Methane-reforming catalyst and method for producing same

Abstract

A method for producing a methane-reforming catalyst according to an embodiment of the present invention includes: a step for oxidizing the surface of a porous metal support; a step for forming a first coating layer, including a first inorganic oxide, on the surface-oxidized porous metal support by atomic layer deposition (ALD), and then performing a first heat treatment process to prepare a catalyst precursor comprising the first coating layer; and a step for coating the catalyst precursor, comprising the first coating layer, with a solution containing a precursor of a perovskite compound represented by chemical formula 1, and then performing a second heat treatment process to prepare a catalyst comprising a second coating layer.

Description

Catalyst for methane reforming and method for producing the same

[0001] This application claims the benefit of the filing dates of Korean Patent Application No. 10-2024-0031318, filed with the Korean Intellectual Property Office on March 5, 2024, and Korean Patent Application No. 10-2024-0031322, filed with the Korean Intellectual Property Office on March 5, 2024, the entire contents of which are incorporated herein by reference.

[0002] The present application relates to a catalyst for methane reforming and a method for producing the same.

[0003] As part of efforts to reduce greenhouse gas emissions due to global warming, extensive research is underway on carbon dioxide conversion technologies. Carbon dioxide reforming, one such carbon dioxide conversion technology, involves reacting methane and carbon dioxide to produce a synthesis gas composed of hydrogen and carbon monoxide.

[0004] Syngas is a highly valuable material for development as a raw material for various downstream applications. Natural gas reforming reactions, which allow for the industrial production of synthesis gas (H2 / CO), can be broadly categorized into steam reforming, CO2 reforming, catalytic partial oxidation, autothermal reforming, and tri-reforming, as shown in Equations 1 through 5 below.

[0005] [Reaction Formula 1]

[0006] CH4+ H2O → 3H2+ CO △H = 226 kJ / mol

[0007] [Reaction Formula 2]

[0008] CH4+ CO2→ 2H2+ 2CO △H = 261 kJ / mol

[0009] [Reaction Formula 3]

[0010] CH4+ 0.5O2→ 2H2+ CO △H = -44 kJ / mol

[0011] [Reaction Formula 4]

[0012] autothermal reforming: Reaction 1 + Reaction 3

[0013] [Reaction Formula 5]

[0014] tri-reforming: Reaction 1 + Reaction 2 + Reaction 3

[0015] Meanwhile, various catalysts can be used in the above reforming process to enhance reforming activity. Among these, the use of precious metal catalysts in the reforming process offers the advantage of high hydrogen conversion efficiency from natural gas. However, the high cost of precious metal catalysts reduces economic feasibility.

[0016] Accordingly, nickel catalysts, which boast high hydrogen conversion efficiency and are relatively inexpensive, are primarily used in reforming processes. However, these catalysts face the problem of deactivation due to the carbon that inevitably forms on their surface.

[0017] Therefore, in this technical field, there is a need for the development of a catalyst that is resistant to carbon deposition and can be effectively applied to the methane reforming process.

[0018] The present application seeks to provide a catalyst for methane reforming and a method for producing the same.

[0019] One embodiment of this application is:

[0020] A step of oxidizing the surface of a porous metal support;

[0021] A step of forming a first coating layer including a first inorganic oxide on a porous metal support having an oxidized surface using ALD (atomic layer deposition), and then performing a first heat treatment process to manufacture a catalyst precursor having a first coating layer; and

[0022] A step of manufacturing a catalyst having a second coating layer by coating a solution containing a precursor of a perovskite compound represented by the following chemical formula 1 on a catalyst precursor having the first coating layer, and then performing a second heat treatment process.

[0023] A method for producing a catalyst for methane reforming including:

[0024] [Chemical Formula 1]

[0025] Sr 1-x A x Ti 1-y B y O 3-δ

[0026] In the above chemical formula 1,

[0027] A is selected from Y, Sc, La and lanthanide series elements,

[0028] B is Cr, Mn, Fe, Co, Ni, Mo, Ru or Rh,

[0029] x is a real number greater than or equal to 0 and less than 1,

[0030] y is a real number greater than or equal to 0 and less than 1,

[0031] δ is a real number greater than or equal to 0 and less than 1,

[0032] (x + y) > 0.

[0033] In addition, another embodiment of the present application is

[0034] A porous metal support with an oxidized surface;

[0035] A first coating layer provided on a porous metal support having an oxidized surface and including a first inorganic oxide; and

[0036] A catalyst for methane reforming comprising a second coating layer provided on the first coating layer and including a perovskite compound represented by the chemical formula 1,

[0037] The thickness of the first coating layer is 5 nm to 100 nm,

[0038] A catalyst for methane reforming is provided, wherein the thickness uniformity (%) of the first coating layer calculated by the following mathematical formula 4 is 60% or more.

[0039] [Equation 4]

[0040] (Minimum thickness of the first coating layer) / (Maximum thickness of the first coating layer) × 100

[0041] A catalyst for methane reforming according to one embodiment of the present application can improve the adhesion between a porous metal support and a second coating layer including a perovskite compound represented by chemical formula 1 by forming a first coating layer including a first inorganic oxide, and can also prevent side reactions of the porous metal support.

[0042] In addition, the catalyst for methane reforming according to one embodiment of the present application has the characteristic of being easy to control the heat of reaction compared to conventional pellet-type or powder-type catalysts, since a perovskite compound is supported on a porous metal support having high thermal conductivity.

[0043] In addition, the catalyst for methane reforming according to one embodiment of the present application has a feature that additional activity increase is possible due to a synergistic effect between the first coating layer including the first inorganic oxide and the second coating layer including the perovskite compound represented by the chemical formula 1.

[0044] Furthermore, according to one embodiment of the present application, by applying the ALD method when forming the first coating layer, a uniform thickness coating is possible without cracks, unlike the existing dip coating method. Accordingly, a more reliable shielding effect can be achieved, and the dissolution / coating of metal components from the support can be prevented during the subsequent catalyst component coating process.

[0045] In addition, the catalyst for methane reforming according to one embodiment of the present application has the characteristic that an oxide film of a metal constituting the porous metal support is formed on the surface of the porous metal support by oxidizing the surface of the porous metal support, so that the elution of the metal constituting the porous metal support can be prevented during the production of the catalyst for methane reforming.

[0046] Figure 1 is a diagram showing a TEM (Transmission Electron Microscope) photograph of a cross-section of a catalyst for methane reforming manufactured in Example 6 of the present application.

