CN119746916B - Nickel-samarium bimetal synergic/MCM-41 molecular sieve catalyst and preparation method and application thereof - Google Patents
Nickel-samarium bimetal synergic/MCM-41 molecular sieve catalyst and preparation method and application thereofInfo
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Abstract
The invention discloses a nickel samarium bimetal synergic/MCM-41 molecular sieve catalyst, a preparation method and application thereof. The catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is an MCM-41 molecular sieve, and the active component is nickel and samarium. Compared with other nickel-based catalysts, the catalyst provided by the invention has the advantages that the interaction between the active components and the carrier is enhanced through the synergistic effect of nickel and samarium bimetallic, the dispersion degree of the active metals is improved, the anti-sintering capability of the active metals is enhanced, and the surface of the catalyst has high oxygen vacancy concentration, so that the activation of CO 2 is promoted, the number of active oxygen species on the surface of the catalyst is increased, and the removal of carbon deposition is promoted. Therefore, the catalyst has good sintering resistance, carbon deposition resistance and high catalytic stability, and meets the use requirements of industrial catalysts.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst and a preparation method and application thereof.
Background
CO 2 exceeding 30Gt is released into the atmosphere each year, causing serious environmental problems such as global warming, while methane (CH 4) is another major greenhouse gas, and the unlimited release of methane caused by the release of natural gas and shale gas in permafrost further exacerbates environmental problems. Therefore, effective measures are taken to be important for recycling, conversion and utilization of the two greenhouse gases.
Carbon dioxide and methane Dry Reforming (DRM) was first widely studied in the beginning of the 20 th century. In 1946, researchers were first finding that cobalt-based catalysts (Co-based catalysts) can promote the dry reforming reaction of CH 4 with Co 2, and pointed out that improving the stability of cobalt-based catalysts is one of the important factors in achieving efficient DRM. In 1958, other studies further showed that Co/La 2O3-SiO2 catalyst supported on SiO 2 carrier, using Co and La 2O3 as active components, exhibited higher catalytic activity and stability in the temperature range 1073K to 1173K. Thereafter, in the optimization research on the DRM catalyst, it was found that the economical and efficient Ni-based and Co-based catalysts can exhibit excellent methane activation performance and anti-carbon deposition ability at a higher temperature compared to the conventional noble metal catalysts (e.g., pt, rh), thereby becoming a research hotspot in this field.
However, a great deal of research results show that Ni-based catalysts still face two general problems of sintering and carbon deposition in DRM reactions, which in turn lead to catalyst deactivation and poor stability. Therefore, how to design the catalyst and further improve the carbon deposition resistance, sintering resistance and the like of the Ni-based catalyst becomes a key whether the dry reforming of methane can be further applied to industrialization and large-scale preparation of the synthesis gas.
Disclosure of Invention
The invention mainly aims to provide a nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst with good sintering resistance, carbon deposition resistance and catalytic stability, and a preparation method and application thereof.
In order to achieve the aim, the invention provides a nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst which comprises a carrier and an active component loaded on the carrier, wherein the carrier is an MCM-41 molecular sieve, and the active components are nickel and samarium.
Further, the nickel content is 5-20wt%, the samarium content is 1-20wt%, and the balance is MCM-41 molecular sieve.
The invention also provides a preparation method of the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst, which comprises the following steps:
(1) Dissolving precursor salts of nickel and samarium in deionized water, adding ammonia water to obtain an alkaline nickel samarium ammonia complex solution, adding an MCM-41 molecular sieve into the alkaline nickel samarium ammonia complex solution, heating and stirring under a closed condition, and heating and evaporating until the pH value of the solution reaches neutrality to obtain a reaction mixed solution;
(2) And (3) centrifuging the reaction mixed solution, drying the obtained solid, grinding the dried solid into powder, and finally calcining the powder in an air atmosphere to obtain the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst.
In the step (1), the addition amount of ammonia water is such that the pH value reaches 10-12, and the stirring treatment condition is room temperature for 8-12 h.
Further, in the step (1), the temperature of heating evaporation is 60-90 ℃.
