Catalyst for methane reforming and preparation method thereof

Abstract

Disclosed is a method for preparing a catalyst for methane reforming, comprising the steps of: preparing a solution containing a precursor of a perovskite-based compound represented by the above Chemical Formula 1; and coating a support with the solution and performing heat treatment to obtain a catalyst, wherein a precursor of the perovskite-based compound represented by the above chemical formula 1 includes strontium hydroxide.

Description

TECHNICAL FIELD

[0001] This application claims the benefit of Korean Patent Application No. 10-2024-0004616, filed on January 11, 2024, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.

[0002] The present disclosure relates to a catalyst for methane reforming and a method of preparing the same. BACKGROUND

[0003] As part of an action for reducing greenhouse gases caused by global warming, many studies have been made on carbon dioxide conversion technology. Carbon dioxide reforming, which is one of carbon dioxide conversion technologies, is a technology that enables methane and carbon dioxide to react with each other to obtain synthesis gas containing hydrogen and carbon monoxide.

[0004] Such synthesis gas is a very valuable material in the development as a raw material for various downstreams. As a method of industrially producing such synthesis gas (H2 / CO), reforming of natural gas can be roughly classified into steam reforming, carbon dioxide (CO2) reforming, catalytic partial oxidation, autothermal reforming, and tri-reforming, as shown in the following Reaction Formulae 1 to 5:

[0005] [Reaction Formula 1]

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

[0007] [Reaction Formula 2]

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

[0009] [Reaction Formula 3]

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

[0011] [Reaction Formula 4]

[0012] Autothermal Reforming: Reaction Formula 1 + Reaction Formula 3

[0013] [Reaction Formula 5]

[0014] Tri-reforming: Reaction Formula 1 + Reaction Formula 2 + Reaction Formula 3

[0015] Meanwhile, various types of catalysts can be used for reforming activity in a reforming process. Among such catalysts, when a noble metal catalyst is used in a reforming process, it is advantageous to obtain high efficiency of hydrogen conversion from natural gas, but there is a problem of reducing cost efficiency due to high cost of the noble metal catalyst.

[0016] Accordingly, a nickel catalyst is often used in a reforming process because it provides high hydrogen conversion efficiency and is relatively inexpensive. However, in this case, there is a problem in that the nickel catalyst is deactivated due to carbon inevitably generated on the surface of the nickel catalyst.

[0017] Accordingly, there is a need to develop a catalyst having carbon deposition resistance and which can be effectively applied to a methane reforming process. SUMMARY

[0018] TECHNICAL PROBLEM

[0019] The present disclosure aims to provide a catalyst for methane reforming and a method of preparing the same.

[0020] TECHNICAL SOLUTION

[0021] One exemplary embodiment of the present disclosure provides a method of preparing a catalyst for methane reforming, comprising the steps of:

[0022] preparing a solution containing a precursor of a perovskite compound represented by the following Chemical Formula 1; and

[0023] coating a support with the solution and performing a heat treatment to obtain a catalyst,

[0024] wherein the precursor of the perovskite compound represented by the following Chemical Formula 1 comprises strontium hydroxide:

[0025] [Chemical Formula 1]

[0026] Sr 1-x A x Ti α B y O 3-δ

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

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

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

[0030] y is a real number equal to or greater than 0 and less than 0.3,

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

[0032] α is a real number greater than 0.7 and equal to or less than 1,

[0033] x and y satisfy (x+y)>0.

[0034] Another exemplary embodiment of the present disclosure provides a catalyst for methane reforming obtained by the above-described method of preparing a catalyst for methane reforming.

[0035] Advantageous Effects

[0036] The catalyst for methane reforming according to one exemplary embodiment of the present disclosure is obtained by using strontium hydroxide as a precursor of the perovskite compound represented by the above-described Chemical Formula 1, and thus can inhibit a factor that causes a component that can cause a side reaction or coke to be leached from a metal support due to low pH.

