A method for producing hydrogen from methanol via steam reforming and its application

Abstract

The application discloses a kind of methanol steam reforming hydrogen production method and application, belong to hydrogen energy and high-temperature fuel cell comprehensive utilization field.The hydrogen production technology of the present application uses perovskite-type oxide catalyst, adjusts high-temperature pretreatment (reduction) condition, can realize the accurate control of Ni-Cu active component, has excellent hydrogen production activity in 300-450 DEG C range, applicable to a variety of hydrogen production scene.The hydrogen production technology of the present application does not need to purify and humidify treatment to hydrogen.The present application can solve the hydrogen source problem of solid oxide fuel cell, change the hydrogen storage and transportation link of high-pressure cylinder into methanol solution, effectively improve the convenience of solid oxide fuel cell power generation.

Description

Technical Field

[0001] This invention belongs to the field of comprehensive utilization of hydrogen energy and high-temperature fuel cells, and more specifically, relates to a method and application of methanol steam reforming for hydrogen production. Background Technology

[0002] Hydrogen is an ideal clean fuel with several advantages unmatched by fossil fuels, such as: high exothermic efficiency; the only waste produced during combustion is water, resulting in virtually zero emissions when used as fuel in fuel cells; strong versatility, applicable to most end-use combustion devices; and it is also a renewable, cyclical fuel that can be transported and stored. Hydrogen has a high energy density and is a highly efficient and clean secondary energy source. Through fuel cells, it can achieve a comprehensive conversion efficiency of over 90%. Therefore, hydrogen energy can serve as a bridge connecting different energy forms such as gas, electricity, and heat, and can complement and coordinate with the power system, making it an ideal interconnecting medium for cross-energy network optimization. As an ideal new alternative energy source, hydrogen energy has attracted widespread attention. However, currently, there is a lack of low-cost, low-carbon, high-purity hydrogen production technology, as well as safe and convenient hydrogen storage, transportation, and utilization technologies.

[0003] Methanol is considered an ideal liquid hydrogen storage platform molecule due to its numerous advantages, including high hydrogen storage capacity per unit volume, low activation temperature, few byproducts, and low cost and availability. Producing hydrogen through methanol-water reforming not only releases the hydrogen stored in methanol but also activates an equimolar amount of water to release additional hydrogen. Methanol-water reforming for hydrogen production offers advantages such as low temperature, low energy consumption, high hydrogen purity, and low cost and availability.

[0004] However, the large-scale application of solid oxide fuel cells still requires further breakthroughs in hydrogen storage and transportation, and the construction of hydrogen refueling stations. High-pressure gaseous hydrogen storage has a small volumetric hydrogen capacity, poor safety, and expensive storage tanks. The immature technology of hydrogen storage tanks also contributes to the safety risks of high-pressure hydrogen. Hydrogen refueling stations are limited in scale and costly, and must be built in remote suburbs. Core equipment such as hydrogen compressors and refueling machines rely on imports. Furthermore, the lack of standards and regulations in these key areas, coupled with insufficient communication and coordination between industries, makes resolving these issues individually costly and difficult.

[0005] Although many hydrogen storage systems have been developed in the prior art, for example, patent application CN114373958A discloses a magnesium-based solid hydrogen storage and supply system for a solid oxide fuel cell. The system includes a magnesium-based solid hydrogen storage device, a solid oxide fuel cell, a first splitter, a second splitter, a circulation pump, a first heat exchanger, a second heat exchanger, a hydrogen pipeline, a tail gas pipeline, and valves. This magnesium-based solid hydrogen storage and supply system features high volumetric hydrogen storage density, simple structure, low cost, and high safety. Patent application CN115395047A discloses a methane-electricity-hydrogen reversible solid oxide fuel cell system with shared system components, belonging to the field of hydrogen energy and energy storage. The system can flexibly switch between power generation and electrolysis modes. Components such as the fuel cell stack, feedwater heat exchanger, fuel heat exchanger, and air heat exchanger are used in both fuel cell and electrolysis modes. The use of shared system components greatly improves the utilization rate of system components, reduces system investment costs, and facilitates system thermal management. In this system, hydrogen produced in electrolysis mode is directly stored in natural gas pipelines without the need for hydrogen storage equipment, significantly reducing hydrogen storage costs. This technology is expected to solve the problem of large-scale energy storage in the use of intermittent renewable energy at low cost, and improve the grid's ability to absorb renewable energy. However, existing technologies still cannot provide on-demand, on-demand energy production and use. Summary of the Invention

