A renewable energy-based acid liquid circulation hydrogen supply device and a hydrogen supply method

Abstract

This invention discloses a hydrogen supply device and method based on renewable energy-based acid-liquid recycling. The acid-liquid recycling hydrogen supply device includes a hydrogen production unit, a renewable energy power supply unit, an acid-liquid recycling unit, and a control unit. The hydrogen production unit has a reaction chamber for reacting hydrogen storage materials and acid to generate hydrogen gas, supplying hydrogen to the outside. The acid-liquid recycling unit is connected to the reaction chamber to restore the waste liquid generated by the hydrogen production unit to the acid used in the hydrogen production reaction and to supply acid to the hydrogen production unit. The renewable energy power supply unit is connected to and supplies power to the hydrogen production unit, the acid-liquid recycling unit, and the control unit. The control unit is connected to and controls the hydrogen production unit, the acid-liquid recycling unit, and the renewable energy power supply unit. This invention utilizes the reaction of hydrogen storage materials and acid to generate hydrogen gas, and uses renewable energy power to start the acid-liquid recycling unit to restore the reaction waste liquid to the acid used in the hydrogen production reaction, achieving a low-cost hydrogen supply technology based on acid-liquid recycling.

Description

Technical Field

[0001] This invention belongs to the technical field of hydrogen production and supply, specifically relating to an acid-liquid circulation hydrogen supply device and method based on renewable energy. Background Technology

[0002] The hydrolysis reaction of magnesium-based hydrogen storage materials can release hydrogen at room temperature and pressure, showing significant application potential in the field of hydrogen energy supply and applicable to fuel cells, industrial hydrogen refueling, and emergency hydrogen supply. However, the hydrolysis process of magnesium-based hydrogen storage materials generates magnesium hydroxide precipitate, which coats the surface of unreacted hydrogen storage materials, forming a dense passivation layer. This layer hinders further contact between water molecules and magnesium hydride, causing the reaction rate to drop rapidly or even terminate, making it impossible to stably and continuously supply hydrogen.

[0003] To address this issue, existing technologies typically employ acidic solutions to dissolve the passivation layer, thereby maintaining the continuous reaction. Patent CN109250683B discloses a hydrogen production device using magnesium hydride as the hydrogen storage material. This device shortens the reaction start-up time by adding reaction promoters such as LiOH, KOH, NaOH, or citric acid. However, during the hydrogen supply process, the continuous generation of magnesium hydroxide necessitates the continuous addition of large amounts of acid, resulting in high raw material costs and poor economic efficiency.

[0004] After the acidolysis reaction is completed, a high concentration of magnesium salt solution remains in the system. This high-concentration magnesium salt waste liquid is difficult to treat. Direct discharge may cause eutrophication and metal ion pollution in water bodies. Recycling and treating it using methods such as chemical precipitation and evaporation crystallization requires additional energy consumption, further increasing the operating cost of hydrogen supply. Japanese Patent JP5640231B2 discloses a magnesium hydride particle hydrolysis hydrogen production device that separates magnesium hydroxide in a separation tank and achieves water circulation. However, this patent only involves the recycling of reaction water and does not solve the problems of acid consumption and treatment of saline waste liquid. In hydrogen supply scenarios using acid-assisted reactions, the difficulty of waste liquid treatment is far greater than that of simple water circulation, which cannot meet the demand for continuous and stable hydrogen supply.

[0005] On the other hand, traditional hydrogen supply methods rely on high-pressure hydrogen cylinders for storage and transportation, which has problems such as high gas source storage costs, low transportation efficiency, and prominent safety hazards. Especially in special hydrogen supply needs such as remote areas and emergency scenarios, the limitations of high-pressure cylinder storage and transportation are more obvious, making it difficult to achieve flexible and efficient hydrogen supply.

[0006] Therefore, how to improve the hydrogen supply and material recycling methods of hydrogen storage material hydrolysis reaction, and provide a hydrogen supply equipment with low material consumption, convenient equipment transportation, excellent safety and strong hydrogen supply stability, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] To address the aforementioned problems in the prior art, this invention provides a hydrogen supply device and method based on renewable energy-based acid-liquid recycling. This device not only utilizes hydrogen storage materials to react with acid to produce hydrogen, achieving stable on-site hydrogen supply and overcoming the limitations of transporting and ensuring the safety of high-pressure hydrogen cylinders, thus meeting hydrogen supply needs in various scenarios, but also uses renewable energy power supply devices to restore the waste liquid generated during hydrogen production to its original acid state. This effectively solves the problems of waste liquid treatment and acid recycling, reducing material consumption and lowering the operating cost of hydrogen supply.

[0008] Based on this, in a first aspect of the present invention, a renewable energy-based acid-liquid circulation hydrogen supply device is proposed, comprising a hydrogen production device, a renewable energy power supply device, an acid-liquid circulation device, and a control device, wherein: The hydrogen production unit has a reaction chamber for reacting hydrogen storage materials and acid to generate hydrogen gas, so as to supply hydrogen to the outside. An acid circulation device is connected to the reaction chamber to restore the waste liquid generated by the hydrogen production device to the acid liquid used in the hydrogen production reaction and to supply the acid liquid to the hydrogen production device. A renewable energy power supply device is connected to the hydrogen production device, the acid circulation device, and the control device, and supplies power to at least one of the hydrogen production device, the acid circulation device, and the control device; A control device is connected to the hydrogen production unit, the acid circulation unit, and the renewable energy power supply unit, and controls the operation of the hydrogen production unit, the acid circulation unit, and the renewable energy power supply unit.

[0009] The hydrogen production unit directly generates hydrogen and supplies it on-site, eliminating the need for storing high-pressure hydrogen and fundamentally removing the limitations of high-pressure hydrogen cylinders. This on-demand hydrogen production model reduces the system's hydrogen storage requirements, and even in the event of a leak, it prevents large-scale hydrogen accumulation, enhancing the safety of the hydrogen supply equipment and adapting to various scenarios requiring immediate hydrogen supply. Secondly, the acid recycling unit, powered by renewable energy, restores the waste liquid generated from the hydrogen production reaction to its original hydrogen-producing acid solution, completing the acid recycling process. This achieves zero waste liquid discharge and continuous acid utilization, solving environmental problems in the hydrogen production and supply process while also reducing hydrogen supply costs.

