KR102607939B1 - LANTHANUM DIOXYCARBONATE (La2O2CO3) SUPPORTED RUTHENIUM-BASED CATALYSTS FOR AMMONIA DEHYDROGENATION REACTION AND THE METHOD FOR PREPARING THE SAME - Google Patents

Abstract

In this specification, a multilayer support comprising a lanthanum compound layer; and an active metal layer located on the multilayer support and containing ruthenium (Ru), wherein the lanthanum compound is lanthanum oxide (La ₂ O ₃ ), lanthanum aluminate (LaAlO ₃ ), and lanthanum oxycarbonate (La). A catalyst for ammonia dehydrogenation reaction comprising any one or more of ₂ O ₂ CO ₃ ) is provided.

Description

Ruthenium-based ammonia decomposition catalyst using lanthanum oxycarbonate as a carrier, method for producing the same, and method for producing hydrogen from ammonia using the same }

Disclosed herein are a ruthenium-based ammonia decomposition catalyst using lanthanum oxycarbonate as a carrier, a method for producing the same, and a method for producing hydrogen from ammonia using the same.

Due to the depletion of fossil energy and environmental pollution problems, there is a great demand for new and renewable alternative energy that can replace fossil fuels, and hydrogen is attracting attention as one of such alternative energy.

Fuel cells and hydrogen combustion devices use hydrogen as a reaction gas, and in order to apply fuel cells and hydrogen combustion devices to automobiles and various electronic products, for example, a stable and continuous supply or storage technology for hydrogen is needed.

In order to supply hydrogen to devices using hydrogen, a method can be used in which hydrogen is supplied from a separately installed hydrogen supply station whenever hydrogen is needed. In this method, compressed hydrogen or liquefied hydrogen can be used to store hydrogen. Alternatively, a method may be used in which a material that stores and generates hydrogen is mounted on a hydrogen utilization device, and then hydrogen is generated through a reaction of the material and supplied to the hydrogen utilization device. For this method, for example, methods using metal hydride, adsorption, desorption/carbon (absorbents/carbon) methods, and chemical methods (chemical hydrogen storage) have been proposed.

For example, ammonia borane, ammonia, etc. can be used as such hydrogen generating substances, and a catalyst is used in the process of dehydrogenation from these. Among them, ammonia in particular has a high hydrogen storage density (about 17.7 wt%) and is easy to synthesize (e.g., Haber-Bosch process).

As a catalyst for ammonia decomposition, a method of using a catalyst in which ruthenium, an active metal, is added to an alumina carrier has been reported. This ammonia treatment method has the advantage of being able to decompose ammonia at a relatively low temperature compared to conventional catalysts such as iron-alumina. However, ruthenium, an active metal species, is a rare precious metal and is difficult to achieve in terms of cost. Therefore, there is a need to develop a catalyst that shows a high ammonia decomposition rate even with a low ruthenium content.

Meanwhile, in the existing method of synthesizing ruthenium/alumina and ruthenium/lanthanum-alumina catalysts, the active metal, ruthenium, does not exist only on the surface of the carrier, which is the active site, but penetrates into sites inside the carrier where ammonia is difficult to adsorb. there is. In this case, there is a disadvantage in that a lower content of ruthenium, a rare noble metal, than the actual content of ruthenium serves as an active site, reducing efficiency.

One aspect of the present invention is that in existing ruthenium-based catalysts, ruthenium, which is an active metal, does not exist only on the surface of the carrier phase, which is the active site, but has the property of penetrating into sites inside the carrier phase where ammonia is difficult to adsorb, making ruthenium, a rare noble metal, We aim to solve the drawback that the efficiency is reduced because a lower content of ruthenium than the actual content acts as an active site.

In order to achieve the above-described object, in one embodiment according to the present invention, a multilayer support including a lanthanum compound layer; and an active metal layer located on the multilayer support and containing ruthenium (Ru), wherein the lanthanum compound is lanthanum oxide (La ₂ O ₃ ), lanthanum aluminate (LaAlO ₃ ), and lanthanum oxycarbonate (La). ₂ O ₂ CO ₃ ) It provides a catalyst for ammonia dehydrogenation reaction, including any one or more.

In one embodiment, the lanthanum compound may be lanthanum oxide (La ₂ O ₃ ).

