CN106902829A - A kind of load type double-metal reforming catalyst and its preparation method and application - Google Patents

Abstract

The invention discloses a supported double metal reforming catalyst as well as its preparation method and application. The catalyst is loaded on an oxide carrier as active components metal nickel and metal cobalt, and the mass ratio of the oxide carrier, metal nickel and metal cobalt is 1:0.01~0.1:0.01~0.1; the oxide carrier is magnesium oxide, One of alumina, silica, ceria, zirconia. The preparation method is as follows: adopting a deposition precipitation method, slowly adding a precipitating agent into a solution of an oxide carrier, metal nickel and metal cobalt for reaction, and then obtaining the catalyst through suction filtration, washing, drying and calcining. The catalyst solves the problems of poor anti-coking capability, complicated preparation method, high catalyst cost and the like existing in the existing catalysts. The whole preparation process of the invention is simple in technology, convenient in operation, easy in control of synthesis conditions and easy in industrialization, and the prepared catalyst has high catalytic activity and anti-carbon deposition performance.

Description

A kind of supported bimetallic reforming catalyst and its preparation method and application

technical field

The invention relates to a supported bimetallic reforming catalyst and its preparation method and application, belonging to the technical field of catalyst preparation.

Background technique

Methane carbon dioxide reforming to synthesis gas has broad application prospects in efficient utilization of natural gas, energy transmission, and solving increasingly serious environmental problems. However, the reaction conditions of methane carbon dioxide reforming to synthesis gas are just in the thermodynamic carbon deposition zone, and the development of efficient, stable and high carbon deposition-resistant catalysts is a key issue for the industrialization of this process. At present, a lot of research is focused on noble metals and nickel-based catalysts. The former is expensive, and the latter has poor stability due to serious carbon deposition.

In recent years, researchers have achieved the purpose of improving the anti-coking performance by modifying nickel-based catalysts. Due to their tunable physical and chemical properties, electronic and geometric effects between bimetallic catalysts, bimetallic catalysts exhibit unique properties and excellent catalytic performance different from monometallic catalysts. The added second metal and Ni may form an alloy phase or exist as a dopant in an independent phase state, which changes the electronic structure and geometric structure of the active metal, thereby changing the activity and stability of the catalyst.

Due to the price advantage of non-noble metals (such as Co, Cu, Sn, Fe), doping nickel-based catalysts with non-noble metals has become a research hotspot. However, even if it is the same active component, the difference in preparation method will affect the particle size, dispersion, reducibility and microstructure of the catalyst, which will cause significant differences in catalyst reactivity and selectivity. There are also significant differences in ability.

Contents of the invention

The present invention aims to provide a supported bimetallic reforming catalyst, with Ni and Co as active components and oxides such as MgO as carriers, and the catalyst prepared by deposition and precipitation can overcome common preparation methods (such as impregnation, co- Precipitation method) defects and deficiencies. The invention also provides the preparation method and application of the supported bimetallic reforming catalyst.

The invention provides a supported bimetallic reforming catalyst, the catalyst is to load active components metal nickel and metal cobalt on an oxide carrier, and the mass ratio of the oxide carrier, metal nickel and metal cobalt is 1:0.01~0.1 : 0.01 ~ 0.1; the oxide carrier is one of magnesium oxide, aluminum oxide, silicon dioxide, cerium oxide, and zirconium oxide.

In the above catalyst, the mass ratio of the oxide carrier, metal nickel and metal cobalt is 1:0.06-0.08:0.02-0.04.

The present invention provides a preparation method of the above-mentioned supported bimetallic reforming catalyst, comprising the following steps:

Step 1. Dissolve the precursor salts of nickel and cobalt in deionized water to form a mixed solution A. The concentration of nickel ions in solution A is 0.01~0.2mol/L, and the molar ratio of cobalt ions to nickel ions is 1:0.01~ 10;

Step 2. Weigh the precipitant and dissolve it in deionized water to obtain solution B, wherein the molar ratio of the precipitant to the sum of nickel ions and cobalt ions is 1:0.1~1; the volume ratio of solution B to solution A is 1:0.1 ~5;

Step 3: Add oxide carrier to solution A, stir at 30~100°C for 0.5~2h to obtain solution C, wherein the mass ratio of oxide carrier to nickel ion is 1:0.01~0.1;

Step 4: Add solution B to solution C, and adjust the addition rate to ensure that the pH of the mixed system is between 8-12. After the addition is complete, keep the mixed system at 60-120°C for 3-30 hours;

Step 5. The material obtained in Step 4 is suction filtered, washed, dried at 80-150° C. for 3-20 hours, and calcined at 400-900° C. for 3-30 hours to obtain a supported bimetallic reforming catalyst.

