A solid hydrogen storage device

Abstract

This invention discloses a solid hydrogen storage device, comprising a vertical tank, a heat exchange medium distribution and collection box, and a hydrogen filling / discharging inner liner. A hydrogen inlet and outlet are provided on the vertical tank corresponding to the gap between the hydrogen filling / discharging inner liner and the vertical tank. A hydrogen storage material inlet pipe is located at the top of the hydrogen filling / discharging inner liner, and a hydrogen storage material outlet pipe forming a sliding seal with the vertical tank at the bottom. An expansion joint is provided on the wall of the hydrogen filling / discharging inner liner, which is filled with solid hydrogen storage material. Hydrogen pores are formed on the liner wall, with the pore diameter smaller than the minimum particle size of the solid hydrogen storage material. The heat exchange medium distribution and collection box is divided into a heat exchange medium inlet box and a heat exchange medium outlet box. A U-shaped heat exchange tube is installed inside the hydrogen filling / discharging inner liner, connecting the heat exchange medium inlet box and the heat exchange medium outlet box. The heat exchange medium inlet box has a heat exchange medium inlet, and the heat exchange medium outlet box has a heat exchange medium outlet. This invention simultaneously solves the heat and volume compensation problems during the hydrogen filling / discharging process, improving the reliability of the device.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen storage technology, and specifically relates to a solid hydrogen storage device. Background Technology

[0002] Hydrogen is considered one of the cleanest and most efficient energy sources because its combustion process does not release greenhouse gases such as carbon dioxide and it has a high calorific value. The utilization of hydrogen is inseparable from its storage, which currently includes three main methods: gaseous hydrogen storage, liquid hydrogen storage, and solid-state hydrogen storage. Solid-state hydrogen storage involves storing hydrogen in the lattice of a solid hydrogen storage alloy material (such as rare earth compounds (LaNi5)), and achieving physically reversible hydrogen addition and release processes by changing the temperature and pressure under certain temperature and pressure conditions. Compared to gaseous and liquid hydrogen storage, solid-state hydrogen storage does not require excessive energy consumption and has advantages such as higher volumetric hydrogen storage density, safety and efficiency, and a stable hydrogen release rate, making it a promising hydrogen storage technology.

[0003] Solid hydrogen storage materials typically expand in volume when absorbing hydrogen and contract in volume when releasing hydrogen. Furthermore, they release a significant amount of heat during hydrogen absorption and require substantial heat replenishment during hydrogen release. Temperature also significantly impacts the hydrogen absorption and desorption rates of the storage material. Therefore, to ensure the long-term use of hydrogen storage materials and the rapid and efficient absorption and desorption of hydrogen, it is essential to simultaneously address the heat and volume changes during hydrogen absorption and desorption, designing hydrogen storage devices with high-efficiency heat exchange performance and volume compensation. Otherwise, the absorption and desorption efficiency of solid hydrogen storage will decrease, and with each hydrogen charge and discharge cycle, the expansion and compression of the solid hydrogen storage alloy will cause lattice deformation, leading to a rapid decrease in its capacity. Additionally, the expansion of the solid hydrogen storage material subjects the storage shell to significant stress, posing a risk of bulging and cracking. Solving the problems of heat absorption / desorption and volume changes during the hydrogen absorption and desorption process of solid hydrogen storage is crucial for ensuring high absorption and desorption rates and directly affects the cost and safety of the hydrogen storage device.

[0004] Patent CN117307953A discloses a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials. After the hydrogen storage alloy's hydrogen charging and releasing capacity deteriorates, a new hydrogen storage alloy is injected through the jacket inlet to replace the original hydrogen storage alloy without moving the entire device. This method is convenient and low-cost. However, the volume expansion absorption of the hydrogen storage alloy during the charging and releasing process is poor, and the capacity of the solid hydrogen storage material may decay rapidly. Patent CN103883874B discloses a hydrogen storage tank with an external heat exchange structure. Its structure is simple, easy to manufacture, and low-cost. It has a better heat exchange effect and excellent hydrogen release performance. However, this hydrogen storage tank only has a heat exchange effect and cannot absorb the volume expansion of the solid hydrogen storage material during the hydrogen absorption and release process. Therefore, it cannot simultaneously solve the problems of volume expansion and heat release, and the tank body is at risk of bulging and rupture. Summary of the Invention

[0005] To address the technical problems of poor absorption efficiency due to volume expansion during hydrogen charging and discharging in existing solid hydrogen storage devices, and the inability to simultaneously solve the problems of volume expansion and heat release during absorption, this invention provides a solid hydrogen storage device that solves the problems of volume expansion and heat release during solid hydrogen storage.

