Solid hydrogen storage and pressurization system and hydrogen pressurization method

Abstract

The invention relates to the field of hydrogen storage, and discloses a solid hydrogen storage and pressurization system and a hydrogen pressurization method. The system comprises n stages of pressure hydrogen storage units connected in series, the hydrogen release balance pressure of the first stage of pressure hydrogen storage unit is larger than the hydrogen absorption balance pressure of the next stage of pressure hydrogen storage unit, and the pressure hydrogen storage units are used for achieving transmission and pressurization of hydrogen. The pressure hydrogen storage unit comprises a hydrogen storage alloy reactor, and the hydrogen storage alloy reactor comprises a vertically arranged inner tank body and an outer tank body arranged outside the inner tank body in a sleeving manner; a plurality of inner tank body partition plates are horizontally arranged in the inner tank body in the vertical direction of the inner tank body; a plurality of outer tank body partition plates are horizontally arranged in the outer tank body in the vertical direction of the outer tank body; an opening is formed in the partition plate of the inner tank body and is used for circulation of hydrogen; the outer tank body partition plate is in an unfilled-corner circular ring shape and used for circulation of heat conduction fluid in the outer tank body, and the heat conduction fluid in the outer tank body circulates through the unfilled corners of the unfilled-corner circular ring. The system adjusts the hydrogen pressure and improves the hydrogen transmission rate at the same time.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen storage, and in particular to a solid hydrogen storage and pressurization system and a hydrogen pressurization method. Background Art

[0002] With the growing global demand for energy, as well as serious CO2 emissions and worsening environmental pollution, people are paying more and more attention to the development of clean and renewable energy. As a secondary energy source, hydrogen energy has the characteristics of wide sources, clean and carbon-free, flexible and efficient, and a wide range of application scenarios. It can be widely used in energy, transportation, industry, construction and other fields. It is an ideal interconnected medium to promote the clean and efficient use of traditional fossil energy and support the large-scale development of renewable energy. It will gradually become an important direction of the global energy technology revolution.

[0003] Hydrogen production by water electrolysis is a new type of hydrogen production method. The carbon emissions of hydrogen produced by it are close to zero, and the hydrogen purity is high. It is a very competitive hydrogen production technology. However, the hydrogen produced by this technology has a low pressure and is difficult to meet the hydrogen pressure requirements of some hydrogen-using terminals. At the same time, different hydrogen-using terminals often have different pressure requirements. Therefore, the establishment of adjustable pressure boosting technology is crucial for the use of hydrogen.

[0004] The process based on hydrogen storage alloy materials is considered to be an excellent hydrogen compression process, which has the advantages of high adjustable pressure, no pollution, high safety, etc., and can reduce the cost of hydrogen compressors. The so-called hydrogen storage alloy material refers to a type of material that stores hydrogen in the form of metal hydrides. Hydrogen storage alloys have the advantages of good reversibility of hydrogen absorption and desorption, high hydrogen storage density per unit volume, high hydrogen desorption purity, and high safety. For hydrogen storage alloys, the hydrogen absorption and desorption pressure is related to the hydrogen absorption and desorption temperature, and different materials have very different hydrogen absorption and desorption properties. Therefore, the hydrogen pressure can be regulated by using suitable hydrogen storage materials and regulating the hydrogen absorption and desorption temperature.

[0005] In addition, the hydrogen absorption process of hydrogen storage alloys releases heat, while the desorption process is an endothermic process. The former only occurs when the supply pressure is greater than the equilibrium pressure, and the latter only occurs when the pressure is lower than the equilibrium pressure. In the hydrogen absorption process, the released heat needs to be removed from the reaction system in time to keep the temperature at a favorable position. This helps to increase the hydrogen absorption rate and at the same time increase the hydrogen storage capacity. When hydrogen needs to be released, the endothermic reaction of the desorption process means that heat needs to be provided from the outside to maintain a suitable hydrogen desorption rate. This means that hydrogen storage alloys require additional energy supply during the absorption and desorption process. At the same time, the existing solid-state hydrogen storage reactor has poor heat transfer performance, resulting in poor control of the hydrogen absorption and desorption rate of the hydrogen storage system and low reversible hydrogen storage density. Therefore, improving the heat transfer efficiency of the system is crucial to improving energy utilization efficiency and establishing a high-performance solid-state hydrogen storage hydrogen compression system. At the same time, adopting a suitable energy management strategy and effectively utilizing the energy in the absorption and desorption process is crucial to reducing system energy consumption. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems existing in the prior art and to provide a solid hydrogen storage and pressurization system and a hydrogen pressurization method, which can improve the hydrogen transmission rate on the basis of multi-stage hydrogen pressure regulation and has the advantage of high safety.

[0007] In order to achieve the above-mentioned object, the first aspect of the present invention provides a solid hydrogen storage pressurization system, wherein the system comprises n stages of pressure hydrogen storage units connected in series, the hydrogen release equilibrium pressure of the first stage of pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the next stage of pressure hydrogen storage unit, and is used to realize the transmission and pressurization of hydrogen, wherein n≥2, n is a positive integer;

[0008] The pressure hydrogen storage unit includes a hydrogen storage alloy reactor, which includes a vertically arranged inner tank body and an outer tank body mounted on the outside of the inner tank body; along the vertical direction of the inner tank body, a plurality of inner tank body partitions are horizontally arranged inside the inner tank body; along the vertical direction of the outer tank body, a plurality of outer tank body partitions are horizontally arranged inside the outer tank body; the inner tank body partitions are provided with openings, and the openings are used for the circulation of hydrogen; the outer tank body partitions are in the shape of a notched circular ring, and the outer tank body partitions are used for the circulation of a heat-conducting fluid inside the outer tank body, and the heat-conducting fluid inside the outer tank body circulates through the notched corners of the notched circular rings.