[0010] Preferably, the hydrogen production apparatus includes: A hydrogen production tube assembly includes a reaction tube with an opening and a reaction tube cap capable of sealing the opening of the reaction tube to form the reaction chamber; The reaction tube cover has a gas outlet connected to a hydrogen supply pipe, which is connected to an external hydrogen supply interface to deliver the hydrogen generated in the reaction chamber to the external hydrogen supply interface. The bottom of the reaction tube has a liquid inlet and outlet to supply acid to the reaction chamber and discharge waste liquid from the reaction chamber.

[0011] Preferably, there are multiple hydrogen production tube groups, and the multiple hydrogen production tube groups are arranged in parallel; Each hydrogen production tube assembly includes multiple reaction tubes and multiple reaction tube caps, which are connected in series.

[0012] Preferably, the reaction tube is provided with a reaction tube plug, which has several through holes that allow gas to pass through while preventing solids and liquids from passing through.

[0013] Preferably, the acid circulation device includes an acid recovery tank, a sedimentation tank, and a cation exchange membrane disposed between the acid recovery tank and the sedimentation tank and separating the two, wherein: The acid recovery tank is connected to the hydrogen production pipeline group to realize the collection of waste liquid and the return of acid liquid, and it has a first electrode; A sedimentation tank, which has a second electrode; The renewable energy power supply device is electrically connected to the first electrode and the second electrode to power the acid circulation device. The cation exchange membrane allows cation filtration and exchange in the acid recovery tank and the precipitation tank to restore the waste liquid in the acid recovery tank to the acid liquid used for hydrogen production reaction.

[0014] Preferably, the hydrogen storage material includes at least one of magnesium, magnesium hydride, and magnesium alloys; optionally, the hydrogen storage material is pre-formed into a propellant column that can be inserted into the reaction chamber. The acid solution includes at least one of citric acid, oxalic acid, acetic acid, phosphoric acid, and dilute sulfuric acid.

[0015] Preferably, the renewable energy power supply device includes a solar power generation module, which includes photovoltaic modules, a battery, and a controller.

[0016] Photovoltaic modules, including solar panels, are the core power generation components of a power generation module, converting solar energy into electrical energy. Batteries are used to store electrical energy, especially to power equipment when sunlight is insufficient. The controller is the "brain" of the system, responsible for controlling the overall operating status of the equipment, and also includes overcharge and over-discharge protection for the batteries to extend their lifespan.

[0017] In a second aspect of the present invention, according to the aforementioned renewable energy-based acid-liquid circulation hydrogen supply device, a renewable energy-based acid-liquid circulation hydrogen supply method is also proposed, comprising the following steps: Add hydrogen storage material to the reaction chamber; The acid solution is sent to the reaction chamber, where it reacts with the hydrogen storage material to release hydrogen gas. The generated hydrogen is transported to an external hydrogen supply interface via a hydrogen supply pipeline to supply hydrogen to the outside. After the reaction is complete, the waste liquid in the reaction chamber is sent to the acid circulation device to be restored to the acid liquid used for the hydrogen production reaction and circulated to the hydrogen production device. The renewable energy power supply unit provides power to the hydrogen production unit, acid circulation unit, and control unit, maintaining the continuous operation of the equipment.

[0018] Preferably, the acid recycling device restores the waste liquid to acid for hydrogen production reaction, including the following steps: The waste liquid in the reaction chamber flows into the acid recovery tank; The first electrode of the acid recovery tank and the second electrode of the sedimentation tank are energized. The cation exchange membrane, which is placed between the acid recovery tank and the sedimentation tank and isolates them, allows cation filtration and exchange in the acid recovery tank and the sedimentation tank, and restores the waste liquid in the acid recovery tank to the acid liquid used for the hydrogen production reaction. The acid solution restored in the acid recovery tank is sent to the reaction chamber.

[0019] Preferably, the hydrogen supply method further includes: The renewable energy power supply device uses a solar power generation module to convert solar energy into electrical energy, which is then transmitted to the battery (22) of the renewable energy power supply device for storage or directly to power the hydrogen production device, acid circulation device and control device. The control device controls the working status of the hydrogen device, acid circulation device, and renewable energy power supply device to achieve at least one of the following operations: intermittent or continuous hydrogen supply to the outside, replenishing hydrogen storage materials according to hydrogen production parameters, adjusting the acid supply rate, discharging hydrogen with substandard purity, and adjusting reaction parameters.

[0020] By implementing the above technical solution, the present invention includes at least one of the following beneficial effects: 1. The hydrogen production device of the present invention utilizes the reaction of hydrogen storage materials and acid to generate hydrogen, and uses renewable energy to power the acid circulation device to restore the reaction waste liquid to the acid used in the hydrogen production reaction, realizing the hydrogen supply technology of acid recycling. This overcomes the defect of magnesium-based hydrogen storage materials forming a passivation layer that affects the reaction process. The produced hydrogen can be directly supplied to the outside. At the same time, the renewable energy power supply device (optionally including a solar power generation module) can achieve internal energy self-sufficiency. This not only gets rid of the storage and transportation restrictions of high-pressure hydrogen cylinders, but also improves the flexibility and independence of the equipment's hydrogen supply, adapting to the on-demand hydrogen supply needs of various scenarios.

