Ammonia dehydrogenation catalyst, its manufacturing method and hydrogen production method using the same

Abstract

A catalyst for ammonia dehydrogenation, a method for producing the same, and a method for producing hydrogen using the same are disclosed. The catalyst for ammonia dehydrogenation disclosed includes a zeolite having intracrystalline cations, and an alkali metal and ruthenium supported on the zeolite.

Description

Detailed Description of the Invention

[0001] [Technical field] This invention discloses an ammonia dehydrogenation catalyst, a method for producing the same, and a method for producing hydrogen using the same. More specifically, this invention discloses an ammonia dehydrogenation catalyst that can produce hydrogen from ammonia at a high yield, a method for producing the same, and a method for producing hydrogen using the same.

[0002] [Background technology] In recent years, there has been increasing interest worldwide in the production and utilization of hydrogen energy (blue and green hydrogen) as a sustainable and environmentally friendly alternative energy source that does not emit carbon dioxide.

[0003] Methods for producing hydrogen energy include green hydrogen production through water electrolysis and nuclear-based pink hydrogen production. In particular, ammonia not only serves as a hydrogen carrier but can also be used as an energy source. Furthermore, when an appropriate catalyst is used, ammonia can be dehydrogenated to produce hydrogen.

[0004] The above-described method for producing hydrogen from ammonia can be applied in the following fields. First, oil refineries such as Hyundai Oil Bank are planning to modify and supplement their existing gas stations, which offer gasoline, diesel, and LPG, to create futuristic gas stations (combined energy stations) that offer a full range of transportation fuels and energy sources, including hydrogen and electrical charging, all in one place. In particular, when "hydrogen-based vehicles using fuel cells," which are currently being developed by Hyundai Motor and other companies, are commercialized, oil refineries are expected to supply hydrogen to these futuristic gas stations. Therefore, hydrogen produced from ammonia could be supplied to gas stations and used as a fuel cell feedstock. In addition, the oil refineries and petrochemical industries require large amounts of hydrogen to produce various products. Using environmentally friendly hydrogen produced through the ammonia dehydrogenation process, which does not emit carbon dioxide, rather than hydrogen produced through existing natural gas reforming processes such as steam methane reforming, which emits a considerable amount of carbon dioxide, is expected to reduce carbon dioxide emissions. The hydrogen produced through the ammonia dehydrogenation reaction can also be used for power generation. Ammonia itself is a raw material for power generation and can be burned to produce energy without emitting carbon dioxide. However, ammonia has chronic problems due to its inherent characteristics, such as low calorific value and difficulty in ignition. To address these issues, several methods have been proposed: converting only a portion of the ammonia into hydrogen and then producing energy through ammonia-hydrogen co-firing, or converting all of the ammonia into hydrogen and then producing energy through hydrogen combustion. In this case, it is believed that environmentally friendly energy can be produced by utilizing the advantages of hydrogen, such as its high calorific value and ease of ignition. Furthermore, ammonia can be used to produce energy not only through co-firing or combustion with hydrogen, but also by converting ammonia into hydrogen and using the produced hydrogen in fuel cells.More specifically, by converting a portion or all of the ammonia into hydrogen depending on the target power generation capacity and then using the hydrogen thus produced as a feedstock for a fuel cell, it is believed possible to produce energy equivalent to the required power generation capacity. Another possible use of ammonia is as a fuel for ships. Similar to the power generation example described above, ammonia can also be used as fuel to produce energy to propel ships. Therefore, if a portion or all of the ammonia is converted into hydrogen, it is believed possible to propel ships by producing energy through co-combustion of ammonia and hydrogen, combustion of hydrogen, or a combination with an additional fuel cell.

[0005] As a result, interest in technology to dehydrogenate ammonia to produce hydrogen is growing worldwide. If a high-performance ammonia dehydrogenation catalyst is developed, it is believed that it will be possible to produce hydrogen through such a catalyst and apply the produced hydrogen to various uses.

[0006] Generally, ruthenium (Ru)-based catalysts used to manufacture highly active ammonia dehydrogenation catalysts are expensive. Furthermore, the high temperature of the ammonia dehydrogenation reaction results in rapid catalyst deactivation. Therefore, it is essential to develop a catalyst that minimizes the Ru content while maintaining high activity even at low temperatures. Currently, there is a global demand for the development of such a catalyst.

