Catalyst for methane reforming and its manufacturing method

Abstract

A catalyst for methane reforming according to one embodiment of the present application comprises a porous metal support; perovskite-based catalyst particles supported on the porous metal support; and a perovskite-based binder supported on the porous metal support, wherein the perovskite-based catalyst particles and the perovskite-based binder each independently comprise a compound represented by Chemical Formula 1 above.

Description

[Technical field]

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2021-0158414, filed with the Korean Intellectual Property Office on November 17, 2021, 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. [Background technology]

[0003] As part of efforts to reduce greenhouse gas emissions due to global warming, much research is being conducted on carbon dioxide conversion technologies. Carbon dioxide reforming, one of the carbon dioxide conversion technologies, is a technology in which methane and carbon dioxide are reacted to produce synthesis gas consisting of hydrogen and carbon monoxide.

[0004] Syngas is a valuable substance for development as a raw material for various downstream processes. Natural gas reforming reactions, which can industrially produce syngas (H2 / CO), can be roughly classified into steam reforming, CO2 reforming, catalytic partial oxidation, autothermal reforming, and tri-reforming, as shown in the following reaction formulas 1 to 5. [Reaction Scheme 1] CH4+H2O → 3H2+CO △H=226kJ / mol [Reaction Scheme 2] CH4+CO2→ 2H2+2CO △H=261kJ / mol [Reaction Scheme 3] CH4+0.5O2→ 2H2+CO △H=-44kJ / mol [Reaction Scheme 4] Autothermal reforming: Reaction 1 + Reaction 3 [Reaction Scheme 5] Tri-reforming: Reaction 1 + Reaction 2 + Reaction 3

[0005] Meanwhile, various catalysts can be used in the reforming process for the purpose of reforming activity. Among them, when a precious metal catalyst is used in the reforming process, the efficiency of converting biogas into hydrogen is high, but the precious metal catalyst is expensive, which reduces the economic efficiency.

[0006] For this reason, nickel catalysts, which have high hydrogen conversion efficiency and are relatively inexpensive, are mainly used in the reforming process, but in such cases, there is a problem that the nickel catalyst is deactivated by carbon that is inevitably generated on the surface of the nickel catalyst.

[0007] Therefore, there is a need in the art to develop a catalyst that is resistant to carbon deposition and can be effectively applied in the methane reforming process. Summary of the Invention [Problem to be solved by the invention]

[0008] The present application seeks to provide a catalyst for methane reforming and a method for producing the same. [Means for solving the problem]

[0009] One embodiment of the present application comprises: porous metal support; perovskite-based catalyst particles supported on the porous metal support; and A perovskite-based binder is supported on the porous metal support, The perovskite catalyst particles and the perovskite binder each independently contain a compound represented by the following Chemical Formula 1, thereby providing a catalyst for methane reforming. [Chemical formula 1] Sr 1-x A x Ti 1-y B y O 3-δ In the above Chemical Formula 1, A is Y, La or Ba; B is Ni, Co, Fe, Mn, Cr, Mo, Ru or Rh; x is a real number between 0 and 1, y is a real number greater than or equal to 0 and less than 0.5, δ is a real number greater than 0 and less than 1, Satisfies x+y>0.

[0010] In addition, another embodiment of the present application is mixing the perovskite catalyst particles and the perovskite catalyst sol to prepare a slurry; impregnating a porous metal support with the slurry; and drying and calcining steps; The perovskite-based catalyst particles and the perovskite-based catalyst sol each independently contain a compound represented by Chemical Formula 1. Effect of the Invention

[0011] A methane reforming catalyst according to an embodiment of the present application is prepared by mixing a catalyst sol of the same or similar series as catalyst particles as an inorganic binder to prepare a slurry, and coating the slurry on a metal support having high thermal conductivity. This allows the catalyst content to be increased at one time, and allows side reactions caused by the binder to be suppressed.