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

[0010] Hydrogen is introduced into the first-stage pressure hydrogen storage unit to perform a hydrogen absorption reaction, and a hydrogen release reaction is performed after the adsorption is saturated, and the hydrogen released by the first-stage pressure hydrogen storage unit is absorbed by the second-stage pressure hydrogen storage unit;

[0011] After the first-stage pressure hydrogen storage unit has finished releasing hydrogen, a hydrogen absorption reaction is performed again to achieve alternating hydrogen absorption / release of n-stage pressure hydrogen storage units, completing 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 the present invention increases the heat exchange area, improves the heat exchange efficiency and hydrogen transmission rate on the basis of achieving hydrogen pressurization, has the advantages of high safety, and is more conducive to industrial production. Through n-stage series-connected pressurized hydrogen storage units, it is possible to maximize the use of the supply pressure of each stage to achieve maximum pressurization and achieve multi-stage pressure output in a wide range.

[0013] The system provided by the present invention uses a hydrogen storage alloy reactor with an inner tank and an outer tank as a pressure hydrogen storage unit to absorb / release hydrogen. A hole is opened on the inner tank baffle to form a gas flow channel to ensure that hydrogen is fully in contact with the solid hydrogen storage composite material during the hydrogen storage process, and to ensure that each part of the solid hydrogen storage material can absorb hydrogen to improve the hydrogen absorption efficiency. At the same time, a plurality of outer tank baffles are arranged in the outer tank, and the outer tank baffles form a liquid flow channel in the outer tank, thereby increasing the heat exchange area and improving the heat exchange efficiency.

[0014] Preferably, the system provided by the present invention can conveniently change the hydrogen absorption / desorption process of each pressure hydrogen storage unit, use the heat released by the hydrogen absorption reaction as the heat required for the hydrogen desorption reaction, and achieve efficient use of energy. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

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

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

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

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

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

[0023] Fig. 9 This is a curve showing the change of hydrogen ratio over time in the pressure hydrogen storage unit of comparative example 1 of the present invention.

[0024] Description of Reference Numerals

[0025] 1. The 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 partition

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

[0029] 2-7, opening 3-1, reactor hydrogen pipeline

[0030] 3-2. Hydrogenation pipeline 3-3. Hydrogenation pipeline

[0031] 3-4, three-way solenoid valve 3-5, one-way valve

[0032] 3-6. Pressure sensor 3-liquid inlet pipeline

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

[0034] 6. Second four-way solenoid valve 7. Low temperature liquid storage tank

[0035] 8. High temperature liquid storage tank 9. Heat exchanger DETAILED DESCRIPTION

[0036] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0037] A first aspect of the present invention provides a solid hydrogen storage and pressurization system, wherein the system comprises n stages of pressure hydrogen storage units connected in series, the hydrogen release equilibrium pressure of the first stage of pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the next stage of pressure hydrogen storage unit, and is used to achieve hydrogen transmission and pressurization, wherein n≥2, n is a positive integer;

[0038] The pressure hydrogen storage unit includes a hydrogen storage alloy reactor 2, which includes a vertically arranged inner tank body 2-1 and an outer tank body 2-2 mounted on the outside of the inner tank body 2-1; along the vertical direction of the inner tank body 2-1, a plurality of inner tank body partitions 2-4 are horizontally arranged inside the inner tank body 2-1; along the vertical direction of the outer tank body 2-2, a plurality of outer tank body partitions 2-5 are horizontally arranged inside the outer tank body 2-2; an opening 2-7 is opened on the inner tank body partition 2-4, and the opening 2-7 is used for the circulation of hydrogen; the outer tank body partition 2-5 is in the shape of a notched circular ring, and the outer tank body partition 2-5 is used for the circulation of the heat-conducting fluid inside the outer tank body 2-2, and the heat-conducting fluid inside the outer tank body 2-2 circulates through the notched corners of the notched circular ring.

[0039] The system provided by the present invention increases the heat exchange area, improves the heat exchange efficiency and hydrogen transmission rate on the basis of achieving hydrogen pressurization, has the advantages of high safety, and is more conducive to industrial production. Through n-stage series-connected pressurized hydrogen storage units, it is possible to maximize the use of the supply pressure of each stage to achieve maximum pressurization and achieve multi-stage pressure output in a wide range.

[0040] The system provided by the present invention uses a pressure hydrogen storage unit with a double tank body, an inner tank body and an outer tank body, to absorb / release hydrogen. A hole is opened on the inner tank body partition to form a gas flow channel, so as to ensure that hydrogen is fully in contact with the solid hydrogen storage composite material during the hydrogen storage process, and to ensure that each part of the solid hydrogen storage material can absorb hydrogen to improve the hydrogen absorption efficiency. At the same time, a plurality of outer tank body partitions are arranged in the outer tank body, and the outer tank body partitions form a liquid flow channel in the outer tank body, thereby increasing the heat exchange area and improving the heat exchange efficiency.

[0041] In the present invention, there is no particular limitation on the number of pressure hydrogen storage units, and those skilled in the art can select the number according to actual needs. Preferably, n is 2-6, and n is a positive integer.

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

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

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

[0045] In the present invention, preferably, the ratio of the inner diameter difference between the outer tank body 2-2 and the inner tank body 2-1 to the inner diameter of the inner tank body 2-1 is 0.2-3:1, preferably 0.35-2:1. The above preferred embodiment reduces the volume of the outer tank body while meeting the heat transfer requirements during the hydrogen absorption and desorption process, thereby providing convenience for the transportation of hydrogen.

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

[0047] In the present invention, there is no particular limitation on the size of the openings, and a suitable opening size can be selected according to the size of the inner tank body partition, as long as the transmission of hydrogen can be achieved. Preferably, the ratio of the opening area of ​​the opening 2-7 to the area of ​​the inner tank body partition 2-4 is 0.01-0.2:1, preferably 0.04-0.1:1. The advantage of adopting this preferred embodiment is that the gas can flow along the openings of adjacent partitions to form a flow direction, while taking into account the gas transmission efficiency.

[0048] In the present invention, there is no particular limitation on the size of the openings. Preferably, the diameter of the openings 2-7 is 2-20 mm, preferably 2-15 mm. The advantage of adopting this preferred embodiment is that the gas can flow along the openings of adjacent partitions to form a flow direction while taking into account the gas transmission efficiency.

