Solid-state hydrogen storage and pressurization systems and methods for hydrogen pressurization

Abstract

This invention relates to the field of hydrogen storage, and discloses a solid hydrogen storage and pressurization system and a method for hydrogen pressurization. The system includes n-stage pressure hydrogen storage units connected in series, where the hydrogen release equilibrium pressure of an earlier stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of a subsequent stage pressure hydrogen storage unit, used to achieve hydrogen transfer and pressurization. Each pressure hydrogen storage unit includes a hydrogen storage alloy reactor, which comprises a vertically arranged inner tank and an outer tank fitted outside the inner tank. Along the vertical direction of the inner tank, multiple inner tank baffles are horizontally arranged inside the inner tank; along the vertical direction of the outer tank, multiple outer tank baffles are horizontally arranged inside the outer tank. The inner tank baffles have openings for hydrogen flow; the outer tank baffles are in the shape of a notched annulus, allowing the flow of heat-conducting fluid inside the outer tank through the notched corner of the annulus. This system regulates hydrogen pressure while increasing the hydrogen transfer rate.

Description

Technical Field

[0001] This invention relates to the field of hydrogen storage, and more specifically to a solid hydrogen storage and pressurization system and a method for pressurizing hydrogen. Background Technology

[0002] With the world's ever-increasing energy demand, coupled with severe CO2 emissions and worsening environmental pollution, people are paying more and more attention to developing clean and renewable energy. Hydrogen energy, as a secondary energy source, has the characteristics of wide availability, cleanliness and carbon-free operation, flexibility and efficiency, and broad application scenarios. It can be widely used in energy, transportation, industry, construction, and other fields. It is an ideal interconnecting medium for promoting the clean and efficient utilization of traditional fossil fuels and supporting the large-scale development of renewable energy, and will gradually become an important direction in the global energy technology revolution.

[0003] Electrolysis of water is a novel method for hydrogen production, producing hydrogen with near-zero carbon emissions and high purity, making it a highly competitive technology. However, the hydrogen produced by this technology has a relatively low pressure, which may not meet the pressure requirements of some hydrogen-using terminals. Furthermore, different hydrogen-using terminals often have different pressure requirements. Therefore, developing adjustable pressure boosting technology is crucial for the effective use of hydrogen.

[0004] Hydrogen storage alloy materials are considered an excellent hydrogen compression technology, offering advantages such as high adjustable pressure, no pollution, and high safety, while reducing the cost of hydrogen compressors. Hydrogen storage alloy materials refer to a class of materials that store hydrogen in the form of metal hydrides. Hydrogen storage alloys offer advantages such as good reversibility of hydrogen absorption and desorption, high hydrogen storage density per unit volume, high hydrogen purity during desorption, and high safety. For hydrogen storage alloys, the hydrogen absorption and desorption pressure is related to the absorption and desorption temperature, and different materials exhibit significantly different hydrogen absorption and desorption properties. Therefore, by using appropriate hydrogen storage materials and controlling the absorption and desorption temperature, the hydrogen pressure can be controlled.

[0005] Furthermore, the hydrogen absorption process of hydrogen storage alloys releases heat, while the hydrogen release process is endothermic. The former occurs only when the supply pressure is greater than the equilibrium pressure, and the latter only occurs when the pressure is lower than the equilibrium pressure. During hydrogen absorption, the released heat needs to be removed from the reaction system in a timely manner to maintain the temperature at a favorable level. This helps to increase the hydrogen absorption rate and thus the hydrogen storage capacity. When hydrogen needs to be released, the endothermic reaction of the desorption process means that external heat needs to be provided to maintain a suitable hydrogen release rate. This means that hydrogen storage alloys require additional energy supply during both hydrogen absorption and release. At the same time, the poor heat transfer performance of existing solid-state hydrogen storage reactors leads to poor control of the hydrogen absorption and release rates and low reversible hydrogen storage density. Therefore, improving the system's heat transfer efficiency is crucial for improving energy utilization efficiency and establishing a high-performance solid-state hydrogen storage and compression system. Simultaneously, adopting appropriate energy management strategies to effectively utilize the energy during hydrogen absorption and release is essential for reducing system energy consumption. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems existing in the prior art and provide a solid hydrogen storage and pressurization system and a method for hydrogen pressurization. This system can improve the hydrogen transmission rate based on multi-stage adjustment of hydrogen pressure and has the advantage of high safety.

[0007] To achieve the above objectives, the first aspect of the present invention provides a solid hydrogen storage pressurization system, wherein the system comprises n-stage pressure hydrogen storage units connected in series, wherein the hydrogen release equilibrium pressure of the preceding stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the following stage pressure hydrogen storage unit, for realizing hydrogen transmission and pressurization, wherein n≥2, and n is a positive integer;

[0008] The pressure hydrogen storage unit includes a hydrogen storage alloy reactor, which comprises a vertically arranged inner tank and an outer tank fitted over the inner tank. Along the vertical direction of the inner tank, multiple inner tank baffles are horizontally arranged inside the inner tank. Along the vertical direction of the outer tank, multiple outer tank baffles are horizontally arranged inside the outer tank. The inner tank baffles have openings for hydrogen gas flow. The outer tank baffles are in the shape of a notched annular ring, and are used for the flow of heat-conducting fluid inside the outer tank, which flows through the notched corner of the annular ring.

[0009] A second aspect of the present invention provides a method for hydrogen storage and pressurization, wherein the method is performed in the system described in the first aspect, the method comprising:

[0010] Hydrogen gas is introduced into the first-stage pressure hydrogen storage unit to carry out a hydrogen absorption reaction. After the adsorption is saturated, a hydrogen release reaction is carried out, and the hydrogen gas released by the first-stage pressure hydrogen storage unit is absorbed in the subsequent-stage pressure hydrogen storage unit.

[0011] After the hydrogen release reaction of the first-stage pressure hydrogen storage unit is completed, the hydrogen absorption reaction is carried out again to realize the alternating hydrogen absorption / release of n-stage pressure hydrogen storage units, and to complete the step-by-step pressurization and transmission of hydrogen. The hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the next-stage pressure hydrogen storage unit.

[0012] The system provided by this invention, while achieving hydrogen pressurization, increases the heat exchange area, improves heat exchange efficiency and hydrogen transfer rate, and has the advantages of high safety, making it more suitable for industrial production. Through n-stage series-connected pressurization and hydrogen storage units, it is possible to maximize the utilization of the supply pressure of each stage to achieve maximum pressurization, realizing multi-stage pressure output over a wide range.

[0013] The system provided by this invention uses a dual-tank hydrogen storage alloy reactor (inner and outer tanks) as the pressure hydrogen storage unit for hydrogen absorption / desorption. Openings are formed in the inner tank's baffles to create gas flow channels, ensuring sufficient contact between hydrogen and the solid hydrogen storage composite material during storage. This ensures that each portion of the solid hydrogen storage material can absorb hydrogen, thereby improving hydrogen absorption efficiency. Simultaneously, multiple outer tank baffles are installed within the outer tank, creating liquid flow channels and increasing the heat exchange area, thus improving heat exchange efficiency.

