Catalyst for methane reforming, method for producing the same, and method for methane reforming

Abstract

The present application provides a catalyst for methane reforming, a method for producing the same, and a method for methane reforming.

Description

[Technical Field]

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0136338, filed with the Korean Intellectual Property Office on October 21, 2022, the entire contents of which are incorporated herein by reference.

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

[0003] As part of efforts to reduce greenhouse gases caused by global warming, much research is being conducted on carbon dioxide conversion technologies. One of these technologies, the carbon dioxide reforming reaction, is a technique 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 are methods for industrially obtaining syngas (H2 / CO), can be broadly 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: Equation 1 + Equation 3 [Reaction Scheme 5] Tri-reforming: Reaction 1 + Reaction 2 + Reaction 3

[0005] Meanwhile, various catalysts can be used in the reforming process for improving reforming activity. Among them, when a noble metal catalyst is used in the reforming process, it has advantages such as relatively less carbon deposition and higher reaction efficiency compared to nickel-based catalysts, but there is a problem in that the noble metal catalyst is expensive, resulting in reduced economic efficiency.

[0006] Therefore, relatively inexpensive nickel catalysts are mainly used in the reforming process. In particular, nickel catalysts in which nickel metal is supported on a support such as alumina are widely used as conventional catalysts. However, in such cases, there is a problem that the nickel catalyst is deactivated by carbon that inevitably forms 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 methane reforming processes. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Republic of Korea Publication Patent No. 10-2019-0076367 Summary of the Invention [Problem to be solved by the invention]

[0009] The present application aims to provide a catalyst for methane reforming, a method for producing the same, and a method for methane reforming. [Means for solving the problem]

[0010] One embodiment of the present application provides a perovskite-based methane reforming catalyst represented by the following chemical formula 1:

[0011] Another embodiment of the present application provides a method for producing a methane reforming catalyst represented by Chemical Formula 1 below, the method including the steps of preparing a solution containing a calcium (Ca) precursor, a precursor comprising A of Chemical Formula 1 below, a zirconium (Zr) precursor, and a precursor comprising B of Chemical Formula 1 below; stirring the solution; and drying and calcining the stirred solution. [Chemical formula 1] Ca 1-x A x Zr 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 0 <x<0.8であり、 y is 0 <y<0.3であり、 δ is in the range of 0≦δ<1.

[0012] Finally, one embodiment of the present application provides a method for reforming methane, comprising the steps of: packing a reactor with the catalyst according to the present application; activating the catalyst; supplying a feed gas to the reactor; and applying heat and pressure to the feed gas. [Effects of the Invention]

[0013] The methane reforming catalyst according to one embodiment of the present application includes a calcium (Ca)-containing perovskite-based compound, which can maximize oxygen vacancies through A-site substitution and more effectively reduce B-site substitution energy, thereby further increasing the amount of active metal substituted into the lattice.

[0014] These features increase the active surface area of ​​the methane reforming catalyst, enabling it to exhibit good activity even at high space velocities during the methane reforming reaction and enabling stable operation for long periods of time without carbon deposition or sintering. DETAILED DESCRIPTION OF THE INVENTION

[0015] This specification will be explained in more detail below.

[0016] In this specification, when a member is said to be located "on" another member, this includes not only when the member is in contact with the other member, but also when another member is present between the two members.

[0017] In this specification, when a part is said to "comprise" a certain component, this does not mean that it may further include other components, unless specifically stated to the contrary, but rather that it does not exclude other components.

[0018] The present application aims to provide a methane reforming catalyst containing a perovskite-based compound containing calcium (Ca). Specifically, the present application aims to provide a methane reforming catalyst represented by the following chemical formula 1: [Chemical formula 1] Ca 1-x A x Zr 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 0 <x<0.8であり、 y is 0 <y<0.3であり、 δ is in the range of 0≦δ<1.

[0019] That is, the methane reforming catalyst according to the present application is a perovskite-based methane reforming catalyst.

[0020] This maximizes oxygen vacancies through A-site substitution and effectively reduces B-site substitution energy, which means that the amount of active metal substituted within the lattice can be increased. This feature increases the active surface area of ​​the methane reforming catalyst, allowing it to exhibit good activity even at high space velocities during the methane reforming reaction and enabling stable operation for long periods of time without carbon deposition or sintering.