[0049] In the present invention, there is no particular limitation on the position of the opening, which can be set at the center of the disk or at a non-center position, preferably at a non-center position. Preferably, the ratio of the distance between the center of the inner tank body partition 2-4 and the center of the opening 2-7 to the inner diameter of the inner tank body 2-1 is 0.15-0.45:1, preferably 0.2-0.37:1. The advantage of adopting this preferred embodiment is that the contact time between the gas and the hydrogen storage material is increased when the gas flows through the openings of the adjacent partitions.

[0050] In the present invention, gas flow channels are formed by setting openings on multiple inner tank body partitions. The present invention has a wide range of selection for the relative position of the openings of each inner tank body partition, and can form a vertical flow channel, an irregular flow channel, or a regular flow channel, such as a serpentine flow channel, and more preferably a serpentine flow channel. Preferably, taking the opening 2-7 on the bottom inner tank body partition 2-4 as a reference, from bottom to top, multiple openings 2-7 are arranged in the same direction along the axial direction of the inner tank body 1, rotating 90-180°, preferably 120-180°. The advantage of adopting this preferred embodiment is that a gas flow channel structure is formed, so that hydrogen is fully in contact with the hydrogen storage material, and the heat exchange efficiency is improved.

[0051] In the present invention, it is schematically explained that in the initial state, the centers of the openings on the multiple inner tank body partitions are on the same axis, and "rotating in the same direction" means that the inner tank body partition at the bottom layer is the first inner tank body partition, the first inner tank body partition remains stationary, and the second inner tank body partition rotates 90-180° counterclockwise along the axis of the inner tank body; after the second inner tank body partition rotates, the second inner tank body partition remains stationary, and the third inner tank body partition continues to rotate 90-180° counterclockwise along the axis of the inner tank body, and so on, so that the openings on each inner tank body partition form a gas flow channel structure, such as a serpentine flow channel. It should be noted that the above content is only schematically explained in terms of counterclockwise rotation, and it can also be clockwise rotation, as long as the rotation directions of the multiple inner tank body partitions remain consistent.

[0052] In the present invention, a plurality of inner tank body partitions are arranged inside the inner tank body, and the spacing between the inner tank body partitions is controlled to achieve sufficient contact between hydrogen and the hydrogen storage material. Preferably, the ratio of the maximum spacing between the adjacent inner tank body partitions 2-4 to the height of the inner tank body 2-1 is 0.05-0.5:1, preferably 0.05-0.35:1. The advantage of adopting this preferred embodiment is that the gas forms a baffle in the inner tank body and is in sufficient contact with the solid hydrogen storage material.

[0053] In the present invention, the outer tank body partition is in the shape of a missing corner circular ring, and the curvature of the missing corners of the plurality of outer tank body partitions can be selected in a wide range, as long as the circulation of the heat transfer fluid can be achieved. Preferably, the curvature of the outer tank body partitions 2-5 is 240-355°, preferably 300-345°. The advantage of adopting this preferred embodiment is that the fluid can be circulated through the gap of the missing corner circular ring to control the flow of the fluid, while taking into account the fluid transmission flux.

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

[0055] In the present invention, the outer tank body partition is in the shape of a circular ring with missing corners, and the arrangement of the missing corners of multiple outer tank body partitions forms a flow channel for the heat transfer fluid. The present invention does not particularly limit the arrangement of the relative positions of the multiple circular rings with missing corners, as long as a vertical flow channel, an irregular flow channel or a regular flow channel can be formed, such as a serpentine flow channel, and more preferably a serpentine flow channel. Taking the missing corners of the outer tank body partition 2-5 of the bottom layer as a reference, from bottom to top, multiple outer tank body partitions 2-5 are rotated in the same direction along the axial direction of the outer tank body 2-2 by 90-180°, preferably 120-180°. The advantage of adopting this preferred embodiment is that a liquid flow channel structure is formed in the outer tank body, which can improve 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 aforementioned inner tank body partition, and will not be repeated here.

[0056] In the present invention, the range of selection for the location of the plurality of outer tank body partitions is relatively wide, and those skilled in the art can select according to actual needs. Preferably, the ratio of the maximum spacing between the adjacent outer tank body partitions 2-5 to the height of the outer tank body 2-2 is 0.05-0.5:1, preferably 0.08-0.25:1. The advantage of adopting this preferred embodiment is that the liquid forms a baffle in the outer tank body, thereby improving the 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 absorbing / desorbing hydrogen, conducting heat, and controlling the absorption / desorption balance pressure of the pressure hydrogen storage unit.

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

[0059] In the present 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 thermal conductive material is 1:0.02-0.1.

[0060] In the present invention, there is no particular limitation on the type of hydrogen storage alloy, and it can be any hydrogen storage alloy conventionally defined in the art. 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. The present invention does not particularly limit the specific types of each series of hydrogen storage alloys, and those skilled in the art can select according to actual needs.

[0061] In the present invention, there is no particular limitation on the type of thermally conductive material, and it 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, foamed aluminum, foamed nickel, and foamed copper.

[0062] In the present invention, there is no particular limitation on the type of heat transfer fluid, which may be any heat transfer fluid conventionally defined in the art. Preferably, the heat transfer fluid is selected from at least one of water, ethylene glycol and heat transfer oil.

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

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

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

[0066] In the present invention, preferably, a second hydrogenation filter 2-3 is provided inside the trachea, and 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 sintered by a powder metallurgy method. In the present invention, there is no particular limitation on the arrangement of the second hydrogenation filter, as long as hydrogen filtration is achieved, for example, it can be arranged at the air inlet of the trachea, or at the air outlet of the trachea, and those skilled in the art can adjust it based on actual needs.

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

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

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

[0070] In the present invention, preferably, the n-stage pressure hydrogen storage units connected in series are connected via a hydrogen pipeline, and the hydrogen pipeline is used to introduce an external hydrogen source into the previous stage pressure hydrogen storage unit or to introduce the pressurized hydrogen released from the previous stage pressure hydrogen storage unit into the next stage pressure hydrogen storage unit, so as to realize the transmission of hydrogen.