Further, in the step (2), the drying treatment condition is that the temperature is 80-110 ℃ and the time is 8-12 hours.
Further, in the step (2), the specific process of the calcination treatment is that the temperature is raised to 550-700 ℃ at a temperature rising rate of 1-5 ℃ per minute, and then the calcination is carried out for 2-6 hours at the constant temperature.
The invention also provides application of the nickel samarium bimetal synergic/MCM-41 molecular sieve catalyst in preparing synthetic gas by catalyzing methane dry reforming.
The invention also provides a method for preparing the synthetic gas by catalyzing methane dry reforming, which comprises the following steps of reducing the catalyst for 2-4 hours in an atmosphere of 10vol% H2/N2 at a temperature of 550-750 ℃, mixing the catalyst with inert silicon carbide, and carrying out a reaction for preparing the synthetic gas by catalyzing methane dry reforming in a reactor.
Further, the catalyst and the inert silicon carbide are subjected to solid-phase grinding and mixing for 10-15 min according to the mass ratio of 1:2-5, wherein the reaction conditions are that the molar ratio of CH4 to CO2 in the reaction feed is 1-2, the space velocity of the gas feed is 40000-120000 mL.h < -1 >. Gcat < -1 >, the catalyst dosage is 0.05-0.5 g, and the reaction temperature is 550-850 ℃. In the process of implementing the invention, the inventor finds that under the reaction condition, the catalyst shows high methane/carbon dioxide conversion rate in the reaction of preparing the synthetic gas by catalyzing methane dry reforming for 800 hours, the conversion rate is more than 80%, and the H 2/CO ratio in the synthetic gas is 0.8-1.2.
The MCM-41 molecular sieve has a two-dimensional hexagonal structure and a large specific surface area, and the unique structural characteristics of the MCM-41 molecular sieve are beneficial to the distribution of active metals to form more active sites.
Compared with a nickel/MCM-41 molecular sieve, the nickel samarium bimetal synergy not only improves the sintering resistance of the active metal through the interaction of the active component and the carrier, but also has high oxygen vacancy concentration which is beneficial to promoting the activation of CO 2 and improving the number of active oxygen species on the surface of the catalyst, thereby promoting the removal of carbon deposit.
The samarium serving as lanthanide metal has good oxidation-reduction performance and high oxygen mobility, and the nickel-samarium bimetallic synergic/MCM-41 molecular sieve catalyst is prepared, so that the removal of carbon on the surface of the catalyst is facilitated, the strong interaction between the metal and a carrier is improved, and the anchoring of active metal nickel is realized.
The beneficial effects of the invention are as follows:
1. The catalyst provided by the invention has the characteristics of green economy and high structural stability, and is applied to the reaction of preparing the synthetic gas by catalyzing CH 4-CO2 reforming, and the catalyst has high methane/carbon dioxide conversion rate which is higher than 80% in the reaction of preparing the synthetic gas by catalyzing methane dry reforming for 800 hours, wherein the H 2/CO ratio in the synthetic gas is 0.8-1.2.
2. The catalyst provided by the invention adopts nickel samarium as active metal, so that the catalyst can be ensured to have high methane C-H bond cracking activity, and the use of the MCM-41 molecular sieve carrier can promote the dispersion of active components while saving the preparation cost of the catalyst.
3. Compared with other nickel-based catalysts, the catalyst provided by the invention has the advantages that the interaction between the active components and the carrier is enhanced through the synergistic effect of nickel and samarium bimetallic, the dispersion degree of the active metals is improved, the anti-sintering capability of the active metals is enhanced, and the surface of the catalyst has high oxygen vacancy concentration, so that the activation of CO 2 is promoted, the number of active oxygen species on the surface of the catalyst is increased, and the removal of carbon deposition is promoted. Therefore, the catalyst has good sintering resistance, carbon deposition resistance and high catalytic stability, and meets the use requirements of industrial catalysts.
