A nickel-based catalyst for methane-carbon dioxide dry reforming reaction and preparation method thereof

Abstract

The present invention belongs to the technical field of catalyst preparation, and specifically relates to a nickel-based catalyst for methane-carbon dioxide dry reforming reaction and a preparation method thereof. The catalyst uses MgAlNbO with a hollow spherical structure as a carrier of Ni, which can create abundant alkaline sites, spatial confinement effects and strong metal-carrier interactions, improve the catalytic activity of the catalyst for methane-carbon dioxide dry reforming reaction, and by phosphating the carrier, the carbon deposition deactivation phenomenon that is easily generated after Ni nanoparticles are loaded on the carrier can be further alleviated, so that the catalyst has high catalytic activity and good stability.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation, and in particular relates to a nickel-based catalyst for methane-carbon dioxide dry reforming reaction and a preparation method thereof. Background Art

[0002] With the rapid development of economy and the continuous growth of world population, global energy and environmental problems are becoming increasingly serious. The utilization and structural adjustment of energy have become the focus of attention of countries around the world. Methane (CH4), as the main component of natural gas, accounts for an increasing proportion of energy consumption. How to efficiently develop and utilize it has become a hot topic of current research. At the same time, the consumption of fossil fuels produces a large amount of greenhouse gases such as carbon dioxide (CO2). The increasingly obvious greenhouse effect has seriously affected the global ecological environment.

[0003] The methane-carbon dioxide dry reforming reaction (DRM) is a reaction pathway with great environmental and economic value. It can convert CH4 and CO2 into synthesis gas, which not only broadens the utilization channels of CH4, but also consumes two greenhouse gases. In addition, the ratio of hydrogen (H2) to carbon monoxide (CO) in the generated synthesis gas is close to 1:1, which can be directly used to produce high-value chemicals. The DRM reaction is an endothermic reaction that needs to be carried out at high temperatures. The use of catalysts can significantly reduce the reaction temperature of DRM. Among them, precious metal catalysts have excellent catalytic activity and stability for the DRM reaction, but their high prices limit their large-scale application. Transition metal nickel (Ni) has catalytic activity comparable to that of precious metal catalysts and is low in price, so it has received widespread attention in the DRM reaction. However, it has serious problems such as sintering and carbon deposition deactivation under high-temperature reaction conditions, which affects the stability of the catalytic process. Summary of the invention

[0004] In view of the problem that nickel-based catalysts for DRM reactions in the prior art suffer from serious sintering and carbon deposition deactivation under high-temperature reaction conditions, the present invention provides a nickel-based catalyst for methane-carbon dioxide dry reforming reaction. The catalyst uses MgAlNbO with a hollow spherical structure as a Ni carrier, which can create abundant basic sites, spatial confinement effect and strong metal-carrier interaction, thereby improving the catalytic activity of the catalyst for methane-carbon dioxide dry reforming reaction. Furthermore, by phosphating the carrier, the carbon deposition deactivation phenomenon that is easily generated after Ni nanoparticles are loaded on the carrier can be further alleviated, so that the catalyst has high catalytic activity and good stability.

[0005] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, comprising the following steps:

[0006] S1: Preparation of MgAlNbO support by hydrothermal method;

[0007] S2: adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate, hydrothermally treating it at 160-190° C. for 8-10 h, and drying it to obtain a P-modified MgAlNbO carrier;

[0008] S3: nickel nitrate hexahydrate is dissolved in a mixture of polyvinyl alcohol and deionized water to form an impregnation solution;

[0009] S4: The P-modified MgAlNbO support is placed in the impregnation solution, aged at room temperature for 4-6 h, dried, placed in a muffle furnace, and calcined at 750-800 °C for 3-4 h.