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

[0072] In the present invention, Figure 1 , Figure 2 and Figure 3 As shown, preferably, the hydrogen pipeline includes a reactor hydrogen pipeline 3-1, a hydrogenation pipeline 3-2, a hydrogenation pipeline 3-3 and a three-way solenoid valve 3-4. The reactor hydrogen pipeline 3-1, the hydrogenation pipeline 3-2 and the hydrogenation pipeline 3-3 are interconnected through the three-way solenoid valve 3-4, and the transmission of hydrogen is achieved by controlling the opening and closing of the outlet of the three-way solenoid valve 3-4.

[0073] In the present invention, 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 body 2-1 of the previous first-stage pressure hydrogen storage unit, the hydrogenation pipeline 3-2 is used to introduce an external hydrogen source into the previous first-stage pressure hydrogen storage unit or to introduce the pressurized hydrogen released from the previous first-stage pressure hydrogen storage unit into the subsequent first-stage pressure hydrogen storage unit, and the hydrogen release pipeline 3-3 is used to introduce the hydrogen released after the previous first-stage pressure hydrogen storage unit is pressurized into the subsequent first-stage pressure hydrogen storage unit and / or supply it to the user unit. Schematically illustrated, when the first-stage pressure hydrogen storage unit undergoes a hydrogen absorption reaction, the outlet of the three-way solenoid valve 3-4 connected to the hydrogen release pipeline 3-3 is closed, and the outlet of the three-way solenoid valve 3-4 connected to the reactor hydrogen pipeline 3-1 and the hydrogenation pipeline 3-2 is opened, and the external hydrogen enters the inner tank body 2-1 of the hydrogen storage alloy reactor of the first-stage pressure hydrogen storage unit through the hydrogenation pipeline 3-2 and the reactor hydrogen pipeline 3-1 to undergo a hydrogen absorption reaction. After the hydrogen absorption is saturated, the outlet of the three-way solenoid valve 3-4 connected to the hydrogen release pipeline 3-3 is opened to undergo a hydrogen release reaction, and the pressurized hydrogen is released to the second-stage pressure hydrogen storage unit through the reactor hydrogen pipeline 3-1 and the hydrogen release pipeline 3-3 to undergo a hydrogen absorption / desorption reaction, until the last-stage pressure hydrogen storage unit is saturated with hydrogen absorption, and then the one-way valve 3-5 on the hydrogen release pipeline 3-2 in the last-stage pressure hydrogen storage unit is opened to release the pressurized hydrogen, thereby realizing step-by-step pressurization and transmission of hydrogen.

[0074] In the present invention, preferably, a pressure sensor 3-6 is provided on the reactor hydrogen pipeline 3-1 to monitor the pressure of the hydrogen storage alloy reactor 2. In the present invention, there is no particular limitation on the location of the pressure sensor, for example, it can be provided close to the hydrogen storage alloy reactor 2, or close to the three-way solenoid valve 3-4, preferably close to the hydrogen storage alloy reactor 2.

[0075] In the present invention, preferably, a first hydrogenation filter 1 is provided on the hydrogenation pipeline 3-2 to filter impurity particles in the hydrogen. The present invention does not particularly limit the location of the hydrogenation filter. The present invention does not particularly limit the accuracy of the first hydrogenation filter, for example, it can be the same as the second hydrogenation filter, or it can be different, preferably the same.

[0076] In the present invention, a heat-conducting fluid is provided by setting a liquid circulation pipeline to absorb the heat released by the hydrogen absorption reaction or provide the heat required for the hydrogen release reaction. Preferably, the system also includes a liquid circulation pipeline and a four-way solenoid valve provided 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 circulation of the heat-conducting fluid to achieve hydrogen absorption / desorption of the spaced pressure hydrogen storage units.

[0077] In the present invention, a heat source is provided to store a heat transfer fluid, and heat is provided for hydrogen absorption / desorption through temperature control. Preferably, the system further comprises a low-temperature liquid storage tank 7 and a high-temperature liquid storage tank 8, wherein the low-temperature liquid storage tank 8 is used to absorb the heat released by the hydrogen absorption reaction, and the high-temperature liquid storage tank 8 is used to provide the heat absorbed by the hydrogen desorption reaction. In the present invention, there is no particular limitation on the types of the low-temperature liquid storage tank and the high-temperature liquid storage tank, for example, both can be liquid storage tanks. In the present invention, there is no particular limitation on the types of the heat transfer fluid stored in the low-temperature liquid storage tank 7 and the high-temperature liquid storage tank 8, and the two can be the same or different, preferably the same. In the present invention, the temperature selection range of the heat transfer fluid stored in the low-temperature liquid storage tank 7 and the high-temperature liquid storage tank 8 is relatively wide, as long as the temperature of the heat transfer fluid stored in the high-temperature liquid storage tank 8 is higher than the temperature of the heat transfer fluid stored in the low-temperature liquid storage tank 7. Those skilled in the art can make a selection according to actual conditions.

[0078] In the present invention, Figure 1As shown, preferably, the liquid circulation pipeline includes a liquid inlet pipeline 3 and a first four-way solenoid valve 5 arranged on the liquid inlet pipeline 3, a liquid outlet pipeline 4 and a second four-way solenoid valve 6 arranged on the liquid outlet pipeline 4, and 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. Schematically illustrated, when the pressure hydrogen storage unit is undergoing a hydrogen absorption reaction, the outlet of the first four-way solenoid valve 5 connected to the liquid inlet pipeline 3 is opened, and the heat transfer fluid in the cryogenic liquid storage tank 7 enters the outer tank body 2-2 of the solid hydrogen storage alloy reactor 2 of the spaced pressure hydrogen storage unit through the liquid inlet pipeline 3 to absorb the heat released by the hydrogen absorption reaction, and then the outlet of the first four-way solenoid valve 5 connected to the liquid inlet pipeline 3 is closed, and the outlet of the second four-way solenoid valve 6 connected to the liquid outlet pipeline 4 is opened, and the heat transfer fluid returns to the cryogenic liquid storage tank 7 through the liquid outlet pipeline 4; when the pressure hydrogen storage unit is undergoing a hydrogen absorption reaction, During the hydrogen desorption reaction, the outlet of the second four-way solenoid valve 6 connected to the liquid outlet pipeline 4 is closed, and the outlet of the first four-way solenoid valve 5 connected to the liquid inlet pipeline 3 is opened again, and the heat transfer fluid in the high-temperature liquid storage tank 8 enters the outer tank body 2-2 of the solid hydrogen storage alloy reactor 2 of the interval pressure hydrogen storage unit through the liquid inlet pipeline 3 to provide the heat required for the hydrogen desorption reaction, and the pressurized hydrogen released by the hydrogen desorption reaction of the first-stage pressure hydrogen storage unit enters the next-stage pressure hydrogen storage unit for hydrogen absorption reaction, and the above steps are repeated to carry out hydrogen absorption / desorption reaction to achieve continuous pressurization and transmission of hydrogen.