In one embodiment, the ruthenium may not be dispersed within the multilayer support but may be selectively included only in the active metal layer.

In one embodiment, the ruthenium may be present in greater amounts outside the multilayer support than inside the multilayer support.

In one embodiment, the multilayer support may include a lanthanum compound layer and an alumina layer.

In one embodiment, the active metal may be included in 0.1-20% by weight based on the total catalyst.

In one embodiment, the active metal may be included in 1-5% by weight based on the total catalyst.

In another embodiment according to the invention, introducing a lanthanum precursor onto a support; and calcining the introduced lanthanum precursor in a specific atmosphere to form a lanthanum compound layer. In the lanthanum compound layer forming step, lanthanum oxide (La ₂ O ₃ ), lanthanum aluminate (LaAlO ₃ ), and lanthanum oxycarbonate ( La ₂ O ₂ CO ₃ ) Provides a method for producing a catalyst for an ammonia dehydrogenation reaction in which one or more lanthanum compounds are formed.

In one embodiment, lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ) may be formed as a lanthanum compound in the lanthanum compound layer forming step.

In one embodiment, the step of forming the lanthanum compound layer may be calcining in an oxidizing agent atmosphere or a CO ₂ atmosphere.

In one embodiment, the step of forming the lanthanum compound layer may be calcining at 400-1000° C. for 1-12 hours.

In one embodiment, the method may further include forming an active metal layer by introducing a ruthenium precursor onto the lanthanum compound layer.

In one embodiment, in the step of forming the active metal layer, the introduced ruthenium precursor is reduced to obtain ruthenium, and the ruthenium may be selectively located only in the active metal layer without being dispersed inside the multilayer support.

In one embodiment, the reduction may be performed in an atmosphere containing nitrogen (N ₂ ) and/or hydrogen (H ₂ ).

Additionally, in another embodiment according to the present invention, a method for producing hydrogen from ammonia using the above-described ammonia dehydrogenation reaction catalyst is provided.

In an embodiment of the present invention, ruthenium, an active metal, is prevented from penetrating into the interior of the support, and ruthenium, a rare noble metal, can be selectively and highly dispersed only in the active metal layer present on the surface of the multilayer support.

Through this, a highly efficient catalyst for ammonia dehydrogenation reaction can be provided.

Figures 1a and 1b show the manufacturing step of the multilayer support during the catalyst synthesis process according to one embodiment of the present invention.
Figures 2a to 2c schematically show multilayer supports manufactured under different calcining atmospheres in one embodiment of the present invention.
Figures 3a to 3c show the layered structure of a catalyst for ammonia dehydrogenation reaction according to an embodiment of the present invention.
Figures 4A and 4B show SEM-EDS of Example 1 (Ru/La ₂ O ₃ ) pellet catalyst samples.
Figures 5A and 5B show SEM-EDS of the Example 3 (Ru/La ₂ O ₂ CO ₃ ) pellet catalyst sample.
Figure 6 shows a comparison of the conversion rates of ammonia (NH ₃ ) in each sample catalyst.
Figure 7 shows the results of TPR analysis to confirm the reducibility of the catalyst samples synthesized in Examples 1-3.

Hereinafter, embodiments of the present invention will be described in more detail.

The embodiments of the present invention disclosed in the text are illustrative only for illustrative purposes, and the embodiments of the present invention may be implemented in various forms and should not be construed as limited to the embodiments described in the text. .

The present invention can make various changes and take various forms, and the embodiments are not intended to limit the present invention to the specific disclosed form, but all changes, equivalents, or substitutes included in the spirit and technical scope of the present invention. It should be understood as including.

Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

Catalyst for ammonia dehydrogenation reaction

In one embodiment according to the present invention, a multilayer support comprising lanthanum compound layers (21, 22, 23, 23'); and an active metal layer 30 located on the multilayer support and containing ruthenium (Ru), wherein the lanthanum compound is lanthanum oxide (La ₂ O ₃ ) (21), lanthanum aluminate (LaAlO ₃ ) ( 22), and lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ) (23).

In an exemplary embodiment, the lanthanum compound (23') may be lanthanum oxide (La ₂ O ₃ ). In particular, the lanthanum oxide (La ₂ O ₃ ) (23') may be formed by reducing lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ) (23), and lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ) is It can prevent ruthenium, an active metal, from penetrating into the support (30'), allowing ruthenium, a rare noble metal, to be highly dispersed on the surface of the support.