[0021] 2. This invention utilizes a cation exchange membrane in an acid circulation device to restore the saline waste liquid generated by the hydrogen production reaction to the acid liquid used in the hydrogen production reaction for recycling. When producing the same amount of hydrogen, the amount of acid used in the recycling process is only less than 10% of the traditional amount, preferably less than 8% (taking citric acid as an example). This means that the actual consumables of the hydrogen supply equipment are basically only water and hydrogen storage materials. This not only eliminates environmental pollution caused by waste liquid discharge but also avoids the large ineffective load caused by carrying large amounts of acid in solution form, solving the problems of high consumable costs and excessive load in traditional hydrogen supply equipment. At the same time, it improves the recyclability of the hydrogen supply equipment, overcoming the shortcomings of existing disposable sealed fuel tanks that are difficult to reuse after startup and shutdown, resulting in material and equipment waste.

[0022] 3. This invention designs multiple parallel hydrogen production tube groups, and in each hydrogen production tube group, multiple series reaction tubes are designed. By optimizing the reaction chamber of the hydrogen production device, the hydrogen supply equipment can flexibly adapt to different hydrogen supply demand scenarios with different rates and amounts. Moreover, the equipment has virtually no waste liquid discharge during use, and has excellent stability and safety throughout the process. It is suitable for various application scenarios such as outdoor, emergency, and industrial auxiliary applications, and has broad promotional value. Attached Figure Description

[0023] The renewable energy-based acid-liquid recycling hydrogen supply device of the present invention will now be described with reference to the accompanying drawings. In the drawings: Figure 1 This is a schematic diagram of the overall structure of the acid circulation hydrogen supply device of the present invention; Figure 2 This is a schematic diagram of the overall structure of the acid circulation hydrogen supply device in this invention from another perspective; Figure 3 This is an enlarged schematic diagram of a portion of the acid-recirculating hydrogen supply device in this invention; Figure 4 This is a cross-sectional schematic diagram of the hydrogen production pipe assembly in the acid circulation hydrogen supply equipment of the present invention; Figure 5 This is a schematic diagram of the propellant column used in the acid circulation hydrogen supply device of the present invention; Figure 6 This is an explosion diagram of the acid circulation device in this invention; Figure 7 This is a schematic diagram of the acid circulation device in this invention.

[0024] Explanation of reference numerals in the attached figures: 1. Hydrogen production unit; 10. Propellant column; 11. Hydrogen production tubing assembly; 111. Reaction tube; 112. Reaction tube cover; 113. Reaction tube plug; 12. Fluid pipeline; 13. Gas pipeline; 2. Renewable energy power supply equipment; 21. Photovoltaic modules; 22. Storage batteries; 3. Acid circulation device; 31. Acid recovery tank; 311. First electrode; 32. Sedimentation tank; 321. Second electrode; 33. Cation exchange membrane; 34. Water tank; 5. Control device. Detailed Implementation

[0025] Preferred embodiments of the present invention will now be described with reference to the accompanying drawings. Those skilled in the art should understand that these embodiments are merely illustrative of the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0026] It should be noted that in the description of this invention, terms such as "upper," "lower," "vertical," "horizontal," and "inner," indicating directional or positional relationships, are based on the directional or positional relationships shown in the accompanying drawings. These are merely for ease of description and do not indicate or imply that the device or element 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. Furthermore, the terms "first," "second," "third," and "fourth" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0027] Furthermore, it should be noted that, in the description of this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0028] As described in the background section, the hydrolysis reaction of magnesium-based hydrogen storage materials can release hydrogen at room temperature and pressure, with a theoretical hydrogen production of up to 15.2 wt%, showing significant application potential in the hydrogen energy supply field and applicable to fuel cells, industrial hydrogen refueling, and emergency hydrogen supply scenarios. However, the hydrolysis process of magnesium-based hydrogen storage materials generates magnesium hydroxide precipitate, which coats the surface of unreacted hydrogen storage materials, forming a dense passivation layer that hinders further contact between water molecules and magnesium hydroxide, causing the reaction rate to drop rapidly or even terminate, making it impossible to stably and continuously supply hydrogen. To solve this problem, existing technologies typically use acidic solutions (such as citric acid) to dissolve the passivation layer to maintain the continuous reaction. However, due to the continuous generation of magnesium hydroxide, a large amount of citric acid (usually more than 5 times the mass of the hydrogen storage material) needs to be added, resulting in high raw material costs and poor economic efficiency. After the acid hydrolysis reaction is completed, the high-concentration magnesium salt waste liquid remaining in the system is difficult to treat. Direct discharge can easily cause eutrophication of water bodies and metal ion pollution. Recycling and treatment using methods such as chemical precipitation and evaporation crystallization requires additional energy consumption, further increasing the operating cost of hydrogen supply.

[0029] In addition to using acidic solutions to dissolve the passivation layer, existing technologies also involve heating during the hydrogen production reaction. However, the core temperature of the reaction chamber needs to be greater than 500°C, which exceeds the explosion temperature of hydrogen. Furthermore, the reaction requires a high-temperature and high-pressure environment, and consumables need to be packaged in metal containers, which increases the transportation weight and is not conducive to flexible hydrogen supply.

[0030] On the other hand, the traditional hydrogen supply model relies on high-pressure gas cylinders to store and transport hydrogen, which has problems such as high gas source storage costs, low transportation efficiency, and prominent safety hazards. Especially in special hydrogen supply needs such as remote areas and emergency scenarios, the storage and transportation limitations of high-pressure gas cylinders are more obvious, making it difficult to achieve flexible and efficient hydrogen supply.

[0031] This invention solves the above-mentioned problems efficiently and at low cost by providing a renewable energy-based acid-liquid circulation hydrogen supply device and its hydrogen supply method, with reference to... Figures 1 to 7 It includes a hydrogen production unit 1, a renewable energy power supply unit 2, an acid circulation unit 3, and a control unit 5. Among them: Hydrogen production unit 1 uses magnesium-based hydrogen storage materials and acid to produce hydrogen, providing a source for external hydrogen supply; The renewable energy power supply device 2 may include a solar power generation module, which includes a photovoltaic module 21, a battery 22 and a controller, and can continuously or intermittently supply power to the acid circulation device 3 and the control device 5. The acid circulation device 3 can restore the waste liquid generated by the hydrogen production unit 1 to the acid liquid used in the hydrogen production reaction and resupply the acid liquid to the hydrogen production unit 1. The battery 22 of the renewable energy power supply device 2 can store electrical energy (including electrical energy generated by the solar power generation module or external supplemental electrical energy) and supply power to devices that require electricity, such as the hydrogen production device 1, the acid circulation device 3, and the control device 5. The control device 5 is powered by the renewable energy power supply device 2 and can control the operation of the hydrogen production device 1, the acid circulation device 3 and the renewable energy power supply device 2 to achieve regulation of the hydrogen supply process.