[0079] In the present invention, the heat between the low temperature liquid storage tank and the high temperature liquid storage tank is transferred to improve the utilization rate of heat and save energy. Preferably, the low temperature liquid storage tank 7 and the high temperature liquid storage tank 8 are connected through a heat exchanger 9, and the heat is transferred from the low temperature liquid storage tank 7 to the high temperature liquid storage tank 8 through the heat exchanger 9 to achieve heat exchange between the pressure hydrogen storage units. The present invention does not specifically limit the specific type of the heat exchanger 9, for example, it can be a heat pump.

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

[0081] Hydrogen is introduced into the first-stage pressure hydrogen storage unit to perform a hydrogen absorption reaction, and a hydrogen release reaction is performed after the adsorption is saturated, and the hydrogen released by the first-stage pressure hydrogen storage unit is absorbed by the second-stage pressure hydrogen storage unit;

[0082] After the first-stage pressure hydrogen storage unit has finished releasing hydrogen, a hydrogen absorption reaction is performed again to achieve alternating hydrogen absorption / release of n-stage pressure hydrogen storage units, completing 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 the present invention, in order to realize the step-by-step pressurization and transmission of hydrogen, preferably, the hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is 0.5-10MPa higher than the hydrogen absorption equilibrium pressure of the second-stage pressure hydrogen storage unit, for example, it can be 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa, 9.5MPa, 10MPa and values ​​between any two points.

[0084] According to a specific embodiment of the present invention, a pressure hydrogen storage unit having an even number of stages (e.g., four stages) connected in series is used as an example for schematic illustration, and the method for storing hydrogen and increasing pressure includes:

[0085] (1) Introducing hydrogen into the primary pressure hydrogen storage unit from an external hydrogen source, and the hydrogen undergoes a hydrogen absorption reaction in the primary pressure hydrogen storage unit;

[0086] (2) After the first-level pressure hydrogen storage unit is saturated with adsorption, a hydrogen release reaction is carried out, and the hydrogen released by the first-level pressure hydrogen storage unit enters the second-level 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 performed, 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 performs a hydrogen absorption reaction;

[0088] (4) After the first-stage pressure hydrogen storage unit and the third-stage pressure hydrogen storage unit are saturated with adsorption, they respectively release hydrogen, 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 fourth pressure hydrogen storage unit are saturated with adsorption, a hydrogen release reaction is performed;

[0090] When the belt is running smoothly, steps (4) and (5) are repeated, and the interval pressure hydrogen storage units absorb / release hydrogen at the same time. When the hydrogen reaches the required pressure, the hydrogen of the last pressure hydrogen storage unit is released. During this operation, the low-temperature liquid storage tank 7 is connected to the pressure hydrogen storage unit that performs the hydrogen absorption reaction through the liquid circulation pipeline to absorb the heat of the hydrogen absorption reaction. The high-temperature liquid storage tank 8 is connected to the pressure hydrogen storage unit that performs the hydrogen release reaction through the 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 liquid storage tank 8, which is used to provide part of the pressure hydrogen storage unit for hydrogen release and heat absorption, 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 for schematic illustration, the hydrogen storage and pressurization method includes:

[0092] (1) Introducing hydrogen into the primary pressure hydrogen storage unit from an external hydrogen source, and the hydrogen undergoes a hydrogen absorption reaction in the primary pressure hydrogen storage unit;

[0093] (2) After the first-level pressure hydrogen storage unit is saturated with adsorption, a hydrogen release reaction is carried out, and the hydrogen released by the first-level pressure hydrogen storage unit enters the second-level 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 performed, 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 performs a hydrogen absorption reaction;

[0095] (4) after the first-stage pressure hydrogen storage unit and the third-stage pressure hydrogen storage unit are saturated with adsorption, they respectively undergo hydrogen release reactions;

[0096] When the belt is running smoothly, steps (3) and (4) are repeated, and the interval pressure hydrogen storage units absorb / release hydrogen simultaneously. When the hydrogen reaches the required pressure, the hydrogen heat source connection method of the last stage pressure hydrogen storage unit is released in the same way as mentioned above.

[0097] The method provided by the present invention can realize continuous step-by-step pressurization and transmission of hydrogen. By switching the pressure hydrogen storage unit and the heat source, the hydrogen absorption / desorption process of each level of pressure hydrogen storage unit can be conveniently changed, and the heat exchange between the low-temperature liquid storage tank and the high-temperature liquid storage tank can realize efficient energy utilization. The method provided by the present invention can pressurize hydrogen to any pressure and release hydrogen at different pressures at the same time, and has the advantages of high adjustable pressure, high safety and no pollution. Furthermore, the selection of the aforementioned preferred hydrogen storage alloy reactor can further improve the heat exchange efficiency and hydrogen transmission rate and improve safety on the basis of realizing continuous step-by-step pressurization and transmission of hydrogen.