In an exemplary embodiment, the ruthenium may be selectively included only in the active metal layer 30 without being dispersed within the multilayer support. For example, the ruthenium may be present in greater amounts on the outside of the multilayer support, for example, inside the active metal layer, than on the inside of the multilayer support. In particular, ruthenium, an active metal, does not exist only on the surface of the carrier, but has the property of penetrating into sites inside the carrier where ammonia is difficult to adsorb (30'). In this case, the content of ruthenium is lower than the actual content of ruthenium, a rare precious metal. This may have the disadvantage of reducing catalytic efficiency by acting as an active site. Therefore, in an embodiment of the present invention, ruthenium, an active metal, is prevented from penetrating into the inside of the support, and ruthenium, a rare noble metal, can be selectively and highly dispersed only in the active metal layer 30 present on the surface of the multilayer support.

For example, the active metal layer 30 has a thickness of 300 um or less, preferably 200 um or less, on the surface of the catalyst for ammonia dehydrogenation reaction. In this range, ruthenium is not dispersed inside the multilayer support and is formed in the active metal layer. Can only be optionally included.

In an exemplary embodiment, the ratio of the ruthenium concentration (C center) at the 'catalyst center', which is the location inside the multi-layer support with the greatest distance from the surface of the multi-layer support (C _center ), and the ruthenium concentration (C _surf ) of the active metal layer ( C _surf /C _center ) may be 3 or more. For example, it may be 3.7 or higher or 4 or higher. Within the above range, a large amount of active metal is present on the surface of the carrier, and excellent catalytic performance can be achieved.

In an exemplary embodiment, the multilayer support may include a lanthanum compound layer (21, 22, 23, 23') and an alumina layer (10). Referring to FIGS. 1A and 1B, the multilayer support is not formed by doping lanthanum into alumina to form perovskite-structured lanthanum aluminate (LaAlO ₃ ) particles on the alumina surface, but by lanthanum layered on an alumina layer. It may have a laminated structure with a compound layer. Specifically, the multilayer support may be laminated in the order of an alumina layer and a lanthanum compound layer, and may have a structure in which an active metal layer is laminated on the lanthanum compound layer.

In the case of the existing ruthenium-lanthanum/alumina catalyst, the active metal, ruthenium, does not exist only on the surface of the carrier, which is the active site, but has the property of penetrating into sites inside the carrier where ammonia is difficult to adsorb (30'). It has the disadvantage of reducing efficiency because a lower content of ruthenium, a rare precious metal, acts as an active site. On the other hand, the multilayer support includes an alumina layer and a lanthanum compound layer, and in particular, the lanthanum compound layer can prevent ruthenium from penetrating into sites inside the support phase.

In an exemplary embodiment, the active metal may be included in an amount of 0.1-20% by weight, preferably 1-5% by weight, based on the total catalyst. If the ruthenium content is less than 0.1% by weight, it may be difficult to expect high activity due to the small number of ruthenium active sites, and if the ruthenium content is more than 20% by weight, the performance of the catalyst may be reduced due to ruthenium aggregation.

Meanwhile, a method for producing hydrogen from ammonia using the ammonia dehydrogenation reaction catalyst described above can be provided.

Method for producing catalyst for ammonia dehydrogenation reaction

In another embodiment according to the invention, introducing a lanthanum precursor onto a support; and calcining the introduced lanthanum precursor in a specific atmosphere to form a lanthanum compound layer. In the lanthanum compound layer forming step, lanthanum oxide (La ₂ O ₃ ), lanthanum aluminate (LaAlO ₃ ), and lanthanum oxycarbonate ( La ₂ O ₂ CO ₃ ) Provides a method for producing a catalyst for an ammonia dehydrogenation reaction in which one or more lanthanum compounds are formed.

First, the lanthanum precursor 20 can be introduced onto the support 10. The lanthanum precursor may be introduced onto the support through vacuum wet impregnation.

Meanwhile, prior to introduction of the lanthanum precursor, the support 10 may be calcined. For example, the alumina support 10 may be prepared by calcining in an air atmosphere.

Next, the introduced lanthanum precursor 20 may be calcined in a specific atmosphere to form the lanthanum compound layers 21, 22, and 23.