[0032] The acid recycling unit 3, powered by the renewable energy power supply unit 2, can restore the waste liquid generated by the hydrogen production reaction to the original hydrogen production acid liquid, completing the recycling and regeneration of the acid liquid. This achieves zero waste liquid discharge and continuous utilization of the acid liquid, solving the environmental problems in the hydrogen production and supply process. Secondly, the hydrogen production unit 1 directly generates hydrogen and supplies it on-site, eliminating the need to store high-pressure hydrogen. This fundamentally eliminates the limitation of high-pressure hydrogen cylinders. The on-demand hydrogen production mode reduces the system's hydrogen storage capacity. Even in the event of a leak, it will not lead to large-scale hydrogen accumulation, significantly improving the safety of the hydrogen supply equipment.

[0033] Furthermore, this product features an assembly frame welded from stainless steel pipes. This frame integrates the hydrogen production unit 1, the renewable energy power supply unit 2, the acid circulation unit 3, and the control unit 5 into a single unit, enhancing the overall portability of the device and facilitating transportation and on-site deployment. Figures 1 to 2 .

[0034] Specifically, refer to Figure 1-3 The hydrogen production device 1 includes a hydrogen production pipe assembly 11, a fluid pipeline 12, a gas pipeline 13, a valve assembly, and a reaction tube holder. The hydrogen production pipe assembly 11 provides a reaction chamber for the hydrogen production reaction; the fluid pipeline 12 transports acid and waste liquid after the reaction; the gas pipeline 13 transports hydrogen, diverting the hydrogen generated by the hydrogen production pipe assembly 11 to an external hydrogen supply interface, or purifying the generated hydrogen before output; the valve assembly controls the flow rate of hydrogen, acid, and waste liquid, ensuring stable hydrogen supply pressure and system safety; and the reaction tube holder supports the hydrogen production pipe assembly 11 and secures the positions of other components.

[0035] Furthermore, the hydrogen production assembly 11 includes a reaction tube 111 and a reaction tube cap 112. The reaction tube 111 is integrally molded from a corrosion-resistant polymer material (such as polytetrafluoroethylene or reinforced polypropylene), with a wall thickness of 2-5 mm, an inner diameter of 30-100 mm, and a height of 150-300 mm, forming a cylindrical reaction chamber with an opening. The bottom of the reaction tube 111 has an opening (with a diameter of 5-10 mm), which is sealed to the fluid pipeline 12 to allow acid to enter and waste liquid to be discharged.

[0036] Furthermore, there are multiple hydrogen production tube groups 11, for example, two. The two hydrogen production tube groups 11 are connected in parallel and connected to the gas pipeline 13 respectively. Each hydrogen production tube group 11 can switch to supply hydrogen to an external hydrogen supply interface. Even if one hydrogen production tube group completes its reaction and enters the waste discharge and refueling cycle recovery stage, the hydrogen production device 1 can effectively ensure a continuous supply of hydrogen. Each hydrogen production tube group 11 includes multiple reaction tubes 111 and reaction tube caps 112, for example, two reaction tubes 111 and reaction tube caps 112. To achieve a compact arrangement and reduce space occupation, the four reaction tubes 111 of the two hydrogen production tube groups 11 are fixed in a rectangular array by a retainer. The reaction tube caps 112 within the same group are connected in series. Due to the very low density of hydrogen, the generated hydrogen, driven by the high internal pressure of the reaction tubes, is led out of each reaction tube 111 through the series vent pipe on the reaction tube cap 112 at the top of the reaction tube 111 and flows into the gas pipeline 13. See Appendix. Figure 4 A reaction tube plug 113 is provided at the end of the reaction tube 111 facing the reaction tube cover 112. The reaction tube plug 113 has several through holes, which allow gas to pass through and prevent solids and liquids from passing through, thereby effectively preventing solid and liquid materials from blocking the gas pipeline 13 and the external hydrogen supply interface.

[0037] In practical applications, the number of hydrogen production tube groups 11 and the number of reaction tubes 111 can be configured according to the maximum hydrogen supply. During the hydrogen production process, different numbers of reaction tubes 111 can be turned on to carry out the hydrogen production reaction according to different hydrogen supply rate requirements. Alternatively, each reaction tube 111 can work in conjunction with the acid circulation device 3 to participate in the hydrogen production reaction alternately. When a certain reaction tube 111 is carrying out the hydrogen production reaction, the other reaction tubes 111 wait for the waste liquid to be restored to acid and re-injected into the reaction tube 111 before carrying out the hydrogen production reaction, ensuring the continuity of hydrogen supply.

[0038] It should be explained that the material of reaction tube 111 is not unique. For example, in addition to the aforementioned corrosion-resistant polymer materials, reaction tube 111 can also be made of titanium alloy to suit high-temperature and high-pressure environments. Its inner wall can be anodized to form a passivation film to enhance acid resistance. Hastelloy can also be used, which has excellent pitting corrosion resistance and is suitable for marine environments, thus meeting the different application scenarios of this product. Stainless steel-plastic composite tubes can also be used, specifically with an outer layer of 316L stainless steel (thickness can be 1-2mm) to provide mechanical strength and an inner PTFE lining (thickness can be 0.5-1mm) to prevent acid corrosion, with a lower cost than pure metals. Alumina ceramics can also be used, which have high hardness and high temperature resistance, suitable for high-temperature scenarios. Silicon carbide ceramics can also be used, which have high thermal conductivity, can quickly dissipate reaction heat, avoid local overheating, and are suitable for high-power continuous hydrogen supply. Borosilicate glass can also be used, whose transparency facilitates observation of the reaction process, is resistant to acids and alkalis, and can be covered with a metal mesh to enhance impact resistance.