[0010] Furthermore, the preparation method of the MgAlNbO carrier comprises the following steps:

[0011] (1) Dissolve polyvinyl pyrrolidone, urea and citric acid in a mixture of deionized water and ethanol, and stir evenly for 1 to 2 hours to obtain a mixed solution;

[0012] (2) adding aluminum nitrate, magnesium nitrate and niobium oxalate to the mixed solution under magnetic stirring, and stirring for 2 to 3 hours to obtain a suspension;

[0013] (3) The suspension was transferred to a hydrothermal reactor and kept at 160-165°C for 7-8 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 60-70°C for 10-12 h to obtain a solid product;

[0014] (4) The solid product is placed in a muffle furnace and calcined at a temperature of 700-800°C for 3-3.5 h at a heating rate of 2-5°C / min to obtain a MgAlNbO support.

[0015] Furthermore, the addition ratio of polyvinyl pyrrolidone, urea, lemon, deionized water and ethanol is 0.3~0.4g:0.6~0.7g:0.2~0.3g:20~30mL:10~15mL.

[0016] Furthermore, the addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate, and the mixed solution is 0.0075~0.01mol:0.015mol:0.005mol:30mL.

[0017] Furthermore, in step S2, the concentration of the aqueous solution of diammonium hydrogen phosphate is 0.02-0.03 g / mL.

[0018] Furthermore, in step S3, the addition ratio of nickel nitrate hexahydrate, polyvinyl alcohol, and deionized water is 0.005-0.015 mol: 5-8 mL: 30 mL.

[0019] Furthermore, in step S4, the addition ratio of the P-modified carrier to the impregnation solution is 2-5 g: 20-30 mL.

[0020] Furthermore, in step S4, drying is performed in an oven at 70-80° C. for 12-24 hours.

[0021] Furthermore, in step S4, calcination is performed in a muffle furnace at a heating rate of 1-2°C / min.

[0022] A second aspect of the present invention provides a nickel-based catalyst for methane-carbon dioxide dry reforming reaction obtained by the above-mentioned preparation method.

[0023] The beneficial effects achieved by one or more technical solutions of the present invention are as follows:

[0024] The present invention synthesizes a MgAlNbO carrier with a hollow spherical structure by a hydrothermal method. The carrier has abundant alkaline sites, spatial confinement effect and strong metal-carrier interaction, thereby improving the catalytic activity of the Ni catalyst for the methane-carbon dioxide dry reforming reaction. By phosphating the carrier, the carbon deposition and deactivation phenomenon that is easily generated after the Ni nanoparticles are loaded on the carrier can be further alleviated. At the same time, after the carrier is phosphated and then loaded with Ni particles, Ni3P and NbOPO4 phases will be generated between the carrier and the active Ni particles, thereby making the catalytic activity higher and the catalytic effect better. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a SEM image of the MgAlNbO carrier in Example 1 of the present invention;

[0026] Figure 2 The CH4 conversion performance diagram of different nickel-based catalysts in the methane-carbon dioxide dry reforming reaction;

[0027] Figure 3 The performance diagram of CO2 conversion rate of different nickel-based catalysts in methane-carbon dioxide dry reforming reaction;

[0028] Figure 4 Graph showing the H2 / CO molar ratio of different nickel-based catalysts in the methane-carbon dioxide dry reforming reaction. DETAILED DESCRIPTION

[0029] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in combination with specific embodiments and comparative examples.

[0030] Example 1

[0031] This embodiment provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, and the specific steps are as follows:

[0032] (1) Dissolve 0.3 g polyvinyl pyrrolidone, 0.6 g urea, and 0.2 g citric acid in a mixture of 20 mL deionized water and 10 mL ethanol, and stir for 2 h to obtain a mixed solution;

[0033] (2) Under magnetic stirring, aluminum nitrate, magnesium nitrate and niobium oxalate were added to the mixed solution (the addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate to the mixed solution was 0.01 mol: 0.015 mol: 0.005 mol: 30 mL), and stirred for 2 h to obtain a suspension;

[0034] (3) The suspension was transferred to a hydrothermal reactor and kept at 165°C for 8 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 60°C for 12 h to obtain a solid product;

[0035] (4) The solid product was placed in a muffle furnace and calcined at 800°C for 3 h at a heating rate of 2°C / min. The obtained material was MgAlNbO support, and its SEM image was shown in FIG. Figure 1 As shown, it can be clearly seen that the hollow spherical structure is present.