4. The catalyst provided by the invention is applied to the reaction of preparing the synthetic gas by catalyzing methane dry reforming, can obviously enhance the adsorption activation capability of catalysis on CH 4、CO2 molecules, has high CH 4、CO2 conversion rate, and shows good industrial application prospects.
Drawings
FIG. 1 is an XRD pattern of the catalysts prepared in example 2 and comparative example 1;
FIG. 2 is an adsorption-desorption isotherm plot of the catalyst prepared in example 2 and of the MCM-41 molecular sieve and N 2;
FIG. 3 is a graph showing pore size distribution of the catalyst prepared in example 2 and an MCM-41 molecular sieve;
FIG. 4 is a TEM image of the catalysts prepared in example 2 and comparative example 1;
FIG. 5 is an EPR chart of the catalysts prepared in example 2 and comparative example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the examples which follow are commercially available from conventional sources or may be obtained by methods known in the art unless otherwise specified, and the methods used in the examples of the present invention are all well known to those skilled in the art. Wherein, the
MCM-41 molecular sieves were purchased from Alatidine Biotechnology Co., ltd., pore size of 2.5nm, particle size of 1-2 μm, specific surface area (m 2/g): 600-800.
Inert silicon carbide was purchased from Shanghai Meilin Biochemical technologies Co., ltd, particle size 200 mesh.
Example 1
Preparation of nickel samarium bimetal synergic/MCM-41 molecular sieve catalyst
The nickel content of the active component in the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst prepared in the embodiment is 5wt percent, the samarium content is 3wt percent, and the rest component is an MCM-41 molecular sieve carrier, and the preparation method comprises the following steps:
(1) Weighing 0.2692g of nickel nitrate hexahydrate and 0.0963g of samarium nitrate hexahydrate, dissolving in 75mL of deionized water, fully stirring and dissolving to form a uniform solution, adding 28% ammonia water to adjust the pH to 10, adding 1g of MCM-41 molecular sieve carrier, sealing by using a preservative film, stirring at the room temperature at the rotating speed of 300r/min for 8 hours, and heating and evaporating (ammonia and water are evaporated) at 90 ℃ until the solution is neutral to obtain a reaction mixed solution;
(2) And (3) centrifugally washing the reaction mixed solution, drying the obtained solid at 80 ℃ for 12 hours, grinding the solid into powder, finally placing the powder in 100mL/min air atmosphere, raising the temperature to 600 ℃ at a temperature raising rate of 1 ℃/min, calcining the powder at a constant temperature for 6 hours, and naturally cooling the powder to room temperature to obtain the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst with the nickel content of 5wt% and the samarium content of 3wt%, wherein the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst is marked as 5Ni3Sm/MCM-41.
Example 2
Preparation of nickel samarium bimetal synergic/MCM-41 molecular sieve catalyst
The nickel content of the active component in the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst prepared in the embodiment is 10wt percent, the samarium content is 1wt percent, and the rest component is an MCM-41 molecular sieve carrier, and the preparation method comprises the following steps:
(1) Weighing 0.5548g of nickel nitrate hexahydrate and 0.0331g of samarium nitrate hexahydrate, dissolving in 75mL of deionized water, fully stirring and dissolving to form a uniform solution, adding 28% ammonia water to adjust the pH to 12, adding 1gMCM-41 molecular sieve carrier, sealing with a preservative film, stirring at the room temperature at the rotating speed of 300r/min for 12 hours, and heating and evaporating at 80 ℃ until the solution is neutral to obtain a reaction mixed solution;
(2) And (3) centrifugally washing the reaction mixed solution, drying the obtained solid for 12 hours at 105 ℃, grinding the solid into powder, finally placing the powder in an air atmosphere of 100mL/min, heating to 550 ℃ at a temperature rising rate of 4 ℃ per min, calcining at a constant temperature for 5 hours, and naturally cooling to room temperature to obtain the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst with the nickel content of 10wt% and the samarium content of 1wt%, wherein the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst is 10Ni1Sm/MCM-41.