[0006] In response to the above-mentioned defects or improvement needs of existing technologies, this invention utilizes the characteristics of methanol such as high hydrogen storage capacity, convenient liquid storage and transportation, and green sustainability. Based on methanol steam reforming technology, it can realize on-demand hydrogen production and use without the need for high-pressure hydrogen storage tanks, only requiring atmospheric pressure methanol storage tanks. This ingeniously solves the problems of high cost and safety in the process of hydrogen storage, transportation and use.

[0007] To achieve the above objectives, the present invention provides a method for producing hydrogen by methanol steam reforming and its application.

[0008] This invention provides a high-efficiency methanol-to-hydrogen coupled solid oxide fuel cell power generation technology. The technology comprises two parts: methanol reforming for hydrogen production and solid oxide fuel cell power generation. The methanol reforming for hydrogen production is methanol steam reforming, and the solid oxide fuel cell uses an oxygen ion conductor as the electrolyte.

[0009] A method for producing hydrogen from methanol via steam reforming in a high-temperature solid oxide fuel cell includes:

[0010] (1) The catalyst is placed in a reforming reactor and pretreated under heating conditions;

[0011] The catalyst is a Cu-Ni co-doped ABO3 perovskite oxide, where A is at least one of La, Ce, and Ba, and B is at least one of Mn and Cr.

[0012] (2) Adjust the temperature inside the reformer to the hydrogen production reaction temperature, preheat and vaporize water and methanol, and then introduce them into the reforming reactor to carry out the hydrogen production reaction.

[0013] (3) The gas obtained from the hydrogen production reaction output from the reforming reactor is used for power generation in a solid oxide fuel cell.

[0014] The solid oxide fuel cell power generation system can produce hydrogen and generate electricity on-site using a methanol storage tank, as detailed in the following steps:

[0015] (1) Hydrogen is obtained by methanol reforming hydrogen production technology. The hydrogen production technology is as follows: methanol aqueous solution (module ①) is vaporized in the vaporization chamber (module ②) and then enters the reforming reactor. Under the action of the catalyst, a high-temperature reforming reaction is carried out to produce hydrogen.

[0016] (2) The hydrogen production technology uses Cu-Ni co-doped ABO3 perovskite oxide (where A is at least one of La, Ce, and Ba, and B is at least one of Mn and Cr) as a catalyst, which is assembled in a reforming reactor (module ③).

[0017] (3) The hydrogen obtained in step (1) is introduced into the anode inlet (module ④) of the solid oxide fuel cell through a low-Ni stainless steel pipe, thereby driving the solid oxide fuel cell to generate current.

[0018] (4) The output power of the system is changed by adjusting the hydrogen production rate in step (1) and the hydrogen inflow rate in step (3).

[0019] Specifically, in step (1), the molar ratio of Cu to Ni in the catalyst is 1:1, and the Cu-Ni co-doping amount is 10%-20% of the total molar amount of B, Cu, and Ni elements after doping.

[0020] Cu-Ni co-doped ABO3 perovskite oxide materials can be synthesized using nanomaterial synthesis methods such as sol-gel method, liquid phase method, solid phase method or electrospinning method.

[0021] Furthermore, in step (1), the pretreatment temperature is 600-700℃;

[0022] Pretreatment and reduction were carried out for 6 hours in an N2 atmosphere containing 5% H2 by volume.

[0023] Furthermore, in step (2), the hydrogen production reaction temperature is 300-450℃.

[0024] Furthermore, in step (2), the vaporization temperature is 200-300℃;

[0025] After vaporization, the molar ratio of water to methanol is 1.2-1.5:1.

[0026] The present invention also provides the application of the method in high-temperature solid oxide fuel cell power generation.

[0027] The fuel gas in the solid oxide fuel cell power generation technology of this invention is produced by methanol reforming reaction, which does not require humidification and purification treatment and can be used directly, thus replacing the traditional high-pressure hydrogen cylinder.

[0028] Specifically, the high-temperature solid oxide fuel cell is an oxygen ion-conductive type, and the power generation operating temperature is 700-800℃.