[0012] In addition, the methane reforming catalyst according to one embodiment of the present application has catalyst particles and a binder supported on a porous metal support having high thermal conductivity, and therefore has the characteristic that it is easier to control the reaction heat compared to conventional pellet-shaped or powder-shaped catalysts. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a diagram showing an electron microscope photograph of the surface of a methane reforming catalyst according to Example 1 of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] This specification will be explained in more detail below.

[0015] In this specification, when a member is said to be located "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where there is another member between the two members.

[0016] In this specification, when a part is said to "comprise" a certain component, this means that it can further include other components, not excluding other components, unless specifically stated to the contrary.

[0017] Currently, catalysts widely used in the field of reformers are generally powder catalysts and pellet support catalysts. The powder catalysts have excellent dispersion and performance, but it is difficult to use them directly in industry. For example, when the powder catalyst is used to drive the reformer, the catalyst comes out together with the material produced after the reaction, and at this time, the powder catalyst gradually accumulates in the flow tube at the outlet, eventually clogging the entire tube. Therefore, there is a disadvantage that the powder catalyst cannot be used in commercial reformers used in industry.

[0018] Also, the pellet-type support catalyst is currently widely used in industrial reformers. Due to the limit of mass transfer rate, it is inferior to powder-type catalysts in terms of catalytic performance alone, but it has the advantage of being able to be used for a long period of time because of the use of a support. However, the γ-Al2O3 pellets that are widely used as the pellet-type support catalyst have a disadvantage of being easily broken due to weak structural strength, which causes a pressure difference in the reactor. In addition, due to the characteristics of the pellet-type support catalyst, it is large in volume, so when it is used in a high-capacity reformer, the volume becomes quite large. In addition, all reforming reactions are sensitive to the reaction temperature, but the existing pellet-type catalyst has a disadvantage of being significantly reduced in thermal conductivity, which prevents heat from being distributed evenly throughout the reactor.

[0019] Therefore, in this application, we have attempted to improve not only the phenomenon of flow tube clogging, which is a drawback of powder-type catalysts, but also the common drawback of both powder-type and pellet-type catalysts, namely, the rate of heat and mass transfer, by coating a catalyst on a porous metal support having a high rate of heat and mass transfer.

[0020] The porous metal support catalyst can be prepared by coating a slurry prepared by mixing a catalyst precursor or a catalyst powder with a binder, additives, etc., on the surface of a porous metal support. In order to introduce catalyst particles onto the surface of the porous metal support, an organic binder and / or an inorganic binder can be added during preparation of the slurry. The organic binder remains in the slurry until drying and firing processes, and can contribute to reducing surface tension and stabilizing the slurry. The inorganic binder remains between catalyst particles or between catalyst particles and the porous metal support after firing processes, and serves to fix the catalyst particles on the porous metal support, and can be added mainly in the form of silica, alumina sol, or colloid. When a large amount of the inorganic binder is used, it has the advantage that the bond between the catalyst particles and the porous metal support is strong, but on the other hand, the presence of a large amount of binder on the surface of the catalyst particles reduces reaction sites, and the binder may affect the catalyst, and at the same time, it may participate in the reaction and induce undesired side reactions. In order to directly introduce a catalyst into a porous metal support without using a binder, a catalyst precursor may be used directly, but this has the disadvantage that the amount of catalyst supported at one time is small.

[0021] Therefore, the present application aims to provide a methane reforming catalyst which can support a large amount of catalyst at one time and can suppress side reactions caused by the binder.

[0022] A catalyst for methane reforming according to one embodiment of the present application includes a porous metal support; perovskite-based catalyst particles supported on the porous metal support; and a perovskite-based binder supported on the porous metal support.