[0098] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all the raw materials used are from 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; the two stages of pressure hydrogen storage units both include a hydrogen storage alloy reactor 2, the hydrogen storage alloy reactor 2 includes a vertically arranged inner tank body 2-1 and an outer tank body 2-2 sleeved on the outside of the inner tank body 2-1, and an air pipe connected to the inner tank body 2-1 and provided with a second hydrogenation filter (sintered stainless steel filter element) 2-3; the height of the inner tank body 2-1 is 150mm, and the inner diameter is 30mm, the height of the outer tank body 2-2 is 150mm, and the inner diameter is 60mm, the ratio of the inner diameter difference between the outer tank body 2-2 and the inner tank body 2-1 to the inner diameter of the inner tank body 2-1 is 1:1; the inner diameter of the air pipe is 3mm. Along the vertical direction of the inner tank body 2-1, a plurality of inner tank body partitions 2-4 are horizontally arranged inside the inner tank body 2-1; along the vertical direction of the outer tank body 2-2, a plurality of outer tank body partitions 2-5 are horizontally arranged inside the outer tank body 2-2; an opening 2-7 is opened on the inner tank body partition 2-4, and the opening 2-7 is used for the circulation of hydrogen; the diameter of the opening 2-7 is 8mm, and the opening area of ​​the opening 2-7 and the area ratio of the inner tank body partition 2-4 are 0.07:1. Taking the adjacent lower inner tank body partition 2-4 as the reference, the inner tank body partition 2 -4 rotates 180° in the same direction along the axis of the inner tank body 2-1; the ratio of the maximum spacing between adjacent inner tank body partitions 2-4 to the height of the inner tank body 2-1 is 0.33:1, multiple inner tank body partitions 2-4 are arranged in parallel, and the openings 2-7 on the inner tank body partitions form a gas flow channel, and hydrogen flows in the gas flow channel; the outer tank body partition 2-5 is in the shape of a missing corner circular ring, and the outer tank body partition 2-5 is used for the circulation of the heat transfer fluid inside the outer tank body 2-2, and the heat transfer fluid inside the outer tank body 2-2 circulates through the missing corner of the missing corner circular ring. The outer arc surface of the missing corner circular ring is detachably connected to the inner peripheral wall of the outer tank body 2-2, and the inner arc surface of the missing corner circular ring is detachably connected to the outer peripheral wall of the inner tank body 2-1, and the arc of the missing corner circular ring is 300°; the ratio of the maximum spacing between adjacent outer tank body partitions 4 to the height of the outer tank body 2 is 0.2:1. Multiple outer tank body partitions 2-5 are arranged in parallel, and with the adjacent lower outer tank body partition 2-5 as a reference, the outer tank body partitions 2-5 are rotated 180° in the same direction along the axial direction of the outer tank body 2-2; a first guide port (not shown in the figure) is provided at the top of the outer tank body 2-2, and a second guide port (not shown in the figure) is provided at the bottom of the outer tank body 2-2. The heat transfer fluid enters the liquid flow channel of the outer tank body 2-2 through the first guide port and fills the interior of the outer tank body 2-2. The heat transfer fluid is deionized water.

[0101] like Figure 2 As shown, the first-stage pressure hydrogen storage unit inner tank 2-1 contains a solid hydrogen storage composite material 2-6, 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 0.1) and expanded graphite, the ratio of the two is 1:0.05. The material has a hydrogen absorption equilibrium pressure of 0.7MPa at 288K and a hydrogen release equilibrium pressure of 3.1MPa at 363K; the second-stage pressure hydrogen storage unit inner tank 2-1 contains a solid hydrogen storage composite material 2-6, which is composed of a titanium-based alloy (Ti 0.7 Zr 0.3 Mn 0.9 Cr 0.7 Fe 0.2 ) and expanded graphite, the ratio of the two is 1:0.05. The material has a hydrogen absorption equilibrium pressure of 1.7MPa at 288K and a hydrogen desorption equilibrium pressure of 5.8MPa at 363K.

[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 connected to the hydrogen discharge pipeline 3-3 of the first-stage pressure hydrogen storage unit is closed, and the outlet of the three-way solenoid valve 3-4 connected to the hydrogen pipeline 3-1 and the hydrogenation pipeline 3-2 of the first-stage pressure hydrogen storage unit reactor is opened, and the external hydrogen is filtered by the first hydrogenation filter 1 (filtering accuracy is 2μm) on the hydrogenation 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 hydrogenation pipeline 3-2 and the reactor hydrogen pipeline 3-1. The inner tank body 2-1 of the reactor is provided with a pressure sensor 3-6 on the hydrogen pipeline 3-1, which is used to monitor the pressure of the hydrogen storage alloy reactor 2. At this time, the hydrogen inlet pressure is maintained at 1MPa and is passed into the inner tank body 2-1 of the first-stage pressure hydrogen storage unit hydrogen storage alloy reactor 2, and the solid hydrogen storage composite material 2-6 in the inner tank body 2-1 undergoes a hydrogen absorption reaction under the pressure of the initial temperature of 288K; deionized water at a temperature of 288K is passed into the outer tank body 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 body 2-1 of the hydrogen storage alloy reactor 2 of the first-stage pressure hydrogen storage unit has finished absorbing hydrogen, the outlet of the three-way solenoid valve 3-4 connected to the hydrogen discharge pipeline 3-3 of the first-stage pressure hydrogen storage unit is opened to start hydrogen discharge, and the hydrogen outlet pressure is maintained at 2.5MPa. The first four-way solenoid valve 5 and the second four-way solenoid valve 6 are regulated, and the outer tank body 2-2 of the first-stage pressure hydrogen storage unit is connected to the high-temperature liquid storage tank 8, and deionized water with a temperature of 363K is introduced into the outer tank body 2-2 at a flow rate of 1.2L / min to provide heat generated by the hydrogen discharge reaction; at the same time, the pressurized hydrogen is discharged through the hydrogen pipeline of the second-stage pressure hydrogen storage unit reactor. 3-1 and the hydrogen release pipeline 3-3 are released to the second-stage pressure hydrogen storage unit to start absorbing hydrogen, the first four-way solenoid valve 5 and the second four-way solenoid valve 6 are regulated, the outer tank body 2-2 of the hydrogen storage alloy reactor 2 of the second-stage pressure hydrogen storage unit is connected to the low-temperature liquid storage tank 7, and deionized water with a temperature of 288K is introduced into the outer tank body 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 low-temperature liquid storage tank 7 to the high-temperature liquid storage tank 8 through the heat exchanger (heat pump) 9 to realize the heat exchange between the first pressure hydrogen storage unit and the second pressure hydrogen storage unit.

