Methanol steam reforming and solid hydrogen storage coupled hydrogen production and storage purification device and method

Abstract

The invention discloses a methanol steam reforming and solid hydrogen storage coupled hydrogen production and storage purification device and method, and relates to the technical field of hydrogen energy utilization and energy system integration, the methanol steam reforming and solid hydrogen storage coupled hydrogen production and storage purification device comprises a methanol aqueous solution supply unit, an evaporation gasification unit, a reforming hydrogen production unit, a solid hydrogen storage unit and a gas-liquid separation unit, wherein the solid hydrogen storage unit adopts a hydrogen storage tank filled with Mg-series metal hydride, and heat transfer is realized between the solid hydrogen storage unit and the evaporation gasification unit as well as between the solid hydrogen storage unit and the reforming hydrogen production unit through a dividing wall type integrated structure. Hydrogen-containing gas generated by reforming is subjected to gas-liquid separation and then guided into a hydrogen storage tank, hydrogen is selectively absorbed, heat is released and used for supporting front-end vaporization and reforming reaction, and energy self-circulation is achieved; the impurity gas is not absorbed and is discharged, so that in-situ purification is completed. And high-purity hydrogen can be released by heating the hydrogen storage tank. According to the scheme, external heat supply is not needed, the heat efficiency is remarkably improved, and hydrogen storage and purification functions are integrated.

Description

Technical Field

[0001] This application relates to the field of hydrogen energy utilization and energy system integration technology, specifically to a methanol steam reforming and solid-state hydrogen storage coupling device and method for hydrogen storage and purification. Background Technology

[0002] Hydrogen energy, as a clean and efficient secondary energy source, has broad application prospects in transportation, energy storage, and industry. Methanol, due to its high hydrogen content (approximately 18.8%) and ease of storage and transportation, is considered one of the ideal hydrogen carriers. Methanol steam reforming technology can convert methanol and water into hydrogen and carbon dioxide through a catalytic reaction, making it an important route for on-site hydrogen production. This process typically includes methanol-water solution supply, evaporation and vaporization, catalytic reforming, and gas separation. It needs to be carried out at 220–280°C and relies on an external heat source to provide the heat required for the reaction, resulting in relatively low system efficiency. Furthermore, the reforming products often contain impurity gases such as carbon monoxide, methane, and carbon dioxide, which adversely affect the subsequent application of proton exchange membrane fuel cells, necessitating the additional configuration of a hydrogen purification unit.

[0003] In existing technologies, methanol steam reforming typically uses electric heating or combustion heating to maintain the reaction temperature, resulting in low energy utilization and complex overall system structure with high energy consumption. Meanwhile, traditional hydrogen purification methods such as pressure swing adsorption (PSA) or membrane separation require independent equipment and additional energy consumption. Furthermore, metal hydrides, especially magnesium-based hydrides, can release a large amount of high-temperature heat (approximately 200–250 kJ / mol) during hydrogen adsorption. Solid-state hydrogen storage has the potential to serve as an internal heat source, and its selective absorption of hydrogen can be used for in-situ hydrogen purification. However, there is currently no integrated system design that efficiently couples the exothermic process of solid-state hydrogen storage with the endothermic process of methanol reforming, making it difficult to achieve energy self-sufficiency and continuous production of high-purity hydrogen. Summary of the Invention

[0004] The purpose of this invention is to provide a device and method for producing hydrogen storage and purification by coupling methanol steam reforming with solid-state hydrogen storage, which can solve the technical problems of low thermal efficiency caused by the need for external heating in methanol steam reforming and the impact of impurities in the reforming products on hydrogen quality.

[0005] To achieve the above objectives, this application provides the following technical solution: The first aspect of this application provides a methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device, including a methanol aqueous solution supply unit, an evaporation and vaporization unit, a reforming hydrogen production unit, a solid-state hydrogen storage unit, and a gas-liquid separation unit; the solid-state hydrogen storage unit includes at least two hydrogen storage tanks filled with Mg-based metal hydrides, and the reforming hydrogen production unit is a methanol steam reforming reactor filled with a catalyst; the hydrogen storage tanks are respectively connected to the evaporation and vaporization unit and the reforming hydrogen production unit through an integrated partition structure to realize the directional transfer of heat released during the hydrogen storage process; the gas phase outlet of the gas-liquid separation unit is connected to the gas inlet of the solid-state hydrogen storage unit for introducing hydrogen from the reforming product into the hydrogen storage tank for hydrogen absorption reaction and impurity separation.