[0007] [Summary of the Invention] [Problem to be solved by the invention] An embodiment of the present invention provides a catalyst for ammonia dehydrogenation that can produce hydrogen from ammonia in high yield.

[0008] Another embodiment of the present invention provides a method for preparing the ammonia dehydrogenation catalyst. Yet another embodiment of the present invention provides a method for producing hydrogen from ammonia using the ammonia dehydrogenation catalyst.

[0009] [Means for solving the problem] One aspect of the present invention is Zeolites with intracrystalline cations and The present invention provides a catalyst for ammonia dehydrogenation, which comprises an alkali metal and ruthenium supported on the zeolite.

[0010] The cations in the crystal are hydrogen ions (H + ), sodium ions (Na + ), potassium ions (K + ), calcium ions (Ca 2+ ), magnesium ions (Mg 2+ ), rubidium ion (Rb + ), cesium ions (Cs + ) or a combination thereof.

[0011] The amount of the alkali metal supported in the ammonia dehydrogenation catalyst may be 5 to 50 parts by weight based on 100 parts by weight of the zeolite. The alkali metal may include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), or a combination thereof.

[0012] The catalyst for ammonia dehydrogenation may have a supported amount of ruthenium of 0.5 to 10 parts by weight based on 100 parts by weight of the zeolite. The catalyst for ammonia dehydrogenation may have a supported amount of ruthenium of 1 to 10 parts by weight based on 100 parts by weight of the zeolite.

[0013] The zeolite may have an Si / Al atomic ratio of 1-30. The zeolite has a BET specific surface area of ​​300 to 900 m 2 / g. The zeolite may further comprise an alkaline earth metal, a lanthanide metal, or a combination thereof supported on the zeolite.

[0014] The total amount of the alkali metal, alkaline earth metal, and lanthanum metal supported may be more than 5 parts by weight and 50 parts by weight or less per 100 parts by weight of the zeolite. The zeolite may include zeolite X, zeolite Y, USY zeolite, ZSM-5, beta zeolite, chabazite zeolite, SAPO series zeolite, mordenite zeolite, zeolite L, zeolite A, RFCC spent catalyst, or a combination thereof.

[0015] Another aspect of the present invention is providing a zeolite having intracrystalline cations (S10); a step (S20) of supporting an alkali metal on the zeolite; a step (S30) of drying the alkali metal-loaded zeolite; A step (S40) of supporting ruthenium on the dried zeolite; and The method for preparing the catalyst for ammonia dehydrogenation includes a step (S50) of drying the alkali metal and ruthenium-supported zeolite.

[0016] The method for preparing the ammonia dehydrogenation catalyst may further include, after the step (S50), a step (S60) of activating the dried zeolite by contacting it with a reducing agent. The reducing agent may include hydrogen, ammonia, or a combination thereof.

[0017] Yet another aspect of the present invention is The present invention provides a method for producing hydrogen, comprising the step (S100) of contacting ammonia with the catalyst for ammonia dehydrogenation to produce hydrogen.

[0018] The step (S100) may be performed at a temperature of 300 to 700°C. The step (S100) is performed for 500 hours. -1 ~25,000hr -1 The reaction can be carried out at a space velocity of 0.1 to 1.0 MPa.

[0019] [Effects of the invention] The ammonia dehydrogenation catalyst according to an embodiment of the present invention can produce hydrogen from ammonia in a high yield. DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, a catalyst for ammonia dehydrogenation according to an embodiment of the present invention will be described in detail. In this specification, the term "intracrystalline cation" refers to a cation that is present within a (Si,Al)O4 tetrahedron, which is a structural unit of zeolite. 4+ is partially Al 3+ These cations exist within the zeolite crystal structure to compensate for the charge deficiency that occurs when cations are substituted with other cations in the vicinity by ion exchange.