In an exemplary embodiment, lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ) may be formed as a lanthanum compound in the step of forming the lanthanum compound layer, and the lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ) is an active metal inside the support. By preventing ruthenium from penetrating 30', it is possible to selectively distribute ruthenium only to the active metal layer 30 without being dispersed inside the multilayer support.

Specifically, the introduced lanthanum precursor can be calcined in a mild oxidizing agent atmosphere, and a lanthanum compound layer can be formed on the support through this oxidation process. Meanwhile, lanthanum tries to form a stable structure by forming an oxide, and when calcined in an air atmosphere, it can combine with oxygen contained in the air to form La ₂ O ₃ , a stable oxide sintered body. However, La ₂ O ₃ may not prevent ruthenium, an active metal, from penetrating into the support.

In an exemplary embodiment, the step of forming the lanthanum compound layer may be calcining in an oxidizing agent atmosphere or a CO ₂ atmosphere. In general, especially when calcined in a CO ₂ atmosphere, the lanthanum compound layer may be composed of lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ), and the lanthanum oxycarbonate (23) is formed by ruthenium, an active metal, penetrating into the support. By preventing this, ruthenium, a rare precious metal, can be highly dispersed on the surface of the support.

In an exemplary embodiment, the step of forming the lanthanum compound layer may be calcining at 400-1000° C. for 1-12 hours. In particular, when calcined above 1000°C, the crystal phase may change from La ₂ O ₂ CO ₃ (23) to La ₂ O ₃ (23') due to CO ₂ vaporization.

Meanwhile, when the lanthanum compound layer is calcined in the range of about 600 to 800° C., carbon dioxide gradually evaporates, so the composition of the lanthanum compound layer may change to La ₂ O ₃ (23').

In an exemplary embodiment, forming the active metal layer 30 by introducing a ruthenium precursor onto the lanthanum compound layers 21, 22, and 23 may be further included. For example, the ruthenium precursor can be introduced onto the lanthanum compound layer through a vacuum wet impregnation method.

In an exemplary embodiment, in the step of forming the active metal layer, the introduced ruthenium precursor is reduced to obtain ruthenium, and the ruthenium is not dispersed (30') inside the multilayer support but is selectively located only in the active metal layer (30). You can.

Specifically, the lanthanum compound layer can prevent ruthenium, an active metal, from penetrating into the interior of the support (30'), thereby allowing ruthenium, a rare noble metal, to be highly dispersed on the surface of the support.

In an exemplary embodiment, the reduction may be performed in an atmosphere containing nitrogen (N ₂ ) and/or hydrogen (H ₂ ). When reduced in such a gaseous atmosphere, it is easy to apply to the process and can be advantageous because it can improve the dispersion of ruthenium and catalytic activity.

Example

Hereinafter, the configuration and effects of the present invention will be described in more detail through examples. However, these examples are provided only for illustrative purposes to aid understanding of the present invention, and the scope and scope of the present invention are not limited by the examples below.

Example 1: Ru/La ₂ O ₃ -Al ₂ O ₃ catalyst manufacturing

10 g of commercial alumina (γ-Al ₂ O ₃ ) support (Figure 1a) was vacuum wet impregnated with an aqueous solution of 25 mL of DI water (Distilled H ₂ O) and 3.5408 g of lanthanum nitrate. ) (Figure 1b) and then calcined for 3 hours in an air atmosphere at 600°C to form a lanthanum compound layer (La ₂ O ₃ ) (Figure 2a). The formed lanthanum compound layer (La ₂ O ₃ ) was subjected to vacuum wet impregnation with an aqueous solution of 25 mL of DI water (Distilled H ₂ O) and 0.4576 g of ruthenium precursor (RuCl _3· xH ₂ O), followed by 500 Ru/La ₂ O ₃ -Al ₂ O ₃ catalyst was prepared by reduction in an atmosphere of ℃ H ₂ /N ₂ (2:1) for 2 hours (FIG. 3a).

Example 2: Ru/LaAlO ₃ -Al ₂ O ₃ catalyst manufacturing

Ru/LaAlO ₃ -Al ₂ O ₃ catalyst was prepared in the same manner as in Example 1, except that lanthanum compound layer (LaAlO ₃ ) was formed by calcining in an air atmosphere at 900°C for 3 hours (FIG. 3b). .