[0006] In one optional embodiment, the solid hydrogen storage unit includes a first hydrogen storage tank and a second hydrogen storage tank. The first hydrogen storage tank and the evaporation and gasification unit form an integrated structure, and the second hydrogen storage tank and the methanol steam reforming reactor form an integrated structure.

[0007] In one optional embodiment, the methanol aqueous solution supply unit includes a storage tank, a transfer pump, and a concentration regulating device. The storage tank is connected to the transfer pump, the outlet of the transfer pump is connected to the inlet pipeline of the evaporation and vaporization unit, and the concentration regulating device is connected to the pipeline between the outlet of the transfer pump and the inlet of the evaporation and vaporization unit. The concentration regulating device can adjust the concentration of the methanol aqueous solution to 10%~50%.

[0008] In one optional embodiment, the evaporation and vaporization unit is an evaporation superheater, and the heating temperature is controlled at 160~200℃; the methanol steam reforming reactor is maintained at a reaction temperature of 220~280℃, and is one of a fixed bed, fluidized bed or membrane reactor.

[0009] In one optional embodiment, the catalyst is one or more combinations of copper-based, nickel-based, or ruthenium-based catalysts; the Mg-based metal hydride is , or One or more of the following.

[0010] The second aspect of this application provides a method for producing and purifying hydrogen through a coupling of methanol steam reforming and solid-state hydrogen storage, comprising the following steps: S1, the methanol aqueous solution is transported to the evaporation and vaporization unit through the methanol aqueous solution supply unit, and the methanol aqueous solution is heated to gaseous methanol aqueous solution by the heat released by the solid hydrogen storage unit. S2, gaseous methanol-water solution is passed into the reforming hydrogen production unit, and a reforming reaction occurs under the action of a catalyst to generate a hydrogen-containing mixed gas; S3, after passing the hydrogen-containing mixed gas through the gas-liquid separation unit, the gaseous product is passed into the solid hydrogen storage unit. The hydrogen in the gaseous product undergoes a hydrogen absorption reaction with the Mg-based metal hydride and releases high-temperature heat. This heat is transferred to the evaporation gasification unit and the reforming hydrogen production unit through the partition wall. S4 uses hydrogen to purge the solid hydrogen storage unit and discharge the unabsorbed impurity gas. S5 obtains high-purity hydrogen by desorption through heating the solid hydrogen storage unit.

[0011] In one optional embodiment, the mass concentration of the methanol-water solution in S1 is controlled at 10% to 50%; the space velocity of the reforming reaction in S2 is 1000 to 10000. .

[0012] In one optional embodiment, the hydrogen absorption reaction in S3 is carried out at a pressure of 0.5~10 MPa and a temperature of 200~300℃, releasing 200~250 kJ / mol of heat. Furthermore, the heat ratio to the methanol reforming reaction is 1:1.2~2.5.

[0013] In one optional embodiment, the hydrogen used for purging in S4 has a purity of ≥99.99%, a flow rate of 0.5 to 5 times the volume of the hydrogen storage tank per hour, and a purging time of 5 to 30 minutes.

[0014] In one optional embodiment, the heating temperature in S5 is 250~350℃, the desorbed hydrogen purity is ≥99.999%, and the desorption process further includes a step of adjusting the hydrogen pressure to 0.1~30MPa. Compared with the prior art, the present invention has the following beneficial technical effects: This invention provides a hydrogen production and purification device that couples methanol steam reforming with solid-state hydrogen storage. By setting up a solid-state hydrogen storage unit and releasing high-temperature heat during the hydrogen storage process, this heat is directionally transferred to the evaporation and vaporization unit and the reforming hydrogen production unit through an integrated partition structure. This achieves self-supply of the heat required for the vaporization and reforming reaction of methanol aqueous solution, solving the problem of low thermal efficiency caused by the reliance on external heating in traditional systems. At the same time, by utilizing the characteristic that Mg-based metal hydrides only react with hydrogen gas to absorb hydrogen, non-hydrogen components cannot be absorbed and are separated, thereby completing hydrogen purification simultaneously during the hydrogen storage process, avoiding additional purification equipment and energy consumption. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of a methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device according to an embodiment of the present invention. Detailed Implementation

[0016] In the following description, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the spirit or scope of the invention. Therefore, the drawings and description are considered to be exemplary in nature and not restrictive.