[0021] In this specification, the term "ion exchange method" refers to a method of exchanging intracrystalline cations present in the zeolite crystal structure with Cs + Ion exchange refers to a method used to exchange a substance with a desired cation, such as SiO2. Generally, the ion exchange method involves preparing an aqueous solution of a substance containing the desired cation, adding zeolite to the prepared aqueous solution to obtain a slurry, and then stirring the slurry at the temperature, pressure, and time conditions desired by the user. After thorough stirring, the zeolite-containing slurry is filtered to obtain only the solid, which is then subjected to an additional washing process and dried. Since only the cations are exchanged due to the properties of the zeolite, the anions that were present in the substance are removed along with the solution during the filtration process. Ion exchange is carried out using Si 4+ Al 3+ Since this reaction occurs when cations are replaced by aluminum, the amount of ion exchange is theoretically equal to the number of moles of aluminum present in the zeolite. However, in practice, the amount of ion exchange is much less than the theoretical value depending on the size and charge of the cations to be exchanged.

[0022] Additionally, in this specification, the term "impregnation method" generally refers to a method used to support an active metal or cocatalyst on a support. This method involves dropping a solution onto the support in a volume equivalent to the pore volume of the support, thereby supporting the active metal or cocatalyst on the surface of the support. Specifically, a solution is prepared by dissolving a material containing the desired metal in a solvent capable of dissolving the material. Depending on the solubility of the material, the volume of the solution may be greater than the pore volume. This method, unlike the ion exchange method, allows the desired amount of metal to be easily supported on the support. However, unlike the ion exchange method, this method does not selectively support cations because the entire material is supported on the support. Therefore, it may be necessary to remove undesired anions through a post-treatment method, such as an additional heat treatment.

[0023] In addition, in this specification, the term "ammonia conversion rate" refers to a value calculated by the following Equation 1:

[0024] [Number 1] Ammonia conversion rate (%) = moles of reacted ammonia / moles of initially supplied ammonia × 100

[0025] In addition, in this specification, the term "RFCC spent catalyst" means a spent catalyst derived from a residue fluid catalytic cracking unit of heavy oil.

[0026] In this specification, the "BET (Brunauer-Emmett-Teller) specific surface area" was measured using an ASAP2460 model device manufactured by Micromeritics.

[0027] The intracrystalline cations are those present within the zeolite crystal structure but not at the surface of the zeolite, and are distinct from ruthenium, alkali metals, alkaline earth metals and / or lanthanide metals present at the surface of the zeolite.

[0028] The cations in the crystal are hydrogen ions (H + ), sodium ions (Na + ), potassium ions (K + ), calcium ions (Ca 2+ ), magnesium ions (Mg 2+ ), rubidium ion (Rb + ), cesium ions (Cs + ) or a combination thereof.

[0029] The alkali metals are supported on the zeolite and are present inside and / or on the surface of the zeolite, but not inside the cavities of the zeolite crystal structure, and are therefore distinguishable from intracrystalline cations present within the zeolite crystal structure.

[0030] The amount of the alkali metal supported may be 5 to 50 parts by weight based on 100 parts by weight of the zeolite. When the amount of the alkali metal supported is within this range, an ammonia dehydrogenation catalyst capable of improving the ammonia conversion rate can be obtained.

[0031] Furthermore, the range of the alkali metal loading does not change depending on the type of zeolite and the type and amount of cations in the crystal, which has been confirmed by the present inventors through numerous repeated experiments.

[0032] The alkali metal may include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), or a combination thereof.

[0033] The ruthenium (Ru), like the alkali metals, is supported on the zeolite and is present on the surface of the zeolite, not inside the cavities of the zeolite crystal structure, and is therefore distinguished from the intracrystalline cations present within the zeolite crystal structure.

[0034] The amount of ruthenium supported may be 0.5 to 10 parts by weight based on 100 parts by weight of the zeolite. When the amount of ruthenium supported is within this range, an ammonia dehydrogenation catalyst capable of improving the ammonia conversion rate can be obtained.

[0035] Furthermore, the range of the ruthenium loading, like the range of the alkali metal loading, does not vary depending on the type of zeolite and the type and amount of intracrystalline cations, a fact confirmed by the present inventors through numerous repeated experiments.

[0036] Specifically, the amount of ruthenium supported may be 1 to 10 parts by weight based on 100 parts by weight of the zeolite. The zeolite may have a Si / Al atomic ratio of 1 to 30. When the Si / Al atomic ratio is within this range, it is possible to obtain an ammonia dehydrogenation catalyst that can improve the ammonia conversion rate.