[0029] Preferably, the electrolyte in the high-temperature solid oxide fuel cell is Y-doped ZrO2 (Y-doped ZrO2), an oxygen ion conductor material. 0.08 Zr 0.92 O2).

[0030] This invention provides technical support for hydrogen production systems such as mobile on-site hydrogen production equipment in applications.

[0031] Unlike low-temperature proton exchange membrane fuel cells, which cannot directly use methanol reformed gas, high-temperature solid oxide fuel cells do not require purification and humidification of the hydrogen obtained from methanol reforming.

[0032] Beneficial effects:

[0033] 1. The hydrogen production technology of the present invention can be used in conjunction with a solid oxide fuel cell without the need for hydrogen purification and humidification.

[0034] 2. The hydrogen production technology of this invention uses a perovskite oxide catalyst and adjusts the high-temperature pretreatment (reduction) conditions to achieve precise control of the Ni-Cu active components. It has excellent hydrogen production activity in the range of 300-450℃ and is suitable for various hydrogen production scenarios.

[0035] 3. This invention can solve the problem of hydrogen source in solid oxide fuel cells by changing the storage and transportation of hydrogen in high-pressure gas cylinders to the storage and transportation of methanol solution, which effectively improves the convenience of power generation by solid oxide fuel cells. Attached Figure Description

[0036] Figure 1 This is a schematic diagram of the methanol reforming hydrogen production coupled with solid oxide fuel cell power generation technology of the present invention.

[0037] Figure 2 This is a schematic diagram of the preparation process of the methanol reforming hydrogen production catalyst of the present invention, including the catalyst precursor and reduction pretreatment steps.

[0038] Figure 3 The image shows the microstructure of the LCMNCu catalyst in Example 1 after reduction pretreatment.

[0039] Figure 4 The methanol reforming activity of LCMNCu catalyst and LCMN in Example 1 at different temperatures is characterized as follows: (a) is the methanol conversion rate, and (b) is the CO concentration in the gaseous products.

[0040] Figure 5 The activity of the LCMNCu catalyst in Example 1 in the methanol reforming reaction at 350°C is characterized as follows: (a) represents methanol conversion rate and hydrogen production rate, and (b) represents the selectivity of CO and CO2.

[0041] Figure 6 The image shows the microstructure of the LBMNCu nanofiber catalyst in Example 2.

[0042] Figure 7 Characterization of the reactivity of the LBMNCu nanofiber catalyst in Example 2 for catalytic methanol reforming to produce hydrogen: (a) shows the methanol conversion rate at different operating temperatures, and (b) shows the methanol conversion rate and CO content in the product after long-term operation at 450℃.

[0043] Figure 8 The XRD pattern of the LBCrNCu catalyst in Example 3 is shown in ((a)) and the characterization of its methanol reforming activity at different temperatures, including methanol conversion and CO concentration in the gaseous products ((b)).

[0044] Figure 9 The methanol conversion rate and CO content in the gaseous products of the LBMNCu nanofiber catalyst and Ni-Cu / Al2O3 catalyst in Example 4 at different temperatures are (a) and (b) respectively.

[0045] Figure 10 The diagram shows the microstructure of the solid oxide fuel cell described in Example 5 ((a)) and the open-circuit voltage of the methanol reforming hydrogen-coupled solid oxide fuel cell under actual conditions ((b)).

[0046] Figure 11 The images show the microstructure of the anode and power generation performance data of the methanol reforming hydrogen-coupled solid oxide fuel cell tested in Example 6 ((a)).

[0047] Figure labels: 1-Methanol-water solution injection box; 2-Vaporization chamber; 3-Methanol-water vapor reforming hydrogen production module; 4-Solid oxide fuel cell module. Detailed Implementation

[0048] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0049] This invention provides a high-performance, universal methanol reforming hydrogen production coupled with a high-temperature solid oxide fuel cell power generation technology. Specifically, a Cu-Ni co-doped ABO3 perovskite oxide catalyst is assembled in a reforming reactor. First, the catalyst undergoes reduction pretreatment at 600-700°C. Then, the molar ratio of water to methanol is controlled between 1.2 and 1.5. The methanol-water solution is vaporized at 200-300°C and then fed into the reforming reactor. Under the action of the catalyst, a high-temperature reforming reaction occurs to produce hydrogen. The hydrogen production reaction temperature is controlled at 300-450°C. The hydrogen produced by this invention can drive a solid oxide fuel cell to generate electricity, which is then directly supplied to end-use equipment.

