Ammonia partial oxidation-based hydrogen extraction catalyst and hydrogen extraction method

Abstract

Disclosed are an ammonia partial oxidation-based hydrogen extraction catalyst, a manufacturing method therefor, and a hydrogen extraction method using the catalyst. The ammonia partial oxidation-based hydrogen extraction catalyst comprises: a support; and ruthenium (Ru) loaded on the support. The hydrogen extraction method using the catalyst allows the temperature inside a reactor to be maintained at a high temperature without an external heat source and has a long reaction time, thereby solving the existing problem of thermal efficiency reduction and enabling a high ammonia conversion rate to be obtained.

Description

Ammonia partial oxidation-based hydrogen extraction catalyst and hydrogen extraction method

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

[0002] Due to the depletion and environmental pollution problems caused by the indiscriminate use of fossil fuels, various studies are being conducted on the production and utilization of new and renewable alternative energy sources that can replace fossil fuels, especially hydrogen. Among the various hydrogen production methods, the method of extracting hydrogen by decomposing ammonia is advantageous because of the high hydrogen storage capacity per weight of ammonia (approximately 17.6 wt% H2) and high energy density per volume (approximately 12.8 GJ / m). 3 , 120 Kg-H2 / m 3 ), ease of liquefaction (0.8 MPa, 20 ℃ or 0.1 MPa, -33 ℃), and no CO2 emission after decomposition as a hydrogen carrier. For reference, the ammonia decomposition reaction is as follows.

[0003] [Reaction Formula 1]

[0004] NH3(g) → 0.5N2(g) + 1.5H2(g) (H =+46 KJ / mol)

[0005] However, the above reaction is endothermic, and the activation energy is also approximately ΔH=+117 KJ / mol, so external heat supply is essential. Therefore, in order to create an internal temperature of 500℃ or higher in the reactor, the combustion heat of a carbon-based fuel such as natural gas is used, but in this process, there is a problem that the thermal efficiency of the entire system is reduced due to the use of a carbon-based fuel to maintain a temperature above 500℃.

[0006] Therefore, it appears 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 the internal temperature of the reactor at a high temperature, as well as a catalyst that makes this possible.

[0007] An object of the present invention is to provide a hydrogen extraction catalyst and system based on ammonia partial oxidation that does not require an external heat source.

[0008] Another object of the present invention is to provide a hydrogen extraction catalyst and system based on ammonia partial oxidation that has a long reaction time and maintains the internal temperature of the reactor at a high temperature to solve the problem of reduced thermal efficiency.

[0009] Another object of the present invention is to provide a method for producing the ammonia partial oxidation-based hydrogen extraction catalyst.

[0010] According to one aspect of the present invention, a catalyst is provided, comprising: a support comprising a compound represented by the following chemical formula 1; and ruthenium (Ru) supported on the support.

[0011] [Chemical Formula 1]

[0012] Ce 1-x M x O 2-δ

[0013] In the above chemical formula 1, x is 0 <x<1이고, M은 란타나이드 금속(lanthanide metal) 또는 전이 금속이고, δ는 0<δ≤0.5 일 수 있다.

[0014] Additionally, the lanthanide metal may include at least one selected from the group consisting of lanthanum (La), samarium (Sm), ytterbium (Yb), gadolinium (Gd), and lutetium (Lu).

[0015] Additionally, the lanthanide metal may include lanthanum (La).

[0016] In addition, the lanthanide metal may include lanthanum (La), and x may be 0.05≤x≤0.8, preferably 0.1≤x≤0.7, and more preferably 0.3≤x≤0.6.

[0017] Additionally, the transition metal may include at least one selected from the group consisting of zirconium (Zr), yttrium (Y), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), and osmium (Os).

[0018] Additionally, the transition metal may include zirconium (Zr).

[0019] In addition, the transition metal may include zirconium (Zr), and x may be 0.05≤x≤0.5, preferably 0.1≤x≤0.4.

[0020] In addition, the catalyst may contain 1 to 3 wt% of the ruthenium, preferably 1.3 to 2.0 wt%. Here, if the ruthenium is less than 1 wt%, hydrogen extraction based on ammonia partial oxidation may not occur, which is undesirable, and if it exceeds 3 wt%, ammonia decomposition efficiency decreases, which is undesirable.

[0021] Additionally, the catalyst may be for decomposing ammonia to extract hydrogen.

[0022] According to another aspect of the present invention, a method for producing a catalyst is provided, comprising: (a) preparing a precursor solution comprising at least one selected from the group consisting of a lanthanide metal precursor and a transition metal precursor, a cerium precursor, and water; (b) coprecipitating the precursor of the precursor solution to synthesize a coprecipitate comprising at least one selected from the group consisting of a lanthanide metal and a transition metal and cerium; (c) heat-treating the coprecipitate to produce a support; and (d) stirring the support solution comprising the support, the ruthenium precursor, and water to produce a catalyst comprising a support on which ruthenium is supported.

[0023] Additionally, the catalyst may include a support comprising a compound represented by the chemical formula 1 below and ruthenium (Ru) supported on the support.

[0024] [Chemical Formula 1]

[0025] Ce 1-x M x O 2-δ

[0026] In the above chemical formula 1, x is 0 <x<1이고, M은 란타나이드 금속(lanthanide metal) 또는 전이 금속이고, δ는 0<δ≤0.5 일 수 있다.

[0027] Additionally, the pH of the precursor solution of step (a) may be 8 to 11, preferably 9 to 10.

[0028] Additionally, the lanthanide metal precursor may include lanthanum nitrate hexahydrate, the transition metal precursor may include zirconium nitrate hexahydrate, and the cerium precursor may include cerium nitrate hexahydrate.

[0029] Additionally, the heat treatment of step (c) can be performed in air.

[0030] Additionally, the heat treatment of step (c) can be performed at 400 to 600°C, preferably 450 to 550°C.

[0031] According to another aspect of the present invention, a hydrogen extraction method is provided, including a step (1) of extracting hydrogen by subjecting ammonia to a partial oxidation reaction in the presence of the catalyst and oxygen.

[0032] Additionally, the partial oxidation reaction may include a decomposition reaction of ammonia and an oxidation reaction of ammonia.

[0033] Additionally, the partial oxidation reaction can be performed by the reaction of the following reaction scheme 1.

[0034] [Reaction Scheme 1: Ammonia Partial Oxidation Reaction (Conversion from Endothermic to Exothermic Reaction through Small Amount of Oxygen Injection)]

[0035] NH3(g) + xO2(g) -> 0.5N2(g)+ 2xH2O(g) + (1.5-2x)H2(g) H = 46-484x kJ mol -1

[0036] In the above reaction formula 1, x is 0 <x<0.75이고, 바람직하게는 0.15<x<0.65 일 수 있다.

[0037] The reaction of the above reaction scheme 1 may be carried out by using the heat of reaction from one or more exothermic reactions selected from the group consisting of the following reaction schemes 2 and 3 and some external heat source.

[0038] [Reaction Scheme 2: Ammonia thermal decomposition reaction (endothermic)]

[0039] NH3(g) -> 0.5N2(g) + 1.5H2(g) △H = 45.9 kJ mol -1

[0040] [Reaction Scheme 3: Complete combustion of ammonia (a reaction in which ammonia is completely burned without producing hydrogen, forming only nitrogen and water vapor)]

[0041] NH3(g) + 0.75O2(g) -> 0.5N2(g) + 1.5H2O(g) △H = -317 kJ mol -1

[0042] In addition, the endothermic reaction of the above reaction formula 2 can proceed with the endothermic reaction using the heat of reaction from one or more exothermic reactions selected from the group consisting of reaction formula 3.

[0043] Additionally, the above step (1) may be performed without external heat supply or using some external heat source.

[0044] In addition, in the above step (1), the gas hour space velocity (GHSV, L / (g)) of ammonia and oxygen cat-h)) may be 2:1 to 6:1, preferably 3:1 to 5:1, more preferably 3.5:1 to 4.5:1. Here, in the step (1), the gas hour space velocity (GHSV, L / (g)) of ammonia and oxygen cat -h)) ratio is less than 6:1 (e.g., 6.5:1 or 7:1), it may be difficult to supply enough heat for the ammonia endothermic reaction to occur, and if it exceeds 2:1 (e.g., 2.5:1 or 1:1), the excessive injection of oxygen causes the reaction to approach complete combustion, and as the combustion reaction approaches, the amount of hydrogen produced decreases, which is not desirable.

[0045] Additionally, the above step (1) can be performed at 450 to 700°C, preferably 500 to 650°C.

[0046] An object of the present invention is to provide an ammonia partial oxidation-based hydrogen extraction system that does not require an external heat source.

[0047] Another object of the present invention is to provide a hydrogen extraction system based on partial oxidation of ammonia that has a long reaction time and maintains the internal temperature of the reactor at a high temperature to solve the problem of reduced thermal efficiency.

[0048] Another object of the present invention is to provide a catalyst for hydrogen extraction based on partial oxidation of ammonia with excellent performance for use in the above system and a method for producing the same.

[0049] These drawings are for reference in explaining exemplary embodiments of the present invention, and therefore, the technical idea of ​​the present invention should not be interpreted as being limited to the attached drawings.

[0050] FIG. 1 is a schematic diagram showing a method for producing a catalyst including a support comprising a lanthanide metal or a transition metal and ruthenium supported on the support according to an embodiment of the present invention.