[0021] In one embodiment of the present application, the above-mentioned Chemical Formula 1 may provide a catalyst for methane reforming represented by the following Chemical Formula 2: [Chemical formula 2] Ca 1-x A x Zr 1-y B y O 3-δ In the above Chemical Formula 2, A is Y, La or Ba; B is Ni, Co, Fe, Mn, Cr, Mo, Ru or Rh; x is 0 <x<0.2であり、 y is 0 <y<0.25であり、 δ is in the range of 0≦δ<1.

[0022] In one embodiment of the present application, A in the above Chemical Formula 1 may be Y and B may be Ni.

[0023] In this specification, δ is a value that satisfies the valence balance.

[0024] In one embodiment of the present application, the methane reforming catalyst may 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 is not particularly limited to a methane reforming process.

[0025] One embodiment of the present application provides a method for producing a methane reforming catalyst represented by Chemical Formula 1, the method comprising the steps of: preparing a solution containing a calcium precursor, a precursor comprising A of Chemical Formula 1, a zirconium precursor, and a precursor comprising B of Chemical Formula 1; stirring the solution; and drying and calcining the stirred solution.

[0026] In addition, in the method for producing a methane reforming catalyst according to one embodiment of the present application, the above Chemical Formula 1 may also be represented by the above Chemical Formula 2.

[0027] One embodiment of the present application provides a method for producing a methane reforming catalyst represented by Chemical Formula 1, which includes the steps of preparing a solution containing a calcium precursor, an yttrium precursor, a zirconium precursor, and a nickel precursor, stirring the solution, and drying and calcining the stirred solution. That is, the method provides a method for producing a methane reforming catalyst, wherein A in Chemical Formula 1 is Y and B is Ni.

[0028] As described above, the method for producing a methane reforming catalyst according to an embodiment of the present application is characterized in that it can produce a methane reforming catalyst that has an increased active surface area, exhibits good activity even at a high space velocity during a methane reforming reaction, and can be operated stably for a long period of time without carbon deposition or sintering.

[0029] The presence or absence of carbon deposition can be confirmed by observing the catalyst surface using a scanning electron microscope (FE-SEM) (Hitachi S-4800 Scanning Electron Microscope) after the reaction using the catalyst to check for the presence or absence of coke.

[0030] In one embodiment of the present application, the calcium precursor, the precursor containing A in Chemical Formula 1, the zirconium precursor, and the precursor containing B in Chemical Formula 1 may be one or more selected from the group consisting of nitrates, carbonates, chlorides, and ammonium salts of the metals or hydrates of the metals contained in the precursors.

[0031] In one embodiment of the present application, the calcium precursor, yttrium precursor, zirconium precursor, and nickel precursor may be one or more selected from the group consisting of nitrates, carbonates, chlorides, and ammonium salts of the metals or hydrates of the metals contained in the precursors, i.e., A in the above Chemical Formula 1 may be Y and B may be Ni.

[0032] In one embodiment of the present application, the calcium precursor may be one or more selected from the group consisting of nitrate, carbonate, chloride, and ammonium salt of calcium or calcium hydrate, and preferably may be, but is not limited to, Ca(NO3)2·H2O.

[0033] In one embodiment of the present application, the precursor containing A in Chemical Formula 1 may be an yttrium precursor.

[0034] In one embodiment of the present application, the yttrium precursor may be one or more selected from the group consisting of nitrate, carbonate, chloride and ammonium salt of yttrium or yttrium hydrate, and preferably may be, but is not limited to, Y(NO3)2.

[0035] In one embodiment of the present application, the zirconium precursor may be one or more selected from the group consisting of nitrate, carbonate, chloride, and ammonium salt of zirconium or zirconium hydrate, and may be preferably, but is not limited to, ZrO(NO3)2·H2O.

[0036] In one embodiment of the present application, the precursor containing B in Chemical Formula 1 may be a nickel precursor.

[0037] In one embodiment of the present application, the nickel precursor may be one or more selected from the group consisting of nitrate, carbonate, chloride and ammonium salt of nickel or nickel hydrate, and preferably may be, but is not limited to, Ni(NO).

[0038] In one embodiment of the present application, the step of preparing the solution containing the calcium precursor, the precursor comprising A of Chemical Formula 1, the zirconium precursor, and the precursor comprising B of Chemical Formula 1 may include the steps of: respectively preparing the calcium precursor, the precursor comprising A of Chemical Formula 1, the zirconium precursor, and the precursor comprising B of Chemical Formula 1; and dissolving the calcium precursor, the precursor comprising A of Chemical Formula 1, the zirconium precursor, and the precursor comprising B of Chemical Formula 1 in a solvent.