[0037] Further, according to one exemplary embodiment of the present disclosure, a hydroxycarboxylic acid and a polyhydroxy compound used in a method of preparing a catalyst for methane reforming according to the related art are used at a minimized level, and thus when the perovskite compound represented by the above-described Chemical Formula 1 is coated on a metal support, a loss of an active component of the catalyst can be minimized, and a catalyst including the perovskite compound represented by the above-described Chemical Formula 1 uniformly coated on a surface of the metal support can be obtained.

[0038] Thus, when the catalyst for methane reforming according to one exemplary embodiment of the present disclosure is applied to a methane reforming reaction, it can achieve high activity even at a high space velocity, and can be stably operated for a long time of 1,000 hours or more without a carbon deposition or sintering phenomenon. DETAILED DESCRIPTION

[0039] Hereinafter, the present disclosure will be explained in more detail.

[0040] Throughout this specification, when a certain part is described as being "on" another part, it can not only include the case where the part is in direct contact with the other part, but also the case where another part is present between the two parts.

[0041] Throughout this specification, when a part is described as "including" a certain component, it does not exclude the presence of another component but means that the additional component can be included, unless the context clearly dictates otherwise.

[0042] Currently, in the case of a catalyst widely used in the field of reformers, a powder type catalyst and a pellet type supported catalyst are generally dominant. In the case of a powder type catalyst, the catalyst has high dispersibility and can show excellent performance, but it is difficult to directly use the catalyst in industry. For example, when a reformer is driven by using a powder type catalyst, the catalyst comes out together with materials generated after a reaction, and in this case, the powder type catalyst can gradually accumulate in a pipe at an outlet, and eventually, the pipe can be completely blocked. Thus, there is a disadvantage that a powder type catalyst cannot be used for a commercial reformer used in industry.

[0043] In addition, in the case of particle-type supported catalysts, it is currently widely used in industrial reformers. Due to the limitation of material transfer rate, when only the performance of the catalyst is considered, the particle-type supported catalyst shows a performance lower than that of the powder-type catalyst, but because a carrier is used, it has the advantage of being able to be used for a long time. However, in the case of γ-Al2O3 particles commonly used as particle-type supported catalysts, it has low structural strength and may be easily broken, so there is a disadvantage of generating a pressure difference in the reactor. In addition, since the particle-type supported catalyst is inherently large in volume, when used in a high-capacity reformer, the volume increases significantly. In addition, all reforming reactions are sensitive to reaction temperature, and in the case of conventional particle-type catalysts, they have significantly low thermal conductivity, so heat is unevenly distributed throughout the reactor. In addition, in the case of reforming reactions, the reaction is very fast, so the particle-type supported and extruded catalysts show an effective coefficient of use of the catalyst of less than 0.3, which indicates a disadvantage of low catalyst utilization.

[0044] Furthermore, in methane dry reforming reactions, coke formation decreases as reactor pressure decreases due to thermodynamic factors. Therefore, the use of metal supports as catalyst supports is increasing to mitigate the pressure drop in the catalyst layer. However, due to the side reactions and coke formation caused by the metal components of the metal supports themselves, no commercial applications have been achieved.

[0045] Under these circumstances, the present disclosure aims to provide a catalyst for methane reforming, which uses a metal support having high heat and mass transfer rates and can suppress side reactions and coke generation caused by metal components of the metal support itself, and a preparation method thereof.

[0046] In an exemplary embodiment of the present disclosure, a method for preparing a catalyst for methane reforming includes the steps of: preparing a solution containing a precursor of a perovskite compound represented by the following Chemical Formula 1; and coating a support with the solution and performing a heat treatment to obtain a catalyst, wherein the precursor of the perovskite compound represented by the following Chemical Formula 1 includes strontium hydroxide:

[0047] [Chemical Formula 1]

[0048] Sr 1-x A x Ti α B y O 3-δ

[0049] wherein A is selected from Y, La and lanthanide elements,

[0050] B is Ni, Co, Fe, Cr, Mo, Ru or Rh,

[0051] x is a real number equal to or greater than 0 and less than 1,

[0052] y is a real number equal to or greater than 0 and less than 0.3,

[0053] δ is a real number equal to or greater than 0 and less than 1,

[0054] α is a real number greater than 0.7 and equal to or less than 1,

[0055] x and y satisfy (x+y)>0.