[0050] The solid oxide fuel cell power generation system can produce hydrogen and generate electricity on-site with direct methanol storage tanks, as shown in the schematic diagram. Figure 1 As shown, the specific steps are as follows:

[0051] (1) Hydrogen is obtained by methanol reforming hydrogen production technology. The hydrogen production technology is as follows: methanol aqueous solution enters gasification chamber 2 through methanol aqueous solution injection box 1, and after being gasified in gasification chamber 2, it enters reforming reactor and undergoes high-temperature reforming reaction to produce hydrogen under the action of catalyst.

[0052] (2) The hydrogen production technology uses Cu and Ni as active metal components and ABO3 perovskite oxide (wherein A is at least one of La, Ce and Ba, and B is at least one of Mn and Cr) as catalyst support, which is assembled in a reforming reactor (methanol steam reforming hydrogen production module 3).

[0053] (3) The hydrogen obtained in step (1) is introduced into the anode inlet of the oxygen ion conduction solid oxide fuel cell (solid oxide fuel cell module 4) through a low-Ni stainless steel pipe, thereby driving the solid oxide fuel cell to generate current.

[0054] (4) The output power of the system can be changed by adjusting the hydrogen production rate in step (1) and the hydrogen inflow rate in step (3).

[0055] Please refer to the specific implementation example:

[0056] Example 1: LCMNCu nanoparticle catalyst for methanol reforming to produce hydrogen

[0057] Synthesis of La using wet chemical method 0.9 Ce 0.1 Mn 0.8 Ni 0.1 Cu 0.1 The O3 (LCMNCu) catalyst was prepared by first weighing La(NO3)3·6H2O, Ce(NO3)3·6H2O, Mn(NO3)2·4H2O, Ni(NO3)3·6H2O, and Cu(NO3)2·H2O according to their stoichiometric ratio and dissolving them in deionized water. Then, ethylenediaminetetraacetic acid (EDTA) dissolved in ammonia and citric acid solid particles were added sequentially. The molar ratio of EDTA to citric acid and the total molar amounts of the five metal elements (La, Ce, Mn, Ni, and Cu) was controlled at 1:1.5:1. The pH of the solution was adjusted to 7. The solution was heated and stirred until a viscous, light green, transparent gel was obtained. The gel was dried in an oven at 200℃ and calcined at 1000℃ for 2 hours to obtain a uniform, fine black LCMNCu powder.

[0058] Next, the granulated and sieved LCMNCu catalyst was placed in a quartz tube reactor. Before testing, the catalyst was pretreated under heating conditions, and reduced by N2 containing 5% H2 at 700°C for 6 hours to obtain a catalyst with Ni-Cu alloy as the active component and La 0.9 Ce 0.1 Mn 0.8 The target catalyst supported by O3 oxide (see schematic diagram) Figure 2 As shown, the catalyst microstructure is as follows Figure 3 (As shown). Using an aqueous methanol solution as the substrate, at a flow rate of 4 ml / h, the solution was vaporized at 200°C and then introduced into the reactor. The water / methanol molar ratio was 1.2. Methanol steam reforming reaction tests were conducted at temperatures ranging from 300°C to 400°C. After a 6-hour reduction pretreatment, the catalyst achieved a methanol conversion rate of nearly 90% at 300°C, and the reaction was nearly complete above 350°C. The CO concentration in the gaseous products was less than 0.1%, meeting the requirements for use in solid oxide fuel cells.

[0059] In contrast, La was synthesized using the same wet chemical method. 0.9 Ce 0.1 Mn 0.8 Ni 0.2 The O3 (LCMN) catalyst, after 6 hours of reduction pretreatment, was tested for methanol steam reforming reaction (water / methanol molar ratio of 1.2). At 300℃, the methanol conversion rate was only 80%, lower than that of the LCMNCu catalyst, and the CO concentration in the gaseous products was also much higher than that of the LCMNCu catalyst. Figure 4The LCMNCu catalyst exhibits superior catalytic activity compared to LCMN, and the Ni-Cu alloy shows even higher activity than pure metallic Ni. In long-term testing at 350℃, the methanol conversion rate of the LCMNCu catalyst remained stable at over 98% for 60 hours. Figure 5 This indicates that the LCMNCu catalyst is effectively suitable for methanol reforming to produce hydrogen.