[0047] Hereinafter, the present specification will be described in more detail.

[0048] In this specification, when it is said that a member is located “on” another member, this includes not only cases where the member is in contact with the other member, but also cases where another member exists between the two members.

[0049] In this specification, when a part is said to "include" a certain component, this means that it may include other components, but not to the exclusion of other components, unless specifically stated otherwise.

[0050] Currently, catalysts widely used in the reformer field are generally powder catalysts and pellet-type support catalysts. While powder catalysts can exhibit excellent performance due to their excellent catalyst dispersion, they are difficult to directly use in industry. For example, when a reformer is operated using a powder catalyst, the catalyst exits together with the substances produced after the reaction. At this time, the powder catalyst may gradually accumulate in the outlet pipe, ultimately clogging the entire pipe. Therefore, there is a drawback in that powder catalysts cannot be used in commercial reformers used in industry.

[0051] In addition, the pellet-type support catalyst is currently widely used in industrial reformers. Due to the limitation of mass transfer rate, the performance of the catalyst is lower than that of powder-type catalysts in terms of catalytic performance alone, but it has the advantage of being usable for a long time because of the support. However, the γ-Al2O3 pellets, which are widely used as the pellet-type support catalyst, have the disadvantage of being easily broken due to weak structural strength, which causes a pressure difference in the reactor. In addition, due to the nature of the pellet-type support catalyst, the volume is large, so when used in a high-capacity reformer, the volume becomes considerably large. In addition, all reforming reactions are sensitive to reaction temperature, and in the case of existing pellet-type catalysts, there is a disadvantage of poor thermal conductivity, which prevents heat from being evenly distributed throughout the reactor. In addition, in the case of the reforming reaction, the reaction is very fast, so in the case of pellet-type support and extruded catalysts, the catalyst utilization ratio (effectiveness factor) is 0.3 or less, which is a disadvantage of low catalyst utilization.

[0052] Furthermore, in the dry reforming of methane, coke formation is thermodynamically mitigated at lower reactor pressures. Therefore, the use of porous metal supports as catalyst supports to mitigate pressure drop across the catalyst bed is on the rise. However, no commercial applications have been reported due to side reactions and coke formation caused by the metal components within the porous metal support itself.

[0053] Accordingly, the present application seeks to provide a catalyst for methane reforming and a method for producing the same, which can suppress side reactions and coke formation due to metal components of the porous metal support itself by applying a porous metal support having a high heat and mass transfer rate.

[0054] A method for manufacturing a catalyst for methane reforming according to one embodiment of the present application comprises: a step of oxidizing the surface of a porous metal support; a step of forming a first coating layer including a first inorganic oxide on the porous metal support having the oxidized surface using ALD (atomic layer deposition), and then performing a first heat treatment process to manufacture a catalyst precursor having a first coating layer; and a step of coating a solution including a precursor of a perovskite compound represented by the following chemical formula 1 on the catalyst precursor having the first coating layer, and then performing a second heat treatment process to manufacture a catalyst having a second coating layer.

[0055] [Chemical Formula 1]

[0056] Sr 1-x A x Ti 1-y B y O 3-δ

[0057] In the above chemical formula 1,

[0058] A is selected from Y, Sc, La and lanthanide series elements,

[0059] B is Cr, Mn, Fe, Co, Ni, Mo, Ru or Rh,

[0060] x is a real number greater than or equal to 0 and less than 1,

[0061] y is a real number greater than or equal to 0 and less than 1,

[0062] δ is a real number greater than or equal to 0 and less than 1,

[0063] (x + y) > 0.

[0064] In one embodiment of the present application, the porous metal support may be a metal foam including NiCrAlFe, NiCrAl, SiC or α-Al2O3.

[0065] The porous metal support is a structure having various shapes, and has a small heat capacity and excellent heat transfer capability, so that it can be formed into a desired shape and used. The shape, size, etc. of the porous metal support are not particularly limited, and the porosity of the porous metal support may be 10% to 99%, 50% to 96%, or 85% to 96%. The pore size (cell size) of the porous metal support may be 400 ㎛ to 1,500 ㎛, or 450 ㎛ to 1,400 ㎛. When the pore size of the porous metal support is less than 400 ㎛, there may be difficulties in coating the precursor solution, and when it exceeds 1,500 ㎛, the surface area capable of coating the catalyst is reduced, which may be disadvantageous in the process, and thus is not preferable. The above porous metal support can be appropriately manufactured by a person skilled in the art using a method known in the art, taking into consideration the material, pore size, porosity, etc. of the porous metal support described above.

[0066] A method for manufacturing a catalyst for methane reforming according to one embodiment of the present application includes a step of oxidizing the surface of the porous metal support.

[0067] The step of oxidizing the surface of the porous metal support may be performed by a process of oxidizing the porous metal support in air at a temperature of 800°C to 1,200°C for 2 hours or less, or a process of oxidizing the porous metal support at a temperature of 900°C to 1,150°C for 1.5 hours or less, but is not limited thereto. In the case where the porous metal support is a metal foam, if the temperature is less than 800°C, the surface of the metal foam cannot be oxidized, and if the temperature exceeds 1,200°C or the oxidation is performed for a time exceeding 2 hours, excessive energy costs may be incurred, which is not preferable.

[0068] A method for manufacturing a catalyst for methane reforming according to one embodiment of the present application includes forming a first coating layer including a first inorganic oxide on a porous metal support having an oxidized surface using ALD (atomic layer deposition), and then performing a first heat treatment process to manufacture a catalyst precursor having the first coating layer.

[0069] By using ALD (atomic layer deposition) to form a first coating layer containing a first inorganic oxide on a porous metal support having an oxidized surface, the first coating layer can be formed on the porous metal support with a uniform thickness without cracks, thereby preventing the elution of metal components of the porous metal support itself.

[0070] The above ALD is a technology that can deposit ultra-thin films at the atomic layer thickness level with each cycle by alternately exposing precursors and reactants, which are the raw materials for thin films, to the surface of a vacuum-conditioned substrate. The precursors, reactants, etc. can be any materials known in the art.

[0071] The above precursor refers to a precursor of an inorganic substance constituting the first inorganic oxide, and more specifically, examples thereof include, but are not limited to, Al(CH3)3, Al(CH3)2Cl, AlCl3, Al(C2H5)3, zirconium tert-butoxide (ZTB), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)zirconium (TDMAZ), etc.