[0014] In a preferred embodiment, the system provided by the present invention can easily change the hydrogen absorption / desorption process of each pressure hydrogen storage unit, using the heat released by the hydrogen absorption reaction as the heat required for the hydrogen desorption reaction, thereby achieving efficient energy utilization. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the system of the present invention;

[0016] Figure 2 This is a schematic diagram of the hydrogen storage alloy reactor of the present invention;

[0017] Figure 3 This is a schematic diagram of the hydrogen pipeline of the present invention;

[0018] Figure 4 This is a schematic diagram of the inner tank partition structure of the hydrogen storage alloy reactor of the present invention;

[0019] Figure 5 This is a schematic diagram of the outer tank partition structure of the hydrogen storage alloy reactor of the present invention;

[0020] Figure 6 This is the curve showing the change of hydrogen ratio over time in the pressure hydrogen storage unit of Embodiment 1 of the present invention;

[0021] Figure 7 This is the curve showing the change of hydrogen ratio over time in the pressure hydrogen storage unit of Embodiment 2 of the present invention;

[0022] Figure 8 This is the curve showing the change of hydrogen ratio over time in the pressure hydrogen storage unit of Embodiment 3 of the present invention;

[0023] Figure 9 This is the curve showing the change in hydrogen ratio over time in the pressure hydrogen storage unit of Comparative Example 1 of this invention.

[0024] Explanation of reference numerals in the attached figures

[0025] 1. First hydrogenation filter; 2. Hydrogen storage alloy reactor

[0026] 2-1 Inner tank 2-2 Outer tank

[0027] 2-3. Second hydrogenation filter; 2-4. Inner tank baffle.

[0028] 2-5. External tank partition; 2-6. Solid hydrogen storage composite material

[0029] 2-7, Opening 3-1, Reactor Hydrogen Piping

[0030] 3-2. Hydrogen filling pipeline; 3-3. Hydrogen discharging pipeline

[0031] 3-4. Three-way solenoid valve; 3-5. Check valve

[0032] 3-6, Pressure sensor 3-Inlet pipe

[0033] 4. Liquid outlet pipeline; 5. First four-way solenoid valve

[0034] 6. Second four-way solenoid valve; 7. Cryogenic storage tank

[0035] 8. High-temperature liquid storage tank; 9. Heat exchanger Detailed Implementation

[0036] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0037] The first aspect of the present invention provides a solid hydrogen storage and pressurization system, wherein the system includes n-stage pressure hydrogen storage units connected in series, wherein the hydrogen release equilibrium pressure of the preceding stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the following stage pressure hydrogen storage unit, for realizing hydrogen transmission and pressurization, wherein n≥2, and n is a positive integer;

[0038] The pressure hydrogen storage unit includes a hydrogen storage alloy reactor 2, which comprises a vertically arranged inner tank 2-1 and an outer tank 2-2 sleeved outside the inner tank 2-1. Along the vertical direction of the inner tank 2-1, multiple inner tank baffles 2-4 are horizontally arranged inside the inner tank 2-1. Along the vertical direction of the outer tank 2-2, multiple outer tank baffles 2-5 are horizontally arranged inside the outer tank 2-2. The inner tank baffles 2-4 have openings 2-7 for hydrogen flow. The outer tank baffles 2-5 are in the shape of a notched annular ring, and are used for the flow of heat-conducting fluid inside the outer tank 2-2, with the heat-conducting fluid flowing through the notched corner of the annular ring.

[0039] The system provided by this invention, while achieving hydrogen pressurization, increases the heat exchange area, improves heat exchange efficiency and hydrogen transfer rate, and has the advantages of high safety, making it more suitable for industrial production. Through n-stage series-connected pressurization and hydrogen storage units, it is possible to maximize the utilization of the supply pressure of each stage to achieve maximum pressurization, realizing multi-stage pressure output over a wide range.

[0040] The system provided by this invention employs a dual-tank pressure hydrogen storage unit consisting of an inner tank and an outer tank for hydrogen absorption / desorption. Openings are formed in the inner tank's partitions to create gas flow channels, ensuring sufficient contact between hydrogen and the solid hydrogen storage composite material during storage. This guarantees that each portion of the solid hydrogen storage material can absorb hydrogen, thereby improving hydrogen absorption efficiency. Simultaneously, multiple outer tank partitions are installed within the outer tank, creating liquid flow channels and increasing the heat exchange area, thus improving heat exchange efficiency.

[0041] In this invention, there is no particular limitation on the number of pressure hydrogen storage units; those skilled in the art can select the appropriate number based on actual needs. Preferably, n is a positive integer, ranging from 2 to 6.

[0042] In this invention, there is no particular limitation on the height of the inner tank and the outer tank; those skilled in the art can select a suitable height according to the needs of hydrogen storage and transportation. Preferably, the height of the inner tank 2-1 and the outer tank 2-2 is independently 50-2000 mm, and more preferably 150-800 mm.

[0043] In this invention, there is no particular limitation on the inner diameter of the inner tank. Those skilled in the art can select a suitable inner diameter according to the requirements of hydrogen storage and operation, as long as the requirements for hydrogen storage, transportation, and pressurization can be met. Preferably, the inner diameter of the inner tank 2-1 is 5-80 mm, more preferably 10-40 mm.

[0044] In this invention, there is no particular limitation on the inner diameter of the outer tank. Those skilled in the art can select a suitable inner diameter according to the requirements of hydrogen storage and operation, as long as the requirements for hydrogen storage, transportation, and pressurization can be met. Preferably, the inner diameter of the outer tank 2-2 is 15-160 mm, more preferably 30-90 mm.

[0045] In this invention, preferably, the ratio of the inner diameter difference between the outer tank 2-2 and the inner tank 2-1 to the inner diameter of the inner tank 2-1 is 0.2-3:1, more preferably 0.35-2:1. This preferred embodiment reduces the volume of the outer tank while meeting the heat transfer requirements during hydrogen absorption and desorption, thus facilitating hydrogen transportation.

[0046] In this invention, openings are provided on the inner tank partition, and the openings on multiple inner tank partitions form a gas flow channel to facilitate the transmission of hydrogen. In this invention, there is no particular limitation on the number of openings, but preferably, the number of openings 2-7 is one.

[0047] In this invention, the size of the opening is not particularly limited; a suitable opening size can be selected according to the size of the inner tank partition, as long as hydrogen transmission can be achieved. Preferably, the ratio of the opening area of ​​the openings 2-7 to the area of ​​the inner tank partitions 2-4 is 0.01-0.2:1, more preferably 0.04-0.1:1. The advantage of this preferred embodiment is that it allows gas to flow along the openings of adjacent partitions, forming a flow direction, while also ensuring gas transmission efficiency.

[0048] In this invention, the size of the openings is not particularly limited. Preferably, the diameter of the openings 2-7 is 2-20 mm, more preferably 2-15 mm. The advantage of this preferred embodiment is that it allows gas to flow along the openings of adjacent partitions to form a flow direction, while also ensuring gas transmission efficiency.

[0049] In this invention, the location of the opening is not particularly limited; it can be located at the center of the disc or at a non-central location, preferably at a non-central location. Preferably, the ratio of the distance between the center of the inner tank partition 2-4 and the center of the opening 2-7 to the inner diameter of the inner tank 2-1 is 0.15-0.45:1, preferably 0.2-0.37:1. The advantage of this preferred embodiment is that it increases the contact time between the gas and the hydrogen storage material during the gas flow process through the openings of adjacent partitions.

[0050] In this invention, gas flow channels are formed by openings on multiple inner tank partitions. The invention offers a wide range of options for the relative positions of the openings on each inner tank partition, allowing for the formation of vertical, irregular, or regular flow channels, such as serpentine channels, with a preference for serpentine channels. Preferably, taking the opening 2-7 on the bottom inner tank partition 2-4 as a reference, multiple openings 2-7 are sequentially rotated 90-180° (preferably 120-180°) in the same direction along the axial direction of the inner tank 1 from bottom to top. The advantage of this preferred embodiment is that it forms a gas flow channel structure, allowing for sufficient contact between hydrogen and the hydrogen storage material, thus improving heat exchange efficiency.