[0060] Example 2: LBMNCu nanofiber catalyst for methanol reforming to produce hydrogen

[0061] La synthesized by electrospinning 0.8 Ba 0.1 Mn 0.8 Ni 0.1 Cu 0.1 O3(LBMNCu) nanofiber catalyst was prepared by first weighing La(NO3)3·6H2O, Ba(CH3COO)2, Mn(NO3)2·4H2O, Ni(CH3COO)2·4H2O, and Cu(CH3COO)2·H2O according to stoichiometric ratios as a precursor solution, which was dissolved in dimethylformamide (DMF). Then, polyvinylpyrrolidone (PVP) was dissolved in the DMF solution, with the added molar amount of PVP being 2.5 times the sum of the molar amounts of the five metal elements (La, Ba, Mn, Ni, and Cu). After thorough mixing, the mixture was transferred to a syringe. The prepared precursor was spun into filamentous nanofibers at 20 kV, and then calcined at 600 °C in air for 6 hours to obtain LBMNCu perovskite oxide fibers. Figure 6 ).

[0062] Before testing, the catalyst was pretreated under heating conditions. It was reduced with N2 containing 5% H2 at 600℃ for 6 hours. Using a methanol-water solution as the substrate, the gas flow rate was 5 ml / h, and the vaporized gas was introduced into the reactor at 300℃ for methanol steam reforming reaction testing. The test temperature ranged from 300℃ to 450℃. At 350℃ and a water / methanol molar ratio of 1.2, the methanol conversion rate of LBMNCu was above 80%, approaching 90% at 400℃. When the temperature reached 450℃, the reaction was nearly complete. Figure 7 The CO concentration in the gaseous products was far below 0.01%, indicating that adding Cu to the Ni-based catalyst can effectively accelerate the water-gas shift reaction and suppress CO production. After 50 hours at 450℃, the LBMNCu catalyst maintained a methanol conversion rate of over 99.9%, with a CO concentration far below 0.01%. The LBMNCu nanocatalyst is also suitable for methanol reforming to produce hydrogen.

[0063] Example 3: LBCrNCu nanocatalyst catalyzes methanol reforming for hydrogen production

[0064] La was synthesized by calcining at 1100°C for 3 hours using La(NO3)3·6H2O, Ba(NO3)2, Cr(NO3)3·9H2O, Ni(NO3)3·6H2O, and Cu(NO3)2·H2O as raw materials according to the wet chemical method in Example 1. 0.9 Ba 0.1 Cr 0.8 Ni 0.1 Cu 0.1 O3(LBCrNCu) catalyst ( Figure 8 (a) is the XRD pattern of LBCrNCu. The LBCrNCu catalyst was placed in a quartz tube reactor and reduced with N2 containing 5% H2 at 700℃ for 6 hours to complete the catalyst pretreatment. Using methanol-water solution as the substrate, at a flow rate of 4 ml / h, the solution was vaporized at 200℃ and then introduced into the reactor for methanol steam reforming reaction testing. At 300℃ and a water / methanol molar ratio of 1.2, the methanol conversion rate was 82%, reaching 96% at 350℃. The CO concentration in the gaseous products was less than 0.1%, and methanol was completely converted at 400℃. The products meet the requirements for use in solid oxide fuel cells. Figure 8 (b) in the figure is a graph showing catalytic performance data.

[0065] Example 4: Comparative Experiment of LBMNCu Catalyst and Ni-Cu / Al2O3 Catalyst

[0066] LBMNCu was synthesized as a catalyst according to the method in Example 2. Commercial γ-Al₂O₃ powder was impregnated with Ni(NO₃)₂·6H₂O and Cu(NO₃)₂·H₂O using an impregnation method. After drying, the powder was calcined at 400°C for 3 hours, and then reduced in N₂ containing 5% H₂ at 300°C for 2 hours to obtain the Ni-Cu / Al₂O₃ catalyst. Using a methanol-water solution as the substrate, with a water / methanol molar ratio of 1.5:1 and a gas flow rate of 5 ml / h, the gas was vaporized at 300°C and then introduced into a reactor for methanol steam reforming reaction testing. The test temperature ranged from 300°C to 450°C. At 400°C, the methanol conversion rate of LBMNCu exceeded 95%, significantly higher than the 84% of the Ni-Cu / Al₂O₃ catalyst. When the temperature reached 450°C, the reaction was nearly complete. Figure 9 It can be found that when the water / methanol molar ratio is 1.5:1, the catalytic activity of LBMNCu is basically the same as that when the water / methanol molar ratio is 1.2:1, indicating that under suitable water / methanol molar ratios and test conditions, the LBMNCu nanocatalyst is also suitable for methanol reforming to produce hydrogen.

