A hydrogen storage device with hydrogen storage material that is easy to replace

Abstract

The present application relates to hydrogen storage device technical field, specifically to a kind of hydrogen storage device of hydrogen storage material is replaced easily, including cylinder, the both ends of cylinder are equipped with tube plate respectively, cylinder is provided with shell side inlet and shell side outlet;Cylinder is provided with multiple jacket pipes inside, each jacket pipe includes inner tube and outer tube, the outer wall between inner tube and the inner wall of outer tube is enclosed to be used to place the jacket ring cavity of hydrogen storage alloy, tube plate is provided with the plate cavity that is connected with jacket ring cavity, plate cavity is equipped with jacket inlet and jacket outlet;The side of tube plate away from cylinder is equipped with pipe box, inner tube passes through the plate cavity of corresponding tube plate and is connected with corresponding pipe box, pipe box is equipped with tube side inlet and tube side outlet;The wall of inner tube is densely covered with multiple gas-permeable holes, hydrogen gas can pass through, but hinder hydrogen storage alloy particles to pass.In the hydrogen storage alloy hydrogen charging and discharging capacity recession, in the case of overall device does not move, it is convenient to replace the original hydrogen storage alloy by filling new hydrogen storage alloy via jacket inlet, convenient operation, low cost.

Description

Technical Field

[0001] This invention relates to the field of hydrogen storage device technology, and specifically to a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials. Background Technology

[0002] With societal development, fossil fuels such as coal, oil, and natural gas can no longer meet humanity's ever-growing needs. Furthermore, the use of fossil fuels has led to ecological degradation, such as the greenhouse effect. In addition, coal, oil, and natural gas are non-renewable resources with limited reserves on Earth, making it impossible for humanity to rely on them indefinitely. Therefore, many countries are researching and developing new alternative energy sources, such as hydrogen, wind, solar, nuclear, biomass, hydropower, and ocean energy. Hydrogen has a high calorific value; the energy released from burning one kilogram of hydrogen is approximately three times that of gasoline, 3.9 times that of alcohol, and 4.5 times that of coke. The product of hydrogen combustion is water, resulting in zero environmental pollution. Hydrogen is the most abundant substance in the universe, constituting 75% of its total mass. Its reserves on Earth are extremely abundant, renewable, and reusable. Therefore, hydrogen energy is considered an ideal energy source for humanity and has received widespread attention worldwide.

[0003] Fuel cells are an important application of hydrogen energy, offering numerous advantages such as high efficiency, environmental friendliness, light weight, and low noise, and showing promising application prospects in transportation, distributed power generation, and backup power. Fuel cells use hydrogen as fuel and require a stable and reliable hydrogen source. Current research on hydrogen energy mainly focuses on three aspects: hydrogen production, hydrogen storage, and hydrogen application. Hydrogen storage is generally divided into gaseous hydrogen storage, liquid hydrogen storage, and solid-state hydrogen storage. High-pressure gaseous hydrogen storage has the main disadvantages of low hydrogen density, requiring large cylinder volumes, and posing significant safety risks. While liquid hydrogen storage has a higher hydrogen density, it requires cryogenic maintenance; the energy consumed in hydrogen liquefaction (21K) is equivalent to one-third of the energy of the liquefied hydrogen, also raising safety concerns. Solid-state hydrogen storage materials offer advantages such as high volumetric hydrogen density and high efficiency and safety. Therefore, solid-state hydrogen storage has become the most active hydrogen storage technology in current research.

[0004] Chinese patent document CN 103883874A discloses a hydrogen storage tank with an external heat exchange structure, belonging to the field of hydrogen storage technology within the hydrogen energy sector. The structure of the hydrogen storage tank is as follows: a skirt is located at the bottom of the tank body; a hydrogen storage material bed is located inside the tank body; a gas guide pipe is located at the center of the tank body and extends directly from the bottom of the tank body to the tank opening; a filter is installed inside the tank opening, and a hydrogen cylinder valve is installed outside the tank opening; an outer shell is located outside the tank body, with a heat transfer liquid inlet and outlet at each end; a heat exchange structure is provided in the annular cavity between the outer shell and the tank body. The heat exchange structure can be direct-flow, baffled, single-spiral, or multi-spiral; the hydrogen storage material bed is a uniform mixture of hydrogen storage material and heat-conducting fibers. The provided hydrogen storage tank has a simple structure, is easy to manufacture, and has low cost; compared with existing hydrogen storage tanks, it has better heat exchange performance and superior hydrogen release performance.