[0023] In one embodiment of the present application, the perovskite-based catalyst particles and the perovskite-based binder may each independently include a compound represented by the following Chemical Formula 1: [Chemical formula 1] Sr 1-x A x Ti 1-y B y O3-δ In the above Chemical Formula 1, A is Y, La or Ba; B is Ni, Co, Fe, Mn, Cr, Mo, Ru or Rh; x is a real number between 0 and 1, y is a real number greater than or equal to 0 and less than 0.5, δ is a real number greater than 0 and less than 1, Satisfies x+y>0.

[0024] In one embodiment of the present application, the perovskite catalyst particles and the perovskite binder may contain the same compound or different compounds. Thus, in one embodiment of the present application, the methane reforming catalyst may contain two different perovskite compounds.

[0025] In one embodiment of the present application, the above Chemical Formula 1 may be represented by any one of the following Chemical Formulas 2 to 4. [Chemical formula 2] SrTi 1-y B y O 3-δ [Chemical formula 3] Sr 1-x Y x TiO 3-δ [Chemical formula 4] Sr 1-x Y x Ti 1-y B y O 3-δ In the above chemical formulas 2 to 4, B is Ni or Ru; x is a real number greater than 0 and less than 1, y is a real number greater than 0 and less than 0.5, δ is a real number greater than 0 and less than 1.

[0026] In one embodiment of the present application, the porous metal support may be made of a material capable of maintaining thermal stability at high temperatures of 800° C. or higher.

[0027] In one embodiment of the present application, the porous metal support may be made of one or more selected from NiFeCrAl, NiCrAl, SiC, Al, stainless steel, and inconel.

[0028] The porous metal support is a support having various shapes, has a small heat capacity, is excellent in heat transfer ability, and can be formed into a desired shape for use. 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%, preferably 50% to 99%. The average pore size of the porous metal support may be 150 μm to 4,000 μm, 200 μm to 3,500 μm, or 400 μm to 3,000 μm. The 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. According to one embodiment of the present application, porous metal supports having various materials, pore sizes, etc. can be applied as in the examples described below.

[0029] In one embodiment of the present application, the total content of the perovskite catalyst particles and the perovskite binder 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. When the total content of the perovskite catalyst particles and the perovskite binder is less than 3 wt% based on the total weight of the methane reforming catalyst, the reactivity is reduced due to the relatively small number of active sites on the catalyst surface, and the desired catalytic performance cannot be achieved. In addition, when the total content of the perovskite catalyst particles and the perovskite binder exceeds 40 wt%, the catalyst contains a relatively large amount of catalyst components compared to the porous metal support, which may clog pores and generate a pressure difference, thereby reducing the practical benefit of the methane reforming reaction.

[0030] In one embodiment of the present application, at least a portion of the surface of the catalyst particle may include a protrusion shape. The protrusion shape may be, but is not limited to, a spherical shape, an elliptical shape, or a combination thereof. The average diameter of each of the protrusions may be 20 nm to 1 μm. The protrusions may cover the entire surface of the catalyst particle, or may cover only a portion of the surface of the catalyst particle.

[0031] In one embodiment of the present application, the perovskite-based binder is an inorganic binder and may serve to fix the perovskite-based catalyst particles on the porous metal support, and may be present in a protruding form on the perovskite-based catalyst particles, thereby increasing the reaction surface area of ​​the catalyst and improving the performance of the methane reforming reaction.

[0032] According to one embodiment of the present application, the amount of catalyst supported on the porous metal support in one coating can be increased by additionally applying a perovskite-based binder in addition to the perovskite-based catalyst particles, compared to the case where the catalyst particles are applied alone. Also, by applying the perovskite-based binder according to one embodiment of the present application, side reactions and catalyst phase changes that may occur when silica or other colloidal inorganic binders are applied can be prevented, thereby improving the performance of the methane reforming reaction.

[0033] In one embodiment of the present application, the methane reforming catalyst can be applied to a steam reforming process, a carbon dioxide 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.

[0034] A method for producing a methane reforming catalyst according to one embodiment of the present application includes the steps of: mixing perovskite-based catalyst particles and a perovskite-based catalyst sol to produce a slurry; impregnating a porous metal support with the slurry; and drying and calcining, wherein the perovskite-based catalyst particles and the perovskite-based catalyst sol each independently comprise a compound represented by Chemical Formula 1 above.