[0051] In this invention, it is illustrated schematically that, in the initial state, the centers of the openings on the multiple inner tank partitions are aligned along the same axis. "Rotation in the same direction" means that the bottommost inner tank partition is the first inner tank partition, which remains stationary. The second inner tank partition rotates counterclockwise by 90-180° along the inner tank axis. After the second inner tank partition finishes rotating, it remains stationary, and the third inner tank partition continues to rotate counterclockwise by 90-180° along the inner tank axis, and so on. This results in the openings on each inner tank partition forming a gas flow channel structure, such as a serpentine flow channel. It should be noted that the above description is only illustrative of counterclockwise rotation; clockwise rotation is also acceptable, as long as the rotation direction of the multiple inner tank partitions remains consistent.

[0052] In this invention, the inner tank is equipped with multiple inner tank baffles. By controlling the spacing between the inner tank baffles, sufficient contact between hydrogen and the hydrogen storage material is achieved. Preferably, the ratio of the maximum spacing between adjacent inner tank baffles 2-4 to the height of the inner tank 2-1 is 0.05-0.5:1, more preferably 0.05-0.35:1. The advantage of this preferred embodiment is that it allows the gas to form a baffle within the inner tank, ensuring sufficient contact with the solid hydrogen storage material.

[0053] In this invention, the outer tank partition is a notched annular shape, and the arc range of the notched corners of the multiple outer tank partitions is relatively wide, as long as it allows for the flow of heat-conducting fluid. Preferably, the arc of the outer tank partitions 2-5 is 240-355°, more preferably 300-345°. The advantage of this preferred embodiment is that it allows the fluid to flow through the notch in the notched annular shape, controlling the fluid flow while also considering the fluid transport throughput.

[0054] In this invention, it can be understood that the "radian" of the missing corner ring refers to the angle between the two vertices of the inner arc surface of the missing corner ring and the center of the circle. The calculation formula is 360° / 2π*l / r, where l is the length of the inner arc surface of the missing corner ring and r is the inner radius of the missing corner ring.

[0055] In this invention, the outer tank partition is a notched annular shape. The notched annular arrangement of multiple outer tank partitions forms a flow channel for the heat-conducting fluid. This invention does not particularly limit the relative positions of the multiple notched annular rings, as long as they can form a vertical, irregular, or regular flow channel, such as a serpentine flow channel, preferably a serpentine flow channel. Using the notched annularity of the bottommost outer tank partition 2-5 as a reference, from bottom to top, multiple outer tank partitions 2-5 are sequentially rotated in the same direction by 90-180°, preferably 120-180°, along the axial direction of the outer tank 2-2. The advantage of this preferred embodiment is that it forms a liquid flow channel structure in the outer tank, which improves the heat exchange effect. It should be noted that the "rotation in the same direction" here is the same as the "rotation in the same direction" of the inner tank partitions mentioned above, and will not be repeated here.

[0056] In this invention, the selection range for the placement of multiple outer tank partitions is relatively wide, and those skilled in the art can choose according to actual needs. Preferably, the ratio of the maximum distance between adjacent outer tank partitions 2-5 to the height of the outer tank 2-2 is 0.05-0.5:1, more preferably 0.08-0.25:1. The advantage of this preferred embodiment is that it causes the liquid to form baffles in the outer tank, thereby improving heat exchange efficiency.

[0057] The present invention does not specifically limit the arrangement of the solid hydrogen storage composite material. Preferably, a solid hydrogen storage composite material 2-6 is placed between the adjacent inner tank partitions 2-4, and the solid hydrogen storage composite material 2-6 is used for hydrogen absorption / desorption, heat conduction, and controlling the hydrogen absorption / desorption balance pressure of the pressure hydrogen storage unit.

[0058] In this invention, a wide range of solid hydrogen storage composite materials can be selected, as long as they can achieve both hydrogen storage and thermal conductivity. Preferably, the solid hydrogen storage composite materials 2-6 include hydrogen storage alloys and / or thermally conductive materials. The advantage of this preferred embodiment is that the solid hydrogen storage composite material, composed of a mixture of hydrogen storage alloys and thermally conductive materials, can effectively improve the heat transfer coefficient of the hydrogen storage material bed while reducing stress changes caused by the expansion and contraction of the hydrogen storage material during hydrogen absorption / desorption.

[0059] In this invention, there is no particular limitation on the amount of each component in the solid hydrogen storage composite material, as long as it can meet the hydrogen storage requirements. Preferably, the mass ratio of the hydrogen storage alloy to the thermally conductive material is 1:0.02-0.1.

[0060] In this invention, the type of hydrogen storage alloy is not particularly limited, and any hydrogen storage alloy conventionally defined in the art can be used. Preferably, the hydrogen storage alloy is selected from at least one of titanium-based hydrogen storage alloys, zirconium-based hydrogen storage alloys, vanadium-based hydrogen storage alloys, and rare earth-based hydrogen storage alloys. This invention does not impose specific limitations on the specific types of each series of hydrogen storage alloys, and those skilled in the art can select them according to actual needs.

[0061] In this invention, there is no particular limitation on the type of thermally conductive material, which can be any thermally conductive material conventionally defined in the art. Preferably, the thermally conductive material is selected from at least one of expanded graphite, thermally conductive fiber, graphite sheet, carbon nanotube, aluminum powder, copper powder, titanium powder, aluminum foam, nickel foam, and copper foam.

[0062] In this invention, the type of heat-conducting fluid is not particularly limited, and it can be any heat-conducting fluid conventionally defined in the art. Preferably, the heat-conducting fluid is selected from at least one of water, ethylene glycol, and heat-conducting oil.

[0063] In this invention, a wide range of materials can be selected for the tank body and partitions. Preferably, the materials of the inner tank body 2-1, outer tank body 2-2, inner tank partition 2-4, and outer tank partition 2-5 are each independently selected from at least one of aluminum, aluminum alloy, copper, copper alloy, carbon steel, and stainless steel. The advantage of this preferred embodiment is that parameters such as tank weight, cost, and thermal conductivity can be adjusted according to the application scenario.

[0064] In this invention, preferably, a gas pipe is provided at the top of the inner tank 2-1, and the gas pipe is used to introduce hydrogen into the inner tank 2-1 or release hydrogen from the inner tank 2-1.

[0065] In this invention, preferably, the inner diameter of the trachea is 3-10 mm.

[0066] In this invention, preferably, a second hydrogenation filter 2-3 is provided inside the gas pipe. The second hydrogenation filter 2-3 is a copper-based and / or stainless steel-based porous sintered body, preferably a copper-based and / or stainless steel-based porous sintered body formed by powder metallurgy. In this invention, the arrangement of the second hydrogenation filter is not particularly limited, as long as hydrogen filtration is achieved. For example, it can be located at the gas inlet or the gas outlet of the gas pipe, and those skilled in the art can adjust it according to actual needs.

[0067] In this invention, preferably, the accuracy of the second hydrogenation filter 2-3 is <0.5μm.

[0068] In this invention, the hydrogen absorption / desorption equilibrium pressure is controlled by adjusting the type of solid composite hydrogen storage material or the temperature in each pressure hydrogen storage unit. Preferably, each pressure hydrogen storage unit performs the hydrogen absorption reaction at -10 to 20°C and the hydrogen desorption reaction at 60 to 150°C.

[0069] In this invention, hydrogen is pressurized in stages by controlling the hydrogen absorption / desorption equilibrium pressure to obtain high-pressure hydrogen. Preferably, the hydrogen desorption equilibrium pressure of the first-stage pressure hydrogen storage unit is 0.5-10 MPa higher than the hydrogen absorption equilibrium pressure of the next-stage pressure hydrogen storage unit. For example, it can be 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa, 6.5 MPa, 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa, 9 MPa, 9.5 MPa, 10 MPa, or any value between any two points.