[0005] Unlike the "hydrogen absorption" and "hydrogen removal" of chemical catalytic reactions, solid-state hydrogen storage alloy materials (such as rare earth compounds (LaNi5)) can reversibly react with gaseous H2 under certain temperature and pressure conditions to generate the hydride LaNi5H. x The relationship between pressure (P), metal hydride composition (C), and temperature (T) was plotted as a curve. Under certain temperature conditions, when the H2 pressure exceeds the hydrogen absorption reaction pressure of the alloy, the alloy begins to absorb hydrogen. As the hydrogen pressure increases, the amount of hydrogen absorbed by the alloy gradually increases until the hydrogen absorption reaction of the alloy reaches saturation. Even if the pressure is increased further, the alloy can no longer absorb hydrogen. When the H2 pressure decreases below the hydrogen release pressure, the metal hydride begins to gradually release hydrogen. There is usually a plateau region in the hydrogen absorption and release process of the alloy. In this region, the amount of hydrogen absorbed increases rapidly with the increase of H2 pressure. The width of the plateau region is related to temperature. The higher the temperature, the narrower the plateau width, and the plateau region may even disappear. The hydrogen absorption curve and the hydrogen release curve do not coincide at the same temperature. The hydrogen release pressure is lower than the hydrogen absorption pressure. This phenomenon is called hysteresis. To achieve the same amount of hydrogen absorption at different temperatures, higher pressure is required at higher temperatures, and the same applies to hydrogen release, i.e., there is a higher plateau pressure at higher temperatures. The hydrogen absorption reaction of LaNi5 has a clear plateau region. As the temperature increases, the pressure of the hydrogen absorption and release curves also increases.

[0006] The hydrogen absorption and desorption process of hydrogen storage materials is a multiphase system: hydrogen gas - hydrogen storage alloy (α phase) - metal hydride (β phase). During the hydrogen absorption and desorption phase transition, there are two degrees of freedom: hydrogen pressure and phase transition temperature. That is, during the hydrogen absorption process, the system has different phase transition temperatures for different hydrogen pressures.

[0007] Taking LaNi5 hydrogen storage alloy as an example, its reaction temperature T and corresponding hydrogen pressure P are as follows: The hydrogen absorption process is described as follows: the hydrogen storage alloy (α phase) is brought into contact with hydrogen, and the hydrogen pressure is continuously increased. At this time, an α-β phase transition occurs, releasing heat and raising the system temperature. As the temperature rises, a higher hydrogen pressure is required to maintain the phase transition until the system temperature reaches about 60-80℃. At this time, the required hydrogen pressure is 1.8-2.4 MPa. If the hydrogen pressure no longer increases, the released heat needs to be quickly dissipated to maintain the system temperature at 60-80℃ so that the reaction (phase transition) can continue. Conversely, if the heat dissipation is insufficient... As the external gas pressure continues to rise, the system temperature will continue to rise. The hydrogen release process is described as follows: the hydride phase (β phase) is heated in a closed system (without hydrogen outflow). The pressure inside the container increases continuously with temperature. For example, at 30-50℃, the pressure inside the container is 0.4-0.8 MPa, and at 60-80℃, the pressure inside the container is 1-1.5 MPa. If hydrogen release is maintained at 80℃, the system needs to continuously replenish heat as hydrogen is released. If the heat replenishment is not timely, the temperature inside the system drops, and the pressure at the outlet drops, making it impossible to maintain a constant hydrogen release pressure. After saturation hydrogen absorption, the LaNi5H6 hydride phase is formed. In summary, the above solid alloy hydrogen storage materials achieve physically reversible hydrogen addition and release processes by changing temperature and gas pressure. For details, please refer to the hydrogen storage device disclosed in Chinese patent document CN215951102U. Solid alloy hydrogen storage materials are those that achieve physically reversible hydrogen addition and desorption processes by changing temperature and pressure. For details, please refer to a hydrogen storage device disclosed in Chinese patent document CN215951102U. Furthermore, existing hydrogen storage devices can also be found in Chinese patent documents CN102649565A, CN202752008U, CN113955110A, and CN114151719A.

[0008] Hydrogen storage alloys possess high hydrogen storage capacity and excellent absorption and desorption kinetics. However, after hydrogen absorption, the cell volume of these alloys expands significantly. As charge-discharge cycles continue, the crystal lattice deforms, leading to severe alloy differentiation and an increase in specific surface area, resulting in rapid capacity decay. More frequent use leads to faster depletion and shorter replacement cycles. However, replacing the hydrogen storage alloy in existing hydrogen storage devices is inconvenient, and equipment upgrades are costly. Summary of the Invention

[0009] To address the aforementioned technical problems in the existing technology, the present invention provides a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials.