[0051] Figure 2a is Ru / Ce according to Example 2-3 0.9 Zr 0.1 O 2-δ Ru / Ce according to catalyst and Example 4-1 0.9 Y 0.1 O 2-δ This is a graph showing the reaction temperature range when using a catalyst, and Figure 2b shows Ru / Ce according to Example 2-3. 0.9 Zr 0.1 O 2-δ Ru / Ce according to catalyst and Example 4-1 0.9 Y 0.1 O 2-δ This is a graph showing the ammonia conversion rate and hydrogen production using a catalyst.

[0052] Figure 3a is Ru / Ce according to Example 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 Ru / Ce according to catalyst and Example 3-2 0.9 Yb 0.1 O 2-δ This is a graph showing the reaction temperature range when using a catalyst, and Figure 3b shows Ru / Ce according to Example 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 Ru / Ce according to catalyst and Example 3-2 0.9 Yb 0.1 O 2-δ This is a graph showing the ammonia conversion rate and hydrogen production using a catalyst.

[0053] Figure 4a is 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 Ni0.1 O 2-δ Ru / Ce according to catalyst and example 4-5 0.9 Co 0.1 O 2-δ This is a graph showing the reaction temperature range when using a catalyst, and Figure 4b shows 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-δ Ru / Ce according to catalyst and example 4-5 0.9 Co 0.1 O 2-δ This is a graph showing the ammonia conversion rate and hydrogen production using a catalyst.

[0054] Figure 5a is a Ru / Ce containing zirconium according to Examples 2-1 to 2-4. 1-x Zr x O 2-δ This is a graph showing the reaction temperature according to the x value using a catalyst, and Figure 5b is a graph showing the Ru / Ce containing zirconium according to Examples 2-1 to 2-4. 1-x Zr x O 2-δ This is a graph showing data on the ammonia conversion rate according to the x value using a catalyst.

[0055] 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 is a graph showing the reaction temperature according to the x value using a catalyst, and FIG. 6b is a graph showing 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 is a graph showing data on the ammonia conversion rate according to the x value using a catalyst.

[0056] Figure 7a is Ru / Ce according to Example 1-2 0.5 La 0.5 O 2-δ A graph showing ammonia conversion rate and chemical formula coefficient data by analyzing the detailed gas concentration of the catalyst, and Fig. 7b shows Ru / Ce according to Example 1-3. 0.7 La 0.3 O 2-δ This graph shows ammonia conversion rate and chemical formula coefficient data by analyzing the detailed gas concentration of the catalyst.

[0057] Figure 8 shows Ru(3 wt%) / Ce according to 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 evaluation protocol of the catalyst (AOR: NH3 / O2ratio, varied from 4 to 6), and the reaction was carried out for 2 hours and 30 minutes for each condition.

[0058] Figure 9 shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing the temperature data for each section of the catalyst.

[0059] Figure 10a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 4 to 5, and FIG. 10b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 4 to 5.

[0060] Figure 11a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6, and FIG. 11b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6.

[0061] Figure 12a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6, and FIG. 12b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6.

[0062] Figure 13a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7, and FIG. 13b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δThis is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7.

[0063] Figure 14a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7, and FIG. 14b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7.

[0064] The 2 wt% described in the above FIGS. 2a to 6b means that an amount of ruthenium precursor corresponding to a ruthenium (Ru) content that is stoichiometrically 2 wt% of the catalyst was used in the catalyst synthesis, and the 3 wt% described in the above FIGS. 8 to 14b means that an amount of ruthenium precursor corresponding to a ruthenium (Ru) content that is stoichiometrically 3 wt% of the catalyst was used in the catalyst synthesis.

[0065] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

[0066] However, the following description is not intended to limit the present invention to a specific embodiment, and when explaining the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description is omitted.

[0067] The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, it should be understood that the terms "comprises" or "has" indicate the presence of a feature, number, step, operation, component, or combination thereof described in the specification, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, or combinations thereof.

[0068] Additionally, terms including ordinal numbers, such as "first," "second," etc., which will be used hereinafter, may be used to describe various components, but these components are not limited by these terms. These terms are used solely to distinguish one component from another. For example, without departing from the scope of the present invention, a first component could be referred to as a second component, and similarly, a second component could also be referred to as a first component.

[0069] Additionally, when it is said that a component is "formed on" or "laminated on" another component, it should be understood that it may be formed or laminated directly on the entire surface or one side of the other component, but there may also be other components present in between.

[0070] Hereinafter, the present invention will be described in detail regarding an ammonia partial oxidation-based hydrogen extraction catalyst, a method for preparing the catalyst, and a hydrogen extraction method using the catalyst. However, these examples are provided by way of example only and are not intended to limit the present invention, which is defined solely by the scope of the claims set forth below.

[0071] According to one aspect of the present invention, a catalyst is provided, comprising: a support comprising a compound represented by the following chemical formula 1; and ruthenium (Ru) supported on the support.

[0072] [Chemical Formula 1]

[0073] Ce 1-x M x O 2-δ

[0074] In the above chemical formula 1, x is 0 <x<1이고, M은 란타나이드 금속(lanthanide metal) 또는 전이 금속이고, δ는 0<δ≤0.5 일 수 있다.

[0075] Additionally, the lanthanide metal may include at least one selected from the group consisting of lanthanum (La), samarium (Sm), ytterbium (Yb), gadolinium (Gd), and lutetium (Lu).

[0076] Additionally, the lanthanide metal may include lanthanum (La).

[0077] In addition, the lanthanide metal may include lanthanum (La), and x may be 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, and if it exceeds 0.8, the specific surface area of ​​the support decreases rapidly, which is not preferable.

[0078] Additionally, the transition metal may include at least one selected from the group consisting of zirconium (Zr), yttrium (Y), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), and osmium (Os).

[0079] Additionally, the transition metal may include zirconium (Zr).

[0080] In addition, the above transition metal may include zirconium (Zr), and x may be 0.05≤x≤0.5, preferably 0.1≤x≤0.4. Here, if the range of x is less than 0.05, an exothermic reaction does not occur, which is undesirable, and if it exceeds 0.5, ammonia decomposition does not occur, which is undesirable.

[0081] In addition, the catalyst may contain 1 to 3 wt% of the ruthenium, preferably 1.3 to 2.0 wt%. Here, if the ruthenium is less than 1 wt%, hydrogen extraction based on ammonia partial oxidation may not occur, which is undesirable, and if it exceeds 3 wt%, ammonia decomposition efficiency decreases, which is undesirable.

[0082] Additionally, the catalyst may be for decomposing ammonia to extract hydrogen.

[0083] According to another aspect of the present invention, a method for producing a catalyst is provided, comprising: (a) preparing a precursor solution comprising at least one selected from the group consisting of a lanthanide metal precursor and a transition metal precursor, a cerium precursor, and water; (b) coprecipitating the precursor of the precursor solution to synthesize a coprecipitate comprising at least one selected from the group consisting of a lanthanide metal and a transition metal and cerium; (c) heat-treating the coprecipitate to produce a support; and (d) stirring the support solution comprising the support, the ruthenium precursor, and water to produce a catalyst comprising a support on which ruthenium is supported.

[0084] Additionally, the catalyst may include a support comprising a compound represented by the chemical formula 1 below and ruthenium (Ru) supported on the support.

[0085] [Chemical Formula 1]

[0086] Ce 1-x M x O 2-δ

[0087] In the above chemical formula 1, x is 0 <x<1이고, M은 란타나이드 금속(lanthanide metal) 또는 전이 금속이고, δ는 0<δ≤0.5 일 수 있다.

[0088] First, a precursor solution containing at least one selected from the group consisting of lanthanide metal precursors and transition metal precursors, a cerium precursor, and water is prepared (step a).

[0089] The pH of the precursor solution of the above step (a) may be 8 to 11, preferably 9 to 10. Here, if the pH of the precursor solution is 8 or higher, Ce in the precursor in the basic solution 3+ , M 3+ It is easy to separate, and the metal cations easily form a precipitate in an aqueous solution, which is desirable. However, when the pH exceeds 11, the solubility of the metal precursor decreases, making it difficult to form a precipitate, which is undesirable.

[0090] Additionally, the lanthanide metal precursor may include lanthanum nitrate hexahydrate, the transition metal precursor may include zirconium nitrate hexahydrate, and the cerium precursor may include cerium nitrate hexahydrate.

[0091] The precursor of the above precursor solution is coprecipitated to synthesize a coprecipitate containing at least one selected from the group consisting of lanthanide metals and transition metals and cerium (step b).

[0092] The above-mentioned precipitate is heat-treated to produce a support (step c).

[0093] The heat treatment of the above step (c) can be performed in air.

[0094] In addition, the heat treatment of step (c) may be performed at 400 to 600°C, preferably 450 to 550°C. Here, in the case of high-temperature air heat treatment, it is preferable because it removes impurities or adsorbates on the surface of the support and improves the crystallinity of the support. At this time, if the heat treatment temperature is performed below 400°C, there is a high possibility that the above-mentioned desirable expected effect will not appear, which is not preferable. If it is performed above 600°C, a phase with low density or specific surface area may appear during the support crystallization process at high temperatures, which is not preferable.

[0095] Finally, a catalyst including a ruthenium-supported support is prepared by stirring a support solution containing the support, a ruthenium precursor, and water (step d).

[0096] According to another aspect of the present invention, a hydrogen extraction method is provided, including a step (1) of extracting hydrogen by subjecting ammonia to a partial oxidation reaction in the presence of the catalyst and oxygen.

[0097] Additionally, the partial oxidation reaction may include a decomposition reaction of ammonia and an oxidation reaction of ammonia.

[0098] Additionally, the above partial oxidation reaction can be performed by the reaction of the reaction scheme 1 below.

[0099] [Reaction Scheme 1: Ammonia Partial Oxidation Reaction (Conversion from Endothermic to Exothermic Reaction through Small Amount of Oxygen Injection)]

[0100] NH3(g) + xO2(g) -> 0.5N2(g)+ 2xH2O(g) + (1.5-2x)H2(g) H = 46-484x kJ mol -1

[0101] In the above reaction formula 1, x is 0 <x<0.75이고, 바람직하게는 0.15<x<0.65이다.

[0102] The reaction of the above reaction scheme 1 may be carried out by using the heat of reaction from one or more exothermic reactions selected from the group consisting of the following reaction schemes 2 and 3 and some external heat source.

[0103] [Reaction Scheme 2: Ammonia thermal decomposition reaction (endothermic)]

[0104] NH3(g) -> 0.5N2(g) + 1.5H2(g) △H = 45.9 kJ mol -1

[0105] [Reaction Scheme 3: Complete combustion of ammonia (a reaction in which ammonia is completely burned without producing hydrogen, forming only nitrogen and water vapor)]

[0106] NH3(g) + 0.75O2(g) -> 0.5N2(g) + 1.5H2O(g) △H = -317 kJ mol -1

[0107] In addition, the endothermic reaction of the above reaction formula 2 can proceed with the endothermic reaction using the heat of reaction from one or more exothermic reactions selected from the group consisting of reaction formula 3.

[0108] Hydrogen is extracted by partially oxidizing ammonia in the presence of the above catalyst and oxygen (step 1).

[0109] Additionally, the above step (1) may be performed without external heat supply or using some external heat source.

[0110] In addition, in the above step (1), the gas space velocity (GHSV, L / (g)) of ammonia and oxygen cat -h)) may be 2:1 to 6:1, preferably 3:1 to 5:1, more preferably 3.5:1 to 4.5:1. Here, in the step (1), the gas space velocity (GHSV, L / (g) of ammonia and oxygen cat-h)) ratio is less than 6:1 (e.g., 6.5:1 or 7:1), it may be difficult to supply enough heat for the ammonia endothermic reaction to occur, and if it exceeds 2:1 (e.g., 2.5:1 or 1:1), the excessive injection of oxygen causes the reaction to approach complete combustion, and as the combustion reaction approaches, the amount of hydrogen produced decreases, which is not desirable.

[0111] In addition, the above step (1) can be performed at 450 to 700°C, preferably 500 to 650°C. Here, the above step (1) corresponds to ammonia thermal decomposition. In the case of the ammonia thermal decomposition reaction, if it is performed below 450°C, the ammonia conversion rate is low, which is not preferable, and if it is performed above 700°C, a large amount of combustion heat is required to maintain the ultra-high temperature, which is not preferable because it affects the overall decrease in thermal efficiency.

[0112] [Example]

[0113] Hereinafter, the present invention will be described in more detail with examples. However, these examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention.

[0114] Manufacturing Example 1: Ce according to lanthanum composition ratio 1-x La x O 2-δ Support synthesis

[0115] Manufacturing Example 1-1: Ce 0.3 La 0.7 O 2-δ Support

[0116] A support solution was prepared by stirring 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, in 200 ml of distilled water at 1000 to 1500 rpm for about 1 hour, and the pH of the support solution was adjusted to about 9 to 10 using ammonia water. Thereafter, the support solution was dried in an oven at a temperature of 100°C for about 12 hours, thereby preparing a support. The prepared support was separated from the distilled water using a centrifugation method and washed. The support separated from the distilled water is further dried in an oven at a temperature of 120°C for about 12 hours, and then, the support is subjected to a heat treatment reaction at a temperature of 500°C for 3 hours in an air atmosphere to obtain Ce 0.3 La 0.7 O 2-δ A support was manufactured. The subscript '2-δ' for oxygen (O) in the chemical formula of the support indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be a value within the range of approximately 0 to 0.05.

[0117] Manufacturing Example 1-2: Ce 0.5 La 0.5 O 2-δ Support

[0118] Instead of using 2.60532 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 6.06214 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor, 4.3422 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 4.3301 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor, Ce was prepared in the same manner as in Manufacturing Example 1-1. 0.5 La 0.5 O 2-δ A support was manufactured.

[0119] Manufacturing Example 1-3: Ce 0.7 La 0.3 O 2-δ Support

[0120] Except that instead of using 2.60532 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 6.06214 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor, 6.08 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 2.60 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor were used, the same method as in Manufacturing Example 1-1 was used. 0.7 La 0.3 O 2-δ A support was manufactured.

[0121] Manufacturing Example 1-4: Ce 0.9 La 0.1 O 2-δ Support

[0122] Except that instead of using 2.60532 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 6.06214 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor, 7.816 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 0.86602 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor, Ce was prepared in the same manner as in Manufacturing Example 1-1. 0.9 La 0.1 O 2-δ A support was manufactured.

[0123] Manufacturing Example 1-5: Ce 0.95 La 0.05 O 2-δ Support

[0124] The same method as Manufacturing Example 1-1 was used except that instead of using 2.60532 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 6.06214 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor, 8.25 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 0.43301 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) as a metal precursor, Ce was prepared. 0.95 La 0.05 O 2-δ A support was manufactured.

[0125] Comparative Manufacturing Example 1-1: La2O3 Support

[0126] A La2O3 support was prepared in the same manner as in Manufacturing 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 prepared.

[0127] Comparative Manufacturing Example 1-2: CeO2 Support

[0128] A CeO2 support was prepared in the same manner as in Manufacturing 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, a CeO2 support was prepared.

[0129] Manufacturing Example 2: Ce according to zirconium composition ratio 1-x Zr x O 2-δ Support synthesis

[0130] Manufacturing Example 2-1: Ce 0.5 Zr 0.5 O 2-δ Support

[0131] A support solution was prepared by stirring 4.3422 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 3.8301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, in 200 ml of distilled water at 1000 to 1500 rpm for about 1 hour, and the pH of the support solution was adjusted to about 9 to 10. Thereafter, the support solution was dried in an oven at a temperature of 100°C for about 12 hours, thereby preparing a support. The manufactured support is washed using a centrifugation method, further dried in an oven at a temperature of 120°C for about 12 hours, and then heat treated in an air atmosphere at a temperature of 500°C for 3 hours to obtain Ce 0.5 Zr 0.5 O 2-δ A support was manufactured. The subscript '2-δ' for oxygen (O) in the chemical formula of the support indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be a value within the range of approximately 0 to 0.05.

[0132] Manufacturing Example 2-2: Ce 0.7 Zr 0.3 O 2-δ Support

[0133] Except that instead of using 4.3422 g of cerium (Ce) precursor, cerium nitrate hexahydrate (Ce(NO3)3·6H2O) and 3.8301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, 6.08 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) and 2.30 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, Ce was prepared in the same manner as in Manufacturing Example 2-1. 0.7 Zr 0.3 O 2-δ A support was manufactured.

[0134] Manufacturing Example 2-3: Ce 0.9 Zr 0.1 O 2-δ Support

[0135] The same method as Manufacturing Example 2-1 was used except that instead of using 4.3422 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 3.8301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O) as a metal precursor, 7.816 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) as a cerium (Ce) precursor and 0.76602 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O) as a metal precursor, Ce was used. 0.9 Zr 0.1 O 2-δ A support was manufactured.

[0136] Manufacturing Example 2-4: Ce 0.95 Zr 0.05 O 2-δ Support

[0137] Except that instead of using 4.3422 g of cerium (Ce) precursor, cerium nitrate hexahydrate (Ce(NO3)3·6H2O) and 3.8301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, 8.25 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) and 0.38301 g of zirconium nitrate hexahydrate (Zr(NO3)3·6H2O), a metal precursor, Ce was prepared in the same manner as in Manufacturing Example 2-1. 0.95 Zr 0.05 O 2-δ A support was manufactured.

[0138] Manufacturing Example 3: Ce according to lanthanide metal type (M) 1-x M x O 2-δ Support synthesis

[0139] Manufacturing Example 3-1: Ce 0.9 Sm 0.1 O 2-δ Support

[0140] A support solution was prepared by stirring 7.816 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), a cerium (Ce) precursor, and 0.88894 g of samarium nitrate hexahydrate (Sm(NO3)3·6H2O), a lanthanide metal precursor, in 200 ml of distilled water at 1000 to 1500 rpm for about 1 hour, and the pH of the support solution was adjusted to about 9 to 10. Thereafter, the support solution was dried in an oven at a temperature of 100°C for about 12 hours, thereby preparing a support. The manufactured support is washed using a centrifugation method, further dried in an oven at a temperature of 120°C for about 12 hours, and then heat treated in an air atmosphere at a temperature of 500°C for 3 hours to obtain Ce 0.9 Sm 0.1 O 2-δ A support was manufactured. The subscript '2-δ' for oxygen (O) in the chemical formula of the support indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be a value within the range of approximately 0 to 0.05.

[0141] Manufacturing Example 3-2: Ce 0.9 Yb 0.1 O 2-δ Support

[0142] Ce was prepared in the same manner as in Manufacturing 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), a lanthanide metal precursor. 0.9 Yb 0.1 O 2-δ A support was manufactured.

[0143] Manufacturing Example 4: Ce according to transition metal type (M) 1-x M x O 2-δ Support synthesis

[0144] Manufacturing Example 4-1: Ce 0.9 Y 0.1 O 2-δ Support

[0145] 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 to 1500 rpm for about 1 hour, and the pH of the support solution was adjusted to about 9 to 10. Thereafter, the support solution was dried in an oven at a temperature of 100°C for about 12 hours, thereby preparing a support. The manufactured support is washed using a centrifugation method, further dried in an oven at a temperature of 120°C for about 12 hours, and then heat treated in an air atmosphere at a temperature of 500°C for 3 hours to obtain Ce 0.9 Y 0.1 O 2-δ A support was manufactured. The subscript '2-δ' for oxygen (O) in the chemical formula of the support indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be a value within the range of approximately 0 to 0.05.

[0146] Manufacturing Example 4-2: Ce 0.9 Fe 0.1 O 2-δ Support

[0147] Ce was synthesized in the same manner as in Manufacturing Example 4-1, except that 0.808 g of iron (III) nitrate nonahydrate (Fe(NO3)3·9H2O) was used instead of 0.76602 g of yttrium (Ⅲ) nitrate hexahydrate (Y(NO3)3·6H2O), a transition metal precursor. 0.9 Fe 0.1 O 2-δ A support was manufactured.

[0148] Manufacturing Example 4-3: Ce 0.9 Cu 0.1 O 2-δ Support

[0149] Ce was synthesized in the same manner as in Manufacturing Example 4-1, except that 0.482 g of copper(II) nitrate trihydrate (Cu(NO3)3·3H2O) was 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 A support was manufactured.

[0150] Manufacturing Example 4-4: Ce 0.9 Ni 0.1 O 2-δ Support

[0151] Ce was prepared in the same manner as in Manufacturing Example 4-1, except that 0.582 g of nickel nitrate hexahydrate (Nickel(Ⅱ) Nitrate Hexahyrate; Ni(NO3)3·6H2O) was used instead of 0.76602 g of yttrium(Ⅲ) Nitrate Hexahydrate (Y(NO3)3·6H2O), a transition metal precursor. 0.9 Ni 0.1 O 2-δ A support was manufactured.

[0152] Manufacturing Example 4-5: Ce 0.9 Co0.1 O 2-δ Support

[0153] Ce was prepared in the same manner as in Manufacturing Example 4-1, except that 0.582 g of cobalt(Ⅱ) nitrate hexahydrate (Co(NO3)3·6H2O) was used instead of 0.76602 g of yttrium(Ⅲ) nitrate hexahydrate (Y(NO3)3·6H2O), a transition metal precursor. 0.9 Co 0.1 O 2-δ A support was manufactured.

[0154] Example 1: Preparation of a catalyst by supporting ruthenium (Ru) on a lanthanum support.

[0155] Example 1-1: Ru / Ce 0.3 La 0.7 O 2-δ

[0156] 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, and 2 ml (2 wt% Ru) of the ruthenium solution was 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 the support in 100 ml of distilled water at 400 rpm for about 24 hours, and the pH of the catalyst solution was adjusted to about 9 to 10. Afterwards, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed, and the catalyst was dried in an oven at a temperature of 120°C for 12 hours to remove the remaining distilled water, thereby obtaining Ru / Ce supported with ruthenium. 0.3 La 0.7 O 2-δA catalyst was prepared. The subscript "2-δ" for oxygen (O) in the chemical formula of the catalyst indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be within the range of approximately 0 to 0.05.

[0157] The 2 wt% described in the examples means that the amount of ruthenium precursor corresponding to the ruthenium (Ru) content that is stoichiometrically 2 wt% of the catalyst was used in the catalyst synthesis.

[0158] Example 1-2: Ru / Ce 0.5 La 0.5 O 2-δ

[0159] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ Instead of using a support, Ce according to Manufacturing Example 1-2 0.5 La 0.5 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 1-1 except that a support was used. 0.5 La 0.5 O 2-δ A catalyst was prepared.

[0160] Example 1-3: Ru / Ce 0.7 La 0.3 O 2-δ

[0161] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ Instead of using a support, Ce according to Manufacturing Example 1-3 0.7 La 0.3 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 1-1 except that a support was used. 0.7 La 0.3 O 2-δ A catalyst was prepared.

[0162] Example 1-4: Ru / Ce0.9 La 0.1 O 2-δ

[0163] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ Instead of using a support, Ce according to Manufacturing Example 1-4 0.9 La 0.1 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 1-1 except that a support was used. 0.9 La 0.1 O 2-δ A catalyst was prepared.

[0164] Example 1-5: Ru / Ce 0.95 La 0.05 O 2-δ

[0165] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ Instead of using a support, Ce according to Manufacturing Example 1-5 0.95 La 0.05 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 1-1 except that a support was used. 0.95 La 0.05 O 2-δ A catalyst was prepared.

[0166] Comparative Example 1-1: Ru / La2O3

[0167] Ce according to Manufacturing Example 1-1 0.5 La 0.5 O 2-δ A ruthenium-supported Ru / La2O3 catalyst was manufactured in the same manner as in Example 1-1, except that a La2O3 support according to Comparative Manufacturing Example 1-1 was used instead of the support.

[0168] Example 2: Preparation of a catalyst by supporting ruthenium (Ru) on a zirconium support.

[0169] Example 2-1: Ru / Ce 0.5 Zr 0.5 O 2-δ

[0170] 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, and 2 ml (2 wt% Ru) of the ruthenium solution was mixed with Ce according to the above Preparation Example 2-1. 0.5 Zr 0.5 O 2-δ A catalyst solution was prepared by stirring 1 g of the support in 100 ml of distilled water at 400 rpm for about 24 hours, and the pH of the catalyst solution was adjusted to about 9 to 10. Afterwards, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed, and the catalyst was dried in an oven at a temperature of 120°C for 12 hours to remove the remaining distilled water, thereby obtaining Ru / Ce supported with ruthenium. 0.5 Zr 0.5 O 2-δ A catalyst was prepared. The subscript '2-δ' for oxygen (O) in the chemical formula of the catalyst indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be within the range of approximately 0 to 0.05.

[0171] Example 2-2: Ru / Ce 0.7 Zr 0.3 O 2-δ

[0172] Ce, a metal precursor according to Manufacturing Example 2-1 0.5 Zr 0.5 O 2-δ Instead of using a support, Ce according to Manufacturing Example 2-2 0.7 Zr 0.3 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 2-1 except that a support was used. 0.7 Zr 0.3 O 2-δ A catalyst was prepared.

[0173] Example 2-3: Ru / Ce 0.9 Zr 0.1 O 2-δ

[0174] Ce, a metal precursor according to Manufacturing Example 2-1 0.5 Zr 0.5 O 2-δ Instead of using a support, Ce according to Manufacturing Example 2-3 0.9 Zr 0.1 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 2-1 except that a support was used. 0.9 Zr 0.1 O 2-δ A catalyst was prepared.

[0175] Example 2-4: Ru / Ce 0.95 Zr 0.05 O 2-δ

[0176] Ce, a metal precursor according to Manufacturing Example 2-1 0.5 Zr 0.5 O 2-δ Instead of using a support, Ce according to Manufacturing Example 2-3 0.95 Zr 0.05 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 2-1 except that a support was used. 0.95 Zr 0.05 O 2-δ A catalyst was prepared.

[0177] Example 3: Preparation of a catalyst by supporting ruthenium (Ru) on a support containing a lanthanide metal.

[0178] Example 3-1: Ru / Ce 0.9 Sm 0.1 O 2-δ

[0179] 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, and 2 ml (2 wt% Ru) of the ruthenium solution was mixed with Ce according to the above Preparation Example 3-1. 0.9Sm 0.1 O 2-δ A catalyst solution was prepared by stirring 1 g of the support in 100 ml of distilled water at 400 rpm for about 24 hours, and the pH of the catalyst solution was adjusted to about 9 to 10. Afterwards, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed, and the catalyst was dried in an oven at a temperature of 120°C for 12 hours, and the remaining distilled water was removed to obtain Ru / Ce supported with ruthenium. 0.9 Sm 0.1 O 2-δ A catalyst was prepared. The subscript '2-δ' for oxygen (O) in the chemical formula of the catalyst indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be within the range of approximately 0 to 0.05.

[0180] Example 3-2: Ru / Ce 0.9 Yb 0.1 O 2-δ

[0181] Ce, a metal precursor according to Manufacturing Example 3-1 0.9 Sm 0.1 O 2-δ Instead of using a support, Ce according to Manufacturing Example 3-2 0.9 Yb 0.1 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 3-1 except that a support was used. 0.9 Yb 0.1 O 2-δ A catalyst was prepared.

[0182] Example 4: Preparation of a catalyst by supporting ruthenium (Ru) on a support containing a transition metal.

[0183] Example 4-1: Ru / Ce 0.9 Y 0.1 O 2-δ

[0184] 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, and 2 ml (2 wt% Ru) of the ruthenium solution was mixed with Ce according to the above manufacturing example 4-1. 0.9 Y 0.1 O 2-δ A catalyst solution was prepared by stirring 1 g of the support in 100 ml of distilled water at 400 rpm for about 24 hours, and the pH of the catalyst solution was adjusted to about 9 to 10. Afterwards, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed, and the catalyst was dried in an oven at a temperature of 120°C for 12 hours to remove the remaining distilled water, thereby obtaining Ru / Ce supported with ruthenium. 0.9 Y 0.1 O 2-δ A catalyst was prepared. The subscript '2-δ' for oxygen (O) in the chemical formula of the catalyst indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be within the range of approximately 0 to 0.05.

[0185] Example 4-2: Ru / Ce 0.9 Fe 0.1 O 2-δ

[0186] Ce, a metal precursor according to Manufacturing Example 4-1 0.9 Y 0.1 O 2-δ Instead of the support, Ce according to Manufacturing Example 4-2 0.9 Fe 0.1 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 4-1 except that a support was used. 0.9 Fe 0.1 O 2-δ A catalyst was prepared.

[0187] Example 4-3: Ru / Ce 0.9 Cu0.1 O 2-δ

[0188] Ce, a metal precursor according to Manufacturing Example 4-1 0.9 Y 0.1 O 2-δ Instead of using a support, Ce according to Manufacturing Example 4-3 0.9 Cu 0.1 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 4-1 except that a support was used. 0.9 Cu 0.1 O 2-δ A catalyst was prepared.

[0189] Example 4-4: Ru / Ce 0.9 Ni 0.1 O 2-δ

[0190] Ce, a metal precursor according to Manufacturing Example 4-1 0.9 Y 0.1 O 2-δ Instead of using a support, Ce according to Manufacturing Example 4-4 0.9 Ni 0.1 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 4-1 except that a support was used. 0.9 Ni 0.1 O 2-δ A catalyst was prepared.

[0191] Example 4-5: Ru / Ce 0.9 Co 0.1 O 2-δ

[0192] Ce, a metal precursor according to Manufacturing Example 4-1 0.9 Y 0.1 O 2-δ Instead of using a support, Ce according to Manufacturing Example 4-5 0.9 Co 0.1 O 2-δ Ru / Ce supported on ruthenium in the same manner as in Example 4-1 except that a support was used. 0.9 Co 0.1 O 2-δ A catalyst was prepared.

[0193] Example 5: Preparation of a catalyst by supporting 3 wt% ruthenium on a lanthanum support.

[0194] Example 5-1: Ru(3 wt%) / Ce 0.3 La 0.7 O 2-δ

[0195] 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, and 3 ml (3 wt% Ru) of the ruthenium solution was 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 the support in 100 ml of distilled water at 400 rpm for about 24 hours, and the pH of the catalyst solution was adjusted to about 9 to 10. Afterwards, the distilled water and the catalyst supported with ruthenium metal were separated using a vacuum filter and washed, and the catalyst was dried in an oven at a temperature of 120°C for 12 hours to remove the remaining distilled water, thereby obtaining Ru / Ce supported with ruthenium. 0.3 La 0.7 O 2-δ A catalyst was prepared. The subscript "2-δ" for oxygen (O) in the chemical formula of the catalyst indicates that oxygen vacancies were formed by adding metal to the support. Since measuring or specifying the exact value of δ does not significantly affect the results of the experimental examples below, it is estimated to be within the range of approximately 0 to 0.05.

[0196] The 3 wt% described in the examples means that the amount of ruthenium precursor corresponding to the ruthenium (Ru) content that is stoichiometrically 3 wt% of the catalyst was used in the catalyst synthesis.

[0197] Example 5-2: Ru(3 wt%) / Ce 0.5 La 0.5 O 2-δ

[0198] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ Instead of using a support, Ce according to Manufacturing Example 1-2 0.5 La 0.5 O 2-δ Ruthenium-supported Ru(3 wt%) / Ce in the same manner as in Example 5-1 except that a support was used. 0.5 La 0.5 O 2-δ A catalyst was prepared.

[0199] Example 5-3: Ru(3 wt%) / Ce 0.7 La 0.3 O 2-δ

[0200] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ Instead of using a support, Ce according to Manufacturing Example 1-3 0.7 La 0.3 O 2-δ Ruthenium-supported Ru(3 wt%) / Ce in the same manner as in Example 5-1 except that a support was used. 0.7 La 0.3 O 2-δ A catalyst was prepared.

[0201] Example 5-4: Ru(3 wt%) / Ce 0.9 La 0.1 O 2-δ

[0202] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ Instead of using a support, Ce according to Manufacturing Example 1-4 0.9 La 0.1 O 2-δ Ruthenium-supported Ru(3 wt%) / Ce in the same manner as in Example 5-1 except that a support was used. 0.9 La 0.1 O 2-δ A catalyst was prepared.

[0203] Comparative Example 2-1: Ru(3 wt%) / La2O3

[0204] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ A ruthenium-supported Ru(3 wt%) / La2O3 catalyst was prepared in the same manner as in Example 5-1, except that the La2O3 support according to Comparative Manufacturing Example 1-1 was used instead of the support.

[0205] Comparative Example 2-2: Ru(3 wt%) / CeO2

[0206] Ce according to Manufacturing Example 1-1 0.3 La 0.7 O 2-δ A Ru(3 wt%) / CeO2 catalyst loaded with ruthenium was manufactured in the same manner as in Example 5-1, except that a CeO2 support according to Comparative Manufacturing Example 1-2 was used instead of the support.

[0207] [Example Exam]

[0208] Partial oxidation reaction gas concentration evaluation

[0209] Catalyst Ru / Ce according to Examples 1-1 to 1-5 and Comparative Example 1-1 1-x La x O 2-δ (x=0.05, 0.1, 0.3, 0.5, 0.7, 1.0) was used to evaluate the partial oxidation reaction gas concentration. Table 1 below shows the data for calculating the gas coefficient change according to the ammonia partial oxidation reaction, and Table 2 below shows the calculation formula for the gas production and conversion index in the ammonia partial oxidation reaction.

[0210] Ammonia partial oxidation NH3(g)0.25 O2(g)→a N2(g)b H2(g)c NH3(g)d H2O(g)Ammonia combustion reaction-0.33-0.25→+0.1670.5Ammonia decomposition reaction-x→+0.5x+1.5x0.67-x

[0211] NH3Conversion (%) α H2Yield (%) N2Yield (%)

[0212] α in Table 2 above can be expressed by Equation 1 below.

[0213] [Formula 1]

[0214] α =

[0215] In the above equation 1, the x value is obtained and the coefficient (a, b, c, d) values ​​corresponding to each gas are obtained. Using the above coefficient values, the detailed gas concentration can be analyzed by applying the equation 2 below to present the catalyst evaluation results.

[0216] [Formula 2]

[0217] NH3(g) + 0.25 O2(g) → aN2(g) + bH2(g) + cNH3(g) + 0.5 H2O(g)

[0218] Test Example 1: Evaluation of inductively coupled plasma (ICP) mass spectrometry

[0219] Inductively coupled plasma (ICP) mass spectrometry evaluation was performed on the supports according to Manufacturing Examples 1-1 to 1-5, 2-1 to 2-4, 3-1, 3-2, 4-1 to 4-5 and Comparative Manufacturing Example 1-1 and the catalysts according to Examples 1-2 and 1-3. Table 3 below is a table showing the metal content data according to the inductively coupled plasma (ICP) mass spectrometry of the supports according to Manufacturing Examples 1-1 to 1-5, 2-1 to 2-4, 3-1, 3-2, 4-1 to 4-5 and Comparative Manufacturing Examples 1-1 to 1-2, and Table 4 below is a table showing the metal content data according to the inductively coupled plasma (ICP) mass spectrometry of the catalysts according to Examples 1 to 5 and Comparative Examples 1 to 2.

[0220] Distinction Support Metal Metal Content (mol%) Manufacturing Example 1-1Ce 0.3 La 0.7 O 2-δLanthanum (La)Ce: 34, La: 66 Manufacturing Example 1-2Ce 0.5 La 0.5 O 2-δ Lanthanum (La)Ce: 50, La: 50 Manufacturing Example 1-3Ce 0.7 La 0.3 O 2-δ Lanthanum (La)Ce: 66, La: 34 Manufacturing Example 1-4Ce 0.9 La 0.1 O 2-δ Lanthanum (La)Ce: 92, La: 8 Manufacturing Example 1-5Ce 0.95 La 0.05 O 2-δ Lanthanum (La) La: Less than 8 Comparative Manufacturing Example 1-1 La2O3 Lanthanum (La) La: 100 Comparative Manufacturing Example 1-2 CeO2 -- Manufacturing Example 2-1 Ce 0.5 Zr 0.5 O 2-δ Zirconium (Zr)Ce: 57, Zr: 43 Manufacturing Example 2-2Ce 0.7 Zr 0.3 O 2-δ Zirconium (Zr)Ce: 68, Zr: 32 Manufacturing Example 2-3Ce 0.9 Zr 0.1 O 2-δ Zirconium (Zr)Ce: 86, Zr: 14 Manufacturing Example 2-4Ce 0.95 Zr 0.05 O 2-δ Zirconium (Zr)Ce: 93, Zr: 7 Manufacturing Example 3-1Ce 0.9 Sm 0.1 O 2-δ Samarium (Sm)Ce: 90, Sm: 10 Manufacturing Example 3-2Ce 0.9 Yb 0.1 O 2-δ Ytterbium (Yb) - Preparation Example 4-1Ce 0.9 Y 0.1 O 2-δ Yttrium (Y)Ce: 84, Y: 16 Manufacturing Example 4-2Ce 0.9 Fe 0.1 O 2-δ Iron (Fe) - Manufacturing Example 4-3Ce 0.9 Cu 0.1 O 2-δ Copper (Cu) - Manufacturing Example 4-4Ce 0.9 Ni 0.1 O 2-δNickel (Ni) - Manufacturing Example 4-5Ce 0.9 Co 0.1 O 2-δ Cobalt (Co)-

[0221] In Table 3 above, the metal contents of Manufacturing Examples 3-2 and 4-2 to 4-5, for which the metal contents were not described, could not be measured through inductively coupled plasma (ICP) mass spectrometry.

[0222] Catalyst name Metal Ru content (wt%) Example 1-1 Ru / Ce 0.3 La 0.7 O 2-δ Lanthanum (La)Ru: 1.0 Example 1-2Ru / Ce 0.5 La 0.5 O 2-δ Lanthanum (La)Ru: 1.5 Example 1-3Ru / Ce 0.7 La 0.3 O 2-δ Lanthanum (La)Ru: 1.82 Example 1-4Ru / Ce 0.9 La 0.1 O 2-δ Lanthanum (La)Ru: 1.1 Example 1-5Ru / Ce 0.95 La 0.05 O 2-δ Lanthanum (La)Ru: <2 Comparative Example 1-1Ru / La2O3 Lanthanum (La)Ru: 2-Example 2-1Ru / Ce 0.5 Zr 0.5 O 2-δ Zirconium (Zr)Ru: 1.4 Example 2-2Ru / Ce 0.7 Zr 0.3 O 2-δ Zirconium (Zr)Ru: 1.4 Example 2-3Ru / Ce 0.9 Zr 0.1 O 2-δ Zirconium (Zr)Ru: 1.5 Example 2-4Ru / Ce 0.95 Zr 0.05 O 2-δ Zirconium (Zr)Ru: 1.1 Example 3-1Ru / Ce 0.9 Sm 0.1 O 2-δ Samarium (Sm)Ru: 0.7 Example 3-2Ru / Ce 0.9 Yb 0.1 O 2-δYtterbium (Yb)Ru: 1.24 Example 4-1Ru / Ce 0.9 Y 0.1 O 2-δ Yttrium (Y)Ru: 2.02 Example 4-2Ru / Ce 0.9 Fe 0.1 O 2-δ Iron (Fe)Ru: 1.0 Example 4-3Ru / Ce 0.9 Cu 0.1 O 2-δ Copper (Cu)Ru: 1.61 Example 4-4Ru / Ce 0.9 Ni 0.1 O 2-δ Nickel (Ni)Ru: 1.0 Example 4-5Ru / Ce 0.9 Co 0.1 O 2-δ Cobalt (Co)Ru: 1.7 Example 5-1Ru / Ce 0.3 La 0.7 O 2-δ Lanthanum (La)Ru: 2.7 Example 5-2Ru / Ce 0.5 La 0.5 O 2-δ Lanthanum (La)Ru: 3.00 Example 5-3Ru / Ce 0.7 La 0.3 O 2-δ Lanthanum (La)Ru: 2.96 Example 5-4Ru / Ce 0.9 La 0.1 O 2-δ Lanthanum (La)Ru: 2.73 Comparative Example 2-1Ru / La2O3 Lanthanum (La)Ru: 3.09 Comparative Example 2-1Ru / CeO2 Lanthanum (La)Ru: 2.99

[0223] In the above Table 4, in the case of Examples 1-1 to 1-5, 2-1 to 2-4, 3-1, 3-2, and 4-1 to 4-5, the ruthenium precursor was used by calculating the ruthenium (Ru) content of the catalyst to be stoichiometrically 2 wt%, but the final ruthenium (Ru) content of the synthesized catalyst was confirmed to be 0.7 to 2.02 wt%, and in the case of Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2, the ruthenium precursor was used by calculating the ruthenium (Ru) content of the catalyst to be stoichiometrically 3 wt%, but the final ruthenium (Ru) content of the synthesized catalyst was confirmed to be 2.7 to 3.09 wt%. In addition, in Comparative Example 1-1, where the metal content was not described, the metal content could not be measured through inductively coupled plasma (ICP) mass spectrometry.

[0224] Test examples 2 to 5 below were performed through steps (1) to (3) below.

[0225] First, 0.2 g of the catalyst was injected into the reactor, and the catalyst was pretreated for 90 minutes in a hydrogen atmosphere at 500°C (step 1).

[0226] Afterwards, the temperature was cooled to room temperature, and the injection of external heat source into the furnace was stopped (step 2).

[0227] Finally, the reaction evaluation was performed with ammonia 120 ml / min, oxygen 30 ml, total GHSV, Gas hourly space velocity 45,000 ml / g cat Evaluation was performed with -h (step 3).

[0228] Experimental Example 2: Reaction temperature, ammonia conversion rate, and hydrogen production amount according to the type of lanthanide metal.

[0229] Test Example 2-1: Lanthanum (La), Samarium (Sm), and Ytterbium (Yb)

[0230] Figure 3a is Ru / Ce according to Example 1-4. 0.9 La 0.1 O 2-δCatalyst, Ru / Ce according to Example 3-1 0.9 Sm 0.1 O 2-δ Ru / Ce according to catalyst and Example 3-2 0.9 Yb 0.1 O 2-δ This is a graph showing the reaction temperature range when using a catalyst, and Figure 3b shows Ru / Ce according to Example 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 Ru / Ce according to catalyst and Example 3-2 0.9 Yb 0.1 O 2-δ This is a graph showing the ammonia conversion rate and hydrogen production amount using a catalyst, and Table 5 below is a table showing the reaction temperature, ammonia conversion rate, and hydrogen production amount using the catalyst according to Examples 1 to 5 and Comparative Examples 1 to 2 of the present invention. The catalyst was used after being calcined at 300°C.

[0231] Referring to FIGS. 3a, 3b and Table 5, Ru / Ce containing samarium (Sm) according to Example 3-1 0.9 Sm 0.1 O 2-δ Ru / Ce containing catalyst and ytterbium (Yb) according to Example 3-2 0.9 Yb 0.1 O 2-δ When using the catalyst, no ammonia decomposition reaction occurred, but Ru / Ce containing lanthanum (La) according to Example 1-4 0.9 La 0.1 O 2-δ When using a catalyst, the reaction temperature was maintained above 500 ℃, and the ammonia conversion rate was approximately 67.3%, and the hydrogen production rate was 1.7 kgH2 / kg. cat -h showed that the overall performance was very good.

[0232] Test Example 2-2: Iron (Fe), copper (Cu), nickel (Ni), and cobalt (Co)

[0233] Figure 4a is 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-δ Ru / Ce according to catalyst and example 4-5 0.9 Co 0.1 O 2-δ This is a graph showing the reaction temperature range when using a catalyst, and Figure 4b shows 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-δ Ru / Ce according to catalyst and example 4-5 0.9 Co 0.1 O 2-δ This is a graph showing the ammonia conversion rate and hydrogen production amount using a catalyst, and Table 5 below is a table showing the reaction temperature, ammonia conversion rate, and hydrogen production amount using the catalyst according to Examples 1 to 5 and Comparative Examples 1 to 2 of the present invention. The catalyst was used after being calcined at 300°C.

[0234] Referring to FIGS. 4a, 4b and Table 5, Ru / Ce containing copper according to Example 4-3 0.9 Cu 0.1 O 2-δ Ru / Ce containing catalyst and nickel according to Example 4-4 0.9 Ni 0.1 O 2-δ The catalyst did not undergo ammonia decomposition reaction, but Ru / Ce containing iron according to Example 4-2 0.9 Fe 0.1 O 2-δThe catalyst maintained the reaction temperature above 500 ℃, and the ammonia conversion rate was approximately 49% and the hydrogen production rate was 0.78 kgH2 / kg. cat -h was indicated, and Ru / Ce containing cobalt according to Example 4-5 0.9 Co 0.1 O 2-δ The catalyst maintained the reaction temperature at about 440°C, and the ammonia conversion rate was about 52% and the hydrogen production rate was 0.93 kgH2 / kg. cat I was able to confirm that it was displayed as -h.

[0235] Experimental Example 3: Reaction temperature, ammonia conversion rate, and hydrogen production amount according to the type of transition metal.

[0236] Test Example 3-1: Yttrium (Y) and zirconium (Zr)

[0237] Figure 2a is Ru / Ce according to Example 2-3 0.9 Zr 0.1 O 2-δ Ru / Ce according to catalyst and 4-1 0.9 Y 0.1 O 2-δ This is a graph showing the reaction temperature range when using a catalyst, and Figure 2b shows Ru / Ce according to Example 2-3. 0.9 Zr 0.1 O 2-δ Ru / Ce according to catalyst and 4-1 0.9 Y 0.1 O 2-δ This is a graph showing the ammonia conversion rate and hydrogen production amount using a catalyst, and Table 5 below is a table showing the reaction temperature, ammonia conversion rate, and hydrogen production amount using the catalyst according to Examples 1 to 5 and Comparative Examples 1 to 2 of the present invention. The catalyst was used after being calcined at 300°C.

[0238] Referring to FIGS. 2a, 2b and Table 5, Ru / Ce according to Example 2-3 0.9 Zr 0.1 O 2-δ Ru / Ce according to catalyst and Example 4-1 0.9 Y 0.1 O2-δ The catalysts have similar reaction temperatures, maintaining about 460°C and about 440°C, respectively. However, Ru / Ce according to Example 2-3 0.9 Zr 0.1 O 2-δ The catalyst has a sustained ammonia conversion rate of approximately 63% and a hydrogen production rate of 1.43 kgH2 / kg. cat -h and Ru / Ce according to Example 4-1 0.9 Y 0.1 O 2-δ The ammonia conversion rate of the catalyst is maintained at approximately 52%, and the hydrogen production is 0.93 kgH2 / kg. cat -h was shown, and it was confirmed that the catalyst according to Example 2-3 had a better ammonia conversion rate and hydrogen production rate than the catalyst according to Example 4-1.

[0239] Test Example 4: Comparison of reaction temperature, ammonia conversion rate, and hydrogen production of catalysts with different lanthanum (La) composition ratios.

[0240] 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 is a graph showing the reaction temperature according to the x value using a catalyst, and FIG. 6b is a graph showing 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 is a graph showing ammonia conversion rate data and hydrogen production amount according to x value using a catalyst, and Table 5 below is a table showing the reaction temperature, ammonia conversion rate, and hydrogen production amount using a catalyst according to Examples 1 to 5 and Comparative Examples 1 to 2 of the present invention. The catalyst was used after being calcined at 300°C.

[0241] Referring to FIGS. 6a, 6b and Table 5, the catalysts containing lanthanum according to Examples 1-2 to 1-4 were found to maintain a reaction temperature of 500°C or higher, but the catalyst containing lanthanum according to Example 1-5 did not undergo a reaction, and the Ru / Ce containing lanthanum according to Example 1-2 0.5 La 0.5 O 2-δ The catalyst had the highest ammonia conversion rate of 95%, and the hydrogen production rate was 3.03 kgH2 / kg. cat -h. Therefore, it was confirmed that the catalyst containing lanthanum according to Example 1 had a much better ammonia conversion rate and hydrogen production rate than the catalyst containing zirconium according to Example 2.

[0242] In addition, when comparing the catalysts of Example 1 (Ru 2 wt%) and Example 5 (Ru 3 wt%), it was confirmed that when the ruthenium content increased from 2 wt% to 3 wt% and the injected gas flow rate increased significantly, the ammonia conversion rate improved and a higher hydrogen production rate was achieved.

[0243] In addition, according to Example 1-1 and Comparative Example 1-1, it was confirmed that as the composition ratio of lanthanum (La) increased, the catalytic activity decreased.

[0244] Test Example 5: Comparison of reaction temperature, ammonia conversion rate, and hydrogen production rate of catalysts with different zirconium (Zr) composition ratios.

[0245] Figure 5a is a Ru / Ce containing zirconium according to Examples 2-1 to 2-4. 1-x Zr x O 2-δ This is a graph showing the reaction temperature according to the x value using a catalyst, and Figure 5b is a graph showing the Ru / Ce containing zirconium according to Examples 2-1 to 2-4. 1-x Zr x O 2-δThis is a graph showing ammonia conversion rate data and hydrogen production amount according to x value using a catalyst, and Table 5 below is a table showing the reaction temperature, ammonia conversion rate, and hydrogen production amount using a catalyst according to Examples 1 to 5 and Comparative Examples 1 to 2 of the present invention. The catalyst was used after being calcined at 300°C.

[0246] Referring to FIGS. 5a, 5b and Table 5, the x values ​​are 0.3 and 0.1 according to Examples 2-2 and 2-3, respectively. The reaction temperatures of the catalysts were excellent at about 500°C or higher and about 460°C, respectively, while the catalysts containing zirconium having x values ​​of 0.5 and 0.05 according to Examples 2-1 and 2-4, respectively, showed poor results with reaction temperatures of less than about 400°C. In addition, the ammonia conversion rate was also poor compared to the catalysts having x values ​​of 0.3 and 0.1 according to Examples 2-2 and 2-3, respectively. The catalysts were excellent at 52.7% and 63%, respectively, and it was confirmed that the catalysts containing zirconium with x values ​​of 0.5 and 0.05 according to Examples 2-1 and 2-4, respectively, did not undergo ammonia decomposition reaction. In Table 5 below, reaction X means that ammonia decomposition reaction did not occur.

[0247] Chemical formula Reaction temperature (℃) Ammonia conversion rate (%) Hydrogen production (kgH2 / kg) cat -h) Example 1-1Ru / Ce 0.3 La 0.7 O 2-δ 500 ℃ or higher792.52Example 1-2Ru / Ce 0.5 La 0.5 O 2-δ 500 ℃ or higher953.03Example 1-3Ru / Ce 0.7 La 0.3 O 2-δ 500 ℃ or higher 80.32.62 Example 1-4Ru / Ce 0.9 La 0.1 O 2-δ 500 ℃ or higher67.31.7Example 1-5Ru / Ce 0.95La 0.05 O 2-δ -Reaction XReaction XComparative Example 1-1Ru / La2O3-Reaction XReaction XExample 2-1Ru / Ce 0.5 Zr 0.5 O 2-δ Reaction below 400 ℃ X Reaction X Example 2-2Ru / Ce 0.7 Zr 0.3 O 2-δ 500 ℃ or higher 52.70.93 Example 2-3Ru / Ce 0.9 Zr 0.1 O 2-δ 460 ℃631.43Example 2-4Ru / Ce 0.95 Zr 0.05 O 2-δ Reaction X below 400 ℃ Reaction X Example 3-1Ru / Ce 0.9 Sm 0.1 O 2-δ -Reaction XReaction XExample 3-2Ru / Ce 0.9 Yb 0.1 O 2-δ -Reaction XReaction XExample 4-1Ru / Ce 0.9 Y 0.1 O 2-δ 440 ℃520.93Example 4-2Ru / Ce 0.9 Fe 0.1 O 2-δ 500 ℃ or higher 490.78 Example 4-3Ru / Ce 0.9 Cu 0.1 O 2-δ -Reaction XReaction XExample 4-4Ru / Ce 0.9 Ni 0.1 O 2-δ -Reaction XReaction XExample 4-5Ru / Ce 0.9 Co 0.1 O 2-δ 400 ℃ or higher 530.99 Example 5-1Ru / Ce 0.3 La 0.7 O 2-δ 500 ℃ or higher 802.57 Example 5-2Ru / Ce 0.5 La 0.5 O 2-δ 500 ℃ or higher 1003.214 Example 5-3Ru / Ce 0.7 La 0.3 O 2-δ400 ℃ or higher 852.73 Example 5-4Ru / Ce 0.9 La 0.1 O 2-δ 300 ℃ or higher <30 <1 Comparative example 2-1Ru / La2O3 400 ℃ or higher 902.9 Comparative example 2-2Ru / CeO2 300 ℃ or higher <30 <1

[0248] In Table 5 above, for Examples 1-5, 3-1, 3-2, 4-3, 4-4 and Comparative Example 1-1, for which the reaction temperature was not described, the reaction temperature could not be measured because the respective catalysts were not activated.

[0249] Test Example 6: Analysis of detailed gas concentration according to lanthanum (La) composition ratio

[0250] Figure 7a is Ru / Ce according to Example 1-2 0.5 La 0.5 O 2-δ A graph showing ammonia conversion rate and chemical formula coefficient data by analyzing the detailed gas concentration of the catalyst, and Fig. 7b shows Ru / Ce according to Example 1-3. 0.7 La 0.3 O 2-δ This is a graph showing ammonia conversion rate and chemical formula coefficient data by analyzing the detailed gas concentration of the catalyst. In addition, Table 1 is a table showing data calculated from changes in gas coefficients according to the ammonia partial oxidation reaction, and Table 2 is a table showing calculation formulas for gas production and conversion indices in the ammonia partial oxidation reaction. Using the above equation 1, the coefficient (a, b, c, d) values ​​corresponding to each gas were obtained and applied to the above equation 2 to analyze the detailed gas concentration, and the graphs of Figures 7a and 7b showing the results of catalyst evaluation were shown.

[0251] Referring to FIGS. 7a and 7b, Ru / Ce according to Example 1-2 0.5 La 0.5 O 2-δ The ammonia conversion rate of the catalyst was the best at 95%, and it was confirmed that the reaction was maintained for 2 hours, which is the longest maintenance time based on a single reaction.

[0252] Test Example 7: Comparison of exothermic temperatures according to protocol (AOR: NH3 / O2ratio)

[0253] Figure 8 shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing the evaluation protocol (AOR: NH3 / O2ratio) of the catalyst, and the reaction was carried out for 2 hours and 30 minutes for each condition. The AOR according to Fig. 8 is divided into sections (a) to (e), and in detail, section (a) has an AOR of 4 to 5 at flow rates of NH3200 to 300 ml / min, O240 to 75 ml / min and N2160 to 300 ml / min, section (b) has an AOR of 5 to 6 at flow rates of NH3200 to 300 ml / min, O232 to 60 ml / min and N2128 to 240 ml / min, section (c) has an AOR of 5 to 6 at flow rates of NH3300 to 400 ml / min, O250 to 80 ml / min and N2200 to 320 ml / min, and section (d) has an AOR of 3200 to 300 ml / min, O228 to 50 ml / min and N2112 to 200 ml / min. 6 to 7, and the (e) section is NH3300 to 400 ml / min, O242 to 67 ml / min and N2168 to 268 ml / min flow rate, and the AOR is 6 to 7. Figure 9 shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing the temperature data for each section of the catalyst.

[0254] Referring to FIGS. 8 and 9, it can be seen that as the oxygen ratio within the protocol decreases, the exothermic temperature decreases, and as the amount of gas injected into the protocol increases, the exothermic temperature increases.

[0255] Test Example 8: Ru(3 wt%) / Ce according to protocol (AOR: NH3 / O2ratio) and lanthanum (La) composition ratio 1-x La x O 2-δ Comparison of ammonia conversion and hydrogen production of catalysts

[0256] Test examples 8-1 to 8-5 below were performed through steps (1') to (3') below.

[0257] First, 0.2 g of catalyst was injected into the reaction system (step 1').

[0258] Afterwards, ammonia, oxygen, and nitrogen were injected in that order to replace the existing pure oxygen in the reaction system, and the molar ratio of oxygen and nitrogen was injected at 1:4 (step 2').

[0259] Finally, the evaluation was performed by adjusting the flow rates of NH3 and O2 so that the ratio of NH3 to O2 was 5 or 6 (step 3').

[0260] Test Example 8-1: 4≤AOR<5, 200≤NH3<300(ml / min), 40≤O2<75(ml / min), 160≤N2<300(ml / min)

[0261] Figure 9 shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing the temperature data for each section of the catalyst, and Fig. 10a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 4 to 5, and FIG. 10b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δThis is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 4 to 5, and the ammonia conversion rate and hydrogen production amount were measured for 150 minutes.