[0036] (5) adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate with a concentration of 0.02 g / mL, hydrothermally treating the carrier at 180° C. for 10 h, and drying the carrier to obtain a P-modified MgAlNbO carrier;

[0037] (6) 2.9 g of nickel nitrate hexahydrate was dissolved in a mixture of 5 mL of polyvinyl alcohol and 30 mL of deionized water to form an impregnation solution;

[0038] (7) A 2gP-modified MgAlNbO support was placed in 30 mL of the impregnation solution, then aged at room temperature for 4 h, dried in an oven at 80 °C for 12 h, and then placed in a muffle furnace and calcined at 800 °C for 4 h at a heating rate of 2 °C / min to obtain a nickel-based catalyst product for methane-carbon dioxide dry reforming reaction.

[0039] Example 2

[0040] This embodiment provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, and the specific steps are as follows:

[0041] (1) Dissolve 0.4 g polyvinyl pyrrolidone, 0.7 g urea, and 0.3 g citric acid in a mixture of 30 mL deionized water and 15 mL ethanol, and stir for 2 h to obtain a mixed solution;

[0042] (2) Under magnetic stirring, aluminum nitrate, magnesium nitrate and niobium oxalate were added to the mixed solution (the addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate to the mixed solution was 0.01 mol: 0.015 mol: 0.005 mol: 30 mL), and stirred for 3 h to obtain a suspension;

[0043] (3) The suspension was transferred to a hydrothermal reactor and kept at 160°C for 7 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 70°C for 12 h to obtain a solid product;

[0044] (4) The solid product was placed in a muffle furnace and calcined at 800°C for 3 h at a heating rate of 2°C / min to obtain a MgAlNbO carrier.

[0045] (5) adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate with a concentration of 0.02 g / mL, hydrothermally treating the carrier at 160° C. for 10 h, and drying the carrier to obtain a P-modified MgAlNbO carrier;

[0046] (6) 4 g of nickel nitrate hexahydrate is dissolved in a mixture of 8 mL of polyvinyl alcohol and 30 mL of deionized water to form an impregnation solution;

[0047] (7) A 2gP-modified MgAlNbO support was placed in 20 mL of the impregnation solution, then aged at room temperature for 6 h. After being dried in an oven at 70 °C for 20 h, it was placed in a muffle furnace and calcined at 750 °C for 4 h at a heating rate of 2 °C / min to obtain a nickel-based catalyst product for methane-CO2 dry reforming reaction.

[0048] Example 3

[0049] This embodiment provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, and the specific steps are as follows:

[0050] (1) Dissolve 0.3 g polyvinyl pyrrolidone, 0.6 g urea, and 0.3 g citric acid in a mixture of 30 mL deionized water and 10 mL ethanol, and stir for 2 h to obtain a mixed solution;

[0051] (2) Under magnetic stirring, aluminum nitrate, magnesium nitrate and niobium oxalate were added to the mixed solution (the addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate to the mixed solution was 0.0075 mol:0.015 mol:0.005 mol:30 mL), and stirred for 2 h to obtain a suspension;

[0052] (3) The suspension was transferred to a hydrothermal reactor and kept at 165°C for 7 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 70°C for 10 h to obtain a solid product;

[0053] (4) The solid product was placed in a muffle furnace and calcined at 700°C for 3.5 h at a heating rate of 2°C / min to obtain a MgAlNbO carrier.

[0054] (5) adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate with a concentration of 0.02 g / mL, hydrothermally treating it at 190°C for 8 h, and drying it to obtain a P-modified MgAlNbO carrier;

[0055] (6) 3 g of nickel nitrate hexahydrate is dissolved in a mixture of 5 mL of polyvinyl alcohol and 30 mL of deionized water to form an impregnation solution;

[0056] (7) 5 g of P-modified MgAlNbO support was placed in 30 mL of impregnation solution, then aged at room temperature for 4 h, dried in an oven at 80 °C for 20 h, placed in a muffle furnace, and calcined at 750 °C for 3 h at a heating rate of 1 °C / min to obtain a nickel-based catalyst product for methane-CO2 dry reforming reaction.