[0072] The above reactants may include, but are not limited to, H2O, H2O2, O2, O3, NO, CO, CO2, CH3OH, C2H5OH, N2O, and mixed gases thereof.

[0073] During the above ALD process, a purge gas may be used, and the purge gas may include, but is not limited to, an inert gas such as Ar, Ne, He, N2, H2, etc.

[0074] The conditions, equipment, etc. of the above ALD process are described in more detail in the examples described below.

[0075] In one embodiment of the present application, prior to forming the first coating layer including the first inorganic oxide, a step of forming a 1-1 coating layer including a second inorganic oxide on the porous metal support having an oxidized surface by dip coating may be additionally included. At this time, the first coating layer including the first inorganic oxide may be formed on the 1-1 coating layer including the second inorganic oxide. The step of forming the 1-1 coating layer including the second inorganic oxide may include a step of coating a solution including a precursor of the second inorganic oxide on the porous metal support having an oxidized surface by dip coating; and a step of performing a third heat treatment process. In this way, when the first coating layer including the first inorganic oxide is formed by ALD after forming the 1-1 coating layer including the second inorganic oxide by dip coating, a shielding effect can be efficiently obtained even with a relatively small number of ALD cycles.

[0076] In one embodiment of the present application, after forming the first coating layer, a step of forming a 1-1 coating layer including a second inorganic oxide by dip coating may be additionally included. At this time, the second coating layer may be formed on the 1-1 coating layer. The step of forming the 1-1 coating layer including the second inorganic oxide by dip coating may be performed by a method of dip coating with a solution including a precursor of the second inorganic oxide.

[0077] Accordingly, the inorganic oxide layer formed on the porous metal support having the oxidized surface may solely include a first coating layer of a first inorganic oxide formed using ALD, or may simultaneously include a first coating layer of a first inorganic oxide formed using ALD and a 1-1 coating layer of a second inorganic oxide formed using dip coating. More specifically, a catalyst for methane reforming according to one embodiment of the present application may have the following structure.

[0078] - Structure of a porous metal support with an oxidized surface / first coating layer (ALD, first inorganic oxide) / second coating layer (perovskite compound of chemical formula 1)

[0079] - Structure of a porous metal support with an oxidized surface / 1-1 coating layer (dip coating, 2nd inorganic oxide) / 1st coating layer (ALD, 1st inorganic oxide) / 2nd coating layer (perovskite compound of chemical formula 1)

[0080] - Structure of a porous metal support with an oxidized surface / first coating layer (ALD, first inorganic oxide) / first-first coating layer (dip coating, second inorganic oxide) / second coating layer (perovskite compound of chemical formula 1)

[0081] In one embodiment of the present application, the first coating layer and the 1-1 coating layer may include the same inorganic oxide, or may include different inorganic oxides. More specifically, the first coating layer and the 1-1 coating layer may each independently include an inorganic oxide including at least one selected from Al, Ce, Zr, Y, Ti, and Si. In addition, the first coating layer and the 1-1 coating layer may each independently include at least one selected from AlOx (0 < x ≤ 1.6), Al2O3, and ZrO2.

[0082] In addition, the first coating layer and the 1-1 coating layer are each independently ZrAlxOy(1 <x<3, 3<y<9)를 포함할 수 있다. 특히, 상기 ZrAlxOy(1<x<3, 3<y<9)는 ZrO2, Al2O3등과 같은 단일 무기 산화물 대비하여 결정립 크기가 작고 더 dense하게 packing 되어 있고, 상기 ZrAlxOy(1<x<3, 3<y<9)의 밀도는 ZrO2및 Al2O3의 혼합물의 밀도 대비 더 증가되므로, 다공성 금속 지지체의 표면을 보다 안정화시킬 수 있는 특징이 있다.

[0083] The solution containing the precursor of the second inorganic oxide may be provided in the form of a sol, gel, or solution containing the precursor of the second inorganic oxide, as well as a dispersion of the second inorganic oxide. The solvent of the solution containing the precursor of the second inorganic oxide may be water or any solvent known in the art, and is not particularly limited.

[0084] There is no particular limitation on the precursor of the second inorganic oxide, and ammonium salt, nitrate, carbonate, chloride, sulfate, hydroxide, organic acid salt, oxide, or a mixture thereof of the inorganic substance may be applied.

[0085] A method for manufacturing a catalyst for methane reforming according to one embodiment of the present application includes the step of coating a solution containing a precursor of a perovskite compound represented by the chemical formula 1 on a catalyst precursor having the first coating layer, and then performing a second heat treatment process to manufacture a catalyst having the second coating layer.

[0086] In one embodiment of the present application, a solution containing a precursor of a perovskite compound represented by the chemical formula 1 can be applied in the form of a sol or gel.

[0087] The precursor of the above perovskite compound is a precursor of a metal that constitutes the perovskite compound, and by controlling the content thereof, the molar ratio of the metal of the perovskite compound can be controlled. In addition, there is no particular limitation on the precursor of the metal, and ammonium salts, nitrates, carbonates, chlorides, sulfates, hydroxides, organic acid salts, oxides, or mixtures thereof of the metal element can be combined and applied.

[0088] In one embodiment of the present application, the chemical formula 1 may be represented by the following chemical formula 2 or 3, but is not limited thereto.

[0089] [Chemical Formula 2]

[0090] SrTi 1-y B y O 3-δ

[0091] [Chemical Formula 3]

[0092] Sr 1-x Y x Ti 1-y B y O 3-δ

[0093] In the above chemical formulas 2 and 3,

[0094] B is Ni or Rh,

[0095] x is a real number greater than 0 and less than 1,

[0096] y is a real number greater than 0 and less than 1,

[0097] δ is a real number greater than 0 and less than 1.

[0098] In one embodiment of the present application, the method of coating a solution containing a precursor of a perovskite compound represented by the chemical formula 1 on a catalyst precursor having the first coating layer may use a method known in the art, for example, dip coating, wash coating, etc., but is not limited thereto.

[0099] In one embodiment of the present application, the first to third heat treatment processes may each independently include drying and firing steps. The drying may be performed at a temperature of 50°C to 150°C for 1 to 48 hours, or at a temperature of 60°C to 100°C for 5 to 36 hours, but is not limited thereto. In addition, the firing may be performed at a temperature of 350°C to 1,100°C in an air atmosphere for 1 to 10 hours, or at a temperature of 500°C to 1,000°C in an air atmosphere for 1.5 to 8 hours, but is not limited thereto. When the firing step is performed at a temperature less than 350°C, the perovskite phase may not be properly formed, and when it exceeds 1,100°C, the durability of the porous metal support may be reduced, which is not preferred.