[0017] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0018] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0019] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a communication connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0020] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, "above," "over," and "on top" of the second feature includes the first feature being directly above or diagonally above the second feature, or simply indicates that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature includes the first feature being directly above or diagonally above the second feature, or simply indicates that the first feature is at a lower horizontal level than the second feature.

[0021] It should be understood that, when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0022] It should also be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0023] It should also be further understood that the term "and / or" as used in this specification and the appended claims refers to any combination of one or more of the associated listed items and all possible combinations, and includes such combinations.

[0024] The accompanying drawings illustrate various structural schematic diagrams according to embodiments disclosed in this invention. These drawings are not to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.

[0025] See Figure 1 This invention provides a methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device, including a methanol aqueous solution supply unit 1, an evaporation and vaporization unit, a reforming hydrogen production unit, a solid-state hydrogen storage unit, and a gas-liquid separation unit 7; the solid-state hydrogen storage unit includes at least two hydrogen storage tanks filled with Mg-based metal hydrides, and the reforming hydrogen production unit is a methanol steam reforming reactor 6 filled with a catalyst; the hydrogen storage tanks are respectively connected to the evaporation and vaporization unit and the reforming hydrogen production unit through an integrated partition structure to realize the directional transfer of heat released during the hydrogen storage process; the gas phase outlet of the gas-liquid separation unit 7 is connected to the gas inlet of the solid-state hydrogen storage unit, and is used to introduce hydrogen from the reforming product into the hydrogen storage tank for hydrogen absorption reaction and impurity separation.

[0026] This application realizes a highly integrated technical architecture for methanol steam reforming to produce hydrogen, solid-state hydrogen storage, and hydrogen purification. The device constructs a closed-loop system comprising five functional modules: supply, vaporization, reforming, hydrogen storage, and separation. It utilizes the high-temperature heat released by Mg-based metal hydrides during hydrogen absorption to directionally supply the heat energy required for the evaporation, vaporization, and catalytic reforming reactions of the methanol solution, thereby significantly improving the device's energy utilization rate. Furthermore, by leveraging the selective absorption characteristics of solid-state hydrogen storage materials, it achieves effective separation of impurity gases while storing hydrogen, thus achieving in-situ purification.

[0027] In a more specific embodiment of the present invention, a methanol-water solution supply unit 1 is responsible for supplying the raw material liquid to the device. The methanol-water solution supply unit 1 includes a storage tank, a transfer pump 2, and a concentration regulating component. The storage tank is connected to the transfer pump 2, and the outlet of the transfer pump 2 is connected to the inlet pipeline of the evaporation and vaporization unit. A concentration regulating device is connected to the pipeline between the outlet of the transfer pump 2 and the inlet of the evaporation and vaporization unit. The concentration regulating device can adjust the concentration of the methanol-water solution to 10%~50%. The concentration regulating component ensures that the concentration of the solution entering subsequent units is controllable. The evaporation and vaporization unit is used to heat the liquid methanol-water solution into a high-temperature gaseous mixture to meet the feed state requirements of the reforming reaction.

[0028] The reforming hydrogen production unit uses a catalyst-loaded methanol-water steam reforming reactor 6, which promotes an endothermic reaction between methanol and water at a suitable temperature to generate a hydrogen-rich mixture, while simultaneously producing a small amount of CO and other gases as side reactions. The gas-liquid separation unit 7 is located within the methanol steam reforming reactor 6. It condenses and removes incompletely vaporized moisture and some condensable components, achieving gas-liquid two-phase separation. The gas phase outlet of the gas-liquid separation unit 7 is connected to the inlet of the solid-state hydrogen storage unit. Mg-based metal hydrides refer to intermetallic compounds or complex hydrides formed based on magnesium, possessing reversible hydrogen storage and release capabilities, exhibiting high theoretical hydrogen storage density and good thermochemical stability. These hydrogen storage tanks are not isolated but integrated with the evaporation and vaporization unit and the reforming hydrogen production unit through a partitioned integrated structure. This partitioned integrated structure refers to the formation of a shared wall or tightly fitted thermal interface between the outer shell of the hydrogen storage tank and adjacent heat exchange units such as the evaporator shell or reactor wall, enabling efficient and directional heat transfer without an intermediate heat transfer medium. This structural design not only improves heat transfer efficiency but also reduces heat loss, facilitating system miniaturization and weight reduction.