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

[0105] The reactor was numerically simulated using COMSO software. The mass, energy and momentum balance equations were constructed. The specific equations are as follows:

[0106] Storage material mass conservation equation:

[0107] The mass conservation equation for gases is:

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

[0109] The velocity field for hydrogen is calculated using Darcy's law:

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

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

[0112]

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

[0114]

[0115] Among them, C a and C d are the pre-exponential factors of hydrogen absorption reaction and hydrogen release reaction, E a and E d are the activation energies of hydrogen absorption and desorption reactions, R g is the gas constant, T is the reaction temperature, P eq is the equilibrium pressure of the chemical reaction, ρ ss 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 of 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 the inner tank 2-1 is as follows:

[0119]

[0120] Among them, M g is the molar mass of hydrogen.

[0121] Among them, 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: e =ελ g +(1-ε)λ s

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

[0124] For the heat transfer fluid, the mass balance equation is:

[0125] Among them, ρ f is the density of the heat transfer fluid, u f is the velocity field of the heat transfer fluid.

[0126] For a heat transfer fluid, the momentum balance equation is as follows:

[0127]

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

[0129]

[0130] in:

[0131] Among them, C p,f is the heat capacity of the heat transfer fluid, λ f is the effective thermal conductivity of the heat transfer fluid, P f is the heat transfer fluid pressure.

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

[0133]

[0134] Among them, (ρc) solid is the heat capacity of the solid (tank wall or partition), λ solid is the effective thermal conductivity of the solid (tank wall or partition).

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

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

[0137] Using the above equation, the curve of the change of hydrogen ratio of the hydrogen storage unit over time is calculated. Figure 6 As shown, 1235 seconds after the reaction started, the second-stage pressure hydrogen storage unit released 95% of the hydrogen at a pressure of 5 MPa, which is 71% less time than that required in Comparative Example 1.

[0138] Example 2

[0139] The system of Example 1 is different in that the height of the inner tank body 2-1 is 720 mm and the inner diameter is 10 mm, the height of the outer tank body 2-2 is 720 mm and the inner diameter is 20 mm, and the ratio of the difference between the inner diameters of the outer tank body 2-2 and the inner tank body 2-1 to the inner diameter of the inner tank body 2-1 is 1:1; the diameter of the air pipe is 4 mm; the opening 2-7 on the inner tank body partition 2-4 is directly 2.4 mm, and the area of ​​the opening 2-7 is the same as that of the inner tank body partition 2 -4 has an area ratio of 0.09; taking the adjacent lower inner tank body partition 3 as a reference, the inner tank body partition 3 is rotated 120° in the same direction along the axial direction of the inner tank body 2-1; the ratio of the maximum spacing between adjacent inner tank body partitions 2-4 to the height of the inner tank body 2-1 is 0.09; the arc of the missing corner ring of the outer tank body partition 2-5 is 330°; the ratio of the maximum spacing between adjacent outer tank body partitions 2-5 to the height of the outer tank body 1 is 0.09. Multiple outer tank body partitions 2-5 are arranged in parallel, and taking the adjacent lower outer tank body partition 2-5 as a reference, the outer tank body partition 4 is rotated 120° in the same direction along the axial direction of the outer tank body 2.

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

[0141] Example 3

[0142] The system is according to Example 1, except that the height of the inner tank body 2-1 is 100mm and the inner diameter is 60mm, the height of the outer tank body 2-2 is 100mm and the inner diameter is 80mm, and the ratio of the difference in inner diameters between the outer tank body 2-2 and the inner tank body 2-1 to the inner diameter of the inner tank body 2-1 is 0.33; the diameter of the air pipe is 6mm; the diameter of the opening 2-7 on the inner tank body partition 2-4 is 6mm, and the ratio of the area of ​​the opening 2-7 to the area of ​​the inner tank body partition 2-4 is 0.01; taking the adjacent lower inner tank body partition 3 as a reference, the inner tank body partition 3 is rotated 60° in the same direction along the axial direction of the inner tank body 2-1 in sequence; the ratio of the maximum spacing between adjacent inner tank body partitions 2-4 to the height of the inner tank body 2-1 is 0.2; the arc of the missing corner ring of the outer tank body partition 2-5 is 240°; the ratio of the maximum spacing between adjacent outer tank body partitions 2-5 to the height of the outer tank body 1 is 0.2. A plurality of outer tank body partitions 2 - 5 are arranged in parallel, and taking the adjacent lower outer tank body partition 2 - 5 as a reference, the outer tank body partitions 2 - 5 are rotated 90 degrees in the same direction along the axial direction of the outer tank body 2 in sequence.

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

[0144] Comparative Example 1

[0145] The method of Example 2 is followed, except that in Comparative Example 1, the inner tank body 2-1 is not provided with the inner tank body partition 2-4, and the outer tank body 2-2 is not provided with the outer tank body partition 2-5.

[0146] The pressure boosting process of the calculation device is simulated by numerical simulation, and the curve of the change of hydrogen ratio of the hydrogen storage unit over time is calculated. Fig. 9 As shown, 4250s after the reaction started, the second-stage pressure hydrogen storage unit released 95% of the hydrogen at a pressure of 5 MPa.

[0147] The embodiment of the present invention has the advantages that the time required for hydrogen compression and transmission process is shorter and the effect is obviously better.

[0148] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A solid hydrogen storage and pressurization system, characterized in that: The system comprises n-stage pressure hydrogen storage units connected in series, wherein the hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is greater than the hydrogen absorption equilibrium pressure of the second-stage pressure hydrogen storage unit, and is used to realize the transmission and pressurization of hydrogen, wherein n≥2, and n is a positive integer; The pressure hydrogen storage unit comprises a hydrogen storage alloy reactor (2), wherein the hydrogen storage alloy reactor (2) comprises a vertically arranged inner tank body (2-1) and an outer tank body (2-2) sleeved outside the inner tank body (2-1); along the vertical direction of the inner tank body (2-1), a plurality of inner tank body partitions (2-4) are horizontally arranged inside the inner tank body (2-1); along the vertical direction of the outer tank body (2-2), a plurality of outer tank body partitions (2-5) are horizontally arranged inside the outer tank body (2-2); an opening (2-7) is provided on the inner tank body partition (2-4), and the opening (2-7) is used for the circulation of hydrogen; the outer tank body partition (2-5) is in the shape of a notched circular ring, and the outer tank body partition (2-5) is used for the circulation of a heat-conducting fluid inside the outer tank body (2-2), and the heat-conducting fluid inside the outer tank body (2-2) circulates through the notched corner of the notched circular ring.