Example 3
Preparation of nickel samarium bimetal synergic/MCM-41 molecular sieve catalyst
The nickel content of the active component in the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst prepared in the embodiment is 12wt percent, the samarium content is 20wt percent, and the rest component is an MCM-41 molecular sieve carrier, and the preparation method comprises the following steps:
(1) Weighing 0.8744g of nickel nitrate hexahydrate and 0.8694g of samarium nitrate hexahydrate, dissolving in 75mL of deionized water, fully stirring and dissolving to form a uniform solution, adding 28% ammonia water to adjust the pH to 11, adding 1gMCM-41 molecular sieve carrier, sealing with a preservative film, stirring at the room temperature at the rotating speed of 300r/min for 9 hours, and heating and evaporating at 70 ℃ until the solution is neutral to obtain a reaction mixed solution;
(2) And (3) centrifugally washing the reaction mixed solution, drying the obtained solid for 8 hours at 110 ℃, grinding the solid into powder, finally placing the powder in an air atmosphere of 100mL/min, raising the temperature to 650 ℃ at a temperature rising rate of 2 ℃/min, calcining the powder at a constant temperature for 3 hours, and naturally cooling the powder to room temperature to obtain the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst with the nickel content of 12wt% and the samarium content of 20wt%, wherein the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst is recorded as 12Ni20Sm/MCM-41.
Example 4
Preparation of nickel samarium bimetal synergic/MCM-41 molecular sieve catalyst
The nickel content of the active component in the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst prepared in the embodiment is 10wt percent, the samarium content is 1wt percent, and the rest component is an MCM-41 molecular sieve carrier, and the preparation method comprises the following steps:
(1) Weighing 0.9908g of nickel nitrate hexahydrate and 0.3941g of samarium nitrate hexahydrate, dissolving in 75mL of deionized water, fully stirring and dissolving to form a uniform solution, adding 28% ammonia water to adjust the pH to 10, adding 1gMCM-41 molecular sieve carrier, sealing with a preservative film, stirring at the room temperature at the rotating speed of 300r/min for 10 hours, and heating and evaporating at 60 ℃ until the solution is neutral to obtain a reaction mixed solution;
(2) And (3) centrifugally washing the reaction mixed solution, drying the obtained solid at 90 ℃ for 11 hours, grinding the solid into powder, finally placing the powder in 100mL/min air atmosphere, raising the temperature to 600 ℃ at a temperature raising rate of 5 ℃/min, calcining the powder at a constant temperature for 4 hours, and naturally cooling the powder to room temperature to obtain the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst with the nickel content of 10wt% and the samarium content of 1wt%, wherein the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst is 15Ni10Sm/MCM-41.
Example 5
Preparation of nickel samarium bimetal synergic/MCM-41 molecular sieve catalyst
The nickel content of the active component in the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst prepared in the embodiment is 20wt percent, the samarium content is 5wt percent, and the rest component is an MCM-41 molecular sieve carrier, and the preparation method comprises the following steps:
(1) Weighing 1.3212g of nickel nitrate hexahydrate and 0.1971g of samarium nitrate hexahydrate, dissolving in 75mL of deionized water, fully stirring and dissolving to form a uniform solution, adding 28% ammonia water to adjust the pH to 12, adding 1gMCM-41 molecular sieve carrier, sealing with a preservative film, stirring at the room temperature at the rotating speed of 300r/min for 11 hours, and heating and evaporating at 80 ℃ until the solution is neutral to obtain a reaction mixed solution;
(2) And (3) centrifugally washing the reaction mixed solution, drying the obtained solid for 10 hours at 100 ℃, grinding the solid into powder, finally placing the powder in an air atmosphere of 100mL/min, heating to 700 ℃ at a temperature rising rate of 3 ℃/min, calcining at a constant temperature for 2 hours, and naturally cooling to room temperature to obtain the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst with the nickel content of 10wt% and the samarium content of 1wt%, wherein the nickel-samarium bimetal synergy/MCM-41 molecular sieve catalyst is recorded as 20Ni5Sm/MCM-41.