[0070] In this invention, preferably, the n-stage series-connected pressure hydrogen storage units are connected by a hydrogen pipeline. The hydrogen pipeline is used to introduce an external hydrogen source into the preceding pressure hydrogen storage unit or to introduce pressurized hydrogen released from the preceding pressure hydrogen storage unit into the subsequent pressure hydrogen storage unit, thereby realizing hydrogen transmission.

[0071] In this invention, a three-way solenoid valve 3-4 is installed on the hydrogen pipeline, and the three-way solenoid valve 3-4 is used to control the transmission of hydrogen.

[0072] In this invention, such as Figure 1 , Figure 2 and Figure 3 As shown, preferably, the hydrogen pipeline includes a reactor hydrogen pipeline 3-1, a hydrogen filling pipeline 3-2, a hydrogen discharging pipeline 3-3, and a three-way solenoid valve 3-4. The reactor hydrogen pipeline 3-1, the hydrogen filling pipeline 3-2, and the hydrogen discharging pipeline 3-3 are interconnected through the three-way solenoid valve 3-4. Hydrogen is transferred by controlling the opening and closing of the outlet of the three-way solenoid valve 3-4.

[0073] In this invention, such as Figure 1 , Figure 2 and Figure 3 As shown, preferably, the reactor hydrogen pipeline 3-1 is used to introduce and / or release hydrogen into the inner tank 2-1 of the preceding stage pressure hydrogen storage unit; the hydrogen filling pipeline 3-2 is used to introduce an external hydrogen source into the preceding stage pressure hydrogen storage unit or to introduce pressurized hydrogen released from the preceding stage pressure hydrogen storage unit into the subsequent stage pressure hydrogen storage unit; and the hydrogen discharging pipeline 3-3 is used to introduce hydrogen released after pressurization in the preceding stage pressure hydrogen storage unit into the subsequent stage pressure hydrogen storage unit and / or supply it to the user unit. To illustrate, when the primary pressure hydrogen storage unit is undergoing a hydrogen absorption reaction, the outlet of the three-way solenoid valve 3-4, which is connected to the hydrogen release pipeline 3-3, is closed, and the outlet of the three-way solenoid valve 3-4, which is connected to the reactor hydrogen pipeline 3-1 and the hydrogen filling pipeline 3-2, is opened. External hydrogen enters the inner tank 2-1 of the hydrogen storage alloy reactor in the primary pressure hydrogen storage unit through the hydrogen filling pipeline 3-2 and the reactor hydrogen pipeline 3-1 for hydrogen absorption. After hydrogen absorption saturation, the outlet of the three-way solenoid valve 3-4, which is connected to the hydrogen release pipeline 3-3, is opened for hydrogen release. The pressurized hydrogen is released to the secondary pressure hydrogen storage unit through the reactor hydrogen pipeline 3-1 and the hydrogen release pipeline 3-3 for hydrogen absorption / release. This process continues until the final pressure hydrogen storage unit is saturated with hydrogen. Then, the one-way valve 3-5 on the hydrogen release pipeline 3-2 in the final pressure hydrogen storage unit is opened to release the pressurized hydrogen, thus achieving step-by-step pressurization and transmission of hydrogen.

[0074] In this invention, preferably, a pressure sensor 3-6 is installed on the hydrogen pipeline 3-1 of the reactor to monitor the pressure of the hydrogen storage alloy reactor 2. The location of the pressure sensor is not particularly limited in this invention; for example, it can be installed near the hydrogen storage alloy reactor 2 or near the three-way solenoid valve 3-4, but preferably near the hydrogen storage alloy reactor 2.

[0075] In this invention, preferably, a first hydrogenation filter 1 is provided on the hydrogenation pipeline 3-2 for filtering impurity particles in the hydrogen gas. The location of the hydrogenation filter is not particularly limited in this invention. The precision of the first hydrogenation filter is not particularly limited in this invention; for example, it can be the same as or different from the second hydrogenation filter, but preferably the same.

[0076] In this invention, a heat-conducting fluid is provided through a liquid circulation pipeline to absorb the heat released by the hydrogen absorption reaction or to provide the heat required for the hydrogen release reaction. Preferably, the system further includes a liquid circulation pipeline and a four-way solenoid valve installed on the liquid circulation pipeline. The liquid circulation pipeline is used to introduce the heat-conducting fluid into the solid hydrogen storage alloy reactor, and the four-way solenoid valve is used to control the flow of the heat-conducting fluid to realize the absorption / release of hydrogen in the intermittent pressure hydrogen storage units.

[0077] In this invention, a heat-conducting fluid is stored in a heat source, and heat is provided for hydrogen absorption / desorption through temperature control. Preferably, the system further includes a cryogenic storage tank 7 and a high-temperature storage tank 8. The cryogenic storage tank 8 is used to absorb the heat released by the hydrogen absorption reaction, and the high-temperature storage tank 8 is used to provide the heat absorbed by the hydrogen desorption reaction. This invention does not particularly limit the types of cryogenic and high-temperature storage tanks; for example, both can be storage tanks. This invention also does not particularly limit the types of heat-conducting fluids stored in the cryogenic and high-temperature storage tanks 7 and 8; they can be the same or different, but the same is preferred. This invention offers a wide range of temperature selection for the heat-conducting fluids stored in the cryogenic and high-temperature storage tanks 7 and 8, as long as the temperature of the heat-conducting fluid stored in the high-temperature storage tank 8 is higher than that of the heat-conducting fluid stored in the cryogenic storage tank 7. Those skilled in the art can select the appropriate temperature based on actual conditions.

[0078] In this invention, such as Figure 1As shown, preferably, the liquid circulation pipeline includes an inlet pipeline 3 and a first four-way solenoid valve 5 installed on the inlet pipeline 3, an outlet pipeline 4 and a second four-way solenoid valve 6 installed on the outlet pipeline 4. The first four-way solenoid valve 5 and the second four-way solenoid valve 6 are used to control the flow of the heat transfer fluid. To illustrate, when the pressure hydrogen storage unit is performing a hydrogen absorption reaction, the outlet of the first four-way solenoid valve 5 connected to the inlet pipeline 3 is opened, and the heat transfer fluid in the cryogenic storage tank 7 enters the outer tank 2-2 of the solid hydrogen storage alloy reactor 2 of the pressure hydrogen storage unit via the inlet pipeline 3 to absorb the heat released by the hydrogen absorption reaction. Then, the outlet of the first four-way solenoid valve 5 connected to the inlet pipeline 3 is closed, and the outlet of the second four-way solenoid valve 6 connected to the outlet pipeline 4 is opened, and the heat transfer fluid returns to the cryogenic storage tank 7 via the outlet pipeline 4. When the pressure hydrogen storage unit is performing a hydrogen absorption reaction, the outlet of the first four-way solenoid valve 5 connected to the inlet pipeline 3 is closed, and the outlet of the second four-way solenoid valve 6 connected to the outlet pipeline 4 is opened, and the heat transfer fluid returns to the cryogenic storage tank 7 via the outlet pipeline 4. During the hydrogen release reaction, the outlet of the second four-way solenoid valve 6 connected to the liquid outlet pipe 4 is closed, and the outlet of the first four-way solenoid valve 5 connected to the liquid inlet pipe 3 is opened again. The heat-conducting fluid in the high-temperature storage tank 8 enters the outer tank 2-2 of the solid hydrogen storage alloy reactor 2 of the interval pressure hydrogen storage unit through the liquid inlet pipe 3 to provide the heat required for the hydrogen release reaction. The pressurized hydrogen released by the hydrogen release reaction in the first-stage pressure hydrogen storage unit enters the hydrogen absorption reaction in the next-stage pressure hydrogen storage unit. The above steps are repeated to carry out the hydrogen absorption / release reaction, so as to realize the continuous pressurization and transmission of hydrogen.