[0056] In one exemplary embodiment of the present disclosure, the support can be a metal support. In the present specification, the metal support can include at least one selected from the group consisting of NiFeCrAl, NiCrAl, Al, stainless steel, and Inconel. In addition, the metal support can be a porous metal support, for example, a metal foam, and can be a metal support having a predetermined shape. In addition, the support can be an inorganic oxide support known to one of ordinary skill in the art.

[0057] The porous metal support can be a structure having various shapes, and can have a low heat capacity and a high heat transfer capacity, shaped in a desired shape and used. The shape, size, etc. of the porous metal support are not particularly limited. The porous metal support can have a porosity of 10% to 99%, 50% to 96%, or 85% to 96%. The porous metal support can have a pore diameter of 400 μm to 1,500 μm or 450 μm to 1,400 μm. When the porous metal support has a pore diameter of less than 400 μm, it is difficult to perform coating of the precursor solution. When the metal support has a pore diameter of greater than 1,500 μm, the surface area on which the catalyst can be coated can be decreased, which is disadvantageous in terms of process and is undesirable. In consideration of the above-described material, pore diameter, porosity, etc. of the porous metal support, one of ordinary skill in the art can appropriately prepare the porous metal support by using a method known in the art.

[0058] In addition, the metal support having a predetermined shape can use a tubular reactor itself as a support, or can use a metal plate having a spring shape with an increased surface area.

[0059] The method of preparing a catalyst for reforming of methane according to one exemplary embodiment of the present disclosure includes a step of preparing a solution containing a precursor of a perovskite compound represented by Chemical Formula 1 described above.

[0060] According to the related art, in order to prepare a powder-type catalyst, a basic component is added to a catalyst precursor solution to form a precipitate. However, the catalyst for the reforming of methane according to one exemplary embodiment of the present disclosure is a supported catalyst including a support coated with a catalyst component, unlike a conventional powder-type catalyst. Accordingly, according to one exemplary embodiment of the present disclosure, a solution including a precursor of a perovskite compound represented by Chemical Formula 1 above can be applied in the form of a sol or a gel.

[0061] The precursor of the perovskite compound is a precursor of a metal forming the perovskite compound, and the molar ratio of the metal of the perovskite compound can be controlled by adjusting the content of the precursor. In addition, as the precursor of the metal, there is no particular limitation on the precursor of other metals in addition to strontium hydroxide.

[0062] In one exemplary embodiment of the present disclosure, the strontium hydroxide can be Sr(OH)2·9H2O. Strontium carbonate, strontium acetate, or the like can be used instead of the strontium hydroxide, but they are insufficient in the effect of increasing pH. Accordingly, it is preferable to use the strontium hydroxide.

[0063] In one exemplary embodiment of the present disclosure, the solution including the precursor of the perovskite compound represented by Chemical Formula 1 can have a pH of 2.5 to 3.7 or 3.0 to 3.5.

[0064] The solution including the precursor of the perovskite compound represented by Chemical Formula 1 can be prepared by the Pechini method as follows. When an aqueous solution of an oxide or a salt required to be prepared is mixed with a hydroxycarboxylic acid, a chelation reaction occurs to form a complex ring compound around a metal cation. Then, when a polyhydroxy compound is added thereto and the resulting mixture is heated at 150 to 250°C to polymerize the formed chelate compound and then remove the remaining water, a solid polymer resin that can be called a precursor of a catalyst component can be obtained. According to the related art, citric acid and ethylene glycol are used together with strontium nitrate, nickel nitrate, titanium isopropoxide, or the like to prepare a perovskite material. The coating solution prepared according to the related art has a pH of 0.1 to 0.5, and thus there is a significant limitation in the process of preparing a catalyst for dry reforming of methane. Due to such high acidity, a special material is required for a system for preparing a catalyst, and an additional coating layer having a protective layer is required to suppress a side effect of leaching when a metal support is used, or the number of times of repeated use of the coating solution needs to be limited.

