanum (La) composition ratio 1-x La x O 2-δ Comparison of ammonia conversion rate and hydrogen production of catalysts The following test examples 8-1 to 8-5 were conducted through stages (1') to (3') below.

[0153] First, 0.2 g of catalyst was injected into the reaction system (step 1').

[0154] Next, ammonia, oxygen, and nitrogen were injected into the reaction system in that order to replace the conventional pure oxygen, with the molar ratio of oxygen to nitrogen being 1:4 (step 2').

[0155] Finally, the flow rates of NH3 and O2 were adjusted so that the ratio of NH3 to O2 was 5 or 6, and the results were evaluated (stage 3').

[0156] Test example 8-1: 4≦AOR<5, 200≦NH3<300(ml / min), 40≦O2<75(ml / min), 160≦N2<300(ml / min) Figure 9 shows the Ru(3wt%) / Ce ratios for Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This graph shows the temperature data for each section of the catalyst. Figure 10a shows the Ru(3wt%) / Ce 1-x La x O 2-δ Figure 10b is a graph showing the ammonia conversion rate data over time when the catalyst AOR (NH3 / O2 ratio) is 4-5. 1-x La x O 2-δ This graph shows the ammonia conversion rate data based on lanthanum (La) content when the catalyst's AOR (NH3 / O2 ratio) is 4-5. The ammonia conversion rate and hydrogen production were measured over a 150-minute period.

[0157] Referring to parts 9(a) and 10a, it can be seen that the catalysts using cerium oxide-based supports in Comparative Example 2-1 and Example 5-4 exhibit degradation after exposure to high temperatures and very low ammonia conversion rates. In contrast, the catalysts in Examples 5-1, 5-2, 5-3 and Comparative Example 2-1, which contain lanthanum metal, showed increased stability at high temperatures as the lanthanum content increased, and it was confirmed that the catalyst in Example 5-2 had the highest ammonia conversion rate.

[0158] Furthermore, referring to Figure 10b, it can be seen that it shows the same trend as the results in Figure 10a.

[0159] Test example 8-2: 5≦AOR<6, 200≦NH3<300(ml / min), 32≦O2<60(ml / min), 128≦N2<240(ml / min) Figure 9 shows the Ru(3wt%) / Ce ratios for Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This graph shows the temperature data for each section of the catalyst. Figure 11a shows the Ru(3wt%) / Ce 1-x La x O 2-δ Figure 11b shows the ammonia conversion rate data over time when the catalyst's AOR (NH3 / O2 ratio) is 5-6. 1-x La x O 2-δ This graph shows the ammonia conversion rate data based on lanthanum (La) content when the catalyst's AOR (NH3 / O2 ratio) is 5-6. The ammonia conversion rate and hydrogen production were measured over 150 minutes.

[0160] Referring to parts 9(a) and 11a, it can be seen that the overall reaction temperature was lower compared to the above test example 8-1 due to the decrease in the injected oxygen fraction. Nevertheless, it can be seen that the catalyst containing a large amount of lanthanum was able to stably maintain a high temperature of over 500°C.

[0161] Next, referring to Figure 11b, we can see that it shows a trend similar to the ammonia conversion rate results in Figure 11a. Furthermore, it can be confirmed that hydrogen production increased due to the reduction in oxygen injection.

[0162] Test example 8-3: 5≦AOR<6, 300≦NH3<400 (ml / min), 50≦O2<80 (ml / min), 200≦N2<320 (ml / min) Figure 12a shows Ru(3wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ Figure 12b is a graph showing the ammonia conversion rate data over time when the catalyst's AOR (NH3 / O2 ratio) is 5-6. 1-x La x O 2-δ This graph shows the ammonia conversion rate data based on lanthanum (La) content when the catalyst's AOR (NH3 / O2 ratio) is 5-6. The ammonia conversion rate and hydrogen production were measured over 150 minutes.

[0163] Referring to Figure 12a, it can be seen that as the total amount of injected material and reactants increases compared to the above-mentioned Test Example 8-2, the reaction temperature in this experimental section rises. This temperature increase effect confirms that the additional ammonia decomposition rate increases.