[0057] Example 4

[0058] This embodiment provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, and the specific steps are as follows:

[0059] (1) Dissolve 0.4 g polyvinyl pyrrolidone, 0.6 g urea, and 0.2 g citric acid in a mixture of 30 mL deionized water and 15 mL ethanol, and stir for 2 h to obtain a mixed solution;

[0060] (2) Under magnetic stirring, aluminum nitrate, magnesium nitrate and niobium oxalate were added to the mixed solution (the addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate to the mixed solution was 0.0075 mol:0.015 mol:0.005 mol:30 mL), and stirred for 2 h to obtain a suspension;

[0061] (3) The suspension was transferred to a hydrothermal reactor and kept at 165°C for 7 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 70°C for 12 h to obtain a solid product;

[0062] (4) The solid product was placed in a muffle furnace and calcined at 750°C for 3 h at a heating rate of 5°C / min to obtain a MgAlNbO carrier.

[0063] (5) adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate with a concentration of 0.02 g / mL, hydrothermally treating the carrier at 180° C. for 10 h, and drying the carrier to obtain a P-modified MgAlNbO carrier;

[0064] (6) 2 g of nickel nitrate hexahydrate is dissolved in a mixture of 8 mL of polyvinyl alcohol and 30 mL of deionized water to form an impregnation solution;

[0065] (7) A 2gP-modified MgAlNbO support was placed in 20 mL of the impregnation solution, then aged at room temperature for 6 h, dried in an oven at 80 °C for 24 h, and then placed in a muffle furnace and calcined at 800 °C for 3 h at a heating rate of 2 °C / min to obtain a nickel-based catalyst product for methane-carbon dioxide dry reforming reaction.

[0066] Comparative Example 1

[0067] This comparative example provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, and the specific steps are:

[0068] (1) Dissolve 0.3 g polyvinyl pyrrolidone, 0.6 g urea, and 0.2 g citric acid in a mixture of 20 mL deionized water and 10 mL ethanol, and stir for 2 h to obtain a mixed solution;

[0069] (2) Under magnetic stirring, aluminum nitrate, magnesium nitrate and niobium oxalate were added to the mixed solution (the addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate to the mixed solution was 0.01 mol: 0.015 mol: 0.005 mol: 30 mL), and stirred for 2 h to obtain a suspension;

[0070] (3) The suspension was transferred to a hydrothermal reactor and kept at 140°C for 8 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 60°C for 12 h to obtain a solid product;

[0071] (4) The solid product was placed in a muffle furnace and calcined at 800°C for 3 h at a heating rate of 2°C / min to obtain a MgAlNbO carrier.

[0072] (5) adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate with a concentration of 0.02 g / mL, hydrothermally treating the carrier at 180° C. for 10 h, and drying the carrier to obtain a P-modified MgAlNbO carrier;

[0073] (6) 2.9 g of nickel nitrate hexahydrate was dissolved in a mixture of 5 mL of polyvinyl alcohol and 30 mL of deionized water to form an impregnation solution;

[0074] (7) A 2gP-modified MgAlNbO support was placed in 30 mL of the impregnation solution, then aged at room temperature for 4 h, dried in an oven at 80 °C for 12 h, and then placed in a muffle furnace and calcined at 800 °C for 4 h at a heating rate of 2 °C / min to obtain a nickel-based catalyst product for methane-carbon dioxide dry reforming reaction.