[0039] In one embodiment of the present application, the step of preparing the solution containing the calcium precursor, the yttrium precursor, the zirconium precursor, and the nickel precursor may include the steps of respectively preparing the calcium precursor, the yttrium precursor, the zirconium precursor, and the nickel precursor; and dissolving the calcium precursor, the yttrium precursor, the zirconium precursor, and the nickel precursor in a solvent. That is, A in the above Chemical Formula 1 may be Y and B may be Ni.

[0040] In one embodiment of the present application, the solvent may be one or more selected from the group consisting of distilled water, citric acid, ethylene glycol, and urea. That is, one or more of the solvents may be selected and used, and preferably, both distilled water and citric acid may be used as the solvent.

[0041] In one embodiment of the present application, A in the chemical formula 1 in the solution may be 5 mol % to 20 mol %, preferably 7 mol % to 18 mol %, relative to the calcium in the solution.

[0042] In one embodiment of the present application, the yttrium in the solution may be 5 mol % to 20 mol %, preferably 7 mol % to 18 mol %, relative to the calcium in the solution. That is, A in the chemical formula 1 may be Y.

[0043] In one embodiment of the present application, the amount of B in the Chemical Formula 1 in the solution may be 3 mol % to 25 mol %, preferably 5 mol % to 22 mol %, relative to the amount of zirconium in the solution.

[0044] In one embodiment of the present application, the nickel content in the solution may be 3 mol % to 25 mol %, preferably 5 mol % to 22 mol %, relative to the zirconium content in the solution, i.e., B in Chemical Formula 1 may be Ni.

[0045] When the above content is satisfied, the stability and performance of the catalyst can be further improved.

[0046] The content can be confirmed by subjecting the catalyst to ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.) to confirm the structure of the catalyst.

[0047] A method for producing a methane reforming catalyst according to one embodiment of the present application includes stirring the solution.

[0048] In one embodiment of the present application, the step of stirring the solution may be carried out at a temperature of 60°C to 90°C for 1 hour to 5 hours, preferably at a temperature of 65°C to 85°C for 2 hours to 4 hours, and more preferably at a temperature of 70°C to 80°C for 3 hours, but is not limited to these.

[0049] In one embodiment of the present application, the method further includes a drying and firing step after the step of stirring the solution, i.e., after the step of stirring the solution is completed, a drying and firing step is further included.

[0050] In this case, the drying may be carried out at a temperature of 80°C to 180°C for 1 hour to 48 hours, preferably at a temperature of 100°C to 160°C for 5 hours to 36 hours, and more preferably at a temperature of 150°C for 24 hours, but is not limited to these.

[0051] The calcination may be carried out in an air atmosphere at a temperature of 350°C to 1,100°C for 1 hour to 10 hours, preferably in an air atmosphere at a temperature of 500°C to 1,000°C for 1.5 hours to 8 hours, and more preferably in an air atmosphere at a temperature of 900°C for 3 hours, but is not limited to these.

[0052] In the method for preparing a methane reforming catalyst according to an embodiment of the present application, the perovskite-based catalyst components and the like are the same as those described above.

[0053] The methane reforming catalyst prepared by the preparation method according to one embodiment of the present application can maximize oxygen vacancies due to A-site substitution and more effectively reduce B-site substitution energy. This means that the amount of active metal substituted in the lattice can be further increased. Due to this feature, the active surface area of ​​the methane reforming catalyst increases, allowing it to exhibit good activity even at high space velocities during the methane reforming reaction and enabling stable operation for long periods of time without carbon deposition or sintering.

[0054] One embodiment of the present application provides a method for reforming methane, including the steps of: packing a catalyst according to the present application into a reactor; activating the catalyst; supplying a feed gas to the reactor; and applying heat and pressure to the feed gas.

[0055] In one embodiment of the present application, the methane reforming method may be a dry reforming reaction.

[0056] In one embodiment of the present application, the step of activating the catalyst may be a heat treatment under H2 / N2 conditions at 700°C to 900°C, preferably 750°C to 850°C, i.e., the catalyst may be activated through a reduction process.

[0057] More specifically, the step of activating the catalyst may be carried out under conditions of 5% to 15%, preferably 7% to 12%, and more preferably 10% H2 / N2.

[0058] In one embodiment of the present application, the feed gas may include methane (CH4) and carbon dioxide (CO2), and may further include an inert gas.