[0037] Furthermore, the limited range of the Si / Al atomic ratio does not change depending on the type of zeolite and the type and amount of intracrystalline cations, which has been confirmed by the present inventors through numerous repeated experiments.

[0038] The zeolite has a BET specific surface area of ​​300 to 900 m 2 When the BET specific surface area is within the above range, an ammonia dehydrogenation catalyst capable of improving the ammonia conversion rate can be obtained.

[0039] Furthermore, the limited range of the BET specific surface area does not change depending on the type of zeolite and the type and amount of intracrystalline cations, which has been confirmed by the present inventors through numerous repeated experiments.

[0040] The ammonia dehydrogenation catalyst may further include an alkaline earth metal, a lanthanum metal, or a combination thereof supported on the zeolite. The total amount of the alkali metal, alkaline earth metal, and lanthanum-based metal supported may be more than 5 parts by weight and not more than 50 parts by weight per 100 parts by weight of the zeolite. Specifically, when the ammonia dehydrogenation catalyst further comprises an alkaline earth metal, a lanthanum-based metal, or a combination thereof supported on the zeolite, the total amount of the alkaline earth metal and the lanthanum-based metal supported may be adjusted as desired within a range that achieves a target ammonia conversion rate. Here, the target ammonia conversion rate refers to an ammonia conversion rate obtained under conditions where the total amount of the alkaline earth metal and the lanthanum-based metal supported is "0" and the amount of the alkali metal supported is 5 to 50 parts by weight per 100 parts by weight of the zeolite.

[0041] The zeolite may include zeolite X, zeolite Y, USY zeolite, ZSM-5, beta zeolite, chabazite zeolite (e.g., SSZ-13), SAPO series zeolite (e.g., SAPO-5, SAPO-11, SAPO-34), mordenite zeolite, zeolite L, zeolite A, RFCC spent catalyst, or a combination thereof. However, the present invention is not limited thereto, and other types of zeolites may also be included within the scope of the present invention.

[0042] Hereinafter, a method for preparing an ammonia dehydrogenation catalyst according to an embodiment of the present invention will be described in detail. A method for preparing an ammonia dehydrogenation catalyst according to an embodiment of the present invention includes the steps of: providing a zeolite having intracrystalline cations (S10); supporting an alkali metal on the zeolite (S20); drying the alkali metal-supported zeolite (S30); supporting ruthenium on the dried zeolite (S40); and drying the alkali metal- and ruthenium-supported zeolite (S50).

[0043] When steps (S20) and (S30) precede steps (S40) and (S50) in time, both the alkali metal and the ruthenium can be uniformly loaded on the zeolite in the desired amounts. When steps (S40) and (S50) precede steps (S20) and (S30) in time, the alkali metal cannot be uniformly loaded on the zeolite in the desired amounts.

[0044] The method for preparing an ammonia dehydrogenation catalyst may further include, after step S50, a step S60 of activating the dried zeolite by contacting it with a reducing agent, which may be performed in situ in the same reactor as step S50.

[0045] The reducing agent may be a substance capable of reducing the ammonia dehydrogenation catalyst (particularly, ruthenium). For example, the reducing agent can include hydrogen, ammonia, or a combination thereof.

[0046] Hereinafter, a method for producing hydrogen using the ammonia dehydrogenation catalyst according to an embodiment of the present invention will be described in detail. A method for producing hydrogen according to an embodiment of the present invention may include the step of contacting ammonia with the above-described ammonia dehydrogenation catalyst to produce hydrogen (S100).

[0047] The step (S100) may be performed at a temperature of 300 to 700°C. Also, the step (S100) is performed for 500 hours. -1 ~25,000hr -1 The process can be carried out at a gas hourly space velocity (GHSV).

[0048] The present invention will be described below with reference to the following examples, but the present invention is not limited to the following examples. Experimental example 1: Cesium (Cs) loading by loading method USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 Cesium (Cs) was loaded onto the catalyst (1 / g) using the incipient wetness impregnation method, and then dried at 80°C for 12 hours. The target and actual loading amounts of Cs (analyzed by ICP) are shown in Table 1 below.

