A supported catalyst, its preparation method and application in hydrogen production by low-temperature methanol reforming

Abstract

The application discloses a supported catalyst and a preparation method and application thereof in hydrogen production by low-temperature methanol reforming, and belongs to the technical field of hydrogen production. The preparation method of the catalyst comprises the following steps: (1) dissolving cerium nitrate and zinc nitrate in deionized water, adding a template agent, stirring uniformly, adjusting pH to 8.0-9.0 by using lye, and performing hydrothermal reaction, and then performing washing, drying, calcination and reduction treatment to obtain a carrier rich in oxygen vacancies; (2) dissolving copper salt and auxiliary salt in deionized water, adding a complexing agent, stirring and dissolving, adjusting pH to 5.0-6.0 by using lye, adding the carrier rich in oxygen vacancies, and then performing impregnation, drying, calcination and reduction treatment to obtain the supported catalyst. The supported catalyst prepared by the application has the advantages of large specific surface area and large pore size, and exhibits excellent performances of high methanol conversion rate and low CO selectivity in the hydrogen production by low-temperature methanol reforming.

Description

Technical Field

[0001] This invention relates to the field of hydrogen production technology, specifically to a supported catalyst, its preparation method, and its application in low-temperature methanol reforming for hydrogen production. Background Technology

[0002] Currently, low-temperature methanol reforming for hydrogen production is an important clean hydrogen source preparation method, possessing advantages such as mild reaction, high hydrogen production selectivity, and few byproducts, and has wide applications in fuel cells and portable hydrogen sources. However, existing copper-based supported catalysts still face many problems in practical applications. On the one hand, traditional Cu / ZnO / Al2O3 catalysts exhibit insufficient activity at low temperatures, and copper particles are prone to agglomeration and sintering, leading to reduced dispersion of active sites, damage to the catalyst's specific surface area and pore structure, and consequently affecting the efficiency and stability of the catalytic reaction. On the other hand, existing supports suffer from insufficient oxygen vacancies on the surface, making it difficult to effectively control the deposition and distribution of copper ions on the support surface. This results in random deposition of active components, low utilization of active sites, and difficulty in forming highly efficient synergistic active centers.

[0003] Chinese invention patent with publication number CN115814804A discloses a supported methanol reforming hydrogen production catalyst and its preparation method and application. The preparation method of the catalyst includes the following steps: (1) mixing the catalyst precursor solution and mesoporous silica, impregnating them, and then post-processing to obtain the mesoporous silica of the supported catalyst precursor; (2) mixing the mesoporous silica of the supported catalyst precursor, binder, metal fiber porous material and solvent, and impregnating and drying them in sequence to obtain the supported methanol reforming hydrogen production catalyst, but its specific surface area needs to be improved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a supported catalyst, its preparation method, and its application in low-temperature methanol reforming for hydrogen production.

[0005] A method for preparing a supported catalyst includes the following steps: (1) Dissolve cerium nitrate and zinc nitrate in deionized water, add template agent, stir evenly, adjust pH to 8.0-9.0 with alkaline solution, carry out hydrothermal reaction, and after washing, drying, calcination and reduction treatment, obtain a carrier rich in oxygen vacancies; (2) Dissolve copper salt and auxiliary salt in deionized water, add complexing agent, stir to dissolve, adjust pH to 5.0-6.0 with alkaline solution, add oxygen-rich support, and after impregnation, drying, calcination and reduction treatment, obtain supported catalyst;

[0006] The structural formula of the complexing agent is as follows: .

[0007] In step (1), the template agent is hexadecyltrimethylammonium bromide.

[0008] In step (1), before adjusting the alkali solution, the concentration of cerium nitrate in the final solution is 0.4-0.6 mol / L, the concentration of zinc nitrate is 0.3-0.4 mol / L, and the concentration of the template agent is 0.02-0.03 mol / L.

[0009] In step (2), the copper salt is copper nitrate and the auxiliary salt is aluminum nitrate.

[0010] In step (2), before the alkali solution is adjusted, the concentration of the copper salt in the final solution is 0.3-0.5 mol / L; the concentration of the auxiliary salt is 0.2-0.3 mol / L; the concentration of the complexing agent is 0.15-0.25 mol / L; and the concentration of the oxygen-vacancy-rich carrier is 50-100 g / L.