[0059] In one embodiment of the present application, the feed gas may contain methane (CH), carbon dioxide (CO), and nitrogen (N). When the feed gas contains methane (CH), carbon dioxide (CO), and nitrogen (N), the volume ratio of the feed gas may be CH:CO:N = 1:1-1.4:0.1-1.

[0060] That is, the volume of the carbon dioxide in the supply gas may be 1 to 1.4 times the volume of the methane, and the volume of the nitrogen in the supply gas may be 0.1 to 1 times the volume of the methane.

[0061] In one embodiment of the present application, in the step of supplying a feed gas to the reactor, the WHSV (Weight Hour Space Velocity) of the feed gas is 3,000 hr -1 ~100,000hr -1 , preferably 20,000 hours -1 ~50,000hr -1may be.

[0062] In one embodiment of the present application, the step of applying heat and pressure to the feed gas may be carried out under a temperature condition of 700°C to 900°C, preferably 750°C to 850°C, and a pressure condition of 0.5 bar to 1.5 bar, preferably 0.8 bar to 1.2 bar.

[0063] In one embodiment of the present application, the step of subjecting the feed gas to heat and pressure may be carried out for 20 hours or more.

[0064] The methane reforming method of the present application may be a method commonly used in methane reforming or dry reforming reactions, except that the catalyst of the present application is used. [Example]

[0065] Hereinafter, in order to specifically explain the present application, a detailed description will be given using examples. However, the examples of the present application may be modified into various other forms, and the scope of the present application should not be construed as being limited to the examples described below. The examples of the present application are provided to more completely explain the present application to those skilled in the art.

[0066] Example 1 Ca(NO3)2·H2O, Y(NO3)2, ZrO(NO3)2·H2O, and Ni(NO3)2 were placed in a reaction flask, and citric acid and distilled water were added to dissolve the solution. The content of the materials was adjusted so that yttrium (Y) in the solution was 8 mol% of the sum of calcium (Ca) and yttrium (Y), and nickel (Ni) was 10 mol% of the sum of zirconium (Zr) and nickel (Ni).

[0067] The solution was stirred at a temperature of about 75°C for 3 hours. The temperature of about 75°C refers to a temperature of 70°C to 80°C. The solution was then dried at a temperature of 150°C for 24 hours. The dried material was then heat-treated in an air atmosphere at a temperature of 900°C for 3 hours to produce a catalyst.

[0068] The catalyst structure was then confirmed using ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.). Specifically, approximately 0.01 g of the prepared catalyst was added to 40 ml of a mixed solution of hydrochloric acid and nitric acid (hydrochloric acid and nitric acid in a volume ratio of 3:1) and reacted at room temperature for 1 hour. The mixture was then heated at 150°C for 3 hours and gradually cooled. After confirming whether the sample was dissolved, 100 μl of a standard substance (Sc, 1,000 ppm) was added and diluted with distilled water to a total volume of 10 ml. The concentration of each element was then measured by adjusting the final concentration and measurement mode.

[0069] The structure of the produced catalyst was confirmed to be Ca 0.92 Y 0.08 Zr 0.90 Ni 0.10 O 3-δ It was confirmed that the catalyst was produced.

[0070] <Example 2> A catalyst was prepared in the same manner as in Example 1, except that the content of nickel (Ni) in the solution was adjusted to 15 mol% based on the sum of zirconium (Zr) and nickel (Ni).

[0071] In addition, ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.) was carried out under the same conditions as in Example 1 to confirm the structure of the catalyst.

[0072] The structure of the produced catalyst was confirmed to be Ca 0.92 Y 0.08 Zr 0.85 Ni 0.15 O 3-δ It was confirmed that the catalyst was produced.

[0073] Example 3 A catalyst was prepared in the same manner as in Example 1, except that the content of nickel (Ni) in the solution was adjusted to 20 mol% based on the sum of zirconium (Zr) and nickel (Ni).

[0074] In addition, ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.) was carried out under the same conditions as in Example 1 to confirm the structure of the catalyst.

[0075] The structure of the produced catalyst was confirmed to be Ca 0.92 Y 0.08 Zr 0.80 Ni 0.20 O 3-δ It was confirmed that the catalyst was produced.

[0076] Example 4 A catalyst was prepared in the same manner as in Example 1, except that the content of yttrium (Y) in the solution was adjusted to 16 mol% relative to the sum of calcium (Ca) and yttrium (Y).