[0079] In this invention, heat is transferred between the cryogenic storage tank and the high-temperature storage tank to improve heat utilization and save energy. Preferably, the cryogenic storage tank 7 and the high-temperature storage tank 8 are connected by a heat exchanger 9, which transfers heat from the cryogenic storage tank 7 to the high-temperature storage tank 8, thus achieving heat exchange between the pressure hydrogen storage units. This invention does not particularly limit the specific type of heat exchanger 9; for example, it can be a heat pump.

[0080] A second aspect of the present invention provides a method for hydrogen storage and pressurization, wherein the method is performed in the system described in the first aspect, the method comprising:

[0081] Hydrogen gas is introduced into the first-stage pressure hydrogen storage unit to carry out a hydrogen absorption reaction. After the adsorption is saturated, a hydrogen release reaction is carried out, and the hydrogen gas released by the first-stage pressure hydrogen storage unit is absorbed in the subsequent-stage pressure hydrogen storage unit.

[0082] After the hydrogen release reaction of the first-stage pressure hydrogen storage unit is completed, the hydrogen absorption reaction is carried out again to realize the alternating hydrogen absorption / release of n-stage pressure hydrogen storage units, and to complete the step-by-step pressurization and transmission of hydrogen. The hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the next-stage pressure hydrogen storage unit.

[0083] In this invention, to achieve the step-by-step pressurization and transport of hydrogen, preferably, the hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is 0.5-10 MPa higher than the hydrogen absorption equilibrium pressure of the next-stage pressure hydrogen storage unit. For example, this can be 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa, 6.5 MPa, 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa, 9 MPa, 9.5 MPa, 10 MPa, or any value between any two points.

[0084] According to a specific embodiment of the present invention, taking an even-numbered (e.g., four-stage) series-connected pressure hydrogen storage unit as an example, the method for hydrogen storage and pressurization includes:

[0085] (1) Hydrogen is introduced into the primary pressure hydrogen storage unit from an external hydrogen source, and the hydrogen absorbs hydrogen in the primary pressure hydrogen storage unit.

[0086] (2) After the primary pressure hydrogen storage unit is saturated with adsorption, a hydrogen release reaction is carried out, and the hydrogen released from the primary pressure hydrogen storage unit enters the secondary pressure hydrogen storage unit for a hydrogen absorption reaction.

[0087] (3) After the secondary pressure hydrogen storage unit is saturated with adsorption, a hydrogen release reaction is carried out. The hydrogen released by the secondary pressure hydrogen storage unit enters the tertiary pressure hydrogen storage unit for a hydrogen absorption reaction, and the primary pressure hydrogen storage unit carries out a hydrogen absorption reaction.

[0088] (4) After the first-stage and third-stage pressure hydrogen storage units are saturated with adsorption, hydrogen release reaction is carried out respectively. The hydrogen released by the first-stage pressure hydrogen storage unit enters the second-stage pressure hydrogen storage unit for hydrogen absorption reaction, and the hydrogen released by the third-stage pressure hydrogen storage unit enters the fourth-stage pressure hydrogen storage unit for hydrogen absorption reaction.

[0089] (5) After the secondary pressure hydrogen storage unit and the quaternary pressure hydrogen storage unit are saturated with adsorption, hydrogen release reaction is carried out.

[0090] During stable operation, steps (4) and (5) are repeated, with the pressure hydrogen storage units alternately absorbing and releasing hydrogen. When the hydrogen reaches the required pressure, the hydrogen from the last pressure hydrogen storage unit is released. During this operation, the cryogenic storage tank 7 is connected to the pressure hydrogen storage unit that performs the hydrogen absorption reaction through a liquid circulation pipeline to absorb the heat from the hydrogen absorption reaction. The high-temperature storage tank 8 is connected to the pressure hydrogen storage unit that performs the hydrogen release reaction through a liquid circulation pipeline to provide the heat required for the hydrogen release reaction. The heat exchanger 9 is turned on to transfer the heat generated by the hydrogen absorption reaction to the high-temperature storage tank 8 to provide some of the heat for the pressure hydrogen storage unit to perform hydrogen release and absorb heat, thereby achieving efficient energy utilization.

[0091] According to another specific embodiment of the present invention, taking an odd-numbered (e.g., three-stage) series-connected pressure hydrogen storage unit as an example, the method of hydrogen storage and pressurization includes:

[0092] (1) Hydrogen is introduced into the primary pressure hydrogen storage unit from an external hydrogen source, and the hydrogen absorbs hydrogen in the primary pressure hydrogen storage unit.

[0093] (2) After the primary pressure hydrogen storage unit is saturated with adsorption, a hydrogen release reaction is carried out, and the hydrogen released from the primary pressure hydrogen storage unit enters the secondary pressure hydrogen storage unit for a hydrogen absorption reaction.

[0094] (3) After the secondary pressure hydrogen storage unit is saturated with adsorption, a hydrogen release reaction is carried out. The hydrogen released by the secondary pressure hydrogen storage unit enters the tertiary pressure hydrogen storage unit for a hydrogen absorption reaction, and the primary pressure hydrogen storage unit carries out a hydrogen absorption reaction.

[0095] (4) After the primary pressure hydrogen storage unit and the tertiary pressure hydrogen storage unit are saturated with adsorption, hydrogen release reaction is carried out respectively.

[0096] During stable operation, steps (3) and (4) are repeated, with the pressure hydrogen storage unit absorbing / releasing hydrogen at intervals. When the hydrogen reaches the required pressure, the hydrogen heat source of the last stage pressure hydrogen storage unit is released in the same way as described above.

[0097] The method provided by this invention enables continuous, step-by-step pressurization and transmission of hydrogen. By switching between the pressure hydrogen storage unit and the heat source, the hydrogen absorption / desorption process of each pressure hydrogen storage unit can be easily changed. Furthermore, through heat exchange between the cryogenic and high-temperature storage tanks, efficient energy utilization is achieved. The method provided by this invention can pressurize hydrogen to any pressure and simultaneously release hydrogen at different pressures, offering advantages such as high adjustable pressure, high safety, and no pollution. Moreover, by selecting the aforementioned preferred hydrogen storage alloy reactor, the heat exchange efficiency and hydrogen transmission rate can be further improved, enhancing safety, while simultaneously achieving continuous, step-by-step pressurization and transmission of hydrogen.

[0098] The present invention will be described in detail below through embodiments. Unless otherwise specified, all raw materials used in the following embodiments are commercially available products.