[0035] In the method for producing a methane reforming catalyst according to one embodiment of the present application, the porous metal support, the perovskite-based catalyst particles, etc. are as described above.

[0036] In particular, the perovskite-based binder of the methane reforming catalyst may be formed from the perovskite-based catalyst sol.

[0037] The perovskite catalyst sol may be formed from a solution containing a precursor of a perovskite compound and a solvent. The precursor of the perovskite compound is a precursor of a metal constituting the perovskite compound, and the metal molar ratio of the perovskite compound may be adjusted by adjusting the content thereof. In addition, the precursor of the metal is not particularly limited, and the ammonium salt, nitrate, carbonate, chloride, lactate, hydroxide, organic acid salt, oxide, or a mixture thereof of the metal element may be applied. The solvent is not particularly limited, and a solvent known in the art may be used. For example, the solvent may be water, an alcohol-based solvent, or the like, but is not limited thereto.

[0038] A method for preparing a methane reforming catalyst according to an embodiment of the present application includes mixing perovskite-based catalyst particles and a perovskite-based catalyst sol to prepare a slurry, and the solvent may be added to adjust the concentration of the slurry.

[0039] A method for producing a methane reforming catalyst according to an embodiment of the present application includes the step of impregnating a porous metal support with the slurry, and may further include the step of removing excess slurry from the porous metal support.

[0040] The method for producing a methane reforming catalyst according to an embodiment of the present application includes the steps of drying and calcining after the step of impregnating the porous metal support with the slurry. The drying may be performed at a temperature of 50°C to 100°C for 20 minutes to 2 hours, or at a temperature of 60°C to 90°C for 30 minutes to 1.5 hours, but is not limited thereto. The calcination may be performed at a temperature of 350°C to 1,100°C for 1 hour to 15 hours in an air atmosphere, or at a temperature of 500°C to 1,000°C for 3 hours to 10 hours in an air atmosphere, but is not limited thereto. If the calcination is performed for less than 1 hour, the perovskite sol used as a binder is not suitable for forming a crystalline phase, and if the calcination is performed for more than 15 hours, it is not preferable in terms of energy consumption.

[0041] In one embodiment of the present application, the method may further include a step of measuring the weight of the catalyst supported on the porous metal support after the drying and calcining steps. Also, by measuring the weight of the catalyst supported on the porous metal support, the steps of impregnating the porous metal support with the slurry and drying and calcining can be repeated 1 to 20 times until a desired amount of catalyst is supported on the porous metal support.

[0042] A methane reforming catalyst according to an embodiment of the present application is prepared by mixing a catalyst sol of the same or similar series as catalyst particles as an inorganic binder to prepare a slurry, and coating the slurry on a metal support having high thermal conductivity. This allows the catalyst content to be increased at one time, and allows side reactions caused by the binder to be suppressed.

[0043] In addition, the methane reforming catalyst according to one embodiment of the present application has catalyst particles and a binder supported on a porous metal support having high thermal conductivity, and therefore has the characteristic that it is easier to control the reaction heat compared to conventional pellet-shaped or powder-shaped catalysts. EXAMPLES

[0044] Hereinafter, the present application will be described in detail with reference to examples in order to specifically explain the present application. However, the examples of the present application may be modified in various different forms, and the scope of the present application is not to be construed as being limited to the examples detailed below. The examples of the present application are provided to more completely explain the present application to those having average knowledge in the art.

[0045] <Example> <Comparative Example 1> 1) Preparation of perovskite catalyst (SrTiO3) sol Perovskite catalyst (SrTiO3) sol was prepared using the citric acid method. Strontium nitrate (Sr(NO3)3H2O) was dissolved in distilled water together with citric acid and ethylene glycol. 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 mixture was cooled to room temperature and stored.