In step 1 of the above method, the nickel precursor salt is one of nickel nitrate, nickel acetate, nickel sulfate, and nickel chloride, and the cobalt precursor salt is cobalt nitrate, cobalt acetate, cobalt sulfate, or nickel chloride. A type of cobalt.

In step 2 of the above method, the precipitating agent is one of sodium carbonate, urea, potassium carbonate, sodium hydroxide and potassium hydroxide.

In step 4 of the above method, the rate of addition is 1-20 mL/min.

A preferred preparation method is provided, comprising the following steps:

Step 1. Dissolve the precursor salts of nickel and cobalt in deionized water to form mixed solution A. The concentration of nickel ions in solution A is 0.05~0.15mol/L, and the molar ratio of cobalt ions to nickel ions is 1:1~ 4;

Step 2. Weigh the precipitant and dissolve it in deionized water to obtain solution B, wherein the molar ratio of the precipitant to the sum of nickel ions and cobalt ions is 1:0.3~0.5, and the volume ratio of solution B to solution A is 1:0.2 ~0.6;

Step 3, adding oxide carrier to solution A, stirring at 60~80°C for 0.5~2h to obtain solution C, wherein the mass ratio of oxide carrier to nickel ion is 1:0.06~0.08;

Step 4: Add solution B to solution C, adjust the addition rate (5~10mL/min) to ensure that the pH of the mixed system is between 9-10, after the addition is complete, keep the mixed system at 80~100°C and continue to stir 6~8h;

Step 5. The material obtained in Step 4 is suction filtered, washed, dried at 90-120° C. for 6-12 hours, and calcined at 700-800° C. for 10-15 hours to obtain a supported bimetallic reforming catalyst.

The invention provides the application of the above-mentioned supported bimetallic reforming catalyst in the carbon dioxide reforming reaction of methane.

In the application described above, the catalyst needs to be reduced with 50% H ₂ /N ₂ mixed gas for 1 hour before use. The suitable reaction conditions are that the volume ratio of raw gas methane to carbon dioxide is 1:1, and the reaction temperature is 800°C. Pressure, raw material space velocity is 36000h ^-1 . The catalyst is used in methane carbon dioxide reforming reaction, can obtain reaction activity close to equilibrium conversion rate, has long service life, and the H ₂ /CO ratio of the product is close to 1.

The catalyst is reduced before use. The purpose is: the prepared catalyst metal exists in the form of oxides (such as NiO, CoO), and it needs to be reduced to a metal state before use.

Since the lattice parameters of NiO, CoO and MgO are similar, solid solutions can be formed, so that there is a strong interaction between the active metal and the support, and a highly dispersed active metal can be obtained after reduction. However, due to the strong interaction, a large part NiO and CoO exist in the MgO bulk phase and are difficult to be reduced, and the reduced active metal is too little, resulting in low catalytic activity. In order to improve the reducibility of the active metal, and at the same time make the active component uniformly dispersed on the carrier, the present invention refers to the deposition precipitation method (commonly used in the preparation of highly dispersed noble metal catalysts), and through the regulation and control of the preparation process, the metal in the solution The ions are uniformly deposited on the surface of the carrier, reducing their distribution in the bulk phase.

Beneficial effects of the present invention:

The invention provides a high-activity bimetallic methane carbon dioxide reforming catalyst, which solves the problems of the existing catalysts such as poor anti-coking ability, complicated preparation method and high catalyst cost. The preparation method provided by the invention has simple process, convenient operation, easy control of synthesis conditions and easy industrialization, and the prepared catalyst has high catalytic activity and anti-coking performance.

Description of drawings

Fig. 1 is the reduced XRD pattern of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2.

2 is a TPR diagram of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2.

Fig. 3 is a pore size distribution diagram of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2.

detailed description

The present invention is further illustrated by the following examples, but not limited to the following examples.