[0077] In addition, ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.) was carried out under the same conditions as in Example 1 to confirm the structure of the catalyst.

[0078] The structure of the produced catalyst was confirmed to be Ca 0.84 Y 0.16 Zr 0.90 Ni 0.10 O 3-δ It was confirmed that the catalyst was produced.

[0079] <Comparative Example 1> The catalyst was prepared in the same manner as in Example 1, except that no Y(NO3)2 was added to the reaction flask, and only Ca(NO3)2·H2O, ZrO(NO3)2·H2O, and Ni(NO3)2 were added.

[0080] In addition, ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.) was carried out under the same conditions as in Example 1 to confirm the structure of the catalyst.

[0081] The structure of the produced catalyst was confirmed to be CaZr 0.90 Ni 0.10 O 3-δIt was confirmed that the catalyst was produced.

[0082] <Comparative Example 2> A catalyst was prepared in the same manner as in Example 1, except that the content of yttrium (Y) in the solution was adjusted to 80 mol % relative to calcium (Ca).

[0083] In addition, ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.) was carried out under the same conditions as in Example 1 to confirm the structure of the catalyst.

[0084] The structure of the produced catalyst was confirmed to be Ca 0.20 Y 0.80 Zr 0.90 Ni 0.10 O 3-δ It was confirmed that the catalyst was produced.

[0085] <Comparative Example 3> The catalyst was prepared in the same manner as in Example 1, except that only Ca(NO3)2·H2O and ZrO(NO3)2·H2O were added to the reaction flask, without Y(NO3)2 and Ni(NO3)2.

[0086] In addition, ICP analysis (ICP-OES; Optima 7300DV, PerkinElmer Co., Ltd.) was carried out under the same conditions as in Example 1 to confirm the structure of the catalyst.

[0087] The structure of the produced catalyst was confirmed to be CaZrO3.

[0088] The structures of the catalysts of Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1 below.

[0089] [Table 1]

[0090] <Experimental Example 1> About 1 g of the catalyst of Example 1 was packed into a quartz tube reactor having an inner diameter of 1 / 2 inch and a length of 50 cm, and the catalyst was activated through a reduction process at 800° C. for 2 hours under 10% H2 / N2 conditions.

[0091] Then, a feed gas having a volume ratio of CH4:CO2:N2=1:1.2:0.96 was introduced into the reactor at a WHSV (Weight Hour Space Velocity) of 30,000 h -1 The dry reforming reaction was carried out for 24 hours at a temperature of 800°C and a pressure of 1 bar while supplying the fuel so as to satisfy the above condition.

[0092] After the reaction was completed, the gas composition inside the reactor was analyzed using gas chromatography (GC), and the results are shown in Table 2 below.

[0093] Thereafter, the dry reforming method was carried out in the same manner as described above, except that one of the catalysts of Examples 2 to 4 and Comparative Examples 1 to 3 was used instead of the catalyst of Example 1. After the reaction was completed, the gas composition inside the reactor was analyzed, and the results are shown in Table 2 below.

[0094] <Experimental Example 2> A dry reforming reaction was carried out for 24 hours using the same method and conditions as in Experimental Example 1. After the reaction, the catalyst was recovered and its thermal decomposition behavior was analyzed using a thermogravimetric analyzer (TGA). The thermal decomposition was carried out in an air atmosphere at a heating rate of 10°C / min up to 800°C. The weight loss of the catalyst between 400°C and 600°C was determined to be coke and converted into a weight ratio (wt%). The results are shown in Table 2 below.

[0095] [Table 2]

[0096] In Table 2, XCH4 and XCO2 respectively represent the conversion rates of CH4 and CO2 in the feed gas, and the values ​​can be calculated by the following Equations 1 and 2.

[0097] [Formula 1] XCH4(%)={(F CH4,in -F CH4,out ) / F CH4,in}×100(%) (F CH4、in : flow rate of CH4 supplied to the reactor, F CH4、out : flow rate of CH4 discharged from the reactor)

[0098] [Formula 2] XCO2(%)={(F CO2,in -F CO2,out ) / F CO2,in}×100(%) (F CO2、in : flow rate of CO2 supplied to the reactor, F CO2、out : flow rate of CO2 emitted from the reactor)

[0099] Also, the H2 / CO ratio means the ratio of H2 and CO after the reaction is completed.

[0100] From the results in Table 2, it was confirmed that the catalysts of Examples 1 to 4 were superior in terms of catalyst life as they generated less coke than the catalysts of Comparative Examples 1 and 2. In the case of Comparative Example 3, although no coke was generated, it was confirmed that the catalyst function was not fulfilled when considering the conversion rates of CH4 and CO2.