[0006] This invention provides a solid hydrogen storage device, comprising a vertical tank, a heat exchange medium distribution and collection box coaxially arranged from top to bottom within the vertical tank, and a hydrogen filling and discharging liner; the heat exchange medium distribution and collection box is cylindrical and is formed by the inner wall of the vertical tank, the top plate of the vertical tank, and the bottom plate of the heat exchange medium distribution and collection box; the hydrogen filling and discharging liner is cylindrical and suspended below the bottom plate of the heat exchange medium distribution and collection box, the bottom plate of the heat exchange medium distribution and collection box and the inner wall of the hydrogen filling and discharging liner forming a closed space, and a teacup-shaped gap is formed between the outer wall of the hydrogen filling and discharging liner and the inner wall of the vertical tank; a hydrogen inlet and a hydrogen outlet are provided on the tank wall corresponding to the teacup-shaped gap;

[0007] A hydrogen storage material inlet pipe is located at the top center of the hydrogen filling / discharging inner liner, connecting to the inner liner. This inlet pipe passes through the heat exchange medium distribution and collection box and extends to the outside of the top plate of the vertical tank. A hydrogen storage material outlet pipe is located at the bottom center of the inner liner, connecting to the inner liner. This outlet pipe passes through the bottom of a teacup-shaped gap and extends to the outside of the bottom plate of the vertical tank. A sliding seal, movable axially along the vertical tank, is provided between the outer wall of the outlet pipe and the bottom plate of the outlet pipe. One or more expansion joints are provided on the cylindrical wall of the inner liner, which can extend or contract axially. The inner liner is filled with solid hydrogen storage material. Hydrogen pores are opened on the wall of the inner liner to allow hydrogen to enter and exit. The pore size of the hydrogen pores is smaller than the minimum particle size of the solid hydrogen storage material.

[0008] Two partition plates are symmetrically arranged along the diameter of the vertical tank inside the heat exchange medium distribution and collection box and outside the hydrogen storage material inlet pipe. The partition plates divide the heat exchange medium distribution and collection box into a heat exchange medium inlet box and a heat exchange medium outlet box that are symmetrically arranged on the left and right sides. U-shaped heat exchange tubes are symmetrically arranged in the hydrogen filling and discharging liner below the bottom plate of the heat exchange medium distribution and collection box corresponding to the heat exchange medium inlet box and the heat exchange medium outlet box. The vertical tank wall corresponding to the heat exchange medium inlet box has a heat exchange medium inlet, and the vertical tank wall corresponding to the heat exchange medium outlet box has a heat exchange medium outlet. The heat exchange medium inlet, heat exchange medium inlet box, U-shaped heat exchange tube, heat exchange medium outlet box and heat exchange medium outlet form a closed and connected cavity, which allows the heat exchange medium to remove heat from the solid hydrogen storage material filled in the hydrogen filling and discharging liner or to replenish heat to the solid hydrogen storage material.

[0009] When loading solid hydrogen storage material, the outlet pipe is closed and the inlet pipe is open. Under gravity, the hydrogen storage material enters the filling / discharging liner through the inlet pipe and is stored there. When the hydrogen storage material needs replacement due to its lifespan decline, the outlet pipe is opened, and the material exits the storage device through the outlet pipe under gravity. The inlet and outlet pipes should preferably be cylindrical with a diameter of 50–400 mm.

[0010] The sliding seal between the outer wall of the hydrogen storage material outlet pipe and the bottom plate of the vertical tank, which moves axially along the vertical tank, can be a packing seal. The packing seal ensures that the hydrogen storage material outlet pipe can maintain a tight seal with the bottom of the vertical tank as it extends and retracts downward along with the hydrogen filling and discharging inner liner.

[0011] Depending on the different needs of hydrogen filling and discharging, during hydrogen filling, the low-temperature heat exchange medium enters the heat exchange medium inlet box from the heat exchange medium inlet. Through the distribution function of the heat exchange medium inlet box, it enters the U-shaped heat exchange tubes, absorbing the heat released by the solid hydrogen storage material in the hydrogen filling / discharging liner due to hydrogen absorption. The heat is then collected in the heat exchange medium outlet box and leaves the hydrogen storage device through the heat exchange medium outlet, thus lowering the temperature of the solid hydrogen storage material. When it is necessary to release hydrogen from the solid hydrogen storage material, the high-temperature heat exchange medium enters the heat exchange medium inlet box from the heat exchange medium inlet. Through the distribution function of the heat exchange medium inlet box, it enters the U-shaped heat exchange tubes, providing heat to the solid hydrogen storage material in the hydrogen filling / discharging liner. The solid hydrogen storage material absorbs heat and releases hydrogen. The heat exchange medium, after releasing heat, collects in the heat exchange medium outlet box and leaves the hydrogen storage device through the heat exchange medium outlet. By using the heat exchange medium to remove heat from the hydrogen storage device or replenish heat to the hydrogen storage device, the hydrogen absorption and discharging process is ensured to proceed at a high rate. Fluids such as water, nitrogen, and air can be used as the heat exchange medium.

[0012] The U-shaped heat exchange tubes are arranged in a ring, equilateral triangle, or regular quadrilateral pattern on the cross-section of the hydrogen filling / discharging liner to ensure that heat can be evenly dissipated or replenished throughout the liner. The U-shaped heat exchange tubes are preferably circular, with an outer diameter of 19–80 mm. When the U-shaped heat exchange tubes are evenly distributed in a ring, the circumferential spacing between the tubes should be 30–100 mm, and the radial spacing should be 40–150 mm. When the U-shaped heat exchange tubes are evenly distributed in an equilateral triangle pattern, the side length of the triangle should be 25–150 mm; when the U-shaped heat exchange tubes are evenly distributed in a regular quadrