AMMONIA DECOMPOSITION CATALYST, AND METHOD OF DECOMPOSING AMMONIA AND PRODUCING HYDROGEN BY USING THE SAME

Abstract

The present invention relates to an ammonia decomposition catalyst that converts ammonia into hydrogen and nitrogen. The catalyst includes ruthenium (Ru) as an active catalytic component and a composite oxide solid solution (La.sub.xCe.sub.1-xO.sub.y) including lanthanum oxide and cerium oxide as a catalyst support. The present invention also relates to an ammonia decomposition method using the catalyst and a hydrogen production method using the catalyst.

Claims

1. An ammonia decomposition catalyst for converting ammonia into hydrogen and nitrogen, the ammonia decomposition catalyst comprising: ruthenium (Ru) as an active catalytic component; and a composite oxide solid solution comprising lanthanum oxide and cerium oxide, as a catalyst support.

2. The ammonia decomposition catalyst of claim 1, wherein a molar ratio of lanthanum (La) to cerium (Ce) in the catalyst support is represented by La.sub.xCe1.sub.- .sub.xO.sub.y, wherein x is in a range of 0.25 to 0.45, and y is in a range of 1.78 to 1.88.

3. The ammonia decomposition catalyst of claim 2, wherein x is 0.33.

4. The ammonia decomposition catalyst of claim 1, further comprising at least one co-catalyst selected from Mg, Y, Ba, La, and Ce.

5. A method of preparing an ammonia decomposition catalyst that converts ammonia into hydrogen and nitrogen, the method comprising: mixing and stirring a cerium precursor and a lanthanum precursor in distilled water to form a cerium lanthanum aqueous solution; a primary drying step including: adding dropwise aqueous ammonia to the cerium lanthanum aqueous solution to produce a precipitate; collecting the precipitate through filtration; washing the precipitate with water; and drying the precipitate in a vacuum oven; crushing the precipitate resulting from the primary drying step and heating the crushed precipitate in a firing machine to prepare a lanthanum cerium composite oxide solid solution; adding the lanthanum cerium composite oxide solid solution to distilled water, adding a ruthenium precursor thereto and stirring the mixture to prepare a ruthenium-added aqueous solution; a secondary drying step including: adding dropwise aqueous ammonia to the ruthenium-added aqueous solution to produce a precipitate; collecting the precipitate through filtration; washing the precipitate with water; and drying the precipitate in a vacuum oven; and crushing the dried precipitate from the secondary drying step and heating the crushed precipitate in a reducing atmosphere to prepare a catalyst in which ruthenium is supported on the lanthanum cerium composite oxide solid solution.

6. The method of claim 5, wherein a molar ratio of lanthanum (La) to cerium (Ce) is in a range of 0.25:0.75 to 0.45:0.55.

7. An ammonia decomposition method for converting ammonia into nitrogen and hydrogen, the method comprising: feeding an ammonia-containing gas into a reactor charged with the ammonia decomposition catalyst of claim 1; and controlling the internal temperature of the reactor supplied with the ammonia-containing gas to be in a range of 300° C. and 600° C.

8. A hydrogen production method for producing hydrogen by converting ammonia into nitrogen and hydrogen, the method comprising: feeding an ammonia-containing gas into a reactor charged with the ammonia decomposition catalyst of claim 1; controlling the internal temperature of the reactor supplied with the ammonia-containing gas to a range of 300° C. to 600° C.; and separating hydrogen from gas discharged from the reactor.

9. An ammonia decomposition method for converting ammonia into nitrogen and hydrogen, the method comprising: feeding an ammonia-containing gas into a reactor charged with an ammonia decomposition catalyst prepared by the method of claim 5; and controlling the internal temperature of the reactor supplied with the ammonia-containing gas to be in a range of 300° C. and 600° C.

10. A hydrogen production method for producing hydrogen by converting ammonia into nitrogen and hydrogen, the method comprising: feeding an ammonia-containing gas into a reactor charged with an ammonia decomposition catalyst prepared by the method of claim 5; controlling the internal temperature of the reactor supplied with the ammonia-containing gas to a range of 300° C. to 600° C.; and separating hydrogen from gas discharged from the reactor.

Description

DESCRIPTION OF DRAWINGS

[0023] FIG. 1 is a flowchart illustrating an ammonia decomposition catalyst preparation method according to one embodiment of the present invention.

BEST MODE

[0024] Hereinafter, an ammonia decomposition catalyst according to one embodiment of the present invention, and ammonia decomposition and hydrogen production methods using the same will be described in detail.

[0025] The ammonia decomposition catalyst according to the present invention includes ruthenium (Ru) as an active catalytic component and a composite oxide solid solution including lanthanum oxide and cerium oxide as a catalytic support. The ammonia decomposition catalyst is a catalyst that converts ammonia into nitrogen and hydrogen through an endothermal reaction. The ammonia decomposition catalyst according to the present invention significantly exhibits a significantly improved ammonia conversion rate over conventional ammonia decomposition catalysts in a temperature range of 400° C. or less this is the range in which an ammonia conversion rate is relatively low. That is, the ammonia decomposition catalyst according to the present invention has a form in which ruthenium (Ru) is supported on lanthanum cerium oxide (LaCeO.sub.x).

[0026] In addition, the ammonia decomposition catalyst according to the present invention exhibits varying ammonia conversion rates in a low temperature zone, depending on the molar ratio of lanthanum (La) and cerium (Ce) in the lanthanum cerium oxide serving as the catalyst support. The catalyst support of the ammonia decomposition catalyst according to the present invention can be represented by Formula 1 below. In Formula 1, x is preferably in a range of greater than 0.2 and less than 0.5, x is more preferably in a range of 0.25 or greater and 0.45 or less, and x is most preferably 0.33. In this case, y is in a range of 1.75 to 1.90.

[00001]${\text{La}}_{\text{x}}{\text{Ce}}_{1-\text{x}}{\text{O}}_{\text{y}}$

[0027] The ammonia decomposition catalyst according to the present invention may further include co-catalytic components to further improve the ammonia decomposition rate. The co-catalytic components include preferably at least one element selected from alkali metal elements, alkaline earth metal elements, and lanthanoids, and include more preferably Mg, Y, Ba, La, Ce.

[0028] A method of preparing an ammonia decomposition catalyst, according to the present invention, will be described below.

[0029] A lanthanum cerium oxide (LaCeO.sub.x) used in the ammonia decomposition catalyst preparation method is obtained by mixing a precursor of lanthanum oxide (La.sub.2O.sub.3) and a precursor of cerium oxide (CeO.sub.2), obtaining hydroxide by using ammonia as a precipitating agent, and oxidizing the hydroxide in an air atmosphere.

[0030] The precursors of lanthanum oxide and cerium oxide may be any one or more of oxides, chlorides, hydroxides, bromides, iodides, nitrates, sulfates, carbonates, acetates, oxalates, fluorides, isopropoxides, and organometallic deposits of lanthanum and cerium.

[0031] Hereinafter, an exemplary ammonia decomposition catalyst preparation method of the present invention will be described, but the ammonia decomposition catalyst preparation method of the present invention is not limited thereto, and any method which makes it possible to achieve the objectives of the present invention can be used.

[0032] FIG. 1 is a flowchart illustrating an ammonia decomposition catalyst preparation method according to one embodiment of the present invention.

[0033] As illustrated in FIG. 1, an ammonia decomposition catalyst preparation method of the present invention first mixes a cerium precursor and a lanthanum precursor in distilled water and stirs the mixture to prepare a cerium lanthanum aqueous solution (S101).

[0034] Aqueous ammonia is added dropwise to the cerium lanthanum aqueous solution to produce a precipitate, the precipitate is collected through a filtering process and washed, and the washed precipitate is dried in a vacuum oven (S102).

[0035] Next, the dried precipitate is crushed and fired in an air atmosphere in a heating furnace to produce a lanthanum cerium composite oxide solid solution (S103).

[0036] Next, the resulting lanthanum cerium oxide solid (composite oxide) is added to distilled water, a ruthenium precursor is added thereto and stirred to prepare an aqueous solution containing ruthenium (S104).

[0037] Aqueous ammonia is added dropwise to the ruthenium-added aqueous solution to produce a precipitate, the precipitate is collected through a filtering process and washed, and the washed precipitate is dried in a vacuum oven (S105).

[0038] Finally, the dry precipitate is crushed and reduced in a reducing gas atmosphere to produce a catalyst in which ruthenium is supported on a lanthanum cerium composite oxide solid solution (S106).

[0039] The firing of S103 in the preparation method may be performed at a temperature in a range of 300° C. to 700° C. and preferably 400° C. to 600° C. or 0.5 to 12 hours and preferably for 1 to 5 hours.

[0040] In the preparation method, the reduction treatment is not particularly limited if it is possible to form a ruthenium metal by reducing a ruthenium compound. Specifically, for example, a method of using a reductive gas such as carbon monoxide, hydrocarbons, or hydrogen, a method of adding a reducing agent such as hydrazine, lithium aluminum hydride, or tetramethyl borohydride may be used. In addition, when the reductive gas is used, the reductive gas may be diluted with other gases (for example, nitrogen carbon dioxide, or the like). Among these methods, a reduction treatment using hydrogen as a reductive gas is preferred.

[0041] In addition, when the reductive gas is used, heating is performed preferably at a temperature in a range of 300° C. to 800° C. and more preferably at a temperature in a range of 400° C. to 600° C. The time for the reduction treatment is preferably in a range of 0.5 to 5 hours and more preferably in a range of 1 to 3 hours. In addition, prior to the reduction treatment using the reductive gas, a preliminary firing process may be performed using an inert gas such as nitrogen or carbon dioxide at a temperature in a range of 200° C. to 400° C. for 1 to 7 hours.

[0042] In the case where the reduction treatment is performed, the ruthenium compound is converted, principally, to a ruthenium metal exhibiting a metal state with a valence of 0. When the reduction treatment is insufficiently performed, the ruthenium compound is only partially reduced, resulting in the catalyst exhibiting low activity. However, in this case, in order for the ruthenium compound to enter a reduced state as hydrogen is generated by the ammonia decomposition reaction, the reduction treatment of the remaining portion that has not yet been reduced proceeds and the valence state of the ruthenium becomes zero, resulting in the catalyst exhibiting high activity.

[0043] In addition, an ammonia decomposition method according to another embodiment of the present invention features that the method produces hydrogen by decomposing ammonia into nitrogen and hydrogen by processing an ammonia-containing gas using the ammonia decomposition catalyst according to the present invention described above.

[0044] More particularly, the method includes: feeding an ammonia-containing gas into a reactor charged with an ammonia decomposition catalyst; and controlling the temperature of the reactor to which the ammonia-containing gas is fed to be in a range of 300° C. to 600° C.

[0045] The ammonia-containing gas which is to be processed is not particularly limited. That is, ammonia gas, gases containing ammonia, and gases containing materials, such as urea, generating ammonia through pyrolysis may be regarded as the ammonia-containing gas to be processed.

[0046] In addition, gases containing ammonia may contain other substances to the extent that they are not toxic to the catalyst.

[0047] The reaction temperature is preferably in a range of 300° C. and 600° C. The reaction pressure is in a range of 0.002 to 2 MPa as the absolute pressure, and more preferably in a range of 0.004 to 1 MPa.

[0048] In the ammonia decomposition method of the present invention, it is possible to obtain high-purity hydrogen by separating nitrogen and hydrogen obtained by decomposing ammonia from each other by conventional means.

[0049] Further, there is provided a hydrogen production method according to a further embodiment of the present invention.

[0050] More particularly, the method includes: feeding an ammonia-containing gas into a reactor charged with an ammonia decomposition catalyst; controlling the temperature of the reactor to which the ammonia-containing gas is fed to be in a range of 300° C. to 600° C.; and separating hydrogen from gas discharged from the reactor.

[0051] Hereinafter, the catalytic activity of the ammonia decomposition catalyst according to the present invention will be examined through examples. The following examples are provided to illustrate one or more preferred embodiments of the invention, but the invention is not limited to those embodiments. A number of changes may be made to the following examples without departing from the scope of the present invention.

Example 1

[0052] 7.57 g of cerium nitrate hydrate and 3.77 g of lanthanum nitrate hydrate were added to 100 mL of distilled water and the mixture was mixed and stirred to prepare a homogeneous aqueous solution. To this aqueous solution, 1 mole of aqueous ammonia was added dropwise until the pH value of the aqueous solution became 9 to produce a precipitate. The precipitate was collected through filtration, washed with water, placed in a vacuum oven, and dried at 110° C. for 12 hours. This dry precipitate was crushed, placed in a firing machine, and treated at 500° C. for 3 hours in an air atmosphere to obtain La.sub.0.33Ce.sub.0.67O.sub.1.84. 1 g of the resulting support (i.e., La.sub.0.33Ce.sub.0.67O.sub.1.84) for supporting 2% by weight of ruthenium (Ru) was added to 50 mL of distilled water, and 0.04 g of ruthenium chloride hydrate was added thereto and stirred. To this aqueous solution, 0.5 mole of aqueous ammonia was added dropwise until the pH value of the aqueous solution became 9 to produce a precipitate. The precipitate was collected through filtration, washed with water, placed in a vacuum oven, and dried at 110° C. for 12 hours. This dry precipitate was crushed and treated at 500° C. for 2 hours in a 100% hydrogen atmosphere to obtain Ru/La.sub.0.33Ce.sub.0.67O.sub.1.84.

Example 2

[0053] After dispersing 3 g of cerium oxide in 100 mL of distilled water, 1.89 g of lanthanum nitrate hydrate was added thereto and mixed. To this aqueous solution, 1 mole of aqueous ammonia was added dropwise until the pH value of the aqueous solution became 9 to produce a precipitate. The precipitate was collected through filtration, washed with water, placed in a vacuum oven, and dried at 110° C. for 12 hours. This dry precipitate was ground, placed in a firing machine, and treated at 500° C. for 3 hours in an air atmosphere to obtain La.sub.0.2Ce.sub.0.8O.sub.1.9. 1 g of the resulting support (i.e., La.sub.0.2Ce.sub.0.8O.sub.1.9) for supporting 2% by weight of ruthenium (Ru) was added to 50 mL of distilled water, and 0.04 g of ruthenium chloride hydrate was added thereto and stirred. To this aqueous solution, 0.5 mole of aqueous ammonia was added dropwise until the pH value of the aqueous solution became 9 to produce a precipitate. The precipitate was collected through filtration, washed with water, placed in a vacuum oven, and dried at 110° C. for 12 hours. This dry precipitate was ground and treated at 500° C. for 2 hours in a hydrogen 100% atmosphere to obtain Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9. The sample was denoted as Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9-DP.

Example 3

[0054] 3 g of cerium oxide was added to and mixed with an aqueous solution prepared by dissolving 1.89 g of lanthanum nitrate hydrate in 50 mL distilled water. The resulting solution was heated at 60° C. with a rotation speed of 160 rpm for 4 hours using a rotary evaporation concentrator to remove water. The resulting powder was placed in a vacuum oven, dried at 110° C. for 12 hours, placed in a firing machine, and treated at 500° C. for 3 hours in an air atmosphere to obtain La.sub.0.2Ce.sub.0.8O.sub.1.9. 2% by weight of ruthenium (Ru) was supported on the support in the same manner as in Example 2 to obtain Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9. The sample was denoted as Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9-WI.

Example 4

[0055] 7.57 g of cerium nitrate hydrate, 1.89 g of lanthanum nitrate hydrate, and 6.28 g of citric acid were added to 30 mL of isopropyl alcohol and mixed through stirring. The solution was stirred at 80° C. until a yellow spongy gel formed. The gel was cooled to room temperature, then placed in a vacuum oven, and dried at 110° C. for 12 hours. The dry gel was crushed and placed in a firing machine, and the temperature of the dry gel was gradually raised in an air atmosphere. The dry gel was then treated at 180° C. for 2 hours, 300° C. for 2 hours, and 500° C. for 3 hours to obtain La.sub.0.2Ce.sub.0.8O.sub.1.9. 2% by weight of ruthenium (Ru) was supported on the support in the same manner as in Example 2 to obtain Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9. The sample was denoted as Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9-SG.