[0039] Correspondingly, the structure of the reaction tube 111 is not unique. For example, in addition to the standard cylindrical shape mentioned above, the reaction tube 111 can also be designed as a multi-stage segmented structure, such as a stepped reducing pipe, where the upper section diameter (e.g., 80 mm) is larger than the lower section (e.g., 50 mm), forming a stratified settling zone and reaction zone, reducing the possibility of unreacted particles being entrained in the waste liquid; for example, a modular series pipe group, where multiple pipes are connected in series through flanges, and each pipe is filled with hydrogen storage material of different particle sizes (e.g., 50-100 μm upstream, ≤50 μm downstream) to achieve staged reaction and improve the hydrogen supply rate; the reaction tube 111 can also be designed as a columnar irregular cross-section structure, such as a square or hexagonal pipe; the reaction tube 111 can also be a dual-chamber structure, with the main chamber filled with hydrogen storage material and the secondary chamber (volume ratio can be 20%) pre-stored with acid, which is slowly released through a controllable diaphragm (e.g., polyethersulfone microporous membrane) or porous diaphragm to achieve self-regulation of the reaction rate and ensure the stability of the hydrogen supply.

[0040] Furthermore, in some embodiments, the bottom of the reaction tube 111 is designed as an inverted conical structure (the cone angle can be 60°-90°) to facilitate the accumulation of unreacted precipitates and the discharge of waste liquid.

[0041] Furthermore, in some other embodiments, the inner wall of the reaction tube 111 is provided with a spiral guide groove (the groove depth can be 1-2 mm, and the pitch can be 30-50 mm) to promote acid turbulence, accelerate the hydrogen generation rate, and improve hydrogen supply efficiency.

[0042] Furthermore, the reaction tube cover 112 is a flange-type sealing cover structure hinged to the reaction tube 111 (the thickness can be 10-15mm). The reaction tube 111 retainer is equipped with an actuator capable of opening and closing the reaction tube cover 112. The actuator is electrically connected to and controlled by the control device 5. The main body material of the reaction tube cover 112 is consistent with that of the reaction tube 111, and an acid-resistant sealing plug is provided at the connection point with the reaction tube 111. A hydrogen outlet is provided in the middle of the reaction tube cover 112 and is sealed to the gas pipeline 13.

[0043] Furthermore, in some other embodiments, a hydrogen concentration sensor and a pressure transmitter are provided on the reaction tube cover 112, and the data is transmitted to the control device 5 to monitor the hydrogen production process and the hydrogen supply pressure, so that the control device 5 can adjust the reaction parameters in a timely manner to ensure a stable hydrogen supply.

[0044] Furthermore, in some other embodiments, the edge of the reaction tube cover 112 is provided with a rupture disc and an electromagnetic pressure relief valve to achieve dual protection, prevent overpressure inside the reaction tube 111, and ensure safe hydrogen supply.

[0045] Specifically, in the exemplary embodiment, hydrogen production device 1 utilizes the hydrolysis reaction of magnesium-based hydrogen storage materials to produce hydrogen. Taking magnesium hydride as an example, its chemical equation is as follows: MgH2 + 2H2O → Mg(OH)2↓ + 2H2↑ In this process, acid circulation device 3 supplies acid to dissolve the magnesium hydroxide passivation layer, and the chemical equation is as follows: 3Mg(OH)2+2C6H8O7→Mg3(C6H5O7)2+6H2O If citric acid is in excess, soluble Mg(C6H6O7) or Mg(C6H7O7)2 may be generated.

[0046] It should be explained that although the hydrogen production device 1 in this embodiment uses magnesium hydride and citric acid to produce hydrogen, the combination is not fixed. Those skilled in the art can change the specific combination according to their needs, as long as it does not affect the subsequent circulation of acid. For example, the hydrogen storage material includes at least one of magnesium, magnesium hydride and magnesium alloy, and the acid includes at least one of citric acid, oxalic acid, acetic acid, phosphoric acid and dilute sulfuric acid.

[0047] Furthermore, referring to Figure 5The hydrogen storage material is prefabricated into a drug column 10 that can be inserted into the reaction tube 111. Specifically, the drug column 10 can be cylindrical to facilitate large-scale pressing and filling, or it can be a hollow ring column to increase the acid contact area and improve the reaction rate; or it can be porous honeycomb to further improve the reaction rate and hydrogen supply efficiency.

[0048] Furthermore, in the demonstration implementation, refer to Figure 2 The fluid pipeline 12 employs a corrosion-resistant double-layer design. The inner layer is made of acid-resistant PTFE material (1-2 mm thick), while the outer layer is covered with stainless steel braided mesh to enhance mechanical strength. The fluid pipeline 12 connects the hydrogen production unit 1 and the acid circulation unit 3 via clamp-type flanges, with fluororubber sealing rings embedded between the flanges. A 100-200 mesh filter (removable and washable) is installed at the bottom connection between the fluid pipeline 12 and the reaction pipe 111 to intercept unreacted particles. A circulation pump is installed on the fluid pipeline 12 to power the acid circulation.

[0049] Furthermore, in the demonstration implementation, refer to Figure 1 and Figure 2 The gas pipeline 13 adopts a composite leak-proof structure, with an inner layer of aluminum alloy (thickness can be 0.5-1mm) and an outer layer of carbon fiber reinforced epoxy resin (thickness can be 2-3mm), ensuring the safety and sealing of the hydrogen transportation process. The gas pipeline 13 connects to the hydrogen outlet of the hydrogen production pipeline group 11 and the external hydrogen supply interface. A pressure regulating valve and a check valve can also be installed at the connection between the gas pipeline 13 and the external hydrogen supply interface. The control device 5 adjusts the pressure according to the hydrogen production situation and the external gas pressure requirements to ensure stable hydrogen supply pressure and prevent hydrogen backflow.

[0050] The purifier connected to the gas pipeline 13 may include components such as a HEPA filter and a molecular sieve drying cylinder to prevent impurities from entering external hydrogen-using equipment and to provide high-purity hydrogen. Furthermore, in some embodiments, the gas pipeline 13 may also be equipped with a hydrogen purity detection device to monitor the purity of the supplied hydrogen in real time. When the purity does not meet the standard, the control device 5 activates the exhaust valve to discharge the substandard hydrogen and adjusts the hydrogen production reaction parameters to ensure the quality of the supplied hydrogen.

[0051] Furthermore, in the demonstration implementation, the valve assembly is installed on the fluid pipeline 12 and the gas pipeline 13. The valve assembly is electrically connected to and controlled by the control device 5. The valve assembly also integrates a flow sensor and a pH electrode, which can feed the data back to the control device 5 in real time, so that the control device 5 can adjust and control the hydrogen reaction rate and the acid circulation efficiency.

[0052] Furthermore, in the demonstration implementation, the main body of the reaction tube 111 retainer is made of aluminum alloy profile and can be quickly assembled using T-slot nuts. The reaction tube 111 retainer is equipped with an adjustable clamping mechanism, which uses V-shaped claws lined with silicone buffer pads. The clamping force is pre-tensioned by a spring to accommodate hydrogen production tube assemblies 11 of different specifications.

[0053] Specifically, refer to Figure 1 and Figure 2 The solar power generation module includes a photovoltaic module 21, a battery 22, and a controller.

[0054] Furthermore, in the demonstration implementation, the storage battery 22 supplies power to the internal components such as the acid circulation device 3, the control device 5, the valve group and actuator of the hydrogen production device, ensuring the coordinated operation of all components of the system.

[0055] Specifically, in the exemplary embodiment, reference is made to Figure 6 and Figure 7 The acid circulation device 3 is integrally formed as a box, which is removable for periodic cleaning of the internal sediment; cation exchange membranes 33 are stacked inside the box, dividing the interior into an acid recovery tank 31 and a sedimentation tank 32; see reference. Figure 2 The acid circulation device 3 also includes a water tank 34, which is fixed on the side of the hydrogen production device 1 away from the solar power generation module. It is connected to the sedimentation tank 32 and can replenish water to the sedimentation tank 32.

[0056] Furthermore, in the exemplary embodiment, reference is made to Figure 6 and Figure 7 The acid recovery tank 31 has a first electrode 311 (positive electrode); the sedimentation tank 32 has a second electrode 321 (negative electrode); the cation exchange membrane 33 can isolate the acid recovery tank 31 and the sedimentation tank 32. The acid recovery tank 31 is connected to the hydrogen production pipeline group 11 to realize the collection of waste liquid and the return of acid liquid.

[0057] The renewable energy power supply device 2 energizes the first electrode 311 (positive electrode) and the second electrode 321 (negative electrode). The cation exchange membrane 33 allows cation filtration and exchange in the acid recovery tank 31 and the sedimentation tank 32, and restores the waste liquid in the acid recovery tank 31 to the acid liquid used for the hydrogen production reaction.

[0058] It should be explained that the cation exchange membrane 33 in this invention only allows cations (Mg) 2+ H + ( ) can pass through, but anions cannot pass through, and it is used to isolate anions and cations.

[0059] Principle of acid circulation device 3: Anode (positive electrode): Oxidation reaction occurs, and OH- in the water... - Losing electrons to generate O2 and H + This leads to H in the anode region+ As the concentration increases, the reaction equation is as follows: 4OH - -4e - =O2↑+2H2O Cathode (negative electrode): A reduction reaction occurs, and H+ in the water... + The gain of electrons generates H2, leading to the formation of OH groups in the cathode region. - As the concentration increases, the reaction equation is as follows: 2H + +2e - =H2↑ Because H + As water is consumed, the ionization equilibrium of water shifts to the right: ; Dissociation of magnesium citrate: Magnesium citrate (Mg3(C6H5O7)2) is a strong electrolyte and completely dissociates in water: Mg3(C6H5O7)2 → 3Mg 2+ +2C6H5O7 3- ; Among them, Mg 2+ It is a cation, C6H5O7 3- (Citrate) is an anion.

[0060] After the first electrode 311 (positive electrode) and the second electrode 321 (negative electrode) are energized: The reaction in the anode zone (acid recovery tank 31): Mg dissociates from magnesium citrate 2+ It will move towards the cathode region (because the cathode is negatively charged and attracts cations), citrate ions (C6H5O7) 3- It cannot pass through the cation exchange membrane 33 and remains in the anode area (acid recovery tank 31). Anode reaction generates H + H + The concentration gradually increased; The citrate ions remaining in the anode area (acid recovery tank 31) will react with H+. + They combine to form citric acid (H3C6H5O7) (a tribasic weak acid that dissociates stepwise, but here H...). + Sufficient, will be fully combined). In other words, the solute in the anode zone (acid recovery tank 31) gradually changes from "magnesium citrate" to "citric acid" because the citrate ions are not removed, and H... + With sufficient acid, the anode zone (acid recovery tank 31) will eventually become a citric acid solution.

[0061] Reactions in the cathode region (precipitation region): Mg 2+ Migrate to the cathode region (precipitation region) through cation exchange membrane 33. The cathode reaction consumes H + H2 is generated, leading to OH - Increased concentration (the ionization equilibrium of water shifts to the right); Mg 2+ With OH - Combined to form magnesium hydroxide precipitate (Mg(OH)2): 3Mg 2+ +6OH - =3Mg(OH)2↓ It is evident that Mg(OH)2 precipitate will be generated in the cathode region (precipitation region).