[0100] In one embodiment of the present application, a step of measuring the weight of the second coating layer supported on the porous metal support after the second heat treatment process may be additionally included. In addition, by measuring the weight of the second coating layer supported on the porous metal support, the step of coating the second solution described above and then performing the second heat treatment process may be repeated 2 to 10 times until the desired amount of catalyst is supported on the porous metal support.

[0101] In addition, another embodiment of the present application provides a methane reforming catalyst manufactured according to the method for manufacturing the methane reforming catalyst.

[0102] In addition, another embodiment of the present application provides a catalyst for methane reforming, comprising: a porous metal support having an oxidized surface; a first coating layer provided on the porous metal support having an oxidized surface and including a first inorganic oxide; and a second coating layer provided on the first coating layer and including a perovskite compound represented by the chemical formula 1.

[0103] In one embodiment of the present application, the thickness of the first coating layer of the methane reforming catalyst is 5 nm to 100 nm, and the thickness uniformity (%) of the first coating layer calculated by the following mathematical formula 4 is 60% or more.

[0104] [Equation 4]

[0105] (Minimum thickness of the first coating layer) / (Maximum thickness of the first coating layer) × 100

[0106] In one embodiment of the present application, the thickness of the first coating layer may be 5 nm to 100 nm, 10 nm to 80 nm, 20 nm to 50 nm, or 50 nm to 70 nm. When the thickness of the first coating layer exceeds 100 nm, the ability to form the second coating layer including the perovskite compound represented by the chemical formula 1 may be reduced, and thus the activity of the catalyst may be lowered compared to the volume of the porous metal support, which is not preferable. In addition, when the thickness of the first coating layer is less than 5 nm, the content thereof may be insignificant, making it difficult to obtain an effect by the first coating layer.

[0107] In one embodiment of the present application, the thickness uniformity (%) of the first coating layer calculated by the mathematical formula 4 may be 60% or more, 65% or more, 70% or more, and 100% or less. When the thickness uniformity (%) of the first coating layer is less than 60%, the thickness deviation is large, making it difficult to uniformly obtain a shielding effect by the first coating layer, and thus, a more certain shielding effect may be obtained, and the metal component of the support may be eluted during the subsequent catalyst component coating process, which is not preferable.

[0108] The thickness of the first coating layer can be measured using a method known in the art. For example, a TEM (Transmission Electron Microscope), an SEM (Scanning Electron Microscope), etc. can be used to measure a cross-sectional image of the catalyst, and the thickness of the first coating layer can be measured, but the present invention is not limited thereto. The cross-section of the catalyst is a plane including the thickness direction of the catalyst, that is, the stacking direction of the porous metal support, the first coating layer, and the second coating layer. More specifically, the thickness of the first coating layer can be measured based on a cross-sectional profile obtained by a TEM or SEM image after preparing any thin film sample including a cross-section in the stacking direction of the porous metal support, the first coating layer, and the second coating layer using a FIB (Focused Ion Beam). Among the cross-sectional profiles obtained by the TEM or SEM image, the maximum and minimum thicknesses of the first coating layer can be measured from the cross-sectional profile corresponding to the first coating layer. When measuring the maximum thickness and minimum thickness of the first coating layer, the thickness at both ends of the cross-sectional profile corresponding to the first coating layer may be excluded.

[0109] In addition, a 1-1 coating layer including a second inorganic oxide may be additionally included between the porous metal support having an oxidized surface and the first coating layer. In addition, a 1-1 coating layer including a second inorganic oxide may be additionally included between the first coating layer and the second coating layer.

[0110] In one embodiment of the present application, the first coating layer may be formed solely of the first inorganic oxide, the 1-1 coating layer may be formed solely of the second inorganic oxide, and the second coating layer may be formed solely of the perovskite compound represented by chemical formula 1.

[0111] In one embodiment of the present application, the total content of the first coating layer and the 1-1 coating layer including the first inorganic oxide and the second inorganic oxide may be 1 wt% to 15 wt%, and may be 2 wt% to 13 wt%, based on the total weight of the porous metal support. When the total content of the first coating layer and the 1-1 coating layer exceeds 15 wt%, the ability to form the second coating layer including the perovskite compound represented by the chemical formula 1 may be reduced, and thus the activity of the catalyst may be lowered relative to the volume of the porous metal support, which is not preferable. In addition, when the total content of the first coating layer and the 1-1 coating layer is less than 1 wt%, the content is so minimal that it may be difficult to obtain the effect of the inorganic oxide coating layer.

[0112] In one embodiment of the present application, the weight ratio of the first coating layer and the 1-1 coating layer: the second coating layer may be 1:5 to 1:20, and may be 1:7 to 1:15. If the weight ratio is out of the above range, the activity of the catalyst may be lowered relative to the volume of the porous metal support, which is not preferable.

[0113] In one embodiment of the present application, the content of the second coating layer including the perovskite compound represented by the chemical formula 1 may be 3 wt% to 40 wt%, 6 wt% to 35 wt%, or 7 wt% to 30 wt%, based on the total weight of the methane reforming catalyst. If the content of the second coating layer including the perovskite compound represented by the chemical formula 1 is less than 3 wt%, based on the total weight of the methane reforming catalyst, the reactivity may be reduced due to a relatively small number of active sites on the catalyst surface, which is not preferable. In addition, if the content of the second coating layer including the perovskite compound represented by the chemical formula 1 exceeds 40 wt%, a relatively large amount of catalyst component is contained compared to the porous metal support, making it difficult to maintain a pore structure, and bonding between the catalyst component and the porous metal support may not be easy, and thus the practical benefit of the methane reforming reaction may be reduced.

[0114] In one embodiment of the present application, the first coating layer and the 1-1 coating layer may be provided on the entire surface of the porous metal support.

[0115] In one embodiment of the present application, the first coating layer including the first inorganic oxide may serve to fix the second coating layer including the perovskite compound represented by the chemical formula 1 on a porous metal support. In addition, the second coating layer including the perovskite compound represented by the chemical formula 1 may be present in a protrusion shape on the first coating layer, thereby increasing the reaction surface area of ​​the catalyst and improving the performance of the methane reforming reaction.