[0164] Furthermore, referring to Figure 12b, it can be seen that hydrogen production increases as the overall gas injection rate increases, which is the same result trend as with the ammonia conversion rate.

[0165] Test example 8-4: 6≦AOR<7, 200≦NH3<300(ml / min), 28≦O2<50(ml / min), 112≦N2<2000(ml / min) Figure 13a shows Ru(3wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ Figure 13b shows the ammonia conversion rate data over time when the catalyst's AOR (NH3 / O2 ratio) is 6-7. 1-x La x O 2-δThis graph shows ammonia conversion rate data based on lanthanum (La) content when the catalyst's AOR (NH3 / O2 ratio) is 6-7. The ammonia conversion rate and hydrogen production were measured over 150 minutes.

[0166] Referring to Figure 13a, it can be seen that the overall reaction temperature decreased as the fraction of injected oxygen decreased. Furthermore, it can be seen that the ammonia decomposition rate decreased as the reaction temperature decreased.

[0167] Furthermore, referring to Figure 13b, it can be seen that the hydrogen production is also lower compared to the above-mentioned test example 8-3 due to the decrease in the ammonia conversion rate.

[0168] Test example 8-5: 6≦AOR<7, 300≦NH3<400 (ml / min), 42≦O2<67 (ml / min), 168≦N2<268 (ml / min) Figure 14a shows Ru(3wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ Figure 14b shows the ammonia conversion rate data over time when the catalyst AOR (NH3 / O2 ratio) is 6-7. 1-x La x O 2-δ This graph shows ammonia conversion rate data based on lanthanum (La) content when the catalyst's AOR (NH3 / O2 ratio) is 6-7. The ammonia conversion rate and hydrogen production were measured over 150 minutes.

[0169] Referring to Figure 14a, it can be seen that as the total amount of injected material and reactants increases compared to the above-mentioned Test Example 8-4, the reaction temperature in this experimental section rises. It can be confirmed that this temperature increase leads to an additional increase in the ammonia decomposition rate.

[0170] Furthermore, referring to Figure 14b, it can be seen that hydrogen production increases as the overall gas injection rate increases, which is the same result trend as with the ammonia conversion rate.

[0171] Test Example 9: Catalyst component analysis based on lanthanum (La) composition ratio Table 6 below shows the specific surface area data of the catalysts based on the ruthenium (Ru), cesium (Ce), and lanthanum (La) content and lanthanum (La) composition ratio according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 of the present invention. In Table 6 below, the ruthenium (C), cesium (Ce), and lanthanum (La) content was analyzed using ICP-OES (Inductively coupled plasma-optical emission spectrometry), and the specific surface area was analyzed using a specific surface area analyzer (BET, Brunauer Emmett Teller).

[0172] Referring to Table 6 below, it can be seen that when we examined Example 5-1 and Comparative Example 2-1, in which an excess amount of lanthanum was added, the specific surface area of ​​the catalyst decreased significantly.

[0173] [Table 6]

[0174] While preferred embodiments of the present invention have been described above, a person with ordinary skill in the art can modify and change the present invention in various ways by adding, changing, deleting, or adding components, without departing from the spirit of the invention as described in the claims, and this is also included within the scope of the rights of the present invention. For example, each component described as a single type can be implemented in a distributed manner, and similarly, components described as distributed can be implemented in a combined form. The scope of the present invention is indicated more by the claims described below than by the detailed description above, and all modified or transformed forms derived from the meaning and scope of the claims and the concept of equivalents should be interpreted as being included within the scope of the present invention.

Claims

1. A support containing a compound represented by the following chemical formula 1; and Ruthenium (Ru) supported on the aforementioned carrier; Includes catalyst: [Chemical formula 1] Yes １－ｘ M ｘ O ２－δ In the aforementioned chemical formula 1, x is 0 < x < 1, M is a lanthanide metal or transition metal. δ is 0 < δ ≤ 0.