[0062] In summary, the cation exchange membrane 33 (isolates anions) and electrolysis (generates H+) + Under the combined effect of [the following], the pool containing magnesium citrate (acid recovery pool 31) will be completely converted into citric acid solution, realizing acid recycling and reducing hydrogen supply costs.

[0063] Specifically, in the exemplary embodiment, reference is made to Figure 2 The battery 22 of the renewable energy power supply device 2 can be fixed to the bottom of the invention, and can store electrical energy and supply power to the electrical components of devices such as hydrogen production device 1, acid circulation device 3 and control device 5, and can also store electrical energy generated by solar power generation module.

[0064] Furthermore, the battery 22 can be composed of 16 lithium iron phosphate cells connected in series, with nickel strips connecting the cells. Simultaneously, the battery pack is equipped with a lithium titanate module for high-frequency charging and discharging scenarios. The battery pack is connected to other components in this invention via power lines and communication lines. The power lines are XLPO insulated copper cables, and the communication lines are twisted-pair shielded cables, physically isolated from the fluid conduit 12.

[0065] Furthermore, the battery 22 may include four battery compartments, each containing four lithium iron phosphate cells, covered with a flame-retardant ABS shell, and equipped with a built-in temperature sensor to monitor the battery temperature in real time and avoid the risk of overheating.

[0066] Furthermore, the battery 22 of the renewable energy power supply device 2 supplies power to the first electrode 311 (anode) of the acid recovery tank 31 and the second electrode 321 (cathode) of the sedimentation tank 32. At the same time, the renewable energy power supply device 2 supports pulse power supply to reduce electrode polarization loss and improve acid regeneration efficiency.

[0067] Specifically, refer to Figure 1 and Figure 2 The control device 5 is electrically connected to the renewable energy power supply device 2. The control device 5 can control the operation of the hydrogen production device 1, the acid circulation device 3 and the renewable energy power supply device 2, and realize intelligent regulation of the hydrogen supply process.

[0068] Furthermore, the control device 5 controls the acid flow rate via a three-way regulating valve and measures the temperature of the hydrogen production pipeline 11. Combined with data from the pressure and flow sensors on the gas pipeline 13, it controls the reaction temperature and hydrogen supply rate. The control device 5 monitors the battery 22's charge level to ensure it matches the power requirements of the internal components and does not affect the stability of the external hydrogen supply. The control device 5 monitors the hydrogen supply pressure, flow rate, and purity of the external hydrogen supply interface in real time. When the hydrogen supply pressure is lower than the set value, the control device 5 increases the acid supply flow rate or opens the additional reaction pipe 111 to increase hydrogen production. When the hydrogen purity is substandard, it activates the exhaust valve to discharge the substandard hydrogen and adjusts the reaction parameters until the hydrogen purity meets the requirements.

[0069] In summary, the acid-circulating hydrogen supply equipment of the present invention can achieve acid regeneration and zero waste discharge through the acid circulation device 3, thereby reducing the cost of hydrogen supply; through on-site hydrogen production and immediate supply, it eliminates the limitations of high-pressure hydrogen cylinders and improves the safety and flexibility of hydrogen supply; through the renewable energy power supply device 2, it realizes internal energy circulation, enhancing the independence and adaptability of the equipment; and through the design of multiple hydrogen production pipeline groups and intelligent control, it ensures the continuity and stability of hydrogen supply, making it suitable for various hydrogen supply scenarios.

[0070] In a second aspect of the invention, a hydrogen supply method according to the acid-recirculating hydrogen supply device described above is also provided, comprising the following steps: S0. Start the equipment through the control device 5 and control the hydrogen production device 1, renewable energy power supply device 2 and acid circulation device 3 to perform self-tests, including the sealing of the hydrogen production pipe group 11, the unobstructedness of the gas pipeline 13, the safety of the external hydrogen supply interface, the conductivity of the electrodes, the power of the storage battery 22, etc. After the self-test is completed, the control device 5 unlocks and opens the reaction tube cover 112 through the driver. S1. Add hydrogen storage material column to the reaction tube 111 of the hydrogen production tube group 11 (the reaction tube 111 can be filled with the column at one time, and the reaction can be started by controlling the acid injection method; or the column can be added to only some reaction tubes 111 according to the amount of hydrogen used), and close and lock the reaction tube cap 112; S2. Control device 5 sends acid to the reaction tube 111 to be started through valve group and circulation pump. The acid reacts with hydrogen storage material to release hydrogen. S3. The hydrogen supply pipeline transports the generated hydrogen to the external hydrogen supply interface to supply hydrogen to the outside; the control device 5 supplies hydrogen to the outside as needed through the regulation of the pressure regulating valve, check valve and exhaust valve and other valve groups on the gas pipeline 13; wherein, the control device 5 realizes intermittent or continuous hydrogen supply to the outside by adjusting the working status of the hydrogen device 1, acid liquid circulation device 3 and renewable energy power supply device 2. S4. After the reaction is complete, the control device 5 supplies the waste liquid in the reaction chamber to the acid recovery tank 31 through the valve group and the circulation pump; the control device 5 sends the water in the water tank 34 to the sedimentation tank 32 through the valve group and the circulation pump; the control device 5 controls the renewable energy power supply device 2 to energize the first electrode 311 and the second electrode 321, and the cation exchange membrane 33 allows cation filtration and exchange in the acid recovery tank 31 and the sedimentation tank 32, restoring the waste liquid in the acid recovery tank 31 to the acid liquid used for the hydrogen production reaction; the control device 5 sends the acid liquid restored by the acid recovery tank 31 to the reaction chamber through the valve group and the circulation pump, realizing the recycling of acid liquid and maintaining a continuous hydrogen supply.

[0071] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention. Clearly, those skilled in the art can make various alterations and modifications to the invention without departing from its spirit and scope. Thus, if these modifications and modifications of the invention fall within the scope of the claims and their equivalents, the invention is also intended to include these modifications and modifications.