[0099] Example 1

[0100] like Figure 1As shown, the solid hydrogen storage and pressurization system includes two stages of pressure hydrogen storage units connected in series. Each stage of pressure hydrogen storage unit includes a hydrogen storage alloy reactor 2. The hydrogen storage alloy reactor 2 includes a vertically arranged inner tank 2-1 and an outer tank 2-2 sleeved outside the inner tank 2-1, as well as a gas pipe connected to the inner tank 2-1 and equipped with a second hydrogenation filter (sintered stainless steel filter element) 2-3. The height of the inner tank 2-1 is 150 mm and the inner diameter is 30 mm. The height of the outer tank 2-2 is 150 mm and the inner diameter is 60 mm. The ratio of the difference in inner diameter between the outer tank 2-2 and the inner tank 2-1 to the inner diameter of the inner tank 2-1 is 1:1. The inner diameter of the gas pipe is 3 mm. Along the vertical direction of the inner tank 2-1, multiple inner tank partitions 2-4 are horizontally arranged inside the inner tank 2-1; along the vertical direction of the outer tank 2-2, multiple outer tank partitions 2-5 are horizontally arranged inside the outer tank 2-2; an opening 2-7 is provided on the inner tank partition 2-4 for the flow of hydrogen; the diameter of the opening 2-7 is 8mm, and the ratio of the opening area of ​​the opening 2-7 to the area of ​​the inner tank partition 2-4 is 0.07:1. Taking the adjacent lower inner tank partition 2-4 as a reference, the inner tank partition 2-5... -4 rotate 180° sequentially in the same direction along the axial direction of the inner tank 2-1; the ratio of the maximum distance between adjacent inner tank partitions 2-4 to the height of the inner tank 2-1 is 0.33:1. Multiple inner tank partitions 2-4 are arranged in parallel, and the openings 2-7 on the inner tank partitions form gas channels in which hydrogen flows; the outer tank partition 2-5 is a notched annular shape, which is used for the flow of heat-conducting fluid inside the outer tank 2-2. The heat-conducting fluid inside the outer tank 2-2 flows through the notched corner of the annular ring. The outer arc surface of the notched annular ring is detachably connected to the inner circumferential wall of the outer tank 2-2, and the inner arc surface of the notched annular ring is detachably connected to the outer circumferential wall of the inner tank 2-1. The arc of the notched annular ring is 300°; the ratio of the maximum distance between adjacent outer tank partitions 4 to the height of the outer tank 2 is 0.2:1. Multiple outer tank partitions 2-5 are arranged in parallel. Taking the adjacent lower outer tank partition 2-5 as a reference, the outer tank partitions 2-5 rotate 180° in the same direction along the axial direction of the outer tank 2-2. The top of the outer tank 2-2 is provided with a first guide port (not shown in the figure), and the bottom of the outer tank 2-2 is provided with a second guide port (not shown in the figure). The heat transfer fluid enters the liquid channel of the outer tank 2-2 through the first guide port and fills the interior of the outer tank 2-2. The heat transfer fluid is deionized water.

[0101] like Figure 2 As shown, the first-stage pressure hydrogen storage unit contains a solid hydrogen storage composite material 2-6 in tank 2-1, which is composed of a rare earth-based alloy (La). 0.7 Ce 0.3 Ni 4.1 Al 0.4 Co 0.4 Mn 0.1The material is composed of titanium-based alloy (Ti) and expanded graphite in a ratio of 1:0.05. The hydrogen absorption equilibrium pressure of this material is 0.7 MPa at 288 K and 3.1 MPa at 363 K. The second-stage pressure hydrogen storage unit contains a solid hydrogen storage composite material 2-6 in tank 2-1, which is composed of titanium-based alloy (Ti). 0.7 Zr 0.3 Mn 0.9 Cr 0.7 Fe 0.2 It is composed of 1 part hydrogen and expanded graphite in a ratio of 1:0.05. The hydrogen absorption equilibrium pressure of this material is 1.7 MPa at 288 K and 5.8 MPa at 363 K.

[0102] like Figure 1 , Figure 2 and Figure 3 As shown, during the hydrogen storage process, the outlet of the three-way solenoid valve 3-4 of the first-stage pressure hydrogen storage unit, which is connected to the hydrogen release pipeline 3-3 of the first-stage pressure hydrogen storage unit, is closed. The outlet of the three-way solenoid valve 3-4, which is connected to the reactor hydrogen pipeline 3-1 and the hydrogen filling pipeline 3-2 of the first-stage pressure hydrogen storage unit, is opened. External hydrogen gas is filtered by the first hydrogen filling filter 1 (with a filtration accuracy of 2μm) on the hydrogen filling pipeline 3-2 of the first-stage pressure hydrogen storage unit and then enters the hydrogen storage alloy reactor 2 of the first-stage pressure hydrogen storage unit through the hydrogen filling pipeline 3-2 and the reactor hydrogen pipeline 3-1. The inner tank 2-1 and the hydrogen pipeline 3-1 of the reactor are equipped with pressure sensors 3-6 to monitor the pressure of the hydrogen storage alloy reactor 2. At this time, the hydrogen inlet pressure is maintained at 1MPa and introduced into the inner tank 2-1 of the first-stage pressure hydrogen storage unit hydrogen storage alloy reactor 2. The hydrogen absorbs the solid hydrogen storage composite material 2-6 in the inner tank 2-1 at an initial temperature of 288K and pressure. Deionized water at 288K is introduced into the outer tank 2-2 at a flow rate of 1.2L / min to absorb the heat generated by the hydrogen absorption reaction.

[0103] After the inner tank 2-1 of the hydrogen storage alloy reactor 2 in the first-stage pressure hydrogen storage unit has finished absorbing hydrogen, the outlet of the three-way solenoid valve 3-4, which is connected to the hydrogen release pipeline 3-3 of the first-stage pressure hydrogen storage unit, is opened to start hydrogen release. The hydrogen outlet pressure is maintained at 2.5 MPa. The first four-way solenoid valve 5 and the second four-way solenoid valve 6 are adjusted to connect the outer tank 2-2 of the first-stage pressure hydrogen storage unit to the high-temperature liquid storage tank 8. Deionized water at a temperature of 363 K is introduced into the outer tank 2-2 at a flow rate of 1.2 L / min to provide heat generated by the hydrogen release reaction. At the same time, the pressurized hydrogen gas flows through the hydrogen pipeline of the reactor in the second-stage pressure hydrogen storage unit. Hydrogen is released from pipe 3-1 and pipe 3-3 to the second-stage pressure hydrogen storage unit to begin absorbing hydrogen. The first four-way solenoid valve 5 and the second four-way solenoid valve 6 are controlled to connect the outer tank 2-2 of the hydrogen storage alloy reactor 2 of the second-stage pressure hydrogen storage unit to the cryogenic storage tank 7. Deionized water at a temperature of 288K is introduced into the outer tank 2-2 of the hydrogen storage alloy reactor 2 of the second-stage pressure hydrogen storage unit at a flow rate of 1.2L / min to absorb the heat generated by the hydrogen absorption reaction. The heat is transferred from the cryogenic storage tank 7 to the high-temperature storage tank 8 through the heat exchanger (heat pump) 9, realizing the heat exchange between the first and second pressure hydrogen storage units.

[0104] After the inner tank 2-1 of the second-stage pressure hydrogen storage unit has finished absorbing hydrogen, hydrogen release begins. The hydrogen outlet pressure is maintained at 5 MPa. The first four-way solenoid valve 5 and the second four-way solenoid valve 6 are adjusted to connect the outer tank 2-2 of the hydrogen storage alloy reactor 2 of the second-stage pressure hydrogen storage unit to the high-temperature liquid storage tank 8. Deionized water at a temperature of 363 K is introduced into the outer tank 2-2 at a flow rate of 1.2 L / min to provide heat generated by the hydrogen release reaction. The entire process increases the pressure of the hydrogen at the inlet from 1 MPa to 5 MPa.

[0105] Numerical simulations of the reactor were performed using COMSOL software. Mass, energy, and momentum balance equations were constructed, as follows:

[0106] Material mass conservation equation:

[0107] The mass conservation equation for gases:

[0108] Where m is the mass change value, ε is the porosity of the hydrogen storage material in inner tank 2-1, and ρ s U is the density of the hydrogen storage material, t is the reaction time, and u is the value of the hydrogen storage material. g Let ρ be the velocity field of hydrogen gas. g This represents the gas density.

[0109] The velocity field of hydrogen gas was calculated using Darcy's law:

[0110] Where K is the permeability, μg P is the viscosity coefficient of hydrogen gas. g This is the pressure of hydrogen gas.