[0262] Referring to part (a) of FIG. 9 and FIG. 10a, it can be seen that the catalysts using cerium oxide-based supports according to Comparative Example 2-1 and Example 5-4 show deterioration and very low ammonia conversion rates after high temperature exposure. In contrast, the catalysts according to Examples 5-1, 5-2, 5-3 and Comparative Example 2-1 containing lanthanum metal show stability at high temperatures as the lanthanum content increases, and it was confirmed that the catalyst according to Example 5-2 showed the highest ammonia conversion rate.

[0263] Also, referring to Fig. 10b, it can be seen that the same trend as the result of Fig. 10a is shown.

[0264] Test Example 8-2: 5≤AOR<6, 200≤NH3<300(ml / min), 32≤O2<60(ml / min), 128≤N2<240(ml / min)

[0265] Figure 9 shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing the temperature data for each section of the catalyst, and Fig. 11a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6, and FIG. 11b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δThis is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6, and the ammonia conversion rate and hydrogen production amount were measured for 150 minutes.

[0266] Referring to part (a) of Fig. 9 and Fig. 11a, it can be confirmed that the overall reaction temperature is lowered due to a decrease in the injected oxygen fraction compared to the above-mentioned Test Example 8-1. Nevertheless, it can be confirmed that the catalyst containing a large amount of lanthanum stably maintains a high temperature of 500°C or higher.

[0267] Next, referring to Figure 11b, it can be seen that the results of ammonia conversion rate in Figure 11a show the same trend. In addition, it can be confirmed that hydrogen production increased due to a decrease in oxygen injection.

[0268] Test Example 8-3: 5≤AOR<6, 300≤NH3<400(ml / min), 50≤O2<80(ml / min), 200≤N2<320(ml / min)

[0269] Figure 12a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6, and FIG. 12b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 5 to 6, and the ammonia conversion rate and hydrogen production amount were measured for 150 minutes.

[0270] Referring to Figure 12a, it can be seen that the reaction temperature in this experimental section increases as the total amount of injectant and reactant increases compared to Test Example 8-2. Due to this temperature increase effect, it can be confirmed that the additional ammonia decomposition rate increases.

[0271] Also, referring to Fig. 12b, it can be seen that as the overall gas injection amount increases, the hydrogen production increases, and the result trend is the same as that in the ammonia conversion rate.

[0272] Test Example 8-4: 6≤AOR<7, 200≤NH3<300(ml / min), 28≤O2<50(ml / min), 112≤N2<2000(ml / min)

[0273] Figure 13a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7, and FIG. 13b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7, and the ammonia conversion rate and hydrogen production amount were measured for 150 minutes.

[0274] Referring to Figure 13a, it can be confirmed that the overall reaction temperature is lowered due to a decrease in the injected oxygen fraction. In addition, it can be confirmed that the ammonia decomposition rate is reduced as the reaction temperature is lowered.

[0275] In addition, referring to Fig. 13b, it can be seen that the hydrogen production amount is also lower compared to Test Example 8-3 due to the decrease in the ammonia conversion rate.

[0276] Test Example 8-5: 6≤AOR<7, 300≤NH3<400(ml / min), 42≤O2<67(ml / min), 168≤N2<268(ml / min)

[0277] Figure 14a shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data over time when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7, and FIG. 14b shows Ru(3 wt%) / Ce according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2. 1-x La x O 2-δ This is a graph showing ammonia conversion data according to lanthanum (La) content when the AOR (NH3 / O2ratio) of the catalyst is 6 to 7, and the ammonia conversion rate and hydrogen production amount were measured for 150 minutes.

[0278] Referring to Figure 14a, it can be seen that the reaction temperature in this experimental section increases as the total amount of injectant and reactant increases compared to Test Example 8-4. Due to this temperature increase effect, it can be confirmed that the additional ammonia decomposition rate increases.

[0279] Also, referring to Fig. 14b, it can be seen that as the overall gas injection amount increases, the hydrogen production increases, and the result trend is the same as that in the ammonia conversion rate.

[0280] Test Example 9: Analysis of catalyst components according to lanthanum (La) composition ratio

[0281] Table 6 below is a table showing the content of ruthenium (Ru), cesium (Ce), and lanthanum (La) of the catalysts according to Examples 5-1 to 5-4 and Comparative Examples 2-1 to 2-2 of the present invention and the support specific surface area data according to the lanthanum (La) composition ratio. In Table 6 below, the content of ruthenium (Ru), cesium (Ce), and lanthanum (La) 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).

[0282] Referring to Table 6 below, when examining Example 5-1 and Comparative Example 2-1, in which lanthanum was added in excess, it can be seen that the specific surface area of ​​the catalyst was greatly reduced.

[0283] Catalyst nameRu content (wt%)Specific surface area (m 2 / g)Ce content (mol%)La content (mol%)Example 5-1Ru / Ce 0.3 La 0.7 O 2-δ 2.7±0.01849.773070Example 5-2Ru / Ce 0.5 La 0.5 O 2-δ 3.00±0.18071.245050Example 5-3Ru / Ce 0.7 La 0.3 O 2-δ 2.96±0.15471.676832Example 5-4Ru / Ce 0.9 La 0.1 O 2-δ 2.73±0.01872.428911Comparative Example 2-1Ru / La2O33.09±0.05336.024-100Comparative Example 2-2Ru / CeO22.99±0.01863.01100-

[0284] Hereinafter, preferred embodiments of the present invention have been described. However, those skilled in the art will appreciate that various modifications and changes to the present invention may be made by adding, changing, deleting, or adding components, without departing from the spirit of the present invention as set forth in the claims, and such modifications and changes are also included within the scope of the present invention. For example, each component described as a single component may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form. The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. A support comprising a compound represented by the chemical formula 1 below; and Ruthenium (Ru) supported on the above support; Catalysts containing: [Chemical Formula 1] What 1-x M x A 2-δ In the above chemical formula 1, x is 0 <x<1이고, M is a lanthanide metal or transition metal, δ is 0<δ≤0.

5.

2. In paragraph 1, A catalyst characterized in that the lanthanide metal comprises at least one selected from the group consisting of lanthanum (La), samarium (Sm), ytterbium (Yb), gadolinium (Gd), and lutetium (Lu).

3. In paragraph 1, A catalyst characterized in that the lanthanide metal comprises lanthanum (La).

4. In paragraph 1, The above lanthanide metal includes lanthanum (La), A catalyst characterized in that x satisfies 0.05≤x≤0.

8.

5. In paragraph 1, A catalyst characterized in that the above transition metal comprises at least one selected from the group consisting of zirconium (Zr), yttrium (Y), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), and osmium (Os).

6. In paragraph 1, A catalyst characterized in that the above transition metal comprises zirconium (Zr).

7. In paragraph 1, The above transition metal includes zirconium (Zr), A catalyst characterized in that x satisfies 0.05≤x≤0.

5.

8. In paragraph 1, A catalyst characterized in that the catalyst comprises 1 to 5 wt% of the ruthenium.

9. In paragraph 8, A catalyst characterized in that the catalyst comprises 1.5 to 3.5 wt% of the ruthenium.

10. In paragraph 1, A catalyst characterized in that the catalyst decomposes ammonia to extract hydrogen. 11.(a) A step of preparing a precursor solution comprising at least one selected from the group consisting of lanthanide metal precursors and transition metal precursors, a cerium precursor, and water; (b) a step of co-precipitating the precursor of the precursor solution to synthesize a coprecipitate containing at least one selected from the group consisting of lanthanide metals and transition metals and cerium; (c) a step of heat-treating the above-mentioned precipitate to prepare a support; and (d) a step of preparing a catalyst including a support supported with ruthenium by stirring a support solution including the support, a ruthenium precursor and water; A method for producing a catalyst comprising:

12. In paragraph 11, A method for producing a catalyst, characterized in that the catalyst comprises a support comprising a compound represented by the chemical formula 1 below and ruthenium (Ru) supported on the support: [Chemical Formula 1] What 1-x M x A 2-δ In the above chemical formula 1, x is 0 <x<1이고, M is a lanthanide metal or transition metal, δ is 0<δ≤0.

5.

13. A hydrogen extraction method comprising a step (1) of extracting hydrogen by partially oxidizing ammonia in the presence of a catalyst and oxygen according to Article 11.

14. In paragraph 13, A hydrogen extraction method characterized in that the partial oxidation reaction includes a decomposition reaction of ammonia and an oxidation reaction of ammonia.

15. In paragraph 14, A hydrogen extraction method characterized in that the above partial oxidation reaction is performed by the reaction of the following reaction formula 1: [Reaction Formula 1] NH3(g) + xO2(g) -> 0.5N2(g)+ 2xH2O(g) + (1.5-2x)H2(g) H = 46-484x kJ mol -1 In the above reaction formula 1, x is 0 <x<0.75이다.

16. In paragraph 15, A hydrogen extraction method characterized in that the reaction of the above reaction formula 1 is performed using heat of reaction by at least one exothermic reaction selected from the group consisting of the following reaction formulas 2 and 3 and some external heat source: [Reaction Formula 2] NH3(g) -> 0.5N2(g) + 1.5H2(g) △H = 45.9 kJ mol -1 [Reaction Formula 3] NH3(g) + 0.75O2(g) -> 0.5N2(g) + 1.5H2O(g) △H = -317 kJ mol -1 17. In paragraph 13, A hydrogen extraction method characterized in that the above step (1) is performed without supplying heat from the outside or using some external heat source.

18. In paragraph 13, In step (1), Gas Hour Space Velocity (GHSV, L / (g)) of ammonia and oxygen cat A hydrogen extraction method characterized in that the ratio of -h)) is 2:1 to 6:

1.

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

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