[0065] According to one exemplary embodiment of the present disclosure, strontium hydroxide is used instead of strontium nitrate that is conventionally used, and thus a coating solution having a pH of 2.5 to 3.7 can be prepared. In this way, the above-described limitation in the material for a system can be overcome, the need for an additional protective layer for enhancing a catalytic effect can be avoided, and a side effect or the like caused by repeated use of the coating solution can be suppressed.

[0066] According to the related art, in the process of coating a catalyst component on the surface of a metal support, an activity loss of the coated catalyst can occur due to an undesirable component caused by leaching and washing. In particular, when a sol solution is prepared by the Pechini method, which has been widely known so far, since a nitrate is used as a precursor of a catalyst component, the method is performed in a strong acid (pH < 0.3) atmosphere. However, when a nitrate is used as a precursor of a catalyst component, a sol solution having a pH significantly low is formed, and thus a metal component of a metal support is leached during a step of coating the metal support with the catalyst component, and a component that is not favorable to catalytic activity is also added, thereby causing a side effect of a decrease in catalytic activity. In addition, although the pH can be slightly increased by adding an alcohol component when a nitrate is used as a precursor of a catalyst component, this results in a significant increase in processing cost, which is not preferred in terms of commercial production.

[0067] In other words, in order to solve the above-described problems, according to one exemplary embodiment of the present disclosure, the pH can be increased by using strontium hydroxide instead of a nitrate, which is conventionally used, thereby providing an advantage of expanding the selection in selecting a reactor material when a large amount of a sol solution is prepared.

[0068] In one exemplary embodiment of the present disclosure, (α+y) in the above-described Chemical Formula 1 can be 1. In addition, in one exemplary embodiment of the present disclosure, (α+y) in Chemical Formula 1 can be a real number greater than 0.90 and less than 1. The B (e.g., Ni) in Chemical Formula 1 partially substitutes Ti, and theoretically (α+y) is 1 according to the stoichiometry. However, when Ti is introduced in a slightly insufficient amount compared to the stoichiometric ratio in preparing a perovskite compound represented by Chemical Formula 1, Ti in Chemical Formula 1 can be more easily substituted by B (e.g., Ni).

[0069] In one exemplary embodiment of the present disclosure, Chemical Formula 1 can be represented by the following Chemical Formula 2 or Chemical Formula 3, but is not limited thereto:

[0070] [Chemical Formula 2]

[0071] SrTi α B y O 3-δ

[0072] [Chemical Formula 3]

[0073] Sr 1-x Y x Ti α B y O 3-δ

[0074] where B is Ni or Rh,

[0075] x is a real number greater than 0 and less than 1,

[0076] y is a real number greater than 0 and less than 0.3,

[0077] δ is a real number greater than 0 and less than 1,

[0078] α is a real number greater than 0.7 and equal to or less than 1.

[0079] In one exemplary embodiment of the present disclosure, the support can be coated with a solution by using a method known to one skilled in the art, for example, dip coating, wash coating, etc., but is not limited thereto.

[0080] In one exemplary embodiment of the present disclosure, the heat treatment process can include a drying step and a firing step. The drying step can be performed at a temperature of 50℃ to 150℃ for 1 hour to 48 hours, or at a temperature of 60℃ to 100℃ for 5 hours to 36 hours, but is not limited thereto. In addition, the firing step can be performed at a temperature of 350℃ to 1,100℃ for 1 hour to 10 hours in an air atmosphere, or at a temperature of 500℃ to 1,000℃ for 1.5 hours to 8 hours in an air atmosphere, but is not limited thereto. When the firing step is performed at a temperature lower than 350℃, a perovskite phase can not be properly formed. When the firing step is performed at a temperature higher than 1,100℃, the metal support can undesirably undergo deterioration in durability.