[0116] In addition, according to one embodiment of the present application, by simultaneously applying the first coating layer including the first inorganic oxide; and the second coating layer including the perovskite compound represented by the chemical formula 1, the total content of the catalyst supported on the porous metal support can be increased compared to when the catalyst particles are applied alone. In addition, according to one embodiment of the present application, by applying the first coating layer including the first inorganic oxide, the phenomenon in which the metal (Ni, Cr, etc.), which is a main component of the porous metal support, is exposed to the surface in the form of a metal oxide (NiO, Cr2O3, etc.) under long-term operation conditions at high temperatures (750°C or higher) can be prevented, and the catalyst component ratio of the chemical formula 1 or the catalyst phase change can be prevented, thereby improving the durability and performance of the catalyst.

[0117] In one embodiment of the present application, the catalyst for methane reforming can be applied to a steam reforming process, a CO2 reforming process, a catalytic partial oxidation process, an autothermal reforming process, a tri-reforming process, or a mixed reforming process, and the methane reforming process is not particularly limited.

[0118] A catalyst for methane reforming according to one embodiment of the present application can improve the adhesion between a porous metal support and a second coating layer including a perovskite compound represented by chemical formula 1 by forming a first coating layer including a first inorganic oxide, and can also prevent side reactions of the porous metal support.

[0119] In addition, the catalyst for methane reforming according to one embodiment of the present application has the characteristic of being easy to control the heat of reaction compared to conventional pellet-type or powder-type catalysts, since a perovskite compound is supported on a porous metal support having high thermal conductivity.

[0120] In addition, the catalyst for methane reforming according to one embodiment of the present application has a feature that additional activity increase is possible due to a synergistic effect between the first coating layer including the first inorganic oxide and the second coating layer including the perovskite compound represented by the chemical formula 1.

[0121] Furthermore, according to one embodiment of the present application, by applying the ALD method when forming the first coating layer, a uniform thickness coating is possible without cracks, unlike the existing dip coating method. Accordingly, a more reliable shielding effect can be achieved, and the dissolution / coating of metal components from the support can be prevented during the subsequent catalyst component coating process.

[0122] In addition, the catalyst for methane reforming according to an embodiment of the present application is characterized in that, since an oxide film of a metal constituting the porous metal support is formed on the surface of the porous metal support by oxidizing the surface of the porous metal support, the elution of the metal constituting the porous metal support can be prevented even in a high-temperature process in the manufacturing process of the methane reforming catalyst and / or the methane reforming reaction process using the same. In particular, the catalyst for methane reforming according to an embodiment of the present application additionally forms a first coating layer including a first inorganic oxide on the oxide film of the metal constituting the porous metal support using ALD (atomic layer deposition), so that components such as NiO and CrOx can be further prevented from being exposed from the oxide film.

[0123] Hereinafter, examples will be provided to specifically explain the present application. However, the embodiments according to the present application may be modified in various ways, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to more fully explain the present application to those of average skill in the art.

[0124] <Example>

[0125] <Example 1>

[0126] 1) Oxidation of porous metal support

[0127] A porous metal support (NiCrAl, average pore size: 1,200 μm) was oxidized by heat treatment at 1,000°C in an air atmosphere for 1 hour.

[0128] 2) Formation of the first coating layer

[0129] A first coating layer containing a first inorganic oxide (AlOx, 0 < x ≤ 1.6) was formed with a thickness of about 25 nm on the porous metal support having the above surface oxidized by the ALD method below. Thereafter, a catalyst precursor having the first coating layer was manufactured by heat treatment at 900°C for 5 hours in an air atmosphere.

[0130] <ALD 공정>

[0131] 1. Load 6 g of the porous metal support with the above surface oxidized into the ALD (CN1) chamber.

[0132] 2. TMA (trimethylaluminum, egchem) canister temperature 25℃, H2O (egchem) canister temperature 25℃

[0133] 3. Process pressure 1.6 Torr, Ar carrier gas flow 300sccm, chamber temperature 150℃

[0134] 4. ALD process:

[0135] [(TMA pulse 3s / purge 120s - H2O pulse 3s / purge 120s)] × 200 cycles

[0136] 3) Formation of the second coating layer

[0137] Perovskite compounds (Sr 0.9 Y 0.1 Ti 0.93 Ni 0.07 O 3-δ , 0 < δ < 1) was prepared by the citric acid method. Strontium nitrate (Sr(NO3)3·H2O) was dissolved in distilled water together with yttrium nitrate (Y(NO3)3), nickel nitrate (Ni(NO3)2), and citric acid. Titanium isopropoxide (Ti(OCH(CH3)2)4) was dissolved in ethylene glycol, and the two solutions were mixed at 70°C. After stirring for 3 hours, the solution was cooled to room temperature and stored. At this time, the concentration of the solution was 0.1 M, and the molar ratio of strontium: yttrium: titanium: nickel was 0.9:0.1:0.93:0.07.

[0138] The catalyst precursor having the first coating layer was dip-coated with a solution containing the catalyst precursor, dried at 150°C for 5 hours, and heat-treated at 900°C in an air atmosphere for 5 hours. The dip-coating, drying, and heat-treating of the solution containing the catalyst precursor were repeated several times to finally form a first coating layer (AlOx, 0 < x ≤ 1.6) and a second coating layer (Sr) on a porous metal support having an oxidized surface. 0.9 Y 0.1 Ti 0.93 Ni 0.07 O 3-δ , 0 < δ < 1) was prepared. Based on the total weight of the catalyst for methane reforming, the perovskite compound represented by the chemical formula 1 (Sr 0.9 Y 0.1 Ti 0.93 Ni 0.07 O 3-δ, the content of 0 < δ < 1) was 20 wt%.

[0139] The content of the perovskite compound represented by the above chemical formula 1 can be calculated by the following mathematical formula 1.

[0140] [Mathematical Formula 1]

[0141] Content (weight%) of perovskite compound represented by chemical formula 1 = (total catalyst weight - total weight after formation of first coating layer) / (total catalyst weight) × 100

[0142] <Example 2>

[0143] The same procedure as Example 1 was followed, except that the ALD process was performed for 400 cycles instead of 200 cycles when forming the first coating layer. At this time, the thickness of the first coating layer of Example 2 was approximately 50 nm.

[0144] <Example 3>

[0145] The same procedure as Example 1 was followed, except that instead of the first coating layer including the AlOx, a first coating layer including the first inorganic oxide (ZrO2) was formed with a thickness of about 50 nm using the ALD method below.