[0011] In step (1), the roasting process is as follows: the temperature is increased to 450-500℃ at a heating rate of 2-4℃ / min, and held for 4-6 hours; in step (2), the roasting process is as follows: the temperature is increased to 500-600℃ at a heating rate of 3-5℃ / min, and held for 4-6 hours.

[0012] In step (2), the soaking time is 6-8 hours.

[0013] In steps (1) and (2), the gas used in the reduction process is hydrogen / argon with a volume concentration of 5%-10%.

[0014] A supported catalyst was prepared by the method described above.

[0015] Application of a supported catalyst in low-temperature methanol reforming for hydrogen production.

[0016] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The supported catalyst prepared by this invention has advantages such as large specific surface area and large pore size. It exhibits high methanol conversion rate and low CO selectivity in the low-temperature methanol reforming hydrogen production reaction, providing an efficient and stable catalytic material for the industrial application of fuel cells and portable hydrogen sources. Attached Figure Description

[0017] Figure 1 The image shows the 1H NMR spectrum of the complexing agent prepared in Example 1.

[0018] Figure 2 The high-resolution mass spectrum of the complexing agent prepared in Example 1 is shown.

[0019] Figure 3The N2 adsorption-desorption isotherm of the supported catalyst prepared in Example 3.

[0020] Figure 4 The X-ray diffraction (XRD) pattern of the supported catalyst prepared in Example 3. Detailed Implementation

[0021] Example 1 Preparation of Complexing Agent Under nitrogen protection, 500 ml of a mixed solvent of DMF and methanol (DMF to methanol volume ratio 9:1), 0.1 mol of glycerol tris(1,2-epoxy)propyl ether, and 0.303 mol of ethylenediaminetriacetic acid were added to a reaction flask and stirred until homogeneous. Then, 0.91 mol of N,N-diisopropylethylamine was slowly added dropwise over 30 min. The mixture was heated to 70 °C and reacted for 12 h. After cooling to room temperature, the mixture was distilled under reduced pressure (0.2 Torr) at 70 °C for 3 h. The solution was dissolved in 300 ml of deionized water, and then the pH was adjusted to 2.5 by slowly adding 2 M hydrochloric acid. Finally, 500 ml of cold acetone was slowly added and stirred to precipitate the precipitate. The precipitate was filtered, washed with cold acetone (2 × 80 ml), and dried under vacuum at 50 °C for 12 h to obtain the surfactant. The reaction equation is shown below:

[0022] Its proton nuclear magnetic resonance spectrum is as follows Figure 1 As shown, its 1H NMR spectrum data are as follows: 1 H NMR (400 MHz, DMSO-d6) δ9.90 (s, 3H), 9.81 (s, 6H), 4.39 (d, J = 6.4 Hz, 1H), 4.18 (d, J = 6.6 Hz, 2H), 3.91 – 3.77 (m, 4H), 3.73 (s, 12H), 3.67 – 3.61 (m, 5H), 3.53 (d, J =4.7 Hz, 6H), 3.50 – 3.44 (m, 2H), 3.42 – 3.35 (m, 3H), 3.03 – 2.93 (m, 9H), 2.89 – 2.77 (m, 6H), 2.71 (ddd, J = 12.2, 5.7, 2.7 Hz, 3H); its high-resolution mass spectra are as follows: Figure 2 As shown, HRMS (m / z): 963.3817 [M+H] + .

[0023] Example 2 Preparation of supported catalysts (1) Dissolve 0.12 mol cerium nitrate and 0.09 mol zinc nitrate in 300 ml deionized water, add 0.006 mol template agent (hexadecyltrimethylammonium bromide), stir evenly, adjust pH to 8.0 with 10 wt% sodium hydroxide, transfer to a stainless steel high-pressure reactor lined with polytetrafluoroethylene, heat to 140℃ for hydrothermal reaction for 24 h, cool to room temperature, filter, wash three times with deionized water (50 ml each time), wash with 50 ml anhydrous ethanol, vacuum dry at 100℃ for 8 h, then place in a tube furnace and heat to 450℃ at 2℃ / min, keep warm for 6 h, cool naturally to room temperature, introduce hydrogen gas with a volume concentration of 10%, use argon gas as carrier gas, control the gas flow rate at 100 ml / min, heat from room temperature to 350℃ at 5℃ / min, reduce for 3 h, cool naturally to room temperature, and obtain a carrier rich in oxygen vacancies; (2) Dissolve 0.09 mol copper nitrate and 0.06 mol aluminum nitrate in 300 ml of deionized water, add 0.045 mol complexing agent (prepared in Example 1), stir until completely dissolved, adjust pH to 5.0 with 5 wt% sodium hydroxide, stir evenly to obtain co-impregnation solution, add 15 g of oxygen-vacancy-rich support to co-impregnation solution, stir and impregnate at 40°C for 6 h, age at room temperature for 2 h, rotary evaporate at 60°C for 2 h, dry at 100°C for 8 h, then place in a tube furnace, heat to 500°C at a heating rate of 3°C / min, hold for 6 h, cool naturally to room temperature, introduce hydrogen gas with a volume concentration of 10%, use argon gas as the carrier gas, control the gas flow rate at 100 ml / min, heat from room temperature to 300°C at a heating rate of 2°C / min, reduce for 4 h, and cool naturally to room temperature to obtain supported catalyst.

[0024] Example 3 Preparation of supported catalysts (1) Dissolve 0.15 mol cerium nitrate and 0.105 mol zinc nitrate in 300 ml deionized water, add 0.0075 mol template agent (hexadecyltrimethylammonium bromide), stir evenly, adjust pH to 8.5 with 10 wt% sodium hydroxide, transfer to a stainless steel high-pressure reactor lined with polytetrafluoroethylene, heat to 140℃ for hydrothermal reaction for 24 h, cool to room temperature, filter, wash three times with deionized water (50 ml each time), wash with 50 ml anhydrous ethanol, vacuum dry at 100℃ for 8 h, then place in a tube furnace and heat to 480℃ at 4℃ / min, keep warm for 5 h, cool naturally to room temperature, introduce hydrogen gas with a volume concentration of 8%, argon gas as carrier gas, control the gas flow rate at 100 ml / min, heat from room temperature to 350℃ at 5℃ / min, reduce for 3 h, cool naturally to room temperature, and obtain a carrier rich in oxygen vacancies; (2) Dissolve 0.12 mol copper nitrate and 0.075 mol aluminum nitrate in 300 ml of deionized water, add 0.06 mol complexing agent (prepared in Example 1), stir until completely dissolved, adjust pH to 5.5 with 5 wt% sodium hydroxide, stir evenly to obtain co-impregnation solution, add 24 g of oxygen-vacancy-rich support to co-impregnation solution, stir and impregnate at 40°C for 7 h, age at room temperature for 2 h, rotary evaporate at 60°C for 2 h, dry at 100°C for 8 h, then place in a tube furnace, heat to 550°C at a heating rate of 4°C / min, hold for 5 h, cool naturally to room temperature, introduce hydrogen gas with a volume concentration of 8%, use argon gas as the carrier gas, control the gas flow rate at 100 ml / min, heat from room temperature to 300°C at a heating rate of 2°C / min, reduce for 4 h, and cool naturally to room temperature to obtain supported catalyst.

[0025] Figure 3 The N2 adsorption-desorption isotherm of the supported catalyst prepared in Example 3 shows that the adsorption curve rises slowly in the low relative pressure region (P / P0<0.6), indicating that there are a small number of micropores or adsorption on the outer surface of the sample; while in the high relative pressure region (P / P0>0.8), significant capillary condensation occurs, and the adsorption volume increases sharply, reflecting the presence of a large number of mesoporous structures in the material.

[0026] Figure 4 The image shows the X-ray diffraction pattern of the supported catalyst prepared in Example 3. As can be seen from the figure, distinct diffraction peaks appear at 2θ = 43.3°, 50.4°, and 74.1°, corresponding to the (111), (200), and (220) crystal planes of metallic Cu, respectively. This indicates that under hydrogen reduction conditions, the copper species has been successfully transformed from the precursor into metallic Cu. 0 This is consistent with the reduction process in the preparation procedure. Furthermore, characteristic diffraction peaks of CeO2 were observed at 2θ = 28.5°, indicating that Ce species exist in the support as crystalline cerium oxide. The presence of CeO2 helps provide oxygen vacancies and reversible Ce formation. 3+ / Ce 4+ The redox pairs enhance the oxygen migration ability and reactivity of the catalyst. Furthermore, the absence of aluminum diffraction peaks in the spectrum indicates that alumina exists in a highly dispersed amorphous form within the catalyst. This highly dispersed structural aid effectively promotes the uniform distribution of active copper particles and inhibits their sintering during high-temperature reactions.

[0027] Example 4 Preparation of supported catalysts (1) Dissolve 0.18 mol cerium nitrate and 0.12 mol zinc nitrate in 300 ml deionized water, add 0.0091 mol template agent (hexadecyltrimethylammonium bromide), stir evenly, adjust pH to 9.0 with 10 wt% sodium hydroxide, transfer to a stainless steel high-pressure reactor lined with polytetrafluoroethylene, heat to 140℃ for hydrothermal reaction for 24 h, cool to room temperature, filter, wash three times with deionized water (50 ml each time), wash with 50 ml anhydrous ethanol, vacuum dry at 100℃ for 8 h, then place in a tube furnace and heat to 500℃ at 4℃ / min, keep warm for 4 h, cool naturally to room temperature, introduce hydrogen gas with a volume concentration of 5%, argon gas as carrier gas, control the gas flow rate at 100 ml / min, heat from room temperature to 350℃ at 5℃ / min, reduce for 3 h, cool naturally to room temperature, and obtain a carrier rich in oxygen vacancies; (2) Dissolve 0.15 mol copper nitrate and 0.09 mol aluminum nitrate in 300 ml of deionized water, add 0.075 mol complexing agent (prepared in Example 1), stir until completely dissolved, adjust pH to 6.0 with 5 wt% sodium hydroxide, stir evenly to obtain co-impregnation solution, add 30 g of oxygen-vacancy-rich support to co-impregnation solution, stir and impregnate at 40°C for 8 h, age at room temperature for 2 h, rotary evaporate at 60°C for 2 h, dry at 100°C for 8 h, then place in a tube furnace, raise the temperature to 600°C at a heating rate of 5°C / min, hold for 4 h, cool naturally to room temperature, introduce hydrogen gas with a volume concentration of 5%, use argon gas as the carrier gas, control the gas flow rate at 100 ml / min, raise the temperature from room temperature to 300°C at a heating rate of 2°C / min, reduce for 4 h, and cool naturally to room temperature to obtain supported catalyst.

[0028] Comparative Example 1 The preparation method of the supported catalyst is basically the same as that in Example 3, except that the complexing agent is replaced with an equimolar amount of a complexing agent prepared by the following method: The preparation method of the complexing agent is basically the same as that in Example 1, except that glycerol tri(1,2-epoxy)propyl ether is replaced with an equimolar amount of 1,6-hexanediol diglycidyl ether, the amount of ethylenediaminetriacetic acid is 0.203 mol, and the amount of N,N-diisopropylethylamine is 0.21 mol.

[0029] Comparative Example 2 The preparation method of the supported catalyst is basically the same as that in Example 3, except that the complexing agent is replaced with an equimolar amount of a complexing agent prepared by the following method: The preparation method of the complexing agent is basically the same as that in Example 1, except that ethylenediaminetriacetic acid is replaced with an equimolar amount of iminodiacetic acid.

[0030] Comparative Example 3 The preparation method of the supported catalyst is basically the same as that in Example 3, except that the complexing agent is replaced with an equimolar amount of citric acid.

[0031] Comparative Example 4 The preparation method of the supported catalyst is basically the same as that in Example 3, except that the amount of complexing agent added is replaced with 0.10 mol.

[0032] Comparative Example 5 The preparation method of the supported catalyst is basically the same as that in Example 3, except that the template agent is replaced with 0.0075 mol of Pluronic® F127 (catalog number 435465, purchased from Sigma-Aldrich).

[0033] Comparative Example 6 The preparation method of the supported catalyst is basically the same as that in Example 3, except that the template agent is replaced with an equimolar amount of dodecyltrimethylammonium bromide.

[0034] Comparative Example 7 The preparation method of the supported catalyst is basically the same as that in Example 3, except that the template agent is replaced with an equimolar amount of octadecyltrimethylammonium bromide.

[0035] Comparative Example 8 The preparation method of the supported catalyst is basically the same as that in Example 3. The difference is that in step (2), the heating rate during calcination is replaced with 7℃ / min, while the calcination temperature and time remain unchanged.

[0036] Comparative Example 9 The preparation method of the supported catalyst is basically the same as that in Example 3. The difference is that in step (2), the calcination temperature is replaced with 650°C, while the calcination time remains unchanged.

[0037] The methanol vapor-to-hydrogen catalysts prepared in the examples and comparative examples were tested for specific surface area, pore size and catalytic performance. The test results are shown in Table 1.

[0038] Specific surface area and pore size were tested using nitrogen adsorption-desorption experiments.

[0039] Catalytic performance testing: First, 0.5g of catalyst was loaded into the isothermal layer of a quartz tube (length: 400mm, inner diameter: 14mm), and nitrogen gas was introduced at a flow rate of 70ml / min. The temperature was then raised to 300℃ at a rate of 10℃ / min. A methanol-water solution (methanol to deionized water molar ratio of 1:1.5) was injected using a feed pump; the feed hourly space velocity (WHSV) was 5.28. -1h, the feed reactants react with a catalyst in the tube to produce hydrogen-rich gas; the gas is condensed to remove water vapor, and the gas flow rate is measured and then collected in a gas bag; the collected gas is sent to a gas chromatograph for component analysis; the gas flow rate is measured at the terminal using a soap film flow meter.

[0040] Methanol conversion rate is calculated using the following formula: ;

[0041] CO selectivity is calculated using the following formula: ; f is the correction factor. ; Among them, F R Where F is the terminal gas flow rate, ρ is the feed rate, α is the density of the mixture, and C is the methanol mass content in the mixture. CO C CO2 T1 and P1 represent the CO and CO2 content in the exhaust gas; T1 and P1 represent the temperature and pressure during the actual reaction evaluation; T2 and P2 represent the temperature and pressure under standard conditions.

[0042] Table 1 Catalyst Performance Test Data project <![CDATA[Specific surface area / m 2 / g]]> Aperture / nm Methanol conversion rate / % CO selectivity / % Example 2 166.4 8.18 99.5 0.8 Example 3 172.8 8.45 99.8 0.6 Example 4 168.2 8.32 99.4 0.7 Comparative Example 1 120.3 6.42 82.3 2.4 Comparative Example 2 113.7 5.27 78.6 3.1 Comparative Example 3 97.5 4.49 71.4 4.2 Comparative Example 4 131.8 6.83 85.7 1.9 Comparative Example 5 117.4 6.16 79.5 2.8 Comparative Example 6 156.6 7.41 99.1 1.0 Comparative Example 7 158.9 7.55 99.2 0.9 Comparative Example 8 139.2 6.97 94.8 1.6 Comparative Example 9 143.5 7.30 95.1 1.3

[0043] As can be seen from the data in Table 1, the supported catalyst prepared by this invention has advantages such as large specific surface area and large pore size, and exhibits excellent performance of high methanol conversion and low CO selectivity in the low-temperature methanol reforming hydrogen production reaction.

[0044] In the catalyst preparation process, a composite oxide support is first prepared using a hydrothermal method. Under alkaline conditions, a precursor with a uniform composition and a certain porous structure is formed through the synergistic precipitation and crystallization process of metal ions. The organic template is removed by calcination, which promotes crystal phase formation. Subsequently, a reduction treatment is performed under a hydrogen atmosphere to introduce oxygen vacancies onto the support surface, thereby improving surface oxygen migration capacity and the number of active sites. Based on this, Cu and Al active components are introduced through a co-impregnation method. Under relatively mild conditions, the active components are highly dispersed on the support surface, reducing their agglomeration and thus enhancing the overall activity and stability of the catalyst.

[0045] In terms of structural regulation, the template agent hexadecyltrimethylammonium bromide utilizes the hydrophobic effect of its long-chain alkyl group and the electrostatic effect of the quaternary ammonium salt cationic head group to form a micelle structure in the reaction system, which plays a structural guiding role in the growth of the inorganic framework, thereby inducing the formation of a porous structure and improving the specific surface area of ​​the material. During the loading process, the introduced complexing agent molecule contains coordinating groups such as polycarboxyl groups and amine groups, which can interact with Cu 2+ Al 3+The formation of stable coordination between metal ions regulates their hydrolysis and deposition rates, promoting their uniform distribution and effective anchoring on the support surface. Simultaneously, the decomposition of the complexing agent during subsequent calcination contributes to the formation of structural defects or refinement of the pore structure. The synergistic effect of the template agent and complexing agent optimizes the catalyst's specific surface area and metal dispersion, and enhances the metal-support interaction, resulting in higher reactivity and methanol conversion in the methanol reforming reaction.

[0046] The coordination ability of the complexing agent used in Comparative Example 2 was weakened, and it interacted with Cu. 2+ The resulting complex has a low stability constant, which weakens the ability to regulate the in-situ uniform deposition of copper ions on the surface of the oxygen-vacancy-rich Ce-Zn support. This leads to a decrease in the dispersion of copper active components, easy agglomeration and sintering of particles, a reduction in specific surface area, and a deterioration in pore uniformity. Ultimately, this reduces the methanol conversion rate and CO selectivity in the low-temperature methanol reforming hydrogen production reaction.

[0047] The template agent Pluronic® F127 used in Comparative Example 5 is a nonionic triblock copolymer. Under hydrothermal conditions, the micelles formed have a large volume, making it difficult to effectively induce the assembly of cerium nitrate and zinc nitrate. The number of ordered self-oxygen vacancies is reduced, which ultimately leads to a decrease in the dispersion of copper active components and easy agglomeration and sintering. As a result, the methanol conversion rate and CO selectivity of the low-temperature methanol reforming hydrogen production reaction are significantly worse than those of the examples.

[0048] In Comparative Example 8, the excessively rapid heating rate accelerated the decomposition of precursors such as copper nitrate and aluminum nitrate, making it difficult to release the generated heat evenly. This easily led to localized high temperatures and violent gas escape, thereby disrupting the ordered mesoporous structure of the carrier and causing some pores to collapse or become blocked. Ultimately, in the low-temperature methanol reforming hydrogen production reaction, the methanol conversion rate and CO selectivity control capability decreased.

[0049] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A method for preparing a supported catalyst, characterized in that, Includes the following steps: (1) Dissolve cerium nitrate and zinc nitrate in deionized water, add template agent, stir evenly, adjust pH to 8.0-9.0 with alkaline solution, carry out hydrothermal reaction, and after washing, drying, calcination and reduction treatment, obtain a carrier rich in oxygen vacancies; (2) Dissolve copper salt and auxiliary salt in deionized water, add complexing agent, stir to dissolve, adjust pH to 5.0-6.0 with alkaline solution, add oxygen-rich support, and after impregnation, drying, calcination and reduction treatment, obtain supported catalyst; The structural formula of the complexing agent is as follows: 。 2. The method for preparing a supported catalyst according to claim 1, characterized in that, In step (1), the template agent is hexadecyltrimethylammonium bromide.

3. The method for preparing a supported catalyst according to claim 1, characterized in that, In step (1), before adjusting the alkali solution, the concentration of cerium nitrate in the final solution is 0.4-0.6 mol / L, the concentration of zinc nitrate is 0.3-0.4 mol / L, and the concentration of the template agent is 0.02-0.03 mol / L.

4. The method for preparing a supported catalyst according to claim 1, characterized in that, In step (2), the copper salt is copper nitrate and the auxiliary salt is aluminum nitrate.

5. The method for preparing a supported catalyst according to claim 1, characterized in that, In step (2), before the alkali solution is adjusted, the concentration of the copper salt in the final solution is 0.3-0.5 mol / L; the concentration of the auxiliary salt is 0.2-0.3 mol / L; the concentration of the complexing agent is 0.15-0.25 mol / L; and the concentration of the oxygen-vacancy-rich carrier is 50-100 g / L.

6. The method for preparing a supported catalyst according to claim 1, characterized in that, In step (1), the roasting process is as follows: the temperature is increased to 450-500℃ at a heating rate of 2-4℃ / min, and held for 4-6 hours; in step (2), the roasting process is as follows: the temperature is increased to 500-600℃ at a heating rate of 3-5℃ / min, and held for 4-6 hours.

7. The method for preparing a supported catalyst according to claim 1, characterized in that, In step (2), the soaking time is 6-8 hours.

8. The method for preparing a supported catalyst according to claim 1, characterized in that, In steps (1) and (2), the gas used in the reduction process is hydrogen / argon with a volume concentration of 5%-10%.

9. A supported catalyst, characterized in that, It is prepared by the preparation method according to any one of claims 1-8.

10. The application of the catalyst according to claim 9 in low-temperature methanol reforming for hydrogen production.

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