Example 5

[0056] 7.85 g of urea was added to and mixed with an aqueous solution prepared by dissolving 1.89 g of lanthanum nitrate hydrate and 7.57 g of cerium nitrate hydrate in 100 mL of distilled water. The solution was refluxed with strong stirring at 100° C. for 12 hours. The solution was filtered to collect the precipitate, and the precipitate was washed with water, placed in a vacuum oven, and dried at 110° C. for 12 hours. This dry powder was crushed, placed in a firing machine, and treated at 500° C. for 3 hours in an air atmosphere to obtain La.sub.0.2Ce.sub.0.8O.sub.1.9. 2% by weight of ruthenium (Ru) was supported on the support in the same manner as in Example 2 to obtain Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9. The sample was denoted as Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9-UCP.

Example 6

[0057] 7.57 g of cerium nitrate hydrate and 1.89 g of lanthanum nitrate hydrate were added to and mixed in 100 mL of distilled water. To this aqueous solution, 1 mole of aqueous ammonia was added dropwise until the pH value of the aqueous solution became 9 to produce a precipitate. The precipitate was collected through filtration, washed with water, placed in a vacuum oven, and dried at 110° C. for 12 hours. This dry precipitate was crushed, placed in a firing machine, and treated at 500° C. for 3 hours in an air atmosphere to obtain La.sub.0.2Ce.sub.0.8O.sub.1.9. 2% by weight of ruthenium (Ru) was supported on the support in the same manner as in Example 2 to obtain Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9. The sample was denoted as Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9-CP.

Comparative Example 1

[0058] The same process as in Example 1 was performed except that 7.57 g of cerium nitrate hydrate was used instead of 7.57 g of cerium nitrate hydrate and 3.77 g of lanthanum nitrate hydrate to obtain Ru/CeO.sub.2 as a catalyst.

Comparative Example 2

[0059] The same process as in Example 1 was performed except that 7.57 g of lanthanum nitrate hydrate was used instead of 7.57 g of cerium nitrate hydrate and 3.77 g of lanthanum nitrate hydrate to obtain Ru/La.sub.2O.sub.3 as a catalyst.

Comparative Example 3

[0060] The same process was in Example 1 was performed except that 7.57 g of praseodymium nitrate hydrate was used instead of 7.57 g of cerium nitrate hydrate and 3.77 g of lanthanum nitrate hydrate to obtain Ru/Pr.sub.2O.sub.3 as a catalyst.

Comparative Example 4

[0061] The same process as in Example 1 was performed except that t 3.79 g of praseodymium nitrate hydrate was used instead of 3.77 g of lanthanum nitrate hydrate to obtain Ru/Pr.sub.0.33Ce.sub.0.67O.sub.1.84 as a catalyst.

Comparative Example 5

[0062] The same process as in Example 1 was performed except that 7.57 g of praseodymium nitrate hydrate was used instead of 7.57 g of cerium nitrate hydrate to obtain Ru/La.sub.0.33Pr.sub.0.67O.sub.1.5 as a catalyst.

Comparative Example 6

[0063] The same process as in Example 1 was performed except that 2.28 g of barium nitrate hydrate was used instead of 3.77 g of lanthanum nitrate hydrate to obtain Ru/Ba.sub.0.33Ce.sub.0.67O.sub.1.67 as a catalyst.

Comparative Example 7

[0064] The same process as in Example 1 was performed except that 7.57 g of zirconium nitrate hydrate was used instead of 7.57 g of cerium nitrate hydrate and 3.77 g of lanthanum nitrate hydrate to obtain Ru/ZrO.sub.2 as a catalyst.

Comparative Example 8

[0065] The same process as in Example 1 was performed except that 7.57 g of cerium nitrate hydrate and 1.16 g of zirconium nitrate hydrate were used instead of 7.57 g of cerium acid hydrate and 3.77 g of lanthanum nitrate hydrate to obtain Ru/Zr.sub.0.2Ce.sub.0.8O.sub.2.0 as a catalyst.