Example 1:

Adopt the inventive method to prepare a kind of highly active bimetallic methane carbon dioxide reforming catalyst, comprise the steps:

(1) Dissolve 0.7946g nickel nitrate and 0.1976g cobalt nitrate in 20mL deionized water to make mixed solution A;

(2) Weigh 0.8194g urea and dissolve it in 60mL deionized water to obtain solution B;

(3) Add 2g of magnesium oxide carrier to solution A, stir at 80°C for 2 hours to obtain solution C;

(4) Add solution B to solution C, adjust the addition rate (8mL/min) to ensure that the pH of the mixed system is around 10, and keep the mixed system at 80°C for 8 hours after the addition is complete;

(5) Suction filter, wash, dry at 100° C. for 6 hours, and calcinate at 800° C. for 10 hours to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Example 2:

Adopt the inventive method to prepare a kind of highly active bimetallic methane carbon dioxide reforming catalyst, comprise the steps:

(1) Dissolve 0.2435g nickel chloride and 0.1615g cobalt chloride in 10mL deionized water to make mixed solution A;

(2) Weigh 0.1023g urea and dissolve it in 10mL deionized water to obtain solution B;

(3) Add 1 g of alumina carrier to solution A, stir at 30°C for 2 hours to obtain solution C;

(4) Add solution B to solution C, adjust the addition rate (5mL/min) to ensure that the pH of the mixed system is around 8, and keep the mixed system at 60°C for 15 hours after the addition is complete;

(5) Suction filter, wash, dry at 80° C. for 12 hours, and calcinate at 600° C. for 16 hours to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Example 3:

Adopt the inventive method to prepare a kind of highly active bimetallic methane carbon dioxide reforming catalyst, comprise the steps:

(1) Dissolve 0.4966g nickel nitrate and 0.0.4770g cobalt sulfate in 30mL deionized water to make mixed solution A;

(2) Weigh 0.4086g sodium hydroxide and dissolve it in 60mL deionized water to obtain solution B;

(3) Add 2 g of magnesium oxide carrier to solution A, stir at 50°C for 2 hours to obtain solution C;

(4) Add solution B to solution C, adjust the addition rate (12mL/min) to ensure that the pH of the mixed system is around 12, and keep the mixed system at 100°C for 8 hours after the addition is complete;

(5) Suction filter, wash, dry at 150° C. for 5 h, and calcinate at 600° C. for 10 h to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Example 4:

Adopt the inventive method to prepare a kind of highly active bimetallic methane carbon dioxide reforming catalyst, comprise the steps:

(1) Dissolve 0.850g nickel acetate and 3.381g cobalt acetate in 100mL deionized water to make mixed solution A;

(2) Weigh 3.602g sodium carbonate and dissolve it in 50mL deionized water to obtain solution B;

(3) Add 10g of silica carrier to solution A, stir at 70°C for 1.5h to obtain solution C;

(4) Add solution B to solution C, adjust the addition rate (10mL/min) to ensure that the pH of the mixed system is around 9, and keep the mixed system at 120°C for 5 hours after the addition is complete;

(5) Suction filter, wash, dry at 90° C. for 10 h, and calcinate at 500° C. for 20 h to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Example 5:

Adopt the inventive method to prepare a kind of highly active bimetallic methane carbon dioxide reforming catalyst, comprise the steps:

(1) Dissolve 0.5385g nickel sulfate and 0.8589g cobalt sulfate in 80mL deionized water to make mixed solution A;

(2) Weigh 1.1433g potassium hydroxide and dissolve it in 20mL deionized water to obtain solution B;

(3) Add 3g of cerium oxide carrier to solution A, stir at 100°C for 0.5h to obtain solution C;

(4) Add solution B to solution C, adjust the addition rate (13mL/min) to ensure that the pH of the mixed system is around 11, and keep the mixed system at 90°C for 10 hours after the addition is complete;

(5) Suction filter, wash, dry at 120° C. for 8 hours, and calcinate at 700° C. for 12 hours to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Embodiment 6:

Adopt the inventive method to prepare a kind of highly active bimetallic methane carbon dioxide reforming catalyst, comprise the steps:

(1) Weigh 0.2975g nickel acetate and 0.1482g cobalt nitrate and dissolve in 50mL deionized water to make mixed solution A;