[0049] Experimental Example 2: Cesium (Cs) substitution by ion exchange method Ion exchange was carried out at 70°C for 20 hours to obtain USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g) of which hydrogen ions (H + ) into cesium ions (Cs + ), and then dried at 80°C for 12 hours. In this case, the target substitution amount of cesium (Cs) and the actual substitution amount (analyzed by ICP) are shown in Table 1 below.

[0050] [Table 1]

[0051] Referring to Table 1, it was confirmed that in the case of the ion exchange method, the actual Cs substitution amount was considerably less than the target Cs substitution amount, and even when the target Cs substitution amount was increased, the actual Cs substitution amount did not increase beyond a predetermined limit value.

[0052] On the other hand, referring to Table 2 below together with Table 1, it was confirmed that in the case of the loading method (i.e., incipient wetness impregnation method), not only was the actual Cs loading similar to the target Cs loading, but also that as the target Cs loading increased, the actual Cs loading also increased.

[0053] Example 1: Preparation of a catalyst for ammonia dehydrogenation First, USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 Cesium (Cs) as a promoter was loaded onto the USY zeolite (0.05 wt. / g) using incipient wetness impregnation, and then dried at 80°C for 12 hours. Ruthenium (Ru) was then additionally loaded onto the cesium-loaded USY zeolite using incipient wetness impregnation, and then dried at 80°C for 12 hours. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 0.5 parts by weight of ruthenium (Ru) were loaded onto 100 parts by weight of USY zeolite.

[0054] Example 2: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the amount of ruthenium (Ru) supported was changed. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 1.0 part by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0055] Example 3: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the amount of ruthenium (Ru) supported was changed. As a result, an ammonia dehydrogenation catalyst in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite was obtained.

[0056] Example 4: Preparation of a catalyst for ammonia dehydrogenation Except for changing the amount of ruthenium (Ru), an ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1. As a result, an ammonia dehydrogenation catalyst in which 30 parts by weight of cesium (Cs) and 5.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite was obtained.

[0057] Example 5: Preparation of a catalyst for ammonia dehydrogenation Except for changing the amount of ruthenium (Ru), an ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1. As a result, an ammonia dehydrogenation catalyst in which 30 parts by weight of cesium (Cs) and 10.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite was obtained.

[0058] Example 6: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the loading amounts of cesium (Cs) and ruthenium (Ru) were changed. As a result, an ammonia dehydrogenation catalyst was obtained in which 5.0 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were loaded on 100 parts by weight of USY zeolite.

[0059] Example 7: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the loading amounts of cesium (Cs) and ruthenium (Ru) were changed. As a result, an ammonia dehydrogenation catalyst in which 50 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were loaded on 100 parts by weight of USY zeolite was obtained.

[0060] Example 8: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 1, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0061] Example 9: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 30, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0062] Example 10: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 300m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0063] Example 11: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 900m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0064] Example 12: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: Na + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0065] Example 13: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: K + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0066] Example 14: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: Ca 2+ , Si / Al atomic ratio: 15, BET specific surface area: 625m 2An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0067] Example 15: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: Mg 2+ , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0068] Example 16: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: Ru + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0069] Example 17: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: Cs + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0070] Example 18: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), instead of zeolite X (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0071] Example 19: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), zeolite Y (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0072] Example 20: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), ZSM-5 (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0073] Example 21: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), instead of beta zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0074] Example 22: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), instead of chabazite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0075] Example 23: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), SAPO series zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0076] Example 24: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), mordenite zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0077] Example 25: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), zeolite L (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0078] Example 26: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), instead of zeolite A (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0079] Example 27: Preparation of a catalyst for ammonia dehydrogenation USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), instead of RFCC waste catalyst (HD Hyundai Oil Bank, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0080] Example 28: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that lithium (Li) was used instead of cesium (Cs) as the promoter. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of lithium (Li) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0081] Example 29: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that sodium (Na) was used instead of cesium (Cs) as the promoter. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of sodium (Na) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0082] Example 30: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that potassium (K) was used instead of cesium (Cs) as the promoter. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of potassium (K) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0083] Example 31: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that rubidium (Rb) was used instead of cesium (Cs) as the promoter. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of rubidium (Rb) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0084] Example 32: Preparation of a catalyst for ammonia dehydrogenation An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that francium (Fr) was used instead of cesium (Cs) as the promoter. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of francium (Fr) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0085] Reference Example 1: Production of ammonia dehydrogenation catalyst An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the amount of ruthenium (Ru) supported was changed. As a result, an ammonia dehydrogenation catalyst in which 30 parts by weight of cesium (Cs) and 0.1 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite was obtained.