[0029] In another embodiment of the present invention, the solid-state hydrogen storage unit includes a first hydrogen storage tank 3 and a second hydrogen storage tank 5. The first hydrogen storage tank 3 and the evaporation and vaporization unit form an integrated structure, and the second hydrogen storage tank 5 and the methanol steam reforming reactor 6 form an integrated structure. The integrated design of the first hydrogen storage tank 3 and the evaporation and vaporization unit allows the heat released during hydrogen absorption to be directly used for the vaporization and superheating of the methanol-water solution. The second hydrogen storage tank 5, integrated with the methanol steam reforming reactor 6, provides the high-temperature heat released therefrom to the reforming reaction, thus meeting the temperature and thermal stability requirements of the reaction.

[0030] In another embodiment of the present invention, the evaporation and vaporization unit is an evaporation superheater 4, with the heating temperature controlled at 160~200℃; the methanol steam reforming reactor 6 maintains a reaction temperature of 220~280℃ and is one of a fixed-bed reactor, a fluidized-bed reactor, or a membrane reactor. The appropriate reactor can be flexibly selected based on different application scenarios. Fixed-bed reactors have a simple structure and low pressure drop, making them suitable for small- to medium-scale continuous hydrogen production systems; fluidized-bed reactors have good heat and mass transfer performance, making them suitable for handling high-load conditions or situations with the risk of particulate catalyst wear; membrane reactors, through the integration of hydrogen separation membranes, can remove product hydrogen in real time during the reaction, shifting the chemical equilibrium towards the production direction and improving single-pass conversion and hydrogen yield.

[0031] In one alternative embodiment, the evaporator superheater 4 can be designed as a shell-and-tube or plate heat exchange structure, with one side flowing through the methanol-water solution to be vaporized, and the other side adjacent to the metal shell of the first hydrogen storage tank 3, forming a direct heat conduction interface. Alternatively, an embedded integrated design can be adopted, where part of the hydrogen storage tank shell serves as the heating surface of the evaporator, improving heat transfer efficiency.

[0032] The catalyst is one or more combinations of copper-based catalysts, nickel-based catalysts, or ruthenium-based catalysts; the Mg-based metal hydride is... , or One or more of the following.

[0033] Since the reforming reaction is a strongly endothermic process, requiring 49 kJ / mol H2, while the reaction of each mole of hydrogen with magnesium-based materials releases approximately 224 kJ of heat, the heat generated from a single hydrogen absorption is sufficient to cover the energy consumption of both the vaporization and reforming stages, forming a self-heating cycle. The first hydrogen storage tank primarily handles the heating task in the lower temperature range of 160~200℃, suitable for sensible heat absorption processes such as evaporation and vaporization; the second hydrogen storage tank is designed for catalytic reaction environments requiring higher temperatures of 220~280℃ and above, providing continuous and stable heat of reaction.

[0034] In another embodiment of the present invention, a method for producing and purifying hydrogen through coupling methanol steam reforming with solid-state hydrogen storage is also provided, comprising the following steps: S1, the methanol aqueous solution is transported to the evaporation and vaporization unit through the methanol aqueous solution supply unit 1, and the methanol aqueous solution is heated to gaseous methanol aqueous solution by the heat released by the solid hydrogen storage unit. The methanol-water solution supply unit 1 is used to provide a feedstock solution with controllable flow rate and concentration. This unit includes a storage tank, a transfer pump 2, and a concentration regulating device. The storage tank stores a certain amount of a methanol-water mixture, which is then pressurized and pumped by the transfer pump 2 to the subsequent evaporation and vaporization unit. The concentration regulating device can adjust the mass concentration of the methanol-water solution online, maintaining it within the range of 10% to 50%, optionally 20% to 40%, to balance reaction efficiency and the risk of carbon buildup.