[0081] In one exemplary embodiment of the present disclosure, the method can further include a step of weighing the coating layer loaded on the support after the step of performing the heat treatment process. In addition, the solution can be coated by weighing the coating layer loaded on the support until a desired amount of catalyst is loaded on the support, and then the step of performing the heat treatment process can be repeatedly performed 2 to 10 times.

[0082] Another exemplary embodiment of the present disclosure provides a catalyst for methane reforming obtained by the above-described method of preparing a catalyst for methane reforming.

[0083] The catalyst for methane reforming according to another exemplary embodiment of the present disclosure includes: a support; and a coating layer disposed on the support and including a perovskite compound represented by the above-described Chemical Formula 1.

[0084] In one exemplary embodiment of the present disclosure, the content of the coating layer including the perovskite compound represented by Chemical Formula 1 can be 3 to 40 wt%, 6 to 35 wt%, or 7 to 30 wt% based on the total weight of the catalyst for methane reforming. When the content of the coating layer including the perovskite compound represented by Chemical Formula 1 is less than 3 wt% based on the total weight of the catalyst for methane reforming, there are a relatively small number of active sites on the surface of the catalyst, resulting in undesirably reduced reactivity. In addition, when the content of the coating layer including the perovskite compound represented by Chemical Formula 1 is more than 40 wt% based on the total weight of the catalyst for methane reforming, there are a relatively large amount of catalyst components compared to the support, making it difficult to maintain the pore structure and achieve the combination of the catalyst components and the support, resulting in a decrease in the benefits of the methane reforming reaction.

[0085] In one exemplary embodiment of the present disclosure, the catalyst for methane reforming can be applied to steam reforming, carbon dioxide (CO2) reforming, catalytic partial oxidation, autothermal reforming, tri-reforming, or hybrid reforming, and is not particularly limited in the methane reforming process.

[0086] Since the catalyst for methane reforming according to one exemplary embodiment of the present disclosure is prepared by using strontium hydroxide as a precursor of the perovskite compound represented by the above Chemical Formula 1, it is possible to suppress the leaching of components capable of causing side reactions or coke formation from the metal support due to low pH.

[0087] In addition, since the hydroxycarboxylic acid and the polyhydroxy compound used in the method of preparing the catalyst for methane reforming according to the related art are used at a minimized level, thus preventing popcorn formation when the perovskite compound represented by Chemical Formula 1 is coated on the metal support, it is possible to minimize the loss of the active components of the catalyst and obtain a catalyst including the perovskite compound represented by the above Chemical Formula 1 uniformly coated on the surface of the metal support.

[0088] Accordingly, when the catalyst for methane reforming according to one exemplary embodiment of the present disclosure is applied to the methane reforming reaction, it can achieve high activity even at a high space velocity, and can be stably operated for a long time of 1,000 hours or more without carbon deposition or sintering phenomena.

[0089] Hereinafter, the present disclosure is described in detail through examples. However, the embodiments according to the present disclosure can vary in several different forms, and the scope of the present disclosure should not be construed as being limited to the examples described below. The examples of the present specification are provided to more fully describe the present disclosure to those of ordinary skill in the art.

[0090] <Example>

[0091] <Example 1>

[0092] A perovskite-based coating solution was prepared by a Pechini method. Strontium hydroxide (Sr(OH)2·9H2O) and nickel nitrate (Ni(NO3)2) were dissolved in distilled water at 80°C together with malic acid. Then, glycerol was further introduced and titanium isopropoxide (Ti(OCH(CH3)2)4) was introduced, and the temperature was maintained until a clear solution was obtained. The content of nickel was 3 mol% based on titanium. Here, the coating solution had a pH of 3.5.