Example 3: Ru/La ₂ O ₂ C.O. ₃ -Al ₂ O ₃ catalyst manufacturing

Ru/La ₂ O 2 CO 3 _{-Al 2} O was produced in the same manner as in _Example 1, except that lanthanum compound layer (La ₂ O ₂ CO ₃ ) was formed by calcining in a 600°C CO ₂ atmosphere for 3 hours (FIG. 2c). ₃ catalysts were prepared (Figure 3c).

Comparative Example 1: Ru/Al ₂ O ₃ catalyst manufacturing

10 g of commercial alumina (γ-Al ₂ O ₃ ) support was vacuum wet impregnated with an aqueous solution of 25 mL of DI water (Distilled H ₂ O) and 0.4576 g of ruthenium precursor (RuCl _3· xH ₂ O). impregnation) and then reduced for 2 hours at 500°C in H ₂ /N ₂ (2:1) atmosphere to prepare a Ru/Al ₂ O ₃ catalyst.

Experimental Example 1: SEM-EDS (Line scan) analysis

The catalyst samples of Examples 1 and 3 before reduction were analyzed by SEM-EDS (Line scan). For analysis, the pellet was cut, a line scan was performed as shown in the green line, and Pt coating was performed at 15 mA for 60 s for SEM measurement.

Figure 4 shows the SEM-EDS of Example 1 (Ru/La ₂ O ₃ -Al ₂ O ₃ ) pellet catalyst sample, where it can be seen that the highest concentration of ruthenium is at both ends of the pellet (counts approximately 1000). It can be seen that the concentration of ruthenium decreases (counts about 500) toward the center of the pellet.

On the other hand, Figure 5 shows the SEM-EDS of Example 3 (Ru/La ₂ O ₂ CO ₃ -Al ₂ O ₃ ) pellet catalyst sample, with the highest concentration of ruthenium at both ends of the pellet (counts approx. 1800), and it can be seen that the concentration of ruthenium decreases rapidly (counts approximately 480) toward the center of the pellet.

In particular, when comparing the ruthenium concentration ratio near the edge and center of the pellet, when La ₂ O ₂ CO ₃ -Al ₂ O ₃ was used as a support (Example 3), it was about 3.75, La ₂ O ₃ -Al ₂ O ₃ When used as a support (Example 1), it is about 2, and in the case of La ₂ O ₂ CO ₃ -Al ₂ O ₃ , it can be indirectly confirmed that ruthenium is highly dispersed on the surface of the support.

Experimental Example 2: Catalytic activity analysis

The ammonia decomposition reaction was simulated experimentally using the catalyst samples of Examples and Comparative Examples. To conduct the experiment, 0.18 g - 0.22 g of each catalyst sample was charged into the reaction unit and reduced at 500°C for 2 hours using a H ₂ /N ₂ (2:1) mixed gas. Ammonia gas reactant with a purity of 99.9999% was supplied at a GHSV of 10,000 mL/g _cat h, and the ammonia decomposition reaction was performed at the reaction temperatures of the reactor at 350°C, 400°C, 450°C, and 500°C, respectively. The composition of the gas product generated through the reaction was determined using a gas chromatograph (GC).

Gas analysis was performed under the following conditions: i) GC-TCD: NH ₃ , N ₂ , ii) Carrier gas: helium, iii) Oven condition: 40℃ → 20℃/min → 120℃.

Figure 6 shows a comparison of the conversion rates of ammonia (NH ₃ ) in each sample catalyst. As a result, in the case of a reaction temperature of 350-400 ^o C, it was difficult to confirm the difference in conversion rate because the temperature of the reactor for ammonia decomposition was not sufficient. However, it was confirmed that the ammonia decomposition conversion rate depending on the catalyst significantly differed as the reaction temperature increased. It was confirmed that the catalyst of Ru/La ₂ O ₂ CO ₃ -Al ₂ O ₃ showed the highest conversion rate, followed by Ru/La ₂ O ₃ -Al ₂ O ₃ and Ru/LaAlO ₃ -Al ₂ O ₃ And this was followed by Ru/Al ₂ O ₃ . It was confirmed that ammonia decomposition performance was improved in the support to which lanthanum was added, and the highest ammonia decomposition catalytic activity was shown when lanthanum was formed in the form of La ₂ O ₂ CO ₃ . This indicates that ruthenium, an active metal, was evenly dispersed on the surface of the catalyst support.