Comparative Example 9

[0066] The same process as in Example 1 was performed except that 7.57 g of cerium nitrate hydrate and 7.57 g of magnesium nitrate hydrate were used instead of 3.77 g of lanthanum nitrate hydrate to obtain Ru/MgO as a catalyst.

Experiment 1

[0067] To show that when ruthenium is an active catalytic component, the use of LaCeO.sub.x as a catalyst support improves an ammonia conversion rate compared to the case of using alumina, zirconia, lanthanum oxide, cerium oxide, or any composite oxide other than LaCeO.sub.x, experiments were performed in which ammonia decomposition reactions were performed at temperatures in a range of 300° C. to 600° C. using the catalysts of Example 1 and Comparative Examples 1 to 6. The results are shown in Table 1.

TABLE-US-00001 Catalyst Reaction Temperature (°C) 300 350 400 450 500 550 600 Example 1 Ru/La.sub.0.33Ce.sub.0.67O.sub.1.84 17.5 53.4 91.9 100 100 100 100 Example 2 Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9 13.8 42.8 83.4 99.6 100 100 100 Comparative Example 1 Ru/CeO.sub.2 10.4 39.0 76.4 98.1 100 100 100 Comparative Example 2 Ru/La.sub.2O.sub.3 3.6 14.6 43.9 82.8 99.8 100 100 Comparative Example 3 Ru/Pr.sub.2O.sub.3 8.0 28.8 67.5 96.7 100 100 100 Comparative Example 4 RU/Pr.sub.0.33Ce.sub.0.67O.sub.1.84 13.1 42.0 81.2 99.2 100 100 100 Comparative Example 5 Ru/La.sub.0.33Pr.sub.0.67O.sub.1.5 7.0 18.1 52.2 88.1 100 100 100 Comparative Example 6 Ru/Ba.sub.0.33Ce.sub.0.67O.sub.1.67 11.2 43.3 79.5 98.8 100 100 100 Comparative Example 7 Ru/ZrO.sub.2 1.2 15.2 46.9 78.2 97.6 100 100 Comparative Example 8 Ru/Zr.sub.0.2Ce.sub.0.8O.sub.2.0 13.0 34.4 72.8 97.2 100 100 100 Comparative Example 9 Ru/MgO 9.9 28.8 66.1 94.3 100 100 100

[0068] As shown in Table 1 above, the ammonia conversion rate varied depending on the material of the catalyst support. The catalyst supports exhibited ammonia conversion rates in this order: La.sub.0.33Ce.sub.0.67O.sub.1.84 > La.sub.0.2Ce.sub.0.8O.sub.1.9 > Pr.sub.0.33Ce.sub.0.67O.sub.1.84 > Zr.sub.0.2Ce.sub.0.8O.sub.2.0 > Ba.sub.0.33Ce.sub.0.67O.sub.1.67 > CeO.sub.2 > MgO > Pr.sub.2O.sub.3 > La.sub.0.33Pr.sub.0.67O.sub.1.5 > La.sub.2O.sub.3 > ZrO.sub.2 In particular, the Ru/La.sub.0.33Ce.sub.0.67O.sub.1.84 showed a relatively high ammonia conversion rate than the catalysts using the other supports in at experimental temperatures in a range of 450° C. or less, which is a relatively low temperature range.

Experiment 2

[0069] Experiments of ammonia decomposition reactions using the catalysts of Examples 2 to 6 were performed at various temperatures in a range of 300° C. to 600° C. The results are shown in Table 2.