[0101] Furthermore, when some of the substances contained in the catalyst of this example were not contained, as in Comparative Examples 1 and 3, it was confirmed that the conversion rates of CH4 and CO2 were low and the proportions of H2 and CO after completion of the reaction were low. In particular, in the case of Comparative Example 3, it was difficult to see that the catalyst was functioning, and it was confirmed that the conversion rates of CH4 and CO2 were low and the proportions of H2 and CO after completion of the reaction were low.

[0102] This means that when the catalysts of Comparative Examples 1 and 3 are used, methane reforming does not occur efficiently.

[0103] In addition, Comparative Example 2 contained the same substances as the catalyst of this example, but unlike the catalyst of this example, it had a low calcium (Ca) content and a high yttrium (Y) content. It was confirmed that the catalyst of Comparative Example 2 had lower CH4 and CO2 conversion rates and lower proportions of H2 and CO after completion of the reaction than Comparative Example 1, which did not contain some of the substances contained in the catalyst of this example.

[0104] That is, it was confirmed that methane reforming does not occur efficiently when a catalyst that does not satisfy the structure of Chemical Formula 1 of the present application is used even if it contains the same materials.

[0105] That is, as can be seen from the results in Table 2, the catalyst according to this example has an increased active surface area for methane reforming, and therefore exhibits good activity even at high space velocities during the methane reforming reaction. This confirms that the catalyst can be operated stably for a long period of time without carbon deposition or sintering.

Claims

1. A methane reforming catalyst represented by the following chemical formula 1: [Chemical formula 1] 5 １－ｘ 5 ｘ Zr 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 0<x<0.8, y is 0<y<0.3; δ is in the range of 0≦δ<1.

2. The methane reforming catalyst according to claim 1, wherein the formula 1 is represented by the following formula 2: [Chemical formula 2] 5 １－ｘ 5 ｘ Zr １－ｙ B ｙ O ３－δ In the above Chemical Formula 2, A is Y, La or Ba; B is Ni, Co, Fe, Mn, Cr, Mo, Ru or Rh; x is 0<x<0.2, y is 0<y<0.25; δ is in the range of 0≦δ<1.

3. The methane reforming catalyst according to claim 1, wherein A in Formula 1 is Y and B is Ni.

4. Steam reforming process, carbon dioxide reforming process (CO 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.

5. preparing a solution containing a calcium precursor, a precursor comprising A of the following Chemical Formula 1, a zirconium precursor, and a precursor comprising B of the following Chemical Formula 1; agitating the solution; and drying and calcining the stirred solution; A method for producing a catalyst for methane reforming represented by the following chemical formula 1, comprising: [Chemical formula 1] 5 １－ｘ 5 ｘ Zr 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 0<x<0.8, y is 0<y<0.3; δ is in the range of 0≦δ<1.

6. 6. The method for preparing a methane reforming catalyst according to claim 5, wherein the calcium precursor, the precursor containing A of Chemical Formula 1, the zirconium precursor, and the precursor containing B of Chemical Formula 1 are at least one selected from the group consisting of nitrates, carbonates, chlorides, and ammonium salts of metals or metal hydrates contained in the precursors.

7. 6. The method of claim 5, wherein A in Formula 1 in the solution is 5 mol % to 20 mol % with respect to calcium in the solution.

8. 6. The method for preparing a methane reforming catalyst according to claim 5, wherein B in Formula 1 in the solution is 3 mol % to 25 mol % with respect to zirconium in the solution.

9. The method for producing a methane reforming catalyst according to claim 5, wherein the chemical formula 1 is represented by the following chemical formula 2: [Chemical formula 2] 5 １－ｘ 5 ｘ Zr １－ｙ B ｙ O ３－δ In the above Chemical Formula 2, A is Y, La or Ba; B is Ni, Co, Fe, Mn, Cr, Mo, Ru or Rh; x is 0<x<0.2, y is 0<y<0.25; δ is in the range of 0≦δ<1.

10. The method for preparing a catalyst for methane reforming according to claim 5, wherein A in Formula 1 is Y and B is Ni.

11. Packing the methane reforming catalyst according to any one of claims 1 to 4 into a reactor; activating the catalyst; Supplying a feed gas to the reactor; and applying heat and pressure to said feed gas; A methane reforming method comprising:

Images