[0075] Comparative Example 2

[0076] This comparative example provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, and the specific steps are:

[0077] (1) Dissolve 0.3 g polyvinyl pyrrolidone, 0.6 g urea, and 0.2 g citric acid in a mixture of 20 mL deionized water and 10 mL ethanol, and stir for 2 h to obtain a mixed solution;

[0078] (2) Under magnetic stirring, aluminum nitrate, magnesium nitrate and niobium oxalate were added to the mixed solution (the addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate to the mixed solution was 0.01 mol: 0.015 mol: 0.005 mol: 30 mL), and stirred for 2 h to obtain a suspension;

[0079] (3) The suspension was transferred to a hydrothermal reactor and kept at 165°C for 8 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 60°C for 12 h to obtain a solid product;

[0080] (4) The solid product was placed in a muffle furnace and calcined at 600°C for 3 h at a heating rate of 2°C / min. The obtained substance was the MgAlNbO carrier.

[0081] (5) adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate with a concentration of 0.02 g / mL, hydrothermally treating the carrier at 180° C. for 10 h, and drying the carrier to obtain a P-modified MgAlNbO carrier;

[0082] (6) 2.9 g of nickel nitrate hexahydrate was dissolved in a mixture of 5 mL of polyvinyl alcohol and 30 mL of deionized water to form an impregnation solution;

[0083] (7) A 2gP-modified MgAlNbO support was placed in 30 mL of the impregnation solution, then aged at room temperature for 4 h, dried in an oven at 80 °C for 12 h, and then placed in a muffle furnace and calcined at 600 °C for 4 h at a heating rate of 2 °C / min to obtain a nickel-based catalyst product for methane-carbon dioxide dry reforming reaction.

[0084] Comparative Example 3

[0085] This comparative example provides a method for preparing a nickel-based catalyst for a methane-carbon dioxide dry reforming reaction, and the specific steps are:

[0086] (1) Dissolve 0.3 g polyvinyl pyrrolidone, 0.6 g urea, and 0.2 g citric acid in a mixture of 20 mL deionized water and 10 mL ethanol, and stir for 2 h to obtain a mixed solution;

[0087] (2) Under magnetic stirring, aluminum nitrate and magnesium nitrate were added to the mixed solution (the addition ratio of aluminum nitrate to magnesium nitrate to the mixed solution was 0.01 mol:0.015 mol:30 mL), and stirred for 2 h to obtain a suspension;

[0088] (3) The suspension was transferred to a hydrothermal reactor and kept at 165°C for 8 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 60°C for 12 h to obtain a solid product;

[0089] (4) The solid product was placed in a muffle furnace and calcined at 800°C for 3 h at a heating rate of 2°C / min. The obtained substance was the MgAlO carrier.

[0090] (5) adding the MgAlO carrier to an aqueous solution of diammonium hydrogen phosphate with a concentration of 0.02 g / mL, hydrothermally treating it at 180°C for 10 h, and drying it to obtain a P-modified MgAlbO carrier;

[0091] (6) 2.9 g of nickel nitrate hexahydrate was dissolved in a mixture of 5 mL of polyvinyl alcohol and 30 mL of deionized water to form an impregnation solution;

[0092] (7) A 2 g P-modified MgAlO support was placed in 30 mL of the impregnation solution, then aged at room temperature for 4 h, dried in an oven at 80 °C for 12 h, and then placed in a muffle furnace and calcined at 800 °C for 4 h at a heating rate of 2 °C / min to obtain a nickel-based catalyst product for methane-CO2 dry reforming reaction.

[0093] Performance Test:

[0094] A fixed bed reactor at atmospheric pressure was loaded with 20 mg of catalyst (catalyst prepared in Example 1 and Comparative Examples 1 to 3) particles (40-60 mesh) to investigate its methane-carbon dioxide dry reforming reaction activity. The total gas flow rate was 50 mL / min, of which the flow rates of N2, CH4 and CO2 were 20 mL / min, 15 mL / min and 15 mL / min, respectively, and the corresponding mass space velocity was 150,000 mL / (gh). The reaction was carried out at 700°C for 40 hours. The catalytic reaction products included CH4, CO2, H2, CO, and N2. The catalytic results are shown in FIG. Figures 2~4 shown.