[0111] For the hydrogen absorption reaction process, the reaction rate equation is as follows:

[0112]

[0113] For the hydrogen exothermic reaction process, the reaction rate equation is as follows:

[0114]

[0115] Among them, C a and C d E represents the pre-exponential factor for hydrogen absorption and hydrogen release reactions, respectively. a and E d The activation energies R for hydrogen absorption and hydrogen release reactions are respectively. g Let P be the gas constant, T be the reaction temperature, and P be the gas constant. eq For the equilibrium pressure of a chemical reaction, ρ ss ρ is the density of the hydrogen storage material after complete hydrogen absorption, and ρ0 is the initial density of the hydrogen storage material.

[0116] The equilibrium pressure for a chemical reaction is given by the Van't Hoff equation:

[0117]

[0118] The energy balance equation for the hydrogen absorption and desorption reaction in inner tank 2-1 is as follows:

[0119]

[0120] Among them, M g denoted as , where is the molar mass of hydrogen gas.

[0121] The effective heat capacity of the hydrogen storage bed (hydrogen and solid hydrogen storage composite material) is: (ρC p ) e =ερ g C p,g +(1-ε)ρ s C p,s

[0122] The effective thermal conductivity of the hydrogen storage bed (hydrogen and solid hydrogen storage composite material) is: λ e =ελ g +(1-ε)λ s

[0123] Among them, C p,g and C p,s The heat capacities of hydrogen gas and solid hydrogen storage composite materials are λ, respectively. g and λs The thermal conductivity of hydrogen gas and solid hydrogen storage composite materials are respectively.

[0124] For heat-conducting fluids, the mass balance equation is:

[0125] Where, ρ f For the density of the thermally conductive fluid, u f This represents the velocity field of the heat-conducting fluid.

[0126] For thermally conductive fluids, the momentum balance equation is as follows:

[0127]

[0128] The heat transfer equation inside the heat-conducting fluid is as follows:

[0129]

[0130] in:

[0131] Among them, C p,f λ is the heat capacity of the thermally conductive fluid. f P is the effective thermal conductivity of the heat-conducting fluid. f This refers to the pressure of the heat-conducting fluid.

[0132] For the tank walls and baffles, the heat transfer equation is as follows:

[0133]

[0134] Where, (ρc) solid λ is the heat capacity of a solid (tank wall or baffle). solid It is the effective thermal conductivity of the solid (tank wall or partition).

[0135] The heat transfer equation between the inner tank, outer tank, and baffle is: q = h(T1 - T2)

[0136] Where q is the heat flux, h is the heat transfer coefficient between the two, and T1 and T2 refer to the temperatures of two adjacent phases with different temperatures (for example, when calculating the heat transfer between the inner tank and the baffle, T1 and T2 refer to the temperatures of the inner tank and the baffle, respectively).

[0137] Using the above equations, the curve of the hydrogen ratio in the hydrogen storage unit changing over time was calculated. For example... Figure 6 As shown, 1235 seconds after the start of the reaction, the second-stage pressure hydrogen storage unit released 95% of the hydrogen gas at a pressure of 5 MPa, which was 71% less than the time required for Comparative Example 1.

[0138] Example 2

[0139] The system according to Embodiment 1 differs in that the height of the inner tank 2-1 is 720mm and the inner diameter is 10mm, the height of the outer tank 2-2 is 720mm and the inner diameter is 20mm, the ratio of the difference in inner diameter between the outer tank 2-2 and the inner tank 2-1 to the inner diameter of the inner tank 2-1 is 1:1; the diameter of the air pipe is 4mm; the opening 2-7 on the inner tank partition 2-4 is 2.4mm in diameter, and the area of ​​the opening 2-7 is equal to that of the inner tank partition 2-4. The area ratio of -4 is 0.09; taking the adjacent lower inner tank partition 3 as a reference, the inner tank partition 3 rotates 120° in the same direction along the axis of the inner tank 2-1; the ratio of the maximum distance between adjacent inner tank partitions 2-4 to the height of the inner tank 2-1 is 0.09; the arc of the missing corner ring of the outer tank partition 2-5 is 330°; the ratio of the maximum distance between adjacent outer tank partitions 2-5 to the height of the outer tank 1 is 0.09. Multiple outer tank partitions 2-5 are arranged in parallel, and taking the adjacent lower outer tank partition 2-5 as a reference, the outer tank partition 4 rotates 120° in the same direction along the axis of the outer tank 2.

[0140] The pressurization process was simulated using a numerical simulation device, and the change curve of the hydrogen ratio in the hydrogen storage unit over time was calculated. For example... Figure 7 As shown, 451 seconds after the reaction started, the second-stage pressure hydrogen storage unit released 95% of the hydrogen gas at a pressure of 5 MPa, which was 89% less than the time required for Comparative Example 1.

[0141] Example 3

[0142] The system according to Embodiment 1 differs in that the height of the inner tank 2-1 is 100mm and the inner diameter is 60mm, the height of the outer tank 2-2 is 100mm and the inner diameter is 80mm, the ratio of the difference in the inner diameter of the outer tank 2-2 and the inner tank 2-1 to the inner diameter of the inner tank 2-1 is 0.33; the diameter of the air pipe is 6mm; the opening 2-7 on the inner tank partition 2-4 is directly 6mm, and the ratio of the area of ​​the opening 2-7 to the area of ​​the inner tank partition 2-4 is 0.01; taking the adjacent lower inner tank partition 3 as a reference, the inner tank partition 3 rotates 60° in the same direction along the axial direction of the inner tank 2-1; the ratio of the maximum distance between adjacent inner tank partitions 2-4 to the height of the inner tank 2-1 is 0.2; the arc of the notched corner ring of the outer tank partition 2-5 is 240°; the ratio of the maximum distance between adjacent outer tank partitions 2-5 to the height of the outer tank 1 is 0.2. Multiple outer tank partitions 2-5 are arranged in parallel. Taking the adjacent lower outer tank partition 2-5 as a reference, the outer tank partitions 2-5 rotate 90° in the same direction along the axial direction of the outer tank 2.

[0143] The pressurization process was simulated using a numerical simulation device, and the change curve of the hydrogen ratio in the hydrogen storage unit over time was calculated. For example... Figure 8As shown, 2426 seconds after the start of the reaction, the second-stage pressure hydrogen storage unit released 95% of the hydrogen gas at a pressure of 5 MPa, which was 43% less time than that required for Comparative Example 1.

[0144] Comparative Example 1

[0145] The method of Example 2 is different in that, in Comparative Example 1, the inner tank 2-1 does not have an inner tank partition 2-4, and the outer tank 2-2 does not have an outer tank partition 2-5.

[0146] The pressurization process was simulated using a numerical simulation device, and the change curve of the hydrogen ratio in the hydrogen storage unit over time was calculated. For example... Figure 9 As shown, 4250 seconds after the reaction begins, the second-stage pressure hydrogen storage unit releases 95% of the hydrogen gas at a pressure of 5 MPa.

[0147] The embodiments of the present invention have the effect of shorter hydrogen compression and transmission time, resulting in significantly better performance.