Claims

1. A renewable energy-based acid-liquid recycling hydrogen supply device, characterized in that, It includes a hydrogen production unit (1), a renewable energy power supply unit (2), an acid circulation unit (3), and a control unit (5), wherein: The hydrogen production device (1) has a reaction chamber for reacting hydrogen storage material and acid to generate hydrogen gas, so as to supply hydrogen to the outside; An acid circulation device (3) is connected to the reaction chamber to restore the waste liquid generated by the hydrogen production device (1) to the acid liquid used for the hydrogen production reaction and to supply the acid liquid to the hydrogen production device (1). A renewable energy power supply device (2) is connected to the hydrogen production device (1), the acid circulation device (3) and the control device (5), and supplies power to at least one of the hydrogen production device (1), the acid circulation device (3) and the control device (5); The control device (5) is connected to the hydrogen production device (1), the acid circulation device (3) and the renewable energy power supply device (2), and controls the operation of the hydrogen production device (1), the acid circulation device (3) and the renewable energy power supply device (2).

2. The renewable energy-based acid-liquid circulation hydrogen supply equipment according to claim 1, characterized in that, The hydrogen production device (1) includes: The hydrogen production tube assembly (11) includes a reaction tube (111) with an opening and a reaction tube cap (112) capable of sealing the opening of the reaction tube (111) to form the reaction chamber; The reaction tube cover (112) has a gas outlet connected to a hydrogen supply pipe, which is connected to an external hydrogen supply interface to deliver the hydrogen generated in the reaction chamber to the external hydrogen supply interface. The bottom of the reaction tube (111) has a liquid inlet and outlet to supply acid to the reaction chamber and discharge waste liquid from the reaction chamber.

3. The renewable energy-based acid-liquid circulation hydrogen supply equipment according to claim 2, characterized in that, There are multiple hydrogen production tube groups (11), and the multiple hydrogen production tube groups (11) are arranged in parallel; Each hydrogen production tube assembly (11) includes multiple reaction tubes (111) and multiple reaction tube caps (112), which are connected in series.

4. The renewable energy-based acid-liquid circulation hydrogen supply equipment according to claim 2, characterized in that, The reaction tube (111) is provided with a reaction tube plug (113), and the reaction tube plug (113) has several through holes, which allow gas to pass through and prevent solids and liquids from passing through.

5. The renewable energy-based acid-liquid circulation hydrogen supply device according to any one of claims 2-4, characterized in that, The acid circulation device (3) includes an acid recovery tank (31), a sedimentation tank (32), and a cation exchange membrane (33) disposed between the acid recovery tank (31) and the sedimentation tank (32) and separating the two, wherein: The acid recovery tank (31) is connected to the hydrogen production tube group (11) to realize the collection of waste liquid and the return of acid liquid, and it has a first electrode (311). A sedimentation tank (32) having a second electrode (321); The renewable energy power supply device (2) is electrically connected to the first electrode (311) and the second electrode (321) to power the acid circulation device (3). The cation exchange membrane (33) allows cation filtration and exchange between the acid recovery tank (31) and the sedimentation tank (32) to restore the waste liquid of the acid recovery tank (31) to the acid liquid used for hydrogen production reaction.

6. The renewable energy-based acid-liquid circulation hydrogen supply device according to claim 5, characterized in that, The hydrogen storage material includes at least one of magnesium, magnesium hydride and magnesium alloy, and optionally, the hydrogen storage material is prefabricated into a propellant column (10) that can be inserted into the reaction chamber. The acid solution includes at least one of citric acid, oxalic acid, acetic acid, phosphoric acid, and dilute sulfuric acid.

7. The renewable energy-based acid-liquid circulation hydrogen supply device according to claim 6, characterized in that, The renewable energy power supply device (2) includes a solar power generation module, which includes a photovoltaic module (21), a battery (22) and a controller.

8. A method for supplying hydrogen via acid recycling based on renewable energy, characterized in that, The acid-liquid recycling hydrogen supply device based on renewable energy, as described in any one of claims 1-7, comprises the following steps: Add hydrogen storage material to the reaction chamber; The acid solution is sent to the reaction chamber, where it reacts with the hydrogen storage material to release hydrogen gas. The generated hydrogen is transported to an external hydrogen supply interface via a hydrogen supply pipeline to supply hydrogen to the outside. After the reaction is complete, the waste liquid in the reaction chamber is sent to the acid circulation device (3) to be restored to the acid liquid used for the hydrogen production reaction and circulated to the hydrogen production device (1). The renewable energy power supply unit (2) supplies power to the hydrogen production unit (1), the acid circulation unit (3) and the control unit (5) to maintain the continuous operation of the equipment.

9. The hydrogen supply method according to claim 8, characterized in that, The acid recycling device (3) restores the waste liquid to acid for hydrogen production reaction, including the following steps: The waste liquid in the reaction chamber flows into the acid recovery tank (31); The first electrode (311) of the acid recovery tank (31) and the second electrode (321) of the sedimentation tank (32) are energized. The cation exchange membrane (33) set between the acid recovery tank (31) and the sedimentation tank (32) and isolates them allows cation filtration and exchange in the acid recovery tank (31) and the sedimentation tank (32), and restores the waste liquid in the acid recovery tank (31) to the acid liquid used for the hydrogen production reaction. The acid solution restored in the acid recovery tank is sent to the reaction chamber.

10. The hydrogen supply method according to claim 9, characterized in that, The hydrogen supply method further includes: The renewable energy power supply device (2) uses a solar power generation module to convert solar energy into electrical energy, which is then transmitted to the battery (22) of the renewable energy power supply device (2) for storage or directly to power the hydrogen production device (1), the acid circulation device (3), and the control device (5). The control device (5) controls the working status of the hydrogen device (1), the acid circulation device (3) and the renewable energy power supply device (2) to realize at least one of the following operations: intermittent or continuous hydrogen supply to the outside, replenishing hydrogen storage materials according to hydrogen production parameters, adjusting the acid supply rate, discharging hydrogen with substandard purity and adjusting reaction parameters.

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