[0093] A porous metal support (NiCrAl, average pore diameter: 1,200 μm) was coated with the perovskite-based coating solution by dip coating (forming a coating layer), and the coated porous metal support was dried at 150°C for 5 hours and then heat-treated at 900°C for 5 hours in an air atmosphere. The dip coating, drying, and heat treatment of the perovskite-based solution were repeated several times, and finally a catalyst comprising a porous metal support having a coating layer (SrTi 0.97 Ni 0.03 O 3-δ , 0 < δ < 1) was obtained. The content of the perovskite-based compound represented by Chemical Formula 1 (SrTi 0.97 Ni 0.03 O 3-δ , 0 < δ < 1) was 10.8 wt% based on the total weight of the catalyst for methane reforming.

[0094] The content of the perovskite-based compound represented by Chemical Formula 1 (SrTi 0.97 Ni 0.03 O 3-δ , 0 < δ < 1) can be calculated by the following Mathematical Formula 1:

[0095] [Mathematical Formula 1]

[0096] Content (wt%) of the perovskite-based compound represented by Chemical Formula 1 = (total weight of the catalyst - weight of the porous metal support) / (total weight of the catalyst) X 100

[0097] <Example 2>

[0098] A catalyst comprising a porous metal support having a coating layer (Sr 0.92 Y 0.08 Ti 0.97 Ni 0.03 O 3-δ , 0 < δ < 1) was obtained in the same manner as in Example 1, except that yttrium nitrate (Y(NO3)2) of 8 mol% based on strontium was further used.

[0099] Here, the pH of the coating solution was 3.0, and the content of the perovskite-based compound represented by Chemical Formula 1 (Sr0.92 Y 0.08 Ti 0.97 Ni 0.03 O 3-δ The content of the perovskite compound represented by the above Chemical Formula 1 (SrTi

[0100] <Comparative Example 1>

[0101] Strontium nitrate (Sr(NO3)2·3H2O) and nickel nitrate (Ni(NO3)2) were dissolved in distilled water at 80°C together with citric acid. Then, titanium isopropoxide (Ti(OCH(CH3)2)4) was dissolved in ethylene glycol at 60°C, the resulting solution was mixed with the distilled water solution, and the temperature was maintained until a clear solution was obtained. The content of nickel was 3 mol% based on titanium. Here, the coating solution had a pH of 0.30.

[0102] A porous metal support (NiCrAl, average pore diameter: 1,200 μm) was coated with the perovskite coating solution by dip coating (forming a coating layer), the coated porous metal support was dried at 150°C for 5 hours, and then heat-treated at 900°C for 5 hours in an air atmosphere. The dip coating, drying, and heat treatment of the perovskite solution were repeated several times, and finally a catalyst comprising a porous metal support having a coating layer (SrTi 0.97 Ni 0.03 O 3-δ The catalyst comprising a porous metal support having a coating layer (SrTi 0.97 Ni 0.03 O 3-δ The content of the perovskite compound represented by the above Chemical Formula 1 (SrTi

[0103] <Comparative Example 2>

[0104] A catalyst comprising a porous metal support having a coating layer (Sr 0.92 Y 0.08 Ti 0.97 Ni 0.03 O 3-δ The catalyst comprising a porous metal support having a coating layer (SrTi

[0105] Here, the pH of the coating solution was 0.30, and the content of the perovskite compound represented by the above Chemical Formula 1 (SrTi 0.92 Y 0.08 Ti 0.97 Ni 0.03 O 3-δ The content of the perovskite compound represented by the above Chemical Formula 1 (SrTi

[0106] <Example 1>Evaluation of Dry Reforming of Methane

[0107] A fixed-bed reaction system was introduced to carry out the dry reforming of methane. Each catalyst (about 2.2 g) according to the examples and comparative examples was filled into a quartz tube reactor (inner diameter = 1 / 2 inch, length = 50 cm). First, reduction was carried out at 800 °C for 2 hours under 10% H2 / N2 conditions, and then the catalytic reaction was carried out for 28 hours.

[0108] Gas composition: CH4:CO2:N2 = 1:1.1:0.1

[0109] Flow rate: GHSV (gas hourly space velocity) = 1,500 hr- 1 (Based on CH4)

[0110] Reaction temperature: 850 °C

[0111] Reaction pressure: 5 bar

[0112] The composition of the product gas was analyzed by using gas chromatography (GC) to calculate the reaction conversion rate after 28 hours of reaction. The results are shown in Table 1 below.