[0148] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A solid hydrogen storage and pressurization system, characterized in that, The system includes n-stage pressure hydrogen storage units connected in series. The hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the next-stage pressure hydrogen storage unit, which is used to realize the transmission and pressurization of hydrogen. Here, n≥2, and n is a positive integer. The pressure hydrogen storage unit includes a hydrogen storage alloy reactor (2), which includes a vertically arranged inner tank (2-1) and an outer tank (2-2) sleeved outside the inner tank (2-1). Along the vertical direction of the inner tank (2-1), multiple inner tank baffles (2-4) are horizontally arranged inside the inner tank (2-1). Along the vertical direction of the outer tank (2-2), multiple outer tank baffles (2-5) are horizontally arranged inside the outer tank (2-2). An opening (2-7) is provided on the inner tank baffle (2-4) for the flow of hydrogen. The outer tank baffle (2-5) is a notched annular shape, and the outer tank baffle (2-5) is used for the flow of heat-conducting fluid inside the outer tank (2-2), which flows through the notched corner of the annular shape. The number of openings (2-7) is one, and the ratio of the opening area of ​​the opening (2-7) to the area of ​​the inner tank partition (2-4) is 0.01-0.2:1; The ratio of the distance between the center of the inner tank partition (2-4) and the center of the opening (2-7) to the inner diameter of the inner tank (2-1) is 0.15-0.45:1; Taking the opening (2-7) on the bottom inner tank partition (2-4) as the reference, from bottom to top, multiple openings (2-7) rotate in the same direction by 90-180° in sequence along the axial direction of the inner tank (1); The curvature of the outer tank partition (2-5) is 240-355°; Using the missing corner of the bottom outer tank partition (2-5) as a reference, from bottom to top, multiple outer tank partitions (2-5) rotate in the same direction by 90-180° along the axis of the outer tank (2-2).

2. The system according to claim 1, wherein, The value of n is 2-6, where n is a positive integer.

3. The system according to claim 1, wherein, The heights of the inner tank (2-1) and the outer tank (2-2) are each independently 50-2000 mm.

4. The system according to claim 3, wherein, The heights of the inner tank (2-1) and the outer tank (2-2) are each 150-800mm.

5. The system according to claim 1, wherein, The inner diameter of the inner tank (2-1) is 5-80mm.

6. The system according to claim 5, wherein, The inner diameter of the inner tank (2-1) is 10-40mm.

7. The system according to claim 1, wherein, The inner diameter of the outer tank (2-2) is 15-160mm.

8. The system according to claim 7, wherein, The inner diameter of the outer tank (2-2) is 30-90mm.

9. The system according to claim 1, wherein, The ratio of the difference in inner diameter between the outer tank (2-2) and the inner tank (2-1) to the inner diameter of the inner tank (2-1) is 0.2-3:

1.

10. The system according to claim 9, wherein, The ratio of the difference in inner diameter between the outer tank (2-2) and the inner tank (2-1) to the inner diameter of the inner tank (2-1) is 0.35-2:

1.

11. The system according to claim 1, wherein, The ratio of the opening area of ​​the opening (2-7) to the area of ​​the inner tank partition (2-4) is 0.04-0.1:

1.

12. The system according to claim 1, wherein, The diameter of the opening (2-7) is 2-20mm.

13. The system according to claim 12, wherein, The diameter of the opening (2-7) is 2-15mm.

14. The system according to claim 1, wherein, The ratio of the distance between the center of the inner tank partition (2-4) and the center of the opening (2-7) to the inner diameter of the inner tank (2-1) is 0.2-0.37:

1.

15. The system according to claim 1, wherein, Based on the opening (2-7) on the bottom inner tank partition (2-4), multiple openings (2-7) are set by rotating in the same direction 120-180° from bottom to top along the axial direction of the inner tank (1).

16. The system according to claim 1, wherein, The ratio of the maximum distance between adjacent inner tank partitions (2-4) to the height of the inner tank (2-1) is 0.05-0.5:

1.

17. The system according to claim 16, wherein, The ratio of the maximum distance between the adjacent inner tank partitions (2-4) to the height of the inner tank (2-1) is 0.05-0.35:

1.

18. The system according to claim 1, wherein, The curvature of the outer tank partition (2-5) is 300-345°.

19. The system according to claim 1, wherein, Based on the missing corner of the bottom outer tank partition (2-5), multiple outer tank partitions (2-5) are rotated 120-180° in the same direction along the axis of the outer tank (2-2) from bottom to top.

20. The system according to claim 1, wherein, The ratio of the maximum distance between adjacent outer tank partitions (2-5) to the height of the outer tank (2-2) is 0.05-0.5:

1.

21. The system according to claim 20, wherein, The ratio of the maximum distance between adjacent outer tank partitions (2-5) to the height of the outer tank (2-2) is 0.08-0.25:

1.

22. The system according to claim 16, wherein, A solid hydrogen storage composite material (2-6) is placed between the adjacent inner tank partitions (2-4). The solid hydrogen storage composite material (2-6) is used for hydrogen absorption / desorption, heat conduction, and controlling the hydrogen absorption / desorption balance pressure of the pressure hydrogen storage unit.

23. The system according to claim 22, wherein, The solid hydrogen storage composite material (2-6) includes a hydrogen storage alloy and / or a thermally conductive material.

24. The system according to claim 23, wherein, The mass ratio of the hydrogen storage alloy to the thermally conductive material is 1:0.02-0.

1.

25. The system according to claim 1, wherein, The hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is 0.5-10 MPa higher than the hydrogen absorption equilibrium pressure of the second-stage pressure hydrogen storage unit.

26. The system according to claim 1, wherein, The n-stage series-connected pressure hydrogen storage units are connected by hydrogen pipelines. These hydrogen pipelines are used to introduce an external hydrogen source into the preceding pressure hydrogen storage unit or to introduce pressurized hydrogen released from the preceding pressure hydrogen storage unit into the subsequent pressure hydrogen storage unit, thereby realizing hydrogen transmission.

27. The system according to claim 26, wherein, A three-way solenoid valve (3-4) is installed on the hydrogen pipeline, and the three-way solenoid valve (3-4) is used to control the transmission of hydrogen.

28. The system according to claim 1, wherein, The system also includes a liquid circulation pipeline and a four-way solenoid valve installed on the liquid circulation pipeline. The liquid circulation pipeline is used to introduce heat-conducting fluid into the solid hydrogen storage alloy reactor (2), and the four-way solenoid valve is used to control the flow of heat-conducting fluid to realize the absorption / release of hydrogen by the pressure hydrogen storage unit.

29. The system according to claim 1, wherein, The system also includes a low-temperature storage tank (7) and a high-temperature storage tank (8). The low-temperature storage tank (7) is used to absorb the heat released by the hydrogen absorption reaction, and the high-temperature storage tank (8) is used to provide the heat absorbed by the hydrogen release reaction.

30. The system according to claim 29, wherein, The low-temperature storage tank (7) and the high-temperature storage tank (8) are connected by a heat exchanger (9). Heat is transferred from the low-temperature storage tank (7) to the high-temperature storage tank (8) through the heat exchanger (9), thereby realizing heat exchange between the pressure hydrogen storage units.

31. A method for storing and pressurizing hydrogen, wherein, The method is performed in the system described in any one of claims 1-30, and the method includes: Hydrogen gas is introduced into the first-stage pressure hydrogen storage unit to carry out a hydrogen absorption reaction. After the adsorption is saturated, a hydrogen release reaction is carried out, and the hydrogen gas released by the first-stage pressure hydrogen storage unit is absorbed in the subsequent-stage pressure hydrogen storage unit. After the hydrogen release reaction of the first-stage pressure hydrogen storage unit is completed, the hydrogen absorption reaction is carried out again to realize the alternating hydrogen absorption / release of n-stage pressure hydrogen storage units, and to complete the step-by-step pressurization and transmission of hydrogen. The hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the next-stage pressure hydrogen storage unit.

32. The method according to claim 31, wherein, The hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is 0.5-10 MPa higher than the hydrogen absorption equilibrium pressure of the second-stage pressure hydrogen storage unit.

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