[0010] To achieve the above objectives, the present invention provides the following technical solution:

[0011] A hydrogen storage and release device that facilitates the replacement of hydrogen storage materials is provided, including a cylindrical body with tube sheets at both ends of the cylindrical body to form a shell side. The cylindrical body is provided with a shell side inlet and a shell side outlet, thereby forming a shell side flow channel such as shell side inlet-cylinder-shell side outlet.

[0012] The cylinder is equipped with multiple jacketed tubes, each of which includes an inner tube and an outer tube. The outer wall of the inner tube and the inner wall of the outer tube form a jacketed annular cavity for placing the hydrogen storage alloy. The tube sheet is provided with a plate cavity that connects to the jacketed annular cavity. The plate cavity has a jacket inlet and a jacket outlet, thus forming a jacket flow channel such as jacket inlet - plate cavity of tube sheet - jacketed annular cavity - plate cavity of another tube sheet - jacket outlet, so as to replace the hydrogen storage alloy in the jacketed annular cavity through the jacket flow channel.

[0013] A tube box is provided on the side of the tube sheet away from the cylinder. The inner tube passes through the corresponding tube sheet cavity and connects to the corresponding tube box. The tube box is provided with a tube inlet and a tube outlet, thus forming a tube flow channel such as tube inlet-tube box-inner tube-another tube box-tube outlet.

[0014] The jacketed tube is densely covered with multiple vent holes along its length, allowing hydrogen gas to pass through while obstructing the passage of hydrogen storage alloy particles; the multiple vent holes are arranged on the inner tube wall, with the tube-side flow channel serving as the channel for flowing hydrogen gas and the shell-side flow channel serving as the channel for flowing heat exchange medium; or: the multiple vent holes are arranged on the outer tube wall, with the shell-side flow channel serving as the channel for flowing hydrogen gas and the tube-side flow channel serving as the channel for flowing heat exchange medium.

[0015] As a further alternative, the cylinder is arranged vertically, and the jacket inlet is located on the tube sheet at the upper end of the cylinder.

[0016] As a further alternative, the tube sheet can be a hollowed-out integral forging structure, a plate welded structure, or a flat round tube welded structure.

[0017] As a further optional solution, the tube sheet includes a first side plate connecting the cylinder and a second side plate connecting the tube box, with the plate cavity located between the first side plate and the second side plate; the end of the inner tube passes through the first side plate and the plate cavity and is fixed to the second side plate to connect to the tube box; the end of the outer tube is fixed to the first side plate to connect to the plate cavity.

[0018] As a further optional solution, the cylinder is equipped with an expansion joint.

[0019] As a further optional solution, the vent holes are covered with a filter membrane.

[0020] The beneficial effects of this invention are:

[0021] The present invention provides a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials. Compared with the prior art, on the one hand, the hydrogen storage alloy is placed in the jacketed annular cavity within the jacketed tube, resulting in uniform particle distribution, a large contact area with hydrogen, and high hydrogen addition and release efficiency; on the other hand, due to the jacketed flow channel, after the hydrogen storage alloy's hydrogen charging and releasing capacity deteriorates, new hydrogen storage alloy can be easily injected through the jacket inlet to replace the original hydrogen storage alloy without moving the entire device, making the operation convenient and cost-effective. Attached Figure Description

[0022] Figure 1 This is a wireframe diagram of a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials, as shown in the embodiment.

[0023] Figure 2 This is a plan sectional view of a hydrogen storage and release device in the embodiment that facilitates the replacement of hydrogen storage materials.

[0024] Figure 3 This is a cross-sectional perspective view of a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials, as described in the embodiment.

[0025] Figure label:

[0026] Shell 1, shell side 11, shell side inlet 12, shell side outlet 13, expansion joint 14;

[0027] Tube sheet 2, plate cavity 21, jacket inlet 22, jacket outlet 23, first side plate 24, second side plate 25;

[0028] Jacketed tube 3, inner tube 31, outer tube 32, jacketed annular cavity 33, vent hole 34;

[0029] Pipe box 4, pipe inlet 41, pipe outlet 42. Detailed Implementation

[0030] The present invention will be described in detail below with reference to specific embodiments and accompanying drawings.

[0031] This embodiment provides a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials, such as... Figures 1 to 3 As shown, the device includes a cylindrical body 1, with tube sheets 2 at both ends, which together form a shell side 11. The cylindrical body 1 has a shell side inlet 12 and a shell side outlet 13, thus forming a shell side flow channel of shell side inlet 12-cylinder body 1-shell side outlet 13. An expansion joint 14 is provided on the side wall of the cylindrical body 1 to overcome the deformation difference caused by temperature difference.