[0113] Conversion rate (Xi, %) = [(Fi 进 - Fi 出 ) / Fi 进 × 100 (Fi = flow rate of i)

[0114] In addition, based on the coke formation amount in Comparative Example 1, the coke formation reduction rate was calculated by using the following formula. The results are shown in Table 1. [[ID=​​​​​​​​​​​​​​​​​​​​​​​​

[0124]

[0125] In the results of Table 1, the fact that the coke generation reduction rate in Comparative Example 2 is a negative (-) value indicates that the results of Comparative Example 2 do not provide a reduction in the amount of coke generation, but rather an increase in the amount of coke generation, as compared to Comparative Example 1.

[0126] As can be seen from the above results, the catalyst for methane reforming according to one exemplary embodiment of the present disclosure is prepared by using strontium hydroxide, and thus provides a reduction in the amount of coke generation as compared to a catalyst for methane reforming prepared by using strontium nitrate, like the comparative example. Thus, it can be seen that the catalyst for methane reforming according to one exemplary embodiment of the present disclosure can reduce side reactions caused by the metal support and the coating layer including the perovskite-based compound.

[0127] Further, the above results were obtained after the catalytic reaction was performed for 28 hours. It is obvious to those skilled in the art that, as in the application in an actual commercialization process, this difference between the coke generation reduction rates of the examples and the comparative example increases when the catalytic reaction is performed for 1,000 hours or more.

[0128] Thus, when the catalyst for methane reforming according to one exemplary embodiment of the present disclosure is applied to methane reforming, it can achieve high activity even at a high space velocity, and can be stably operated for a long time of 1,000 hours or more without carbon deposition or sintering phenomena.

Claims

1. A method of preparing a catalyst for reforming of methane, comprising the steps of: preparing a solution containing a precursor of a perovskite compound represented by the following Chemical Formula 1; and coating a support with the solution and performing a heat treatment to obtain a catalyst, wherein the precursor of the perovskite compound represented by the following Chemical Formula 1 comprises strontium hydroxide: [Chemical Formula 1] A x B y O 3-8δ (1) wherein A is selected from Y, La, and lanthanide elements, Sr 1-x A x Ti α B y O 3-δ B is Ni, Co, Fe, Cr, Mo, Ru, or Rh, x is a real number equal to or greater than 0 and less than 1, y is a real number equal to or greater than 0 and less than 0.3, δ is a real number equal to or greater than 0 and less than 1, α is a real number greater than 0.7 and equal to or less than 1, x and y satisfy (x+y) > 0. the support is a metal support.

2. The method of making a catalyst for the reforming of methane according to claim 1, wherein, the metal support comprises at least one selected from NiFeCrAl, NiCrAl, Al, stainless steel, and Inconel.

3. The method of making a catalyst for the reforming of methane according to claim 2, wherein, the solution containing the precursor of the perovskite compound represented by Chemical Formula 1 has a pH of 2.5 to 3.

7.

4. The method of making a catalyst for the reforming of methane according to claim 1, wherein, the strontium hydroxide is Sr(OH) 2 9H 2 O.

5. The method of making a catalyst for the reforming of methane according to claim 1, wherein, Chemical Formula 1 is represented by the following Chemical Formula 2 or Chemical Formula 3:

6. The method of making a catalyst for the reforming of methane according to claim 1, wherein, [Chemical Formula 2] A x B y O 3-8δ (2) wherein B is Ni or Rh, x is a real number greater than 0 and less than 1, SrTi α B y O 3-δ y is a real number greater than 0 and less than 0.3, Sr 1-x Y x Ti α B y O 3-δ δ is a real number greater than 0 and less than 1, α is a real number greater than 0.7 and equal to or less than 1.

7. A catalyst for reforming of methane obtained by the method of any one of claims 1 to 6. ​ ​ ​

Images