TABLE-US-00002 Catalyst Reaction Temperature (°C) 300 350 400 450 500 550 600 Example 2 Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9– [DP] 8.8 29.8 71.9 96.9 100 100 100 Example 3 Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9–[WI] 9.7 31.5 72.3 98.0 100 100 100 Example 4 Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9–[SG] 12.2 38.1 76.3 98.5 100 100 100 Example 5 Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9– [UCP] 12.4 41.6 78.8 99.0 100 100 100 Example 6 Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9– [CP] 13.8 42.8 83.4 99.6 100 100 100

[0070] As shown in Table 2 above, the ammonia conversion rate varied depending on the catalyst support preparation method even though the catalysts have the same composition. The catalyst supports prepared by the respective methods described above exhibited ammonia conversion rates in this order: La.sub.0.2Ce.sub.0.8O.sub.1.9- [CP] > La.sub.0.2Ce.sub.0.8O.sub.1.9- [UCP] > La.sub.0.2Ce.sub.0.8O.sub.1.9- [SG] > La.sub.0.2Ce.sub.0.8O.sub.1.9– [WI] > Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9– [DP] . In particular, the catalyst Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9-[CP] prepared by the method of Example 6 showed a higher ammonia conversion rate in the experimental temperature range of 450° C. or less, which is a relatively low temperature range, than the catalysts using the supports prepared by other methods.

Examples 7 to 19

[0071] By changing the contents of cerium nitrate hydrate and lanthanum nitrate hydrate from those in Example 1, Catalysts 7 to 19 represented by Ru/La.sub.xCe1.sub.-xO.sub.y (X = 0.05, 0.09, 0.2, 0.25, 0.3, 0.33, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9) and shown in Table 3 was prepared.

Comparative Example 10

[0072] 2.04 g Ce (NO.sub.3).sub.3.6.sub.2O (≥ 99%, Sigma) and 0.51 g La (NO.sub.3) .sub.3. 6H.sub.2O (99.99%, Sigma) were dissolved in 50 mL of deionized water (DI) at room temperature for 30 minutes. Next, 0.04 g of RuCl.sub.3.xH.sub.2O (99.98%, Sigma) was added to the solution and stirred for 30 minutes. 0.5 M NH.sub.4OH prepared by diluting 16.3 mL of NH.sub.4OH (28% to 30%, Samchun) in D.I water was added dropwise at a rate of 40 mL/h to 0.5 L of the final solution until the pH of the mixed solution reached ~ 9.0. The suspension was stirred at room temperature for 12 hours then filtered to collect a precipitate. The precipitate was washed with DI water several times, dried in a vacuum oven at 110° C. for 12 hours, and fired at 500° C. for 3 hours at a ramp rate of 4° C./min to prepare Ru@La.sub.0.2Ce.sub.0.8O.sub.1.9 (by co-precipitation) .

Comparative Example 11

[0073] 0.81 g of CeO.sub.2 and 0.19 g of La.sub.2O.sub.3 support (lab-made) were placed in 50 mL of DI water, and 0.04 g of RuCl.sub.3.xH.sub.2O (99.98%, Sigma) was added to the suspension. A 0.5 M NH.sub.4OH solution was added to the suspension to adjust the pH to 9, and the resulting suspension was aged at room temperature for 12 hours with stirring at 400 rpm. The resulting precipitate was collected through filtration and dried at 110° C. for 12 hours to prepare Ru/(0.2)La.sub.2O.sub.3-(0.8)CeO.sub.2 (by deposition-precipitation (DP)).

Experiment 3

[0074] In order to observe the preparation methods of the final catalysts and the activity change according to the molar ratio of La and Ce, experiments of ammonia decomposition reactions using the catalysts of Examples 7 to 19 and the catalysts of Comparative Examples 1, 2, 10, and 11 were performed at various temperatures in a temperature range of 300° C. to 600° C. The results are shown in Table 3.