[0146] <ALD 공정>

[0147] 1. Load 6 g of porous metal support with oxidized surface into the ALD (CN1) chamber.

[0148] 2. TEMAZ (tetrakis(ethylmethylamino) Zirconium, egchem) canister temperature 80℃, H2O (egchem) canister temperature 25℃

[0149] 3. Process pressure 1.6 Torr, Ar carrier gas flow 300sccm, chamber temperature 150℃

[0150] 4. ALD process:

[0151] [(TEMAZ pulse 20s / purge 600s - H2O pulse 3s / purge 300s)] × 250 cycles

[0152] <Example 4>

[0153] The porous metal support was oxidized as in Example 1 above.

[0154] An aqueous solution containing 25 wt% Al(NO3)3·9H2O as a precursor of the second inorganic oxide was prepared. The solution containing the precursor of the second inorganic oxide was dip-coated on the porous metal support having the oxidized surface to form a first-first coating layer containing the second inorganic oxide, followed by drying at 150°C for 5 hours and heat treatment at 900°C in an air atmosphere for 5 hours. The dip-coating, drying, and heat treatment of the solution containing the precursor of the second inorganic oxide were performed once or repeatedly several times.

[0155] A first coating layer including a first inorganic oxide (AlOx, 0 < x ≤ 1.6) was formed on the porous metal support having the above-mentioned 1-1 coating layer using ALD. At this time, the same procedure as Example 1 was followed, except that the ALD process was performed for 48 cycles instead of 200 cycles when forming the first coating layer. At this time, the thickness of the first coating layer of Example 4 was approximately 6 nm.

[0156] A second coating layer is formed on the porous metal support having the first coating layer and the first coating layer formed thereon using the same method as in Example 1, and finally, the first coating layer (AlOx, 0 < x ≤ 1.6), the first coating layer (AlOx, 0 < x ≤ 1.6), and the second coating layer (Sr) are formed on the porous metal support having the surface oxidized. 0.9 Y 0.1 Ti 0.93 Ni 0.07 O 3-δ, 0 < δ < 1) was prepared. Based on the total weight of the catalyst for methane reforming, the content of the 1-1 coating layer was 5 wt%, and the perovskite compound represented by the chemical formula 1 (Sr 0.9 Y 0.1 Ti 0.93 Ni 0.07 O 3-δ , the content of 0 < δ < 1) was 20 wt%.

[0157] The content of the above-mentioned 1-1 coating layer and the content of the perovskite compound represented by chemical formula 1 can be calculated by the following mathematical formulas 2 and 3, respectively.

[0158] [Equation 2]

[0159] Content of the 1-1 coating layer (weight%) = (total weight after forming the 1-1 coating layer - total weight before forming the 1-1 coating layer) / (total weight of catalyst) × 100

[0160] [Equation 3]

[0161] Content (weight%) of perovskite compound represented by chemical formula 1 = (total catalyst weight - total weight after formation of first coating layer and first coating layer) / (total catalyst weight) × 100

[0162] <Example 5>

[0163] The same procedure as Example 4 was followed, except that the 1-1 coating layer including the second inorganic oxide (ZrO2) was formed by using ZrO(NO3)2·xH2O (30 wt%) instead of Al(NO3)3·9H2O when preparing a solution including the precursor of the second inorganic oxide.

[0164] <Example 6>

[0165] 1) Oxidation of porous metal support

[0166] A porous metal support (NiCrAl, average pore size: 1,200 μm) was oxidized by heat treatment at 1,000°C in an air atmosphere for 1 hour.

[0167] 2) Formation of the first coating layer

[0168] ZrAlxOy(1) was synthesized on the porous metal support with the above surface oxidized by the ALD method below. <x<3, 3<y<9)를 포함하는 제1 코팅층을 약 25nm의 두께로 형성하였다. 그 후, 공기 분위기 하에서 900℃에서 5시간 동안 열처리하여 제1 코팅층이 구비된 촉매 전구체를 제조하였다.

[0169] <ALD 공정>

[0170] 1. Load 6 g of the porous metal support with the oxidized surface into the ALD (CN1) chamber.

[0171] 2. TEMAZ (tetrakis(ethylmethylamino) Zirconium, egchem) canister temperature 80℃, TMA (trimethylaluminum, egchem) canister temperature 25℃, H2O (egchem) canister temperature 25℃

[0172] 3. Process pressure 1.6 Torr, Ar carrier gas flow 300sccm, chamber temperature 150℃

[0173] 4. ALD process:

[0174] [(TMA pulse 3s / purge 120s - H2O pulse 3s / purge 120s) - (TEMAZ pulse 20s / purge 600s - H2O pulse 3s / purge 300s)] × 114 cycles

[0175] 3) Formation of the second coating layer

[0176] Perovskite compound (SrTi 0.93 Ni 0.07 O 3-δ, 0 < δ < 1) was prepared by the citric acid method. Strontium nitrate (Sr(NO3)3·H2O), nickel nitrate (Ni(NO3)2), citric acid, and ethylene glycol were dissolved in distilled water. Titanium isopropoxide (Ti(OCH(CH3)2)4) was dissolved in ethanol, and the two solutions were mixed at 70°C. After stirring for 3 hours, the solution was cooled to room temperature and stored. At this time, the concentration of the solution was 0.1 M, and the molar ratio of strontium: titanium: nickel was 1:0.97:0.03.

[0177] After dip coating a solution containing the catalyst precursor on the catalyst precursor having the first coating layer, drying was performed at 150°C for 5 hours, and heat treatment was performed at 900°C in an air atmosphere for 5 hours. The dip coating, drying, and heat treatment of the solution containing the catalyst precursor were repeated several times to finally form a first coating layer (ZrAlxOy, 1) on the porous metal support with an oxidized surface. <x<3, 3<y<9) 및 제2 코팅층(SrTi 0.93 Ni 0.07 O 3-δ , 0 < δ < 1) was prepared. Based on the total weight of the catalyst for methane reforming, the perovskite compound represented by the chemical formula 1 (SrTi 0.93 Ni 0.07 O 3-δ , the content of 0 < δ < 1) was 15 wt%.

[0178] A TEM (Transmission Electron Microscope) photograph of a cross-section of the catalyst for methane reforming manufactured in Example 6 is shown in Figure 1 below.

[0179] <Example 7>

[0180] When preparing a solution containing a precursor for the second coating layer, the same procedure as in Example 1 was followed, except that ruthenium chloride (RuCl3) was used instead of nickel nitrate and the precursor was used so that the molar ratio of strontium:titanium:ruthenium was 1:0.93:0.07.