[0035] S2, gaseous methanol-water solution is passed into the reforming hydrogen production unit, and a reforming reaction occurs under the action of a catalyst to generate a hydrogen-containing mixed gas; The evaporation and vaporization unit is the evaporation superheater 4. The function of the evaporation superheater 4 is to completely vaporize and moderately superheat the liquid methanol-water solution to form a homogeneous gaseous reactant. The heat required for this process does not come from external electric heating or combustion heating, but rather from the heat of chemical reaction released by the solid-state hydrogen storage unit during hydrogen absorption. Mg-based metal hydrides, such as MgH2, release 200-250 kJ / mol H2 in an exothermic hydrogen absorption reaction with hydrogen, reaching temperatures of 200-300℃, which is sufficient to meet the 160-200℃ operating temperature range required by the evaporation superheater. The heat is conducted from the outer wall of the hydrogen storage tank to the inner cavity of the evaporator through a partitioned integrated structure, achieving efficient thermal coupling.

[0036] S3, after passing through the gas-liquid separation unit 7, the gaseous product of the hydrogen-containing mixed gas is introduced into the solid hydrogen storage unit. The hydrogen in the gaseous product undergoes a hydrogen absorption reaction with the Mg-based metal hydride and releases high-temperature heat. This heat is transferred to the evaporation gasification unit and the reforming hydrogen production unit through the partition wall. The product of the reforming reaction is a high-temperature gas-liquid mixture containing H2, CO2, CO, CH4, and unreacted H2O vapor. This mixture flows through gas-liquid separation unit 7, where entrained liquid water is removed by condensation or cyclone separation to obtain a dry gaseous product. Gas-liquid separation unit 7 can be equipped with a temperature control valve and a pressure regulating device to ensure a stable flow of outlet gas into the solid-state hydrogen storage unit.

[0037] S4 uses hydrogen to purge the solid hydrogen storage unit and discharge the unabsorbed impurity gas. After the hydrogen absorption reaction is complete, although most of the hydrogen has been absorbed by the metal hydride, a certain volume of non-hydrogen gases, mainly including CO2, CO, and CH4, still remain in the hydrogen storage tank. If these impurities remain in the hydrogen storage system, they will affect the purity of the hydrogen desorbed subsequently. Therefore, the hydrogen storage tank needs to be purged before entering the desorption stage. S5 obtains high-purity hydrogen by desorption through heating the solid hydrogen storage unit.

[0038] When it is necessary to release the stored hydrogen, external heat is applied to the hydrogen storage tank that has been absorbed and purged, causing MgH2 to undergo a reverse dehydrogenation reaction.

[0039] In another embodiment of the present invention, the mass concentration of the methanol aqueous solution in S1 is controlled at 10% to 50%; the space velocity of the reforming reaction in S2 is 1000 to 10000. .

[0040] In another embodiment of the present invention, the hydrogen absorption reaction pressure in S3 is 0.5~10MPa, the temperature is 200~300℃, and the released heat is 200~250kJ / mol. Furthermore, the heat ratio to the methanol reforming reaction is 1:1.2~2.5.

[0041] In another embodiment of the present invention, the hydrogen used for purging in S4 has a purity of ≥99.99%, a flow rate of 0.5 to 5 times the volume of the hydrogen storage tank per hour, and a purging time of 5 to 30 minutes.

[0042] In another embodiment of the present invention, the heating temperature in step S5 is 250~350℃, the purity of the desorbed hydrogen is ≥99.999%, and the step of adjusting the hydrogen pressure to 0.1~30MPa after desorption is further included.

[0043] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples and are not intended to limit the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device, characterized in that, The system includes a methanol-water solution supply unit (1), an evaporation and vaporization unit, a reforming hydrogen production unit, a solid hydrogen storage unit, and a gas-liquid separation unit (7). The solid hydrogen storage unit contains at least two hydrogen storage tanks filled with Mg-based metal hydrides. The reforming hydrogen production unit is a methanol-water vapor reforming reactor (6) filled with a catalyst. The hydrogen storage tanks are connected to the evaporation and vaporization unit and the reforming hydrogen production unit through an integrated, partitioned structure to achieve directional transfer of heat released during the hydrogen storage process. The gas phase outlet of the gas-liquid separation unit (7) is connected to the inlet of the solid hydrogen storage unit to introduce hydrogen from the reforming products into the hydrogen storage tank for hydrogen absorption reaction and impurity separation.