[0032] In this embodiment, the cylinder 1 is provided with multiple jacketed tubes 3 (two are briefly shown in the figure). Each jacketed tube 3 includes an inner tube 31 and an outer tube 32 that are coaxial but have different diameters. The outer wall of the inner tube 31 and the inner wall of the outer tube 32 form a jacketed annular cavity 33 for placing the hydrogen storage alloy. The tube sheet 2 is provided with a plate cavity 21 that communicates with the jacketed annular cavity 33. One tube sheet 2 is provided with a jacket inlet 22, and the other tube sheet 2 is provided with a jacket outlet 23, thereby forming a jacketed flow channel such as jacket inlet 22-plate cavity 21 of tube sheet 2-jacketed annular cavity 33-plate cavity 21 of another tube sheet 2-jacket outlet 23, so as to replace the hydrogen storage alloy in the jacketed annular cavity 33 through the jacketed flow channel. The tube sheet 2 is an integral forged hollow structure, a plate welded structure, or a flat round tube welded structure (a round tube is flattened and then sealed with plates at both ends), and can be manufactured in various ways.

[0033] In this embodiment, a tube box 4 is provided on the side of the tube sheet 2 away from the cylinder 1. The inner tube 31 passes through the plate cavity 21 of the corresponding tube sheet 2 and connects to the corresponding tube box 4. The tube box 4 is provided with a tube inlet 41 and a tube outlet 42, thereby forming a tube flow channel such as tube inlet 41-tube box 4-inner tube 31-another tube box 4-tube outlet 42.

[0034] In this embodiment, the inner tube 31 has a plurality of vent holes 34 densely distributed along its length. The pore size of the vent holes 34 satisfies the condition that hydrogen gas can pass through while hindering the passage of hydrogen storage alloy particles. Specifically, the pore size of the vent holes 34 can be 0.1 to 0.9 times the size of the hydrogen storage alloy particles, or a filter membrane can be used to cover the vent holes 34. This allows the vent holes 34 to be made larger for easier processing, and the filter membrane, being permeable, further hinders the passage of hydrogen storage alloy particles. The vent holes 34 of the inner tube 31 can be arranged only in the corresponding segments of the cylinder 1, or they can be arranged simultaneously in the corresponding segments of the inner tube 31 in the plate cavity 21. The plate cavity 21 is also filled with hydrogen storage alloy, making full use of the internal space.

[0035] In practical applications, the tube-side flow channel serves as the passage for flowing hydrogen. During hydrogen addition, the tube-side outlet 42 is closed, and hydrogen is injected through the tube-side inlet 41. The heat exchange medium flowing through the shell-side flow channel adjusts the hydrogen storage alloy particles to a preset temperature range via the tube wall of the outer tube 32, allowing the hydrogen in the inner tube 31 to be added to the hydrogen storage alloy through the vent 34 and stored. During hydrogen release, the tube-side outlet 42 is opened, and the tube-side inlet 41 is closed. The heat exchange medium at another temperature in the shell-side flow channel adjusts the temperature of the hydrogen storage alloy to another preset temperature range, causing the hydrogen storage alloy in the jacket annular cavity 33 to release hydrogen, which enters the inner tube 31 through the vent 34 and flows out from the tube-side outlet 42.

[0036] The jacket inlet 22 and jacket outlet 23 are normally closed and are only opened when the hydrogen storage alloy particles in the jacket annular cavity 33 need to be replaced. New hydrogen storage alloy particles can be poured into the jacket inlet 22, and the incoming hydrogen storage alloy particles will push the original hydrogen storage alloy particles out of the jacket outlet 23. Alternatively, the original hydrogen storage alloy particles can be flushed out by air pressure or water pressure before the new hydrogen storage alloy particles are poured in.

[0037] In practice, as a non-preferred option, it can be modified as follows: multiple vent holes 34 are arranged on the tube wall of the outer tube 32, the shell-side flow channel serves as the flow channel for flowing hydrogen, and the tube-side flow channel serves as the flow channel for flowing heat exchange medium.

[0038] Compared with existing technologies, this technology offers several advantages. First, the hydrogen storage alloy is placed in the jacketed annular cavity 33 within the jacketed tube. This results in uniform particle distribution, a large contact area with hydrogen, and high efficiency in hydrogen addition and removal. Second, due to the jacketed flow channel, once the hydrogen storage alloy's charging and discharging capacity deteriorates, new hydrogen storage alloy can be easily introduced through the jacket inlet to replace the original alloy without moving the entire device. This makes the operation convenient, cost-effective, and particularly suitable for medium to large-scale hydrogen charging and discharging equipment.