[0181] <Comparative Example 1>

[0182] The same procedure as Example 1 was followed, except that the step of forming the second coating layer was applied without the step of forming the first coating layer.

[0183] Comparative Example 2

[0184] The same procedure as Example 1 was followed, except that the steps of forming the first coating layer and the second coating layer were applied without the step of oxidizing the porous metal support.

[0185] <Comparative Example 3>

[0186] The same procedure as Example 3 was followed, except that instead of forming the first coating layer using the ALD process, the first coating layer was formed using a solution containing an inorganic oxide precursor (ZrO(NO3)2·xH2O (20 wt%)) and a dip coating process.

[0187] Comparative Example 4

[0188] The same procedure as Example 4 was followed, except that the steps of forming the first-1 coating layer and the second coating layer were applied without the first coating layer.

[0189] Comparative Example 5

[0190] The same procedure as Example 6 was followed, except that the step of forming the second coating layer was applied without the step of forming the first coating layer.

[0191] Comparative Example 6

[0192] The same procedure as Example 1 was performed without the step of forming a second coating layer.

[0193] [Table 1]

[0194]

[0195] <Experimental Example 1> Evaluation of dry reforming reaction of methane

[0196] A fixed-bed reaction system was introduced to perform the dry reforming reaction of methane. A quartz tube reactor (inner diameter = 1 / 2 inch, length = 50 cm) was used and each catalyst (approximately 2 g) of the examples and comparative examples was charged. First, a reduction process was performed at 800°C for 2 hours under 10% H2 / N2 conditions, followed by a catalytic reaction for 24 hours. To more clearly compare the differences in coke production between the catalysts, the activity characteristics of the catalysts were evaluated under pressurized conditions.

[0197] Gas composition: CH4: CO2: He = 1:1.12:0.3

[0198] Flow rate: GHSV (Gas Hour Space Velocity) = 1,640 hr -1 (based on CH4)

[0199] Reaction temperature: 800℃

[0200] Reaction pressure: 5 barg

[0201] The composition of the generated gas was analyzed using gas chromatography (GC) and the reaction conversion rate was calculated after 24 hours of reaction, which is shown in Table 2 below.

[0202] Conversion rate (Xi, %) = [(Fi in - Fi out ) / Fi in ] × 100 (Fi = flow rate of i)

[0203] Coke production (wt%) = (weight of C produced / total weight of catalyst before reaction) × 100

[0204] The above coke production amount (wt%) was calculated by obtaining the weight of C produced through temperature-elevated oxidation analysis of the catalyst after the reaction and dividing it by the total weight of the catalyst before the reaction. The temperature-elevated oxidation analysis was performed under 5% O2 / He conditions while heating to 800°C at a rate of 10°C per minute.

[0205] <GC 분석 조건>

[0206] 1) GC model: Agilent 6890

[0207] 2) Oven temp.: 40℃ / 7min-90℃ / 5min-180℃ / 6min

[0208] 3) Detector: TCD, 250℃

[0209] 4) Sample loop: 0.25 mL

[0210] 5) Valve box Temp.: 150℃

[0211] [Table 2]

[0212]

[0213] <Experimental Example 2> Evaluation of dry reforming reaction of methane

[0214] A fixed-bed reaction system was introduced to perform the dry reforming of methane. A quartz tube reactor (inner diameter = 1 / 2 inch, length = 50 cm) was used and each catalyst (approximately 2 g) of the examples and comparative examples was charged. First, a reduction process was performed at 800°C for 2 hours under 10% H2 / N2 conditions, followed by a catalytic reaction for 24 hours. To more clearly compare the differences in coke production between the catalysts, the activity characteristics of the catalysts were evaluated under pressurized conditions.

[0215] Gas composition: CH4: CO2: He = 1:1.12:0.3

[0216] Flow rate: GHSV (Gas Hour Space Velocity) = 1,640 hr -1 (based on CH4)

[0217] Reaction temperature: 800℃

[0218] Reaction pressure: 5 barg

[0219] The composition of the generated gas was analyzed using gas chromatography (GC) and the reaction conversion rate was calculated after 24 hours of reaction, which is shown in Table 3 below.

[0220] Conversion rate (Xi, %) = [(Fi in - Fi out ) / Fi in ] × 100 (Fi = flow rate of i)

[0221] Coke production (mol%) = (C produced mol / CH4 mol reacted) × 100

[0222] <GC 분석 조건>

[0223] 1) GC model: Agilent 6890

[0224] 2) Oven temp.: 40℃ / 7min-90℃ / 5min-180℃ / 6min

[0225] 3) Detector: TCD (thermal conductivity detector), 250℃

[0226] 4) Sample loop: 0.25 mL

[0227] 5) Valve box Temp.: 150℃

[0228] [Table 3]

[0229]

[0230] As shown in the results in Tables 2 and 3 above, it can be confirmed that the methane reforming catalyst of the example according to one embodiment of the present application has a higher CH4 conversion rate and significantly lower coke production compared to the comparative example. Accordingly, it can be confirmed that the methane reforming catalyst of the example according to one embodiment of the present application includes an oxidation-treated porous metal support, a first coating layer formed by an ALD method, and a second coating layer including a perovskite-based compound represented by the above chemical formula 1, thereby reducing side reactions caused by the porous metal support and the second coating layer including the perovskite-based compound.

[0231] <Experimental Example 3> Evaluation of the thickness uniformity (%) of the first coating layer of the catalyst

[0232] The uniformity (%) of the thickness of the first coating layer of the methane reforming catalysts manufactured in Example 3 and Comparative Example 3 was evaluated and shown in Table 4 below. The uniformity (%) of the thickness of the first coating layer of the methane reforming catalyst was obtained by manufacturing an arbitrary thin film sample including a cross-section of the porous metal support, the first coating layer, and the second coating layer in the stacking direction of the methane reforming catalyst using FIB (Focused Ion Beam), and then measuring the maximum and minimum thicknesses of the first coating layer from the cross-sectional profile corresponding to the first coating layer among the cross-sectional profiles obtained by TEM (Transmission Electron Microscope) images, and calculating according to the following mathematical equation 4. When analyzing the TEM images, the experimental device used was Talos F200X (FETEM, ThermoFisher), and an acceleration voltage of 200 kV was applied as the experimental condition.