[0086] Reference Example 2: Production of ammonia dehydrogenation catalyst An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the amount of ruthenium (Ru) supported was changed. As a result, an ammonia dehydrogenation catalyst in which 30 parts by weight of cesium (Cs) and 15 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite was obtained.

[0087] Reference Example 3: Production of ammonia dehydrogenation catalyst An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the loading amounts of cesium (Cs) and ruthenium (Ru) were changed. As a result, an ammonia dehydrogenation catalyst in which 0.3 parts by weight of cesium (Cs) and 2 parts by weight of ruthenium (Ru) were loaded on 100 parts by weight of USY zeolite was obtained.

[0088] Reference Example 4: Production of ammonia dehydrogenation catalyst An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the loading amounts of cesium (Cs) and ruthenium (Ru) were changed. As a result, an ammonia dehydrogenation catalyst was obtained in which 0.5 parts by weight of cesium (Cs) and 2 parts by weight of ruthenium (Ru) were loaded on 100 parts by weight of USY zeolite.

[0089] Reference Example 5: Production of ammonia dehydrogenation catalyst An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the loading amounts of cesium (Cs) and ruthenium (Ru) were changed. As a result, an ammonia dehydrogenation catalyst in which 60 parts by weight of cesium (Cs) and 2 parts by weight of ruthenium (Ru) were loaded on 100 parts by weight of USY zeolite was obtained.

[0090] Reference Example 6: Production of ammonia dehydrogenation catalyst USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 0.5, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0091] Reference Example 7: Production of ammonia dehydrogenation catalyst USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 35, BET specific surface area: 625m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0092] Reference Example 8: Production of ammonia dehydrogenation catalyst USY zeolite (Zeolyst, crystalline cation: H +, Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 250m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0093] Reference Example 9: Production of ammonia dehydrogenation catalyst USY zeolite (Zeolyst, crystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 625m 2 / g), USY zeolite (Zeolyst, intracrystalline cation: H + , Si / Al atomic ratio: 15, BET specific surface area: 950m 2 An ammonia dehydrogenation catalyst was prepared in the same manner as in Example 1, except that a 100-part USY zeolite carrier (USY zeolite carrier) was used. As a result, an ammonia dehydrogenation catalyst was obtained in which 30 parts by weight of cesium (Cs) and 2.0 parts by weight of ruthenium (Ru) were supported on 100 parts by weight of USY zeolite.

[0094] Comparative Example 1: Preparation of Control Catalyst First, an ion exchange method was carried out at 70°C for 20 hours to obtain USY zeolite (Zeolyst, intracrystalline cation: H + ) hydrogen ions (H + ) into cesium ions (Cs + ), and then dried at 80°C for 12 hours. Ruthenium (Ru) was then supported on the cesium ion-substituted USY zeolite using incipient wetness impregnation, and then dried at 80°C for 12 hours. As a result, a control catalyst was obtained in which 2.1 parts by weight of cesium (Cs) was substituted for 100 parts by weight of USY zeolite and 2 parts by weight of ruthenium (Ru) was supported.

[0095] The compositions of the catalysts produced in Examples 1 to 32, Reference Examples 1 to 9, and Comparative Example 2 are summarized in Table 2 below.

[0096] [Table 2] TIFF2025531262000003.tif110170

[0097] Evaluation example 1: Evaluation of ammonia conversion rate The catalysts prepared in Examples 1 to 32, Reference Examples 1 to 9, and Comparative Example 1 were activated by in-situ hydrogen treatment. Then, they were heated at atmospheric pressure (1 atm), 450°C, and a space velocity of 12,000 h -1 After contacting 100% ammonia gas with each of the catalysts under the above conditions, the ammonia conversion rate was evaluated according to Equation 1, and the results are shown in Table 3 below.