2. The system according to claim 1, wherein: The n is 2-6, and n is a positive integer.

3. The system according to claim 1 or 2, wherein: The heights of the inner tank body (2-1) and the outer tank body (2-2) are independently 50-2000 mm, preferably 150-800 mm; And / or, the inner diameter of the inner tank body (2-1) is 5-80 mm, preferably 10-40 mm; And / or, the inner diameter of the outer tank body (2-2) is 15-160 mm, preferably 30-90 mm; And / or, the ratio of the difference in inner diameters between the outer tank body (2-2) and the inner tank body (2-1) to the inner diameter of the inner tank body (2-1) is 0.2-3:1, preferably 0.35-2:

1.

4. The system according to any one of claims 1 to 3, wherein: The number of the opening (2-7) is one, and the ratio of the opening area of ​​the opening (2-7) to the area of ​​the inner tank body partition (2-4) is 0.01-0.2:1, preferably 0.04-0.1:1; And / or, the diameter of the opening (2-7) is 2-20 mm, preferably 2-15 mm; and / or, the ratio of the distance between the center of the inner tank body partition (2-4) and the center of the opening (2-7) to the inner diameter of the inner tank body (2-1) is 0.15-0.45:1, preferably 0.2-0.37:1; And / or, taking the opening (2-7) on the bottom inner tank body partition (2-4) as a reference, from bottom to top, the plurality of openings (2-7) are arranged in the same direction along the axial direction of the inner tank body (1) in sequence and rotated by 90-180°, preferably 120-180°; And / or, the ratio of the maximum distance between adjacent inner tank body partitions (2-4) to the height of the inner tank body (2-1) is 0.05-0.5:1, preferably 0.05-0.35:

1.

5. The system according to any one of claims 1 to 4, wherein: The curvature of the outer tank body partition (2-5) is 240-355°, preferably 300-345°; And / or, taking the missing corner of the outer tank body partition (2-5) at the bottom layer as a reference, from bottom to top, a plurality of outer tank body partitions (2-5) are sequentially rotated in the same direction by 90-180°, preferably 120-180°, along the axial direction of the outer tank body (2-2); And / or, the ratio of the maximum distance between adjacent outer tank body partitions (2-5) to the height of the outer tank body (2-2) is 0.05-0.5:1, preferably 0.08-0.25:

1.

6. The system according to any one of claims 1 to 5, wherein: A solid hydrogen storage composite material (2-6) is placed between the adjacent inner tank body partitions (2-4), and the solid hydrogen storage composite material (2-6) is used for absorbing / desorbing hydrogen, conducting heat, and controlling the absorption / desorption equilibrium pressure of the pressure hydrogen storage unit; And / or, the solid hydrogen storage composite material (2-6) comprises a hydrogen storage alloy and / or a thermal conductive material, and preferably the mass ratio of the hydrogen storage alloy to the thermal conductive material is 1:0.02-0.1; And / or, 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 second-stage pressure hydrogen storage unit.

7. The system according to any one of claims 1 to 6, wherein: The n-stage series-connected pressure hydrogen storage units are connected via a hydrogen pipeline, and the hydrogen pipeline is used to introduce an external hydrogen source into the previous stage pressure hydrogen storage unit or to introduce the pressurized hydrogen released by the previous stage pressure hydrogen storage unit into the next stage pressure hydrogen storage unit to achieve hydrogen transmission; And / or, a three-way solenoid valve (3-4) is provided on the hydrogen pipeline, and the three-way solenoid valve (3-4) is used to control the transmission of hydrogen.

8. The system according to any one of claims 1 to 7, wherein: The system further comprises a liquid circulation pipeline and a four-way solenoid valve arranged on the liquid circulation pipeline, wherein the liquid circulation pipeline is used to introduce a heat-conducting fluid into the solid hydrogen storage alloy reactor (2), and the four-way solenoid valve is used to control the circulation of the heat-conducting fluid to achieve hydrogen absorption / desorption of the spaced pressure hydrogen storage units; Preferably, the system further comprises a low-temperature liquid storage tank (7) and a high-temperature liquid storage tank (8), wherein the low-temperature liquid storage tank (7) is used to absorb the heat released by the hydrogen absorption reaction, and the high-temperature liquid storage tank (8) is used to provide the heat absorbed by the hydrogen release reaction; Preferably, the low-temperature liquid storage tank (7) and the high-temperature liquid storage tank (8) are connected via a heat exchanger (9), and heat is transferred from the low-temperature liquid storage tank (7) to the high-temperature liquid storage tank (8) via the heat exchanger (9), thereby achieving heat exchange between the pressure hydrogen storage units.

9. A method for storing and pressurizing hydrogen, wherein: The method is performed in a system according to any one of claims 1 to 8, and the method comprises: Hydrogen is introduced into the first-stage pressure hydrogen storage unit to perform a hydrogen absorption reaction, and a hydrogen release reaction is performed after the adsorption is saturated, and the hydrogen released by the first-stage pressure hydrogen storage unit is absorbed by the second-stage pressure hydrogen storage unit; After the first-stage pressure hydrogen storage unit has finished releasing hydrogen, a hydrogen absorption reaction is performed again to achieve alternating hydrogen absorption / release of n-stage pressure hydrogen storage units, completing 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.

10. The method according to claim 9, wherein: The hydrogen release equilibrium pressure of the first-stage pressure hydrogen storage unit is 0.5-10MPa higher than the hydrogen absorption equilibrium pressure of the second-stage pressure hydrogen storage unit.

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