[0233] [Equation 4]

[0234] (Minimum thickness of the first coating layer) / (Maximum thickness of the first coating layer) × 100

[0235] [Table 4]

[0236]

[0237] As shown in the results in Table 4 above, the thickness uniformity (%) of the first coating layer of the methane reforming catalyst according to Example 3 was 71.4%, indicating that the first coating layer was formed with a uniform thickness on the support, but the thickness uniformity (%) of the first coating layer of the methane reforming catalyst according to Comparative Example 3 was 33.3%, indicating that there was a large thickness deviation in the first coating layer. In addition, it was confirmed that the first coating layer was not formed in some areas of the first coating layer of the methane reforming catalyst according to Comparative Example 3.

[0238] Therefore, in the methane reforming catalyst according to one embodiment of the present application, since an oxide film of a metal constituting the porous metal support is formed on the surface of the porous metal support by oxidizing the surface of the porous metal support, the elution of the metal constituting the porous metal support can be prevented during the production of the methane reforming catalyst. In addition, in one embodiment of the present application, a first coating layer including a first inorganic oxide is additionally formed on the oxide film of the metal constituting the porous metal support using ALD (atomic layer deposition), so that components such as NiO and CrOx can be further prevented from being exposed from the oxide film.

Claims

1. A step of oxidizing the surface of a porous metal support; A step of forming a first coating layer including a first inorganic oxide on a porous metal support having an oxidized surface using ALD (atomic layer deposition), and then performing a first heat treatment process to manufacture a catalyst precursor having a first coating layer; and A step of manufacturing a catalyst having a second coating layer by coating a solution containing a precursor of a perovskite compound represented by the following chemical formula 1 on a catalyst precursor having the first coating layer, and then performing a second heat treatment process. Method for producing a catalyst for methane reforming comprising: [Chemical Formula 1] Sr 1-x A x Ti 1-y B y The 3-δ In the above chemical formula 1, A is selected from Y, Sc, La and lanthanide series elements, B is Cr, Mn, Fe, Co, Ni, Mo, Ru or Rh, x is a real number greater than or equal to 0 and less than 1, y is a real number greater than or equal to 0 and less than 1, δ is a real number greater than or equal to 0 and less than 1, (x + y) > 0.

2. A method for producing a catalyst for methane reforming according to claim 1, wherein the porous metal support is a metal foam containing NiCrAlFe, NiCrAl, SiC or α-Al2O3.

3. In claim 1, the step of oxidizing the surface of the porous metal support comprises: A method for producing a catalyst for methane reforming, comprising oxidizing the porous metal support in air at a temperature of 800°C to 1,200°C for 2 hours or less.

4. In claim 1, prior to forming the first coating layer including the first inorganic oxide, a step of forming a 1-1 coating layer including a second inorganic oxide on the porous metal support having an oxidized surface by dip coating is additionally included. A method for producing a catalyst for methane reforming, wherein the first coating layer including the first inorganic oxide is formed on the first-first coating layer including the second inorganic oxide.

5. In claim 4, the step of forming the 1-1 coating layer including the second inorganic oxide is, A method for producing a catalyst for methane reforming, comprising: a step of coating a solution containing a precursor of the second inorganic oxide on a porous metal support having an oxidized surface using dip coating; and a step of performing a third heat treatment process.

6. In claim 1, after forming the first coating layer including the first inorganic oxide, a step of forming a 1-1 coating layer including a second inorganic oxide using dip coating is additionally included. A method for manufacturing a catalyst for methane reforming, wherein the second coating layer is formed on the first coating layer.

7. A method for producing a catalyst for methane reforming according to claim 4 or 6, wherein the first coating layer and the 1-1 coating layer each independently include an inorganic oxide including at least one of Al, Ce, Zr, Y, Ti, and Si.

8. In claim 4 or 6, the first coating layer and the 1-1 coating layer each independently comprise AlOx (0 < x ≤ 1.6), Al2O3, ZrO2 and ZrAlxOy (1 <x<3, 3<y<9) 중에서 선택되는 1종 이상을 포함하는 것인 메탄 개질용 촉매의 제조방법.

9. A method for producing a catalyst for methane reforming, wherein the chemical formula 1 in claim 1 is represented by the following chemical formula 2 or 3: [Chemical Formula 2] SrTi 1-y B y The 3-δ [Chemical Formula 3] Mr 1-x AND x You 1-y B y EITHER 3-δ In the above chemical formulas 2 and 3, B is Ni or Rh, x is a real number greater than 0 and less than 1, y is a real number greater than 0 and less than 1, δ is a real number greater than 0 and less than 1.

10. A method for manufacturing a catalyst for methane reforming according to claim 1, wherein the method for coating a solution containing a precursor of a perovskite compound represented by the chemical formula 1 on a catalyst precursor having the first coating layer uses dip coating.

11. Porous metal support with oxidized surface; A first coating layer provided on a porous metal support having an oxidized surface and including a first inorganic oxide; and A catalyst for methane reforming comprising a second coating layer provided on the first coating layer and including a perovskite compound represented by the following chemical formula 1, The thickness of the first coating layer is 5 nm to 100 nm, A catalyst for methane reforming, wherein the thickness uniformity (%) of the first coating layer calculated by the following mathematical formula 4 is 60% or more: [Equation 4] (Minimum thickness of the first coating layer) / (Maximum thickness of the first coating layer) × 100 [Chemical Formula 1] Sr 1-x A x Ti 1-y B y The 3-δ In the above chemical formula 1, A is selected from Y, Sc, La and lanthanide series elements, B is Cr, Mn, Fe, Co, Ni, Mo, Ru or Rh, x is a real number greater than or equal to 0 and less than 1, y is a real number greater than or equal to 0 and less than 1, δ is a real number greater than or equal to 0 and less than 1, (x + y) > 0.

12. A catalyst for methane reforming according to claim 11, further comprising a first-first coating layer comprising a second inorganic oxide between the porous metal support having an oxidized surface and the first coating layer; or between the first coating layer and the second coating layer.

13. A catalyst for methane reforming according to claim 12, wherein the first coating layer and the 1-1 coating layer each independently include an inorganic oxide including at least one of Al, Ce, Zr, Y, Ti, and Si.

14. In claim 12, the first coating layer and the 1-1 coating layer each independently comprise AlOx (0 < x ≤ 1.6), Al2O3, ZrO2 and ZrAlxOy (1 <x<3, 3<y<9) 중에서 선택되는 1종 이상을 포함하는 것인 메탄 개질용 촉매.

Images