(2) Weigh 0.5118g urea and dissolve it in 75mL deionized water to obtain solution B;

(3) Add 1 g of zirconia carrier to solution A, stir at 60°C for 2 hours to obtain solution C;

(4) Add solution B to solution C, adjust the addition rate (15mL/min) to ensure that the pH of the mixed system is around 10, and keep the mixed system at 70°C for 20 hours after the addition is complete;

(5) Suction filter, wash, dry at 130° C. for 8 hours, and calcinate at 400° C. for 25 hours to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Comparative example 1

The bimetallic methane carbon dioxide reforming catalyst is prepared by co-precipitation, comprising the following steps:

(1) Dissolve 0.7946g nickel nitrate, 0.1976g cobalt nitrate and 12.82g magnesium nitrate in 200mL deionized water to make mixed solution A;

(2) Dissolve 10g of sodium hydroxide in 150mL of deionized water to obtain solution B;

(3) Dissolve 5.512g of sodium carbonate in 200mL of deionized water to obtain solution C;

(4) Pour solution A and solution B into two constant pressure dropping funnels respectively, pour solution C into a three-necked flask, add solution A to the three-necked flask at 60°C, and use solution B to adjust the solution during the process pH, keep the pH at about 10;

(5) Aging the precipitate obtained in step 4 at 60°C for 18 hours, and then washing with suction until the filtrate is neutral;

(6) Dry the material obtained in Step 5 in a drying oven at 120° C. overnight, and calcinate at 800° C. for 10 hours to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Comparative example 2

Prepare bimetallic methane carbon dioxide reforming catalyst by impregnation method, comprising the following steps:

(1) Dissolve 0.7946g nickel nitrate and 0.1976g cobalt nitrate in 6mL deionized water to make mixed solution A;

(2) Add 2g of magnesium oxide carrier to solution A, and stir until dry at room temperature;

(3) The material obtained in step 2 was dried overnight at 120°C in a drying oven, and calcined at 800°C for 10 hours to obtain a supported bimetallic methane carbon dioxide reforming catalyst.

Data detection:

The reduced XRD patterns of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2 are provided, as shown in FIG. 1 . Compared with the standard spectral peaks, the diffraction peaks at 2θ=36.8 ^o , 42.8 ^o , 62.3 ^o , 74.6 ^o , and 78.5 ^o belong to MgO (JCPDS No. 78-0643); the diffraction peaks at 2θ=44.2 ^o ~44.5 ^o The peaks belong to Ni (JCPDS No. 04-0850) and Co (JCPDS No. 15-0806); 2θ=74.6 ^o , a single diffraction peak at 78.5 ^o indicates that NiO and CoO form a solid solution with MgO. As can be seen from the figure, the bimetallic catalyst prepared by the present invention and the bimetallic catalyst prepared by Comparative Example 1 appear Ni, the peak of Co metal simple substance, but the bimetallic catalyst prepared by Comparative Example 2 does not present the peak of simple metal, It may be that the amount of reduction is too small to be lower than the detection limit of XRD.

TPR diagrams of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2 are provided, as shown in FIG. 2 . It can be seen from the figure that the reduction properties of the bimetallic catalysts prepared in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention are significantly different. The bimetallic catalysts prepared in Example 1 and Comparative Example 1 of the present invention have NiO and CoO reduction peaks that have no interaction with MgO, and also have reduction peaks that exist in solid solutions; the reduction of the bimetallic catalysts prepared in Comparative Example 1 before 600 ° C The amount is significantly greater than that of the bimetallic catalysts prepared in Example 1 and Comparative Example 2, and the reduction amount of the bimetallic catalysts prepared in Comparative Example 2 is very small before 900°C.

The pore size distribution diagrams of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2 are provided, as shown in FIG. 3 . It can be seen from the figure that the most probable pore diameter of the bimetallic catalyst prepared by the present invention is the smallest, which is 9.3nm, and the most probable pore diameter of the bimetallic catalyst prepared by Comparative Example 1 and Comparative Example 2 is 10.0nm and 14.5nm respectively. Calculated by the BET formula, the specific surface area of the bimetallic catalyst prepared in the present invention is the largest, which is 68.9 m ² /g, and the specific surface area of the bimetallic catalyst prepared in Comparative Example 1 and Comparative Example 2 is 61.2 m ² /g and 42.9 m ² /g, respectively. g.