[0098] [Table 3]

[0099] Referring to Table 3, it can be seen that the catalysts prepared in Examples 1 to 32 have higher ammonia conversion rates than the catalysts prepared in Reference Examples 1 to 9 and Comparative Example 1. In addition, in this specification, an ammonia dehydrogenation catalyst was prepared by supporting only cesium (Cs) as an alkali metal, and the activity (i.e., ammonia conversion rate) of the ammonia dehydrogenation catalyst thus prepared was evaluated. However, since all alkali metals have substantially the same properties, substantially the same results as those shown in Tables 2 and 3 can be obtained even when an ammonia dehydrogenation catalyst is prepared by supporting other alkali metals, such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), francium (Fr), or a combination thereof, instead of cesium (Cs). This is obvious to a person skilled in the art.

[0100] While the preferred embodiments of the present invention have been described above with reference to the examples, these are merely illustrative and those skilled in the art will recognize that various modifications and equivalent embodiments are possible. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. Zeolites with intracrystalline cations and The catalyst for ammonia dehydrogenation contains an alkali metal and ruthenium supported on the zeolite.

2. The intracrystalline cations are hydrogen ions (H + ), sodium ions (Na + ), potassium ions (K + ), calcium ions (Ca 2+ ), magnesium ions (Mg 2+ ), rubidium ion (Rb + ), cesium ions (Cs + 2. The ammonia dehydrogenation catalyst of claim 1, comprising:

3. 2. The ammonia dehydrogenation catalyst according to claim 1, wherein the amount of the alkali metal supported is 5 to 50 parts by weight per 100 parts by weight of the zeolite.

4. 2. The ammonia dehydrogenation catalyst of claim 1, wherein the alkali metal comprises lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), or a combination thereof.

5. 2. The ammonia dehydrogenation catalyst according to claim 1, wherein the amount of the ruthenium supported is 0.5 to 10 parts by weight based on 100 parts by weight of the zeolite.

6. 6. The ammonia dehydrogenation catalyst according to claim 5, wherein the amount of the ruthenium supported is 1 to 10 parts by weight per 100 parts by weight of the zeolite.

7. 2. The ammonia dehydrogenation catalyst according to claim 1, wherein the zeolite has a Si / Al atomic ratio of 1 to 30.

8. The zeolite has a BET specific surface area of ​​300 to 900 m 2 2. The ammonia dehydrogenation catalyst according to claim 1, wherein the ammonia dehydrogenation catalyst has a Cr content of 1.00 or more.

9. 10. The ammonia dehydrogenation catalyst of claim 1, further comprising an alkaline earth metal, a lanthanide metal, or a combination thereof supported on the zeolite.

10. 10. The ammonia dehydrogenation catalyst according to claim 9, wherein the total amount of the alkali metal, the alkaline earth metal, and the lanthanum metal supported is more than 5 parts by weight and not more than 50 parts by weight per 100 parts by weight of the zeolite.

11. 2. The ammonia dehydrogenation catalyst according to claim 1, wherein the zeolite comprises zeolite X, zeolite Y, USY zeolite, ZSM-5, beta zeolite, chabazite zeolite, SAPO series zeolite, mordenite zeolite, zeolite L, zeolite A, RFCC spent catalyst, or a combination thereof.

12. Providing a zeolite having intracrystalline cations (S10); A step (S20) of supporting an alkali metal on the zeolite; Drying the alkali metal-loaded zeolite (S30); (S40) supporting ruthenium on the dried zeolite; and The method for preparing an ammonia dehydrogenation catalyst includes a step (S50) of drying the alkali metal and ruthenium-loaded zeolite.

13. 13. The method of claim 12, further comprising, after step S50, contacting the dried zeolite with a reducing agent to activate it (S60).

14. The method for producing an ammonia dehydrogenation catalyst according to claim 13, wherein the reducing agent comprises hydrogen, ammonia, or a combination thereof.

15. A method for producing hydrogen, comprising the step (S100) of contacting ammonia with the ammonia dehydrogenation catalyst according to any one of claims 1 to 11 to produce hydrogen.

16. 16. The method of claim 15, wherein the step (S100) is performed at a temperature of 300 to 700°C.

17. The step (S100) lasts for 500 hours. -1 ~25,000hr -1 The method for producing hydrogen according to claim 15, wherein the hydrogen is produced at a space velocity of

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