Experimental Example 3: TPR analysis

Temperature Programmed Reduction analysis was performed to confirm the reducibility of the catalyst samples of the examples, and the results are shown in FIG. 7.

In Figure 7, it can be seen that Ru metal was reduced at 210°C or lower in all catalysts synthesized in Examples 1-3. Meanwhile, the lower the temperature at which ruthenium is reduced, the higher the ruthenium concentration on the catalyst surface. Therefore, it can be confirmed that ruthenium was reduced at 109, 135 ^o C in the case of Ru/La ₂ O ₂ CO ₃ -Al ₂ O ₃ , and at 140, 176, 204 ^o C and Ru in the case of Ru/LaAlO _{3 -Al 2} O ₃ /La ₂ O ₃ -Al ₂ O ₃ was confirmed to be reduced at 131, 209 ^o C. Therefore, when a support of La ₂ O ₂ CO ₃ was used, ruthenium, an active metal, was most highly dispersed on the surface of the support.

The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The scope of protection of the present invention is limited only by the matters stated in the claims, and those skilled in the art can improve and change the technical idea of the present invention into various forms. Accordingly, such improvements and changes will fall within the scope of protection of the present invention as long as they are obvious to those skilled in the art.

Claims (16)

A multilayer support comprising a lanthanum compound layer; and
An active metal layer located on the lanthanum compound layer of the multilayer support and containing ruthenium (Ru),
The lanthanum compound is lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ),
The active metal layer containing ruthenium is formed by using ruthenium (III) chloride as a ruthenium precursor and reducing the ruthenium (III) chloride in an atmosphere containing hydrogen and nitrogen. According to paragraph 1,
The active metal layer containing ruthenium is formed by reducing the ruthenium (III) chloride in an atmosphere containing hydrogen and nitrogen at a volume ratio of 2:1. According to paragraph 1,
A catalyst for an ammonia dehydrogenation reaction in which the ruthenium is not dispersed within the multilayer support but is selectively included only in the active metal layer. According to paragraph 1,
A catalyst for ammonia dehydrogenation reaction, wherein the ruthenium exists in greater amounts outside the multilayer support than inside the multilayer support. According to paragraph 1,
The ratio (C surf /C center) of the ruthenium concentration (C _center ) at the center of the catalyst, which is the position inside the multilayer support having the greatest distance from the surface _of the multilayer support (C center ₎ , and the ruthenium concentration (C _surf ) of the active metal layer is 3. Lee Sang-in, catalyst for ammonia dehydrogenation reaction. According to paragraph 1,
A catalyst for ammonia dehydrogenation reaction, wherein the multilayer support includes a lanthanum compound layer and an alumina layer. According to claim 1,
An ammonia dehydrogenation reaction catalyst, characterized in that the active metal is contained in 1-10% by weight based on the total catalyst. According to claim 7,
An ammonia dehydrogenation reaction catalyst, characterized in that the active metal is contained in 1-5% by weight based on the total catalyst. A method for producing the catalyst for ammonia dehydrogenation reaction of any one of claims 1 to 8, the method comprising:
introducing a lanthanum precursor onto the support;
Calcining the introduced lanthanum precursor in a CO ₂ atmosphere to form a lanthanum compound layer; and
Introducing a ruthenium precursor onto the formed lanthanum compound layer and reducing it in an atmosphere containing hydrogen and nitrogen to form an active metal layer,
The lanthanum compound layer is lanthanum oxycarbonate (La ₂ O ₂ CO ₃ ),
A method for producing a catalyst for ammonia dehydrogenation reaction, wherein the ruthenium precursor is ruthenium (III) chloride. delete delete According to clause 9,
A method of producing a catalyst for ammonia dehydrogenation reaction in which the lanthanum compound layer forming step is calcined at 400-1000° C. for 1-5 hours. According to clause 9,
A method of producing a catalyst for ammonia dehydrogenation reaction, wherein the active metal layer forming step is reduced at 500° C. for 2 hours. delete delete A method of producing hydrogen from ammonia using the ammonia dehydrogenation reaction catalyst of any one of claims 1 to 8.