Table 1 is a comparison of the metal surface area, particle size and dispersibility of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalyst prepared in Comparative Example 1 and Comparative Example 2.

Table 1 Metal properties of bimetallic methane carbon dioxide reforming catalyst prepared by the present invention

It can be seen that the dispersion degree of the active metal of the bimetallic catalyst prepared by the present invention is obviously better than that of Comparative Example 1 and Comparative Example 2. Due to the poor reducibility of the bimetallic catalyst prepared in Comparative Example 2 (Fig. 2), the amount of active metal reduced is very small, resulting in poor metal dispersion. Although the reducibility of the bimetallic catalyst prepared in Comparative Example 1 is greater than that of the bimetallic catalyst prepared in the present invention, and the amount of active metal it reduces is large, the active metal surface area exposed by the catalyst after reduction is smaller than that of the bimetallic catalyst prepared in the present invention. Poor metal dispersion and large metal particle size. This is because the preparation method of the present invention does not have the local supersaturation phenomenon in the preparation process of Comparative Example 1, and the precipitation agent can be uniformly hydrolyzed in the solution to release ^OH- , so that active metal ions can be uniformly precipitated and smaller metal particles can be produced. , more active surfaces can be exposed after reduction.

Embodiment 7: activity evaluation experiment

The bimetallic catalyst prepared in Example 1 was used in the carbon dioxide reforming reaction of methane, and the catalytic effect was compared with that of the catalysts prepared in Comparative Example 1 and Comparative Example 2.

The specific experiment is as follows: 0.2g catalyst is packed in a fixed bed reactor, the reaction temperature is 800°C, 0.1MPa, the flow rate of CH ₄ and CO ₂ is 60mL/min, and the space velocity is 36000h ^-1 . Before the reaction, the catalyst was reduced with 120mL/min (50% H ₂ /N ₂ ) mixed gas for 1h. Collected by gas sampling bag and analyzed offline by gas chromatography. The chromatographic conditions are: argon as carrier gas, vaporizer temperature 120°C, column furnace temperature 70°C, thermal conductivity temperature 70°C, current 50mA. At the same time, the proportion of reactants in the inlet gas and the proportion of different products in the outlet gas, as well as the flow rate of the reactor inlet gas and the reactor outlet gas flow rate are measured, and finally the conversion rate of the reactant and the selectivity of the product are calculated.

Embodiment 8: Life evaluation experiment

According to the steps of Example 7, the time of methane carbon dioxide reforming reaction was prolonged, and the life evaluation experiment was carried out.

Table 2 compares the activity and lifetime evaluation results of the bimetallic catalyst prepared in Example 1 of the present invention and the bimetallic catalyst prepared in Comparative Example 1 and Comparative Example 2. It can be seen that the bimetallic catalyst prepared by the present invention has the highest initial CH ₄ and CO ₂ conversion rates, which are 90.5% and 95.9% respectively, and after 8 hours of reaction, the amount of carbon deposited on the catalyst is 0; The initial CH ₄ and CO ₂ conversion rates of the bimetallic catalyst were significantly lower than those of the bimetallic catalyst prepared in the present invention. After 8 hours of reaction, the carbon deposits of the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2 were 1.7 wt% and 2.8 wt%, respectively. %.

In order to examine the service life of the bimetallic catalyst prepared by the present invention, compare the CH ₄ , CO ₂ conversion rates after the reaction of 8h, 50h and 200h, as can be seen from Table 2, after a long period of reaction, the bimetallic catalyst prepared by the present invention The catalyst still maintains a high conversion rate of CH ₄ and CO ₂ , and its carbon deposition is only 1.2wt% after 200 hours of reaction, which is much smaller than the carbon deposition of the bimetallic catalysts prepared in Comparative Example 1 and Comparative Example 2 for 8 hours (Table 2) . It can be seen that the bimetallic catalyst prepared by the method of the present invention not only has high catalytic activity, but also has good anti-coking performance and long catalyst life.