2. The methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device according to claim 1, characterized in that, The solid-state hydrogen storage unit includes a first Hydrogen storage tank (3) and second Hydrogen storage tank (5), first The hydrogen storage tank (3) and the evaporation and vaporization unit form an integrated structure, the second The hydrogen storage tank (5) and the methanol steam reforming reactor (6) form an integrated structure.

3. The methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device according to claim 1, characterized in that, The methanol aqueous solution supply unit (1) includes a storage tank, a transfer pump (2) and a concentration regulating device. The storage tank is connected to the transfer pump (2). The outlet of the transfer pump (2) is connected to the inlet pipeline of the evaporation and vaporization unit. The outlet of the transfer pump (2) is connected to the inlet pipeline of the evaporation and vaporization unit and the concentration regulating device can adjust the concentration of the methanol aqueous solution to 10%~50%.

4. The methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device according to claim 1, characterized in that, The evaporation and vaporization unit is an evaporation superheater (4), and the heating temperature is controlled at 160~200℃; the methanol steam reforming reactor (6) maintains a reaction temperature of 220~280℃ and is one of a fixed bed reactor, a fluidized bed reactor or a membrane reactor.

5. The methanol steam reforming and solid-state hydrogen storage coupled hydrogen production and purification device according to claim 1, characterized in that, The catalyst is one or more combinations of copper-based catalysts, nickel-based catalysts, or ruthenium-based catalysts; the Mg-based metal hydride is... , or One or more of the following.

6. A method for producing and purifying hydrogen by coupling methanol steam reforming with solid-state hydrogen storage based on the apparatus of claim 1, characterized in that, Includes the following steps: S1, the methanol aqueous solution is transported to the evaporation and vaporization unit through the methanol aqueous solution supply unit (1), and the methanol aqueous solution is heated to gaseous methanol aqueous solution by the heat released by the solid hydrogen storage unit. S2, gaseous methanol-water solution is passed into the reforming hydrogen production unit, and a reforming reaction occurs under the action of a catalyst to generate a hydrogen-containing mixed gas; S3, after passing the hydrogen-containing mixed gas through the gas-liquid separation unit (7), the gas phase product is passed into the solid hydrogen storage unit. The hydrogen in the gas phase product reacts with the Mg-based metal hydride to absorb hydrogen and release high-temperature heat. This heat is transferred to the evaporation gasification unit and the reforming hydrogen production unit through the partition wall. S4 uses hydrogen to purge the solid hydrogen storage unit and discharge the unabsorbed impurity gas. S5 obtains high-purity hydrogen by desorption through heating the solid hydrogen storage unit.

7. The method for producing and purifying hydrogen through coupling methanol steam reforming and solid-state hydrogen storage according to claim 6, characterized in that, In step S1, the mass concentration of the methanol-water solution is controlled between 10% and 50%; in step S2, the space velocity of the reforming reaction is 1000 to 10000. .

8. The method for producing and purifying hydrogen by coupling methanol steam reforming with solid-state hydrogen storage according to claim 6, characterized in that, The hydrogen absorption reaction in S3 is carried out at a pressure of 0.5~10 MPa and a temperature of 200~300℃, releasing 200~250 kJ / mol of heat. Furthermore, the heat ratio to the methanol reforming reaction is 1:1.2~2.

5.

9. The method for producing and purifying hydrogen by coupling methanol steam reforming with solid-state hydrogen storage according to claim 6, characterized in that, In step S4, the purity of the hydrogen used for purging is ≥99.99%, the flow rate is 0.5 to 5 times the volume of the hydrogen storage tank per hour, and the purging time is 5 to 30 minutes.

10. The method for producing and purifying hydrogen by coupling methanol steam reforming with solid-state hydrogen storage according to claim 6, characterized in that, The heating temperature in step S5 is 250~350℃, the hydrogen purity after desorption is ≥99.999%, and the hydrogen pressure after desorption is adjusted to 0.1~30MPa.

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