Comparative example 1
Preparation of comparative catalyst
A catalyst was prepared in accordance with the comparative example in the same manner as in example 2 except that the addition of samarium nitrate hexahydrate was omitted and the amount of nickel nitrate hexahydrate was adjusted to 0.5504g, to finally obtain an MCM-41 molecular sieve supported nickel catalyst having a nickel content of 10wt%, designated as 10Ni/MCM-41.
Comparative example 2
Preparation of comparative catalyst
The catalyst was prepared in the same manner as in example 3, except that the addition of nickel nitrate hexahydrate was omitted and the amount of samarium nitrate hexahydrate was adjusted to 0.7389g, to finally obtain an MCM-41 molecular sieve-supported samarium catalyst having a samarium content of 20wt%, designated as 20Sm/MCM-41.
Comparative example 3
Preparation of comparative catalyst
A catalyst was prepared in the same manner as in example 2 except that samarium nitrate hexahydrate was replaced with zirconium nitrate pentahydrate in an amount of 0.0471g, and finally a nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst having a nickel content of 10wt% and a zirconium content of 1wt% was obtained, which was designated as 10Ni1Zr/MCM-41.
Comparative example 4
Preparation of comparative catalyst
A catalyst was prepared in the same manner as in example 2, except that the carrier was replaced with an equivalent amount of SBA-15 molecular sieve, and finally a nickel-samarium bimetallic synergy/SBA-15 molecular sieve catalyst having a nickel content of 10wt% and a samarium content of 1wt%, designated as 10Ni1Sm/SBA-15, was obtained.
Experimental example 1
Determination of physical and chemical properties of nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst
The structure of the supported MCM-41 molecular sieve and the catalysts prepared in the examples and comparative examples were analyzed and the results are shown in fig. 1 to 5.
Referring to fig. 1, two peaks corresponding to (111) and (200) of NiO phases are detected at the positions of 2 theta=37.3 DEG and 43.2 DEG of the XRD spectrum of the metal-supported MCM-41 molecular sieve catalyst, and the peaks are more sharp compared with XRD peaks without adding samarium, which proves that the addition of samarium can lead to more uniform dispersion of metallic nickel by taking the MCM-41 molecular sieve as a carrier.
Referring to FIG. 2, according to the IUPAC classification, the comparative MCM-41 molecular sieves, the nickel samarium bimetallic/MCM-41 molecular sieves, show an IV isotherm accompanied by a type H3 hysteresis loop. The nickel samarium bimetallic/MCM-41 molecular sieve catalyst prepared by the method has obvious mesoporous structure formed by high-temperature calcination internal aperture expansion, and is beneficial to the entry of load metal.
Referring to fig. 3, the mcm-41 molecular sieve concentrates at 2.5nm, and the pore size distribution at 0.5nm and 5.8nm after calcination of the metal loading further demonstrates the existence of such a micropore-mesopore composite pore structure, which is beneficial to promote the dispersion of the active metal at the surface of the support and promote the mass transfer of the reaction.
Referring to fig. 4, it can be observed from the TEM image that the active metal is dispersed on the surface of the MCM-41 molecular sieve carrier, and after samarium is added, the particle size is smaller, the dispersion is more uniform, which is beneficial to exposing more active centers and promoting the adsorption activation of methane molecules in the reaction process of preparing the synthesis gas by catalyzing the dry reforming of methane.
Referring to fig. 5, it can be seen from the EPR map that the EPR signal at g=2.003 corresponds to the presence of an oxygen defect bit. The signal intensity of the catalyst after samarium is added is obviously higher than that of the nickel/MCM-41 molecular sieve catalyst, and the synergistic effect of nickel and samarium is proved to promote the formation of a large number of oxygen defect sites. This facilitates the adsorption activation of CO 2 during the reaction, forming active O intermediate species, thereby facilitating the removal of char.