Table 2 Reaction performance of bimetallic methane carbon dioxide reforming catalyst prepared by the present invention

Claims (9)

1. A supported bimetallic reforming catalyst, characterized in that: the catalyst is loaded active component metal nickel and metal cobalt on the oxide carrier, and the mass ratio of the oxide carrier, metal nickel and metal cobalt is 1:0.01 ~0.1:0.01~0.1; The oxide carrier is one of magnesium oxide, aluminum oxide, silicon dioxide, cerium oxide and zirconium oxide. 2. The supported bimetallic reforming catalyst according to claim 1, characterized in that: the mass ratio of the oxide carrier, metal nickel and metal cobalt is 1:0.06~0.08:0.02~0.04. 3. A preparation method of the supported bimetallic reforming catalyst according to claim 1 or 2, characterized in that it may further comprise the steps: Step 1. Dissolve the precursor salts of nickel and cobalt in deionized water to form a mixed solution A. The concentration of nickel ions in solution A is 0.01~0.2mol/L, and the molar ratio of cobalt ions to nickel ions is 1:0.01~ 10; Step 2. Weigh the precipitant and dissolve it in deionized water to obtain solution B, wherein the molar ratio of the precipitant to the sum of nickel ions and cobalt ions is 1:0.1~1; the volume ratio of solution B to solution A is 1:0.1 ~5; Step 3: Add oxide carrier to solution A, stir at 30~100°C for 0.5~2h to obtain solution C, wherein the mass ratio of oxide carrier to nickel ion is 1:0.01~0.1; Step 4: Add solution B to solution C, and adjust the addition rate to ensure that the pH of the mixed system is between 8-12. After the addition is complete, keep the mixed system at 60-120°C for 3-30 hours; Step 5. The material obtained in Step 4 is suction filtered, washed, dried at 80-150° C. for 3-20 hours, and calcined at 400-900° C. for 3-30 hours to obtain a supported bimetallic reforming catalyst. 4. the preparation method of supported type bimetallic reforming catalyst according to claim 3 is characterized in that: in step 1, described nickel precursor salt is nickel nitrate, nickel acetate, nickel sulfate, nickel chloride One, the cobalt precursor salt is one of cobalt nitrate, cobalt acetate, cobalt sulfate, and cobalt chloride. 5. the preparation method of supported type bimetallic reforming catalyst according to claim 3 is characterized in that: in step 2, described precipitating agent is sodium carbonate, urea, salt of wormwood, sodium hydroxide, potassium hydroxide kind of. 6. The preparation method of the supported bimetallic reforming catalyst according to claim 3, characterized in that: in step 4, the dropping rate is 1-20 mL/min. 7. The preparation method of supported bimetallic reforming catalyst according to claim 3, is characterized in that: comprises the following steps: Step 1. Dissolve the precursor salts of nickel and cobalt in deionized water to form mixed solution A. The concentration of nickel ions in solution A is 0.05~0.15mol/L, and the molar ratio of cobalt ions to nickel ions is 1:1~ 4; Step 2. Weigh the precipitant and dissolve it in deionized water to obtain solution B, wherein the molar ratio of the precipitant to the sum of nickel ions and cobalt ions is 1:0.3~0.5; the volume ratio of solution B to solution A is 1:0.2 ~0.6; Step 3, adding oxide carrier to solution A, stirring at 60~80°C for 0.5~2h to obtain solution C, wherein the mass ratio of oxide carrier to nickel ion is 1:0.06~0.08; Step 4. Add solution B to solution C, adjust the addition rate to ensure that the pH of the mixed system is between 9-10, and control the addition rate at 5-10mL/min. After the addition, keep the mixed system at 80-100°C Continue to stir for 6~8h; Step 5. The material obtained in Step 4 is suction filtered, washed, dried at 90-120° C. for 6-12 hours, and calcined at 700-800° C. for 10-15 hours to obtain a supported bimetallic reforming catalyst. 8. The application of the supported bimetallic reforming catalyst according to claim 1 or 2 in the carbon dioxide reforming reaction of methane. 9. The application according to claim 8, characterized in that: before the catalyst is used, it needs to be reduced with 50% H ₂ /N ₂ mixed gas for 1 hour, and the condition of the reforming reaction is the volume ratio of the raw material gas methane to carbon dioxide The ratio is 1:1, the reaction temperature is 800°C, normal pressure, and the raw material space velocity is 36000h ^-1 .