[0095] according to Figures 2~4It can be clearly seen that the catalyst prepared in Example 1 was used to carry out the methane-carbon dioxide dry reforming reaction, and in the initial 5 hours, a methane conversion rate of about 95%, a carbon dioxide conversion rate of about 92%, and a H2 / CO molar ratio of about 0.88 were shown, and after 40 hours of reaction, the methane conversion rate, the carbon dioxide conversion rate, and the H2 / CO molar ratio all showed a certain improvement without obvious attenuation, which indicates that the catalyst prepared in Example 1 has a high catalytic activity for the methane-carbon dioxide dry reforming reaction and excellent catalytic stability.

Claims

1. A method for preparing a nickel-based catalyst for methane-carbon dioxide dry reforming reaction, characterized in that: The following steps are involved: S1: Preparation of MgAlNbO support by hydrothermal method; S2: adding the MgAlNbO carrier to an aqueous solution of diammonium hydrogen phosphate, hydrothermally treating it at 160-190° C. for 8-10 h, and drying it to obtain a P-modified MgAlNbO carrier; S3: nickel nitrate hexahydrate is dissolved in a mixture of polyvinyl alcohol and deionized water to form an impregnation solution; S4: placing the P-modified MgAlNbO support in the impregnation solution, aging at room temperature for 4-6 h, drying, placing in a muffle furnace, and calcining at 750-800 °C for 3-4 h; The preparation method of the MgAlNbO carrier comprises the following steps: (1) Dissolve polyvinyl pyrrolidone, urea and citric acid in a mixture of deionized water and ethanol, and stir evenly for 1 to 2 hours to obtain a mixed solution; (2) adding aluminum nitrate, magnesium nitrate and niobium oxalate to the mixed solution under magnetic stirring, and stirring for 2 to 3 hours to obtain a suspension; (3) The suspension was transferred to a hydrothermal reactor and kept at 160-165°C for 7-8 h, then naturally cooled to room temperature, filtered, washed, and dried in an oven at 60-70°C for 10-12 h to obtain a solid product; (4) placing the solid product in a muffle furnace and calcining it at a temperature of 700-800°C for 3-3.5 hours at a heating rate of 2-5°C / min to obtain a MgAlNbO support; The addition ratio of aluminum nitrate, magnesium nitrate, niobium oxalate and mixed solution is 0.0075~0.01mol:0.015mol:0.005mol:30mL.

2. The method for preparing a nickel-based catalyst for methane-carbon dioxide dry reforming reaction according to claim 1, characterized in that: The addition ratio of polyvinyl pyrrolidone, urea, citric acid, deionized water and ethanol is 0.3~0.4g:0.6~0.7g:0.2~0.3g:20~30mL:10~15mL.

3. The method for preparing a nickel-based catalyst for methane-carbon dioxide dry reforming reaction according to claim 1, characterized in that: In step S2, the concentration of the aqueous solution of diammonium hydrogen phosphate is 0.02-0.03 g / mL.

4. The method for preparing a nickel-based catalyst for methane-carbon dioxide dry reforming reaction according to claim 1, characterized in that: In step S3, the addition ratio of nickel nitrate hexahydrate, polyvinyl alcohol, and deionized water is 0.005-0.015 mol: 5-8 mL: 30 mL.

5. The method for preparing a nickel-based catalyst for methane-carbon dioxide dry reforming reaction according to claim 1, characterized in that: In step S4, the addition ratio of the P-modified carrier to the impregnation solution is 2-5 g: 20-30 mL.

6. The method for preparing a nickel-based catalyst for methane-carbon dioxide dry reforming reaction according to claim 1, characterized in that: In step S4, drying is performed in an oven at 70-80° C. for 12-24 hours.

7. The method for preparing a nickel-based catalyst for methane-carbon dioxide dry reforming reaction according to claim 1, characterized in that: In step S4, the sintered product is calcined in a muffle furnace at a heating rate of 1-2°C / min.

8. A nickel-based catalyst for methane-carbon dioxide dry reforming reaction obtained by the preparation method according to any one of claims 1 to 7.

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