Experimental example 2
Performance test for preparing synthetic gas by catalyzing methane dry reforming of nickel samarium bimetallic synergic/MCM-41 molecular sieve catalyst
The test method comprises the steps of taking 0.05-0.4 g of catalyst, grinding the catalyst with an inert silicon carbide solid phase according to a mass ratio of 1:4 for 10min, then putting the catalyst into a vertical micro fixed bed reactor, and carrying out catalytic reaction after reduction treatment for 4h at 550-750 ℃ in 10vol% H 2/N2 flow at 100mL/min, wherein the molar ratio of methane to carbon dioxide in the feed is 1, the space velocity of gas feed is 40000-120000 mL.h -1·gcat -1, and the reaction temperature is 650-850 ℃. Specific reaction conditions and results are shown in tables 1 and 2.
TABLE 1
TABLE 2
Table 1 shows the catalytic effect of each catalyst for 5H under the corresponding reaction conditions, and Table 2 shows the time of the deactivation inflection point of each catalyst and the catalytic effect under the time, so that the catalyst can still show higher methane/carbon dioxide conversion rate in the reaction of preparing the synthetic gas by catalyzing CH 4-CO2 reforming for 700H, the conversion rate of the catalyst with the synergistic effect of nickel and samarium bimetal is more than 80%, the H 2/CO ratio in the synthetic gas is 0.8-1.2, the catalyst has good stability and long service life, the catalytic performance of 10Ni1Sm/MCM-41 is the best, the deactivation time is more than 1000H, and the catalyst has overlength durability.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The nickel-samarium bimetal synergetic/MCM-41 molecular sieve catalyst is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is an MCM-41 molecular sieve, the active component is nickel and samarium, the nickel content is 5-20wt%, the samarium content is 1-20wt%, and the balance is the MCM-41 molecular sieve.
2. The method for preparing the nickel samarium bimetallic synergic/MCM-41 molecular sieve catalyst according to claim 1, characterized by comprising the following steps:
(1) Dissolving precursor salts of nickel and samarium in deionized water, adding ammonia water to obtain an alkaline nickel samarium ammonia complex solution, adding an MCM-41 molecular sieve into the alkaline nickel samarium ammonia complex solution, heating and stirring under a closed condition, and heating and evaporating until the pH value of the solution reaches neutrality to obtain a reaction mixed solution;
(2) And (3) centrifuging the reaction mixed solution, drying the obtained solid, grinding the dried solid into powder, and finally calcining the powder in an air atmosphere to obtain the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst.
3. The method for preparing the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst according to claim 2, wherein in the step (1), the addition amount of ammonia water is such that the pH value reaches 10-12, and the stirring treatment condition is room temperature for 8-12 h.
4. The method for preparing the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst according to claim 2, wherein in the step (1), the heating evaporation temperature is 60-90 ℃.
5. The method for preparing the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst according to claim 2, wherein in the step (2), the drying treatment condition is that the temperature is 80-110 ℃ and the time is 8-12 hours.
6. The method for preparing the nickel samarium bimetal synergy/MCM-41 molecular sieve catalyst according to claim 2, wherein in the step (2), the specific process of calcination treatment is that the temperature rising rate is increased to 550-700 ℃ at 1-5 ℃ per minute, and then the calcination is carried out for 2-6 hours at constant temperature.
7. The use of the nickel samarium bimetallic co-catalyst/MCM-41 molecular sieve catalyst of claim 1 for the catalytic dry methane reforming to produce synthesis gas.
8. A method for preparing synthesis gas by catalytic methane dry reforming is characterized by comprising the following steps of reducing the catalyst according to claim 1 in an atmosphere of 10vol% H 2/N2 at a temperature of 550-750 ℃ for 2-4 h, mixing the catalyst with inert silicon carbide, and carrying out catalytic methane dry reforming reaction in a reactor to prepare synthesis gas.
9. The method for preparing synthesis gas by catalytic methane dry reforming according to claim 8, wherein the catalyst and the inert silicon carbide are subjected to solid-phase grinding and mixing for 10-15 min according to a mass ratio of 1:2-5, the reaction condition is that the molar ratio of CH 4 to CO 2 in the reaction feed is 1-2, the gas feed space velocity is 40000-120000 mL.h -1·gcat-1, the catalyst dosage is 0.05-0.5 g, and the reaction temperature is 550-850 ℃.
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