[0039] In this embodiment, the cylinder 1 is arranged vertically, and the jacket inlet 22 is located on the tube sheet 2 at the upper end of the cylinder 1. When replacing the hydrogen storage alloy particles, the jacket outlet 23 is opened to facilitate the flow of the hydrogen storage alloy particles out due to gravity.

[0040] In this embodiment, the tube sheet 2 includes a first side plate 24 connecting the cylinder 1 and a second side plate 25 connecting the tube box 4. The plate cavity 21 is located between the first side plate 24 and the second side plate 25. The end of the inner tube 31 passes through the first side plate 24 and the plate cavity 21 and is fixed to the second side plate 25 to connect the tube box 4. The end of the outer tube 32 is fixed to the first side plate 24 to connect the plate cavity 21.

[0041] In practice, an expansion joint can be installed on the wall of the cylinder 1 to facilitate the thermal expansion and deformation of the jacketed tube 3.

[0042] In the description of this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0043] All standard parts used in this invention can be purchased from the market, and irregular parts can be customized according to the description and drawings. The specific connection methods of each part adopt conventional methods such as bolts, rivets, and welding that are mature in the prior art. The machinery, parts and equipment adopt conventional models in the prior art, and the circuit connection adopts conventional connection methods in the prior art, which will not be described in detail here.

[0044] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

[0045] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A hydrogen storage and release device that facilitates the replacement of hydrogen storage materials, characterized in that: The system includes a cylindrical body, with tube sheets at both ends of the cylindrical body to form a shell side. The cylindrical body has a shell-side inlet and a shell-side outlet, thus forming a shell-side flow channel such as shell-side inlet-cylinder-shell-side outlet. The cylinder is equipped with multiple jacketed tubes, each of which includes an inner tube and an outer tube. The outer wall of the inner tube and the inner wall of the outer tube form a jacketed annular cavity for placing the hydrogen storage alloy. The tube sheet is provided with a plate cavity that connects to the jacketed annular cavity. The plate cavity has a jacket inlet and a jacket outlet, thus forming a jacket flow channel such as jacket inlet - plate cavity of tube sheet - jacketed annular cavity - plate cavity of another tube sheet - jacket outlet, so as to replace the hydrogen storage alloy in the jacketed annular cavity through the jacket flow channel. A tube box is provided on the side of the tube sheet away from the cylinder. The inner tube passes through the corresponding tube sheet cavity and connects to the corresponding tube box. The tube box is provided with a tube inlet and a tube outlet, thus forming a tube flow channel such as tube inlet-tube box-inner tube-another tube box-tube outlet. The jacketed tube is densely covered with multiple vent holes along its length, allowing hydrogen gas to pass through while obstructing the passage of hydrogen storage alloy particles; multiple vent holes are arranged on the inner tube wall, with the tube-side flow channel serving as the channel for flowing hydrogen gas and the shell-side flow channel serving as the channel for flowing heat exchange medium; or: multiple vent holes are arranged on the outer tube wall, with the shell-side flow channel serving as the channel for flowing hydrogen gas and the tube-side flow channel serving as the channel for flowing heat exchange medium.

2. The hydrogen storage and release device according to claim 1, which facilitates the replacement of hydrogen storage materials, is characterized in that: The cylinder is arranged vertically, and the jacket inlet is located on the tube sheet at the upper end of the cylinder.

3. The hydrogen storage and release device according to claim 1, which facilitates the replacement of hydrogen storage materials, is characterized in that: The tube sheet can be a hollowed-out integral forging structure, a plate welded structure, or a flat round tube welded structure.

4. A hydrogen storage and release device that facilitates the replacement of hydrogen storage materials according to claim 1 or 3, characterized in that: The tube sheet includes a first side plate connecting the cylinder and a second side plate connecting the tube box, with the plate cavity located between the first and second side plates; the end of the inner tube passes through the first side plate and the plate cavity and is fixed to the second side plate to connect to the tube box; the end of the outer tube is fixed to the first side plate to connect to the plate cavity.

5. A hydrogen storage and release device for easy replacement of hydrogen storage materials according to claim 1, characterized in that: The cylinder is equipped with an expansion joint.

6. A hydrogen storage and release device for easy replacement of hydrogen storage materials according to claim 1, characterized in that: The vent holes are covered with a filter membrane.

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