5.

2. The catalyst according to claim 1, characterized in that the lanthanide metal comprises one or more selected from the group consisting of lanthanum (La), samarium (Sm), ytterbium (Yb), gadolinium (Gd), and lutetium (Lu).

3. The catalyst according to claim 1, characterized in that the lanthanide metal contains lanthanum (La).

4. The lanthanide metal includes lanthanum (La), The catalyst according to claim 1, characterized in that x is 0.05 ≤ x ≤ 0.

8.

5. The catalyst according to claim 1, characterized in that the transition metal comprises one or more selected from the group consisting of zirconium (Zr), yttrium (Y), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), and osmium (Os).

6. The catalyst according to claim 1, characterized in that the transition metal includes zirconium (Zr).

7. The transition metal includes zirconium (Zr), The catalyst according to claim 1, characterized in that x is 0.05 ≤ x ≤ 0.

5.

8. The catalyst according to claim 1, characterized in that the catalyst contains 1 to 5% by weight of the ruthenium.

9. The catalyst according to claim 8, characterized in that the catalyst contains 1.5 to 3.5% by weight of the ruthenium.

10. The catalyst according to claim 1, characterized in that the catalyst is for decomposing ammonia and extracting hydrogen.

11. (a) A step of preparing a precursor solution containing one or more metal precursors selected from the group consisting of lanthanide metal precursors and transition metal precursors, a cerium precursor, and water; (b) A step of coprecipitation of the precursor in the precursor solution to synthesize a coprecipitate containing one or more selected from the group consisting of lanthanide metals and transition metals and cerium; (c) The step of heat-treating the coprecipitate to produce a carrier; and (d) A step of producing a catalyst containing a carrier on which ruthenium is supported by stirring the carrier solution containing the carrier, a ruthenium precursor and water; A method for manufacturing a catalyst, including

12. A method for producing the catalyst according to claim 11, characterized in that the catalyst comprises a carrier containing a compound represented by the following chemical formula 1, and ruthenium (Ru) supported on the carrier: [Chemical formula 1] Yes １－ｘ M ｘ O ２－δ In the aforementioned chemical formula 1, x is 0 < x < 1, M is a lanthanide metal or transition metal. δ is 0 < δ ≤ 0.

5.

13. A hydrogen extraction method comprising step (1) of partially oxidizing ammonia in the presence of the catalyst and oxygen described in claim 11 to extract hydrogen.

14. The hydrogen extraction method according to claim 13, characterized in that the partial oxidation reaction includes a decomposition reaction of ammonia and an oxidation reaction of ammonia.

15. The hydrogen extraction method according to claim 14, characterized in that the partial oxidation reaction is carried out by the reaction shown in the following reaction formula 1: [Reaction Equation 1] NH ３ (g)+xO ２ (g)→0.5N ２ (g)+2xH ２ O(g)+(1.5-2x)H ２ (g) H=46-484x kJ mol －１ In the above reaction equation 1, x is 0 < x < 0.

75.

16. The hydrogen extraction method according to claim 15, characterized in that the reaction of reaction formula 1 is carried out using the reaction heat from one or more exothermic reactions selected from the group consisting of reaction formulas 2 and 3 below, and a portion of an external heat source: [Reaction Equation 2] NH ３ (g)→0.5N ２ (g)+1.5H ２ (g) ΔH=45.9 kJ mol －１ [Reaction Equation 3] NH ３ (g)+0.75O ２ (g)→0.5N ２ (g)+1.5H ２ O(g) ΔH=-317 kJ mol －１

17. The hydrogen extraction method according to claim 13, characterized in that step (1) is carried out without the supply of heat from an external source, or using a part of an external heat source.

18. In stage (1), Gas hour space velocity (GHSV, L / g) of ammonia and oxygen ｃａｔ The hydrogen extraction method according to claim 13, characterized in that the ratio of -h)) is 2:1 to 6:

1.

19. The hydrogen extraction method according to claim 13, characterized in that the above step (1) is performed at 450 to 700°C.

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