TABLE-US-00003 Catalyst Reaction Temperature (°C) 300 350 400 450 500 550 600 Ru/La.sub.0.5Ce.sub.0.95O.sub.1.98 Example 7 11.4 38.4 75.8 98.0 100 100 100 Ru/La.sub.0.09Ce.sub.0.91O.sub.1.96 Example 8 12.4 38.6 76.8 98.7 100 100 100 Ru/La.sub.0.2Ce.sub.0.8O.sub.1.9 Example 9 13.8 42.8 83.4 99.6 100 100 100 Ru/La.sub.0.25Ce.sub.0.75O.sub.1.88 Example 10 15.4 48.7 87.2 100 100 100 100 Ru/La.sub.0.3Ce.sub.0.7O.sub.1.85 Example 11 16.9 50.2 90.3 100 100 100 100 Ru/La.sub.0.33Ce.sub.0.67O.sub.1.84 Example 12 17.5 53.4 91.9 100 100 100 100 Ru/La.sub.0.4CeO.sub.0.6O.sub.1.80 Example 13 16.5 52.2 90.8 100 100 100 100 Ru/La.sub.0.45Ce.sub.0.55O.sub.1.78 Example 14 15.3 50.4 89.6 100 100 100 100 Ru/La.sub.0.5Ce.sub.0.5O.sub.1.75 Example 15 14.0 47.9 88.7 100 100 100 100 Ru/La.sub.0.6Ce.sub.0.4O.sub.1.70 Example 16 11.3 37.1 71.3 88.0 100 100 100 Ru/La.sub.0.7Ce.sub.0.30O.sub.1.65 Example 17 9.9 27.7 54.4 75.1 95.4 100 100 Ru/La.sub.0.8Ce.sub.0.2O.sub.1.60 Example 18 7.6 16.3 36.4 63.1 92.0 99.8 100 Ru/La.sub.0.9Ce.sub.0.1O.sub.1.55 Example 19 5.1 6.9 19.6 51.6 86.8 99.3 100 Ru/CeO.sub.2 Comparative Example 1 10.4 39.0 76.4 98.1 100 100 100 Ru/La.sub.2O.sub.3 Comparative Example 2 3.6 14.6 43.9 82.8 99.8 100 100 Ru@La.sub.0.2Ce.sub.0.8O.sub.1.9 Comparative Example 10 4.3 14.3 48.3 81.7 98.4 100 100 Ru/ (0.2) La.sub.2O.sub.3- (0.8) CeO.sub.2 Comparative Example 11 9.4 35.5 75.3 98.1 100 100 100

[0075] As shown in Table 3 above, it was confirmed that the ammonia conversion rate depends on the molar ratio of La to Ce (Examples 7 to 19). The ammonia conversion rate increased as the content of La increased from 0.05 over the entire temperature range, resulting in the highest conversion when the molar ratio of La to Ce was 0.33:0.67, i.e., a ratio of La to Ce was 1:2. There was a tendency in which the ammonia conversion rate decreased rapidly as the content of La increased from 0.4 to 0.9, resulting in the lowest conversion when the molar ratio of La to Ce was 0.9:0.1. In particular, when the reaction temperature was 350° C. and 400° C., in a certain range of the mixing ratios of La.sub.2O.sub.3 and CeO.sub.2, a lower activity was exhibited than the case where either La.sub.2O.sub.3 alone or CeO.sub.2 alone was used whereas in a different range of the mixing ratios, a higher activity was exhibited than the case where either La.sub.2O.sub.3 alone or CeO.sub.2 alone was used. That is, it was confirmed that a different tendency than the effects of simple physical mixing ratios of La.sub.2O.sub.3 and CeO.sub.2 was observed

[0076] It can be seen from these experiments that the Ru/LaCeO.sub.x catalyst has the optimal performance when the molar ratio of La to Ce is 1:2.

[0077] On the other hand, the ammonia conversion rate was higher when the LaCeO.sub.x solid was used as a support for Ru than when either La.sub.2O.sub.3 or CeO.sub.2 was used alone or when La.sub.2O.sub.3 and CeO.sub.2 were simply physically mixed (Comparative Example 11). In addition, it was shown that the catalysts prepared by co-precipitating the La precursor and the Ce precursor to prepare the support and then impregnating the support with Ru as in Examples exhibited a significantly higher ammonia conversion rate than the catalysts prepared by dissolving the Ru precursor, the La precursor, and the Ce precursor at the same time and co-precipitating the precursors, in a relatively low temperature range.

[0078] While the present disclosure has been described with reference to exemplary embodiments illustrated in the accompanying drawings, those skilled in the art will appreciate that the exemplary embodiments are presented only for illustrative purposes. On the contrary, it will be understood that various modifications and equivalents to the exemplary embodiments are possible. Accordingly, the technical scope of the present disclosure should be defined by the following claims.