[0046] 2) Perovskite catalyst particles (SrTi 0.995 Ni 0.005 O 3-δ , 0<δ<1) The same procedure as in 1) above was repeated except that nickel nitrate (Ni(NO3)2) was added at 0.5 mol% relative to the titanium.

[0047] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0048] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared above were mixed to prepare a slurry, in which the content of the perovskite catalyst particles was 5 wt %, the concentration of the perovskite catalyst sol was 0.1 M, and water was used as a solvent.

[0049] A porous metal support (NiFeCrAl, average pore size: 800μm) was immersed in the slurry for 1 minute, and excess slurry was removed from the porous metal support using a blower. The porous metal support was then dried at 70℃ for 1 hour, and then heat-treated at 900℃ for 5 hours in an air atmosphere to produce a methane reforming catalyst in which perovskite catalyst particles and a perovskite binder were coated on the porous metal support. This process was repeated several times to produce the final methane reforming catalyst.

[0050] <Example 1> 1) Perovskite catalyst (Sr 0.95 Y 0.05 Ti 0.97 Ru 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 3 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol % relative to strontium.

[0051] 2) Perovskite catalyst particles (Sr 0.85 Y 0.15 Ti 0.95 Ru 0.05 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 5 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 15 mol % relative to strontium.

[0052] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0053] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 1 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiFeCrAl (average pore size: 400 μm) was used as a porous metal support.

[0054] <Example 2> 1) Perovskite catalyst (SrTi 0.97 Ni 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out, except that nickel nitrate (Ni(NO3)2) was added at 3 mol % relative to titanium.

[0055] 2) Perovskite catalyst particles (SrTi 0.95 Ni 0.05 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 5 mol % relative to titanium.

[0056] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0057] 3) Manufacturing of catalysts for methane reforming The same procedure as in 3) of Comparative Example 1 was carried out, except that the perovskite catalyst particles and the perovskite catalyst sol produced in Example 2 were mixed to produce a slurry.

[0058] <Example 3> 1) Perovskite catalyst (Sr 0.95 Y 0.05 Ti 0.97 Ru 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 3 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol % relative to strontium.

[0059] 2) Perovskite catalyst particles (Sr 0.95 Y 0.05 Ti 0.90 Ni 0.10 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 10 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0060] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0061] 3) Manufacturing of catalysts for methane reforming The same procedure as in 3) of Comparative Example 1 was carried out, except that the perovskite catalyst particles and the perovskite catalyst sol produced in Example 3 were mixed to produce a slurry.

[0062] <Example 4> 1) Perovskite catalyst (SrTi 0.97 Ru 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out, except that ruthenium chloride (RuCl3) was added at 3 mol % relative to titanium.

[0063] 2) Perovskite catalyst particles (SrTi 0.93 Ni 0.07 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 7 mol % relative to titanium.

[0064] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0065] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 4 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiFeCrAl (average pore size: 1,200 μm) was used as a porous metal support.

[0066] <Example 5> 1) Perovskite catalyst (Sr 0.95 Y 0.05 Ti 0.93 Ni 0.07 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 7 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0067] 2) Perovskite catalyst particles (Sr 0.95 Y 0.05 Ti 0.93 Ni 0.07 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 7 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0068] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0069] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 5 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiFeCrAl (average pore size: 1,200 μm) was used as a porous metal support.

[0070] <Example 6> 1) Perovskite catalyst (Sr 0.95 Y 0.05 Ti 0.85 Ru 0.15 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 15 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol % relative to strontium.

[0071] 2) Perovskite catalyst particles (Sr 0.95 Y 0.05 Ti 0.80 Ni 0.20 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 20 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0072] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0073] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 6 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiFeCrAl (average pore size: 3,000 μm) was used as a porous metal support.

[0074] <Example 7> 1) Perovskite catalyst (Sr 0.95 Y0.05 Ti 0.90 Ru 0.10 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 10 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol % relative to strontium.

[0075] 2) Perovskite catalyst particles (Sr 0.95 Y 0.05 Ti 0.80 Ni 0.20 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 20 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0076] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0077] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 7 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiFeCrAl (average pore size: 3,000 μm) was used as a porous metal support.

[0078] <Example 8> 1) Perovskite catalyst (SrTi 0.97 Ni 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out, except that nickel nitrate (Ni(NO3)2) was added at 3 mol % relative to titanium.

[0079] 2) Perovskite catalyst particles (SrTi 0.97 Ni 0.03 O3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out, except that nickel nitrate (Ni(NO3)2) was added at 3 mol % relative to titanium.

[0080] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0081] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 8 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiCrAl (average pore size: 400 μm) was used as a porous metal support.

[0082] <Example 9> 1) Perovskite catalyst (Sr 0.95 Y 0.05 Ti 0.97 Ni 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 3 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0083] 2) Perovskite catalyst particles (Sr 0.95 Y 0.05 Ti 0.97 Ni 0.03 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 3 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0084] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0085] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 9 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiCrAl (average pore size: 800 μm) was used as a porous metal support.

[0086] <Example 10> 1) Perovskite catalyst (Sr 0.95 Y 0.05 Ti 0.97 Ru 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 3 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol % relative to strontium.

[0087] 2) Perovskite catalyst particles (SrTi 0.90 Ni 0.10 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out, except that nickel nitrate (Ni(NO3)2) was added at 10 mol % relative to titanium.

[0088] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0089] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 10 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiCrAl (average pore size: 1,200 μm) was used as a porous metal support.

[0090] <Example 11> 1) Perovskite catalyst (Sr 0.95 Y 0.05 Ti0.90 Ru 0.10 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 10 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol % relative to strontium.

[0091] 2) Perovskite catalyst particles (Sr 0.95 Y 0.05 Ti 0.80 Ni 0.20 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 20 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 5 mol% relative to strontium.

[0092] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0093] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 11 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiCrAl (average pore size: 1,500 μm) was used as a porous metal support.

[0094] <Example 12> 1) Perovskite catalyst (Sr 0.85 Y 0.15 Ti 0.97 Ni 0.03 O 3-δ , 0<δ<1) Preparation of sol The same procedure as in 1) of Comparative Example 1 was carried out except that nickel nitrate (Ni(NO3)2) was added at 3 mol% relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 15 mol% relative to strontium.

[0095] 2) Perovskite catalyst particles (Sr 0.85 Y 0.15 Ti 0.97 Ru 0.03 O 3-δ , 0<δ<1) The same procedure as in 1) of Comparative Example 1 was carried out except that ruthenium chloride (RuCl3) was added at 3 mol % relative to titanium, and yttrium nitrate (Y(NO3)2) was added at 15 mol % relative to strontium.

[0096] The solution thus prepared was placed in a crucible, dried at 150° C. for 24 hours, and calcined at 900° C. to prepare perovskite catalyst particles.

[0097] 3) Manufacturing of catalysts for methane reforming The perovskite catalyst particles and the perovskite catalyst sol prepared in Example 12 were mixed to prepare a slurry, and the same procedure as in 3) of Comparative Example 1 was carried out except that NiCrAl (average pore size: 3,000 μm) was used as a porous metal support.

[0098] <Comparative Example 2> A catalyst was prepared in the same manner as in Example 8, except that an inorganic binder, SiO2 (Ludox), was used instead of the perovskite catalyst sol, and NiCrAl (average pore size: 1,200 μm) was used as the porous metal support.

[0099] <Comparative Example 3> A catalyst was prepared in the same manner as in Example 2, except that perovskite catalyst particles were not used, but the perovskite catalyst sol was used alone, and NiFeCrAl (average pore size: 1,200 μm) was used as a porous metal support.

[0100] <Comparative Example 4> A catalyst was prepared in the same manner as in Example 9, except that the perovskite catalyst sol was not used, but the perovskite catalyst particles were used alone, and NiFeCrAl (average pore size: 3,000 μm) was used as a porous metal support.

[0101] <Comparative Example 5> A catalyst was prepared in the same manner as in Example 8, except that the porous metal support and the perovskite catalyst sol were not used, and the perovskite catalyst particles were used alone.

[0102] <Comparative Example 6> A catalyst was prepared in the same manner as in Comparative Example 1, except that perovskite catalyst particles were not used, but the perovskite catalyst sol was used alone, and NiCrAl (average pore size: 3,000 μm) was used as a porous metal support.

[0103] The configurations of the porous metal support, catalyst particles and binder in the above examples and comparative examples are shown in Table 1 below. [Table 1]

[0104] <Experimental Example 1> Evaluation of catalyst for methane reforming An electron microscope photograph of the surface of the methane reforming catalyst according to Example 1 of the present application is shown in FIG.

[0105] In preparing the methane reforming catalysts of the above Examples and Comparative Examples, the content of the perovskite catalyst supported on the porous metal support after one coating was measured and is shown in the following Table 2. In addition, in the methane reforming catalysts of the above Examples and Comparative Examples, the presence or absence of protrusions on the surface of the catalyst particles coated on the porous metal support was confirmed and is shown in the following Table 2.

[0106] The catalyst loading amount can be calculated by the following Equation 1, and the presence or absence of protrusions can be confirmed by observing a surface image using a SEM. [Formula 1] Catalyst loading amount (wt%)=(total weight of catalyst-weight of porous metal support) / (total weight of catalyst)×100

[0107] [Table 2]

[0108] As shown in the above results, in Comparative Examples 1 to 3, since the catalyst content carried during one coating is small and the number of coating times has to be increased, there is a problem that the process cost increases. In Comparative Example 4, no catalyst was attached at all. In addition, in Comparative Example 5, it was impossible to measure the content of the catalyst particles supported on the porous metal support by applying them alone, and in Comparative Example 6, the content of the active metal capable of playing the role of the catalyst was not measured.

[0109] <Experimental Example 2>Reforming reaction evaluation of methane To carry out the dry reforming reaction of methane, a fixed-bed reaction system was introduced. Using a quartz tube reactor (inner diameter = 1 / 2 inch, length = 50 cm), each catalyst (about 2.5 g) of the examples and comparative examples was filled. First, after undergoing a reduction process at 800 °C for 2 hours under the condition of 10% H2 / N2, the catalytic reaction proceeded for 100 hours.

[0110] Gas composition: CH4:CO2:N2 = 1:1.2:0.96 Flow rate: WHSV (Weight Hour Space Velocity) = 3,000 cc / g·hr~ 100,000 cc / g·hr Reaction temperature: 800 °C Reaction pressure: 1 bar

[0111] The composition of the product gas was analyzed using gas chromatography (GC), and the reaction conversion rate after 100 hours of reaction was calculated and shown in Table 3 below. Conversion rate (Xi, %) = [(Fi in - Fi out ) / Fi in × 100 (Fi = flow rate of i)

[0112] <GC analysis conditions> 1) GC model: Agilent 6890 2) Oven temperature: 40 °C / 7 min - 90 °C / 5 min - 180 °C / 6 min 3) Detector: TCD, 250℃ 4) Sample loop: 0.25 mL 5) Valve box temperature: 150℃

[0113] [Table 3]

[0114] As a result of the above, it can be confirmed that the methane reforming catalyst according to one embodiment of the present application has excellent methane conversion rate and CO2 conversion rate during the methane reforming reaction.

[0115] A methane reforming catalyst according to an embodiment of the present application is prepared by mixing a catalyst sol of the same or similar series as catalyst particles as an inorganic binder to prepare a slurry, and coating the slurry on a metal support having high thermal conductivity. This allows the catalyst content to be increased at one time, and allows side reactions caused by the binder to be suppressed.

[0116] In addition, the methane reforming catalyst according to one embodiment of the present application has catalyst particles and a binder supported on a porous metal support having high thermal conductivity, and therefore has the characteristic that it is easier to control the reaction heat compared to conventional pellet-shaped or powder-shaped catalysts.

Claims

1. porous metal support; perovskite-based catalyst particles supported on the porous metal support; and A perovskite-based binder is supported on the porous metal support, The perovskite-based catalyst particles and the perovskite-based binder each independently contain a compound represented by the following chemical formula 1: [Chemical formula 1] Sr １－ｘ A ｘ Three １－ｙ B ｙ Oh ３－δ In the above Chemical Formula 1, A is Y, B is Ni or Ru; 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 0.5; δ is a real number greater than 0 and less than 1, The condition x+y>0 is satisfied.

2. The methane reforming catalyst according to claim 1, wherein the formula 1 is represented by any one of the following formulas 2 to 4: [Chemical formula 2] Srti １－ｙ B ｙ Oh ３－δ [Chemical formula 3] Sr １－ｘ Y ｘ TiO ３－δ [Chemical formula 4] Sr １－ｘ Y ｘ Ti １－ｙ B ｙ O ３－δ In the above Chemical Formulas 2 to 4, B is Ni or Ru; x is a real number greater than 0 and less than 1, y is a real number greater than 0 and less than 0.5; δ is a real number greater than 0 and less than 1.

3. The methane reforming catalyst according to claim 1 , wherein the perovskite catalyst particles and the perovskite binder contain different compounds.

4. The methane reforming catalyst according to claim 1 , wherein the perovskite catalyst particles and the perovskite binder each contain the same compound.

5. 2. The methane reforming catalyst according to claim 1, wherein the porous metal support is made of at least one material selected from the group consisting of NiFeCrAl, NiCrAl, Al, stainless steel, and inconel.

6. 2. The methane reforming catalyst according to claim 1, wherein a total content of the perovskite-based catalyst particles and the perovskite-based binder is 3 wt % to 40 wt %, based on a total weight of the methane reforming catalyst.

7. 2. The methane reforming catalyst according to claim 1, wherein at least a portion of the surface of the perovskite catalyst particles includes a protruding shape.

8. Steam reforming, carbon dioxide reforming 2 2. The methane reforming catalyst according to claim 1, which is applied to a methane reforming process, a catalytic partial oxidation process, an autothermal reforming process, a tri-reforming process or a mixed reforming process.

9. Mixing the perovskite catalyst particles and the perovskite catalyst sol to prepare a slurry; impregnating a porous metal support with the slurry; and drying and calcining steps; The perovskite-based catalyst particles and the perovskite-based catalyst sol each independently contain a compound represented by the following chemical formula 1: [Chemical formula 1] Sr １－ｘ A ｘ Three １－ｙ B ｙ Oh ３－δ In the above Chemical Formula 1, A is Y, B is Ni or Ru; 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 0.5; δ is a real number greater than 0 and less than 1, The condition x+y>0 is satisfied.

10. The method for producing a methane reforming catalyst according to claim 9, wherein the formula 1 is represented by any one of the following formulas 2 to 4: [Chemical formula 2] Srti １－ｙ B ｙ Oh ３－δ [Chemical formula 3] Sr １－ｘ Y ｘ TiO ３－δ [Chemical formula 4] Sr １－ｘ Y ｘ Ti １－ｙ B ｙ O ３－δ In the above Chemical Formulas 2 to 4, B is Ni or Ru; x is a real number greater than 0 and less than 1, y is a real number greater than 0 and less than 0.5; δ is a real number greater than 0 and less than 1.

11. 10. The method for producing a methane reforming catalyst according to claim 9, wherein the porous metal support is made of at least one material selected from the group consisting of NiFeCrAl, NiCrAl, Al, stainless steel, and inconel.

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