[0067] Example 5: Power generation performance of methanol reforming to hydrogen using LBMNCu as a catalyst coupled with a high-temperature solid oxide fuel cell.

[0068] Using LBMNCu as a catalyst in Example 2, methanol and water vapor were reformed into hydrogen at 450°C. The gaseous product was directly introduced into the oxygen ion conductor material (ZrO2 doped with 8% Y element in a molar ratio) at a rate of 20 ml / min through a stainless steel pipe. 0.08 Zr 0.92 At the anode inlet of a solid oxide fuel cell using O2 as the electrolyte, an air compressor introduces air into the oxygen inlet. The open-circuit voltage of the battery at 700°C is recorded using an electrochemical workstation. Within 50 hours, the open-circuit voltage of the battery stabilizes at 1.1V. Figure 10 The microstructure of the battery remained unchanged, with no carbon buildup or structural damage observed, further validating the suitability of the LBMNCu nanocatalyst for methanol reforming to produce hydrogen and its further application in solid oxide fuel cells.

[0069] Example 6: Power generation performance of methanol reforming to hydrogen using LCMNCu as catalyst coupled with a high-temperature solid oxide fuel cell

[0070] Using LCMNCu as the catalyst in Example 1, methanol and aqueous solution were vaporized in the gasification chamber at a flow rate of 10 ml / h. Subsequently, the methanol and water vapor were reformed into hydrogen at 350°C. The gaseous product was used as fuel and directly introduced into the anode inlet of the solid oxide fuel cell through a stainless steel pipe at a rate of 20 ml / min. A load was connected to allow the cell to operate at 750°C at 400 mA / cm². -2 Discharge was performed, and power generation performance data was recorded. Within 60 hours, the battery's operating voltage stabilized at 0.75V, and its power density was 300mW / cm³. -2 ( Figure 11 The reaction achieved the conditions for practical application. No damage was found to the battery structure after the reaction, indicating the stability of the entire methanol reforming-to-hydrogen coupled solid oxide fuel cell power generation system.

[0071] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for hydrogen production by methanol steam reforming for high-temperature solid oxide fuel cells, characterized by, The method comprises: (1) placing a catalyst in a reforming reactor and pre-treating the catalyst under heating; wherein the catalyst is La 0.9 Ce 0.1 Mn 0.8 Ni 0.1 Cu 0.1 O3, La 0.8 Ba 0.1 Mn 0.8 Ni 0.1 Cu 0.1 O3, or La 0.9 Ba 0.1 Cr 0.8 Ni 0.1 Cu 0.1 O3; (2) adjusting the temperature in the reformer to a hydrogen production reaction temperature, pre-heating and vaporizing water and methanol, and then feeding them into the reforming reactor for hydrogen production reaction; the vaporization temperature is 200-300℃; after vaporization, the molar ratio of water to methanol is 1.2-1.5:1; (3) using the gas output from the reforming reactor for hydrogen production reaction to generate electricity in a solid oxide fuel cell.

2. The method of claim 1, wherein, In step (1), the pre-treatment temperature is 600-700℃; the pre-treatment is carried out under a N2 atmosphere containing 5% H2 by volume for 6 hours.

3. The method of claim 1, wherein, In step (2), the hydrogen production reaction temperature is 300-450℃.

4. Use of the method according to any one of claims 1-3 in high-temperature solid oxide fuel cell power generation.

5. Use according to claim 4, characterized in that, The electrolyte in the high-temperature solid oxide fuel cell is an oxygen ion-conducting solid electrolyte.

6. Use according to claim 5, characterized in that, The oxygen ion-conducting solid electrolyte is ZrO2 doped with 8% Y element by molar ratio.

7. Use according to claim 4, characterized in that, The working temperature of the high-temperature solid oxide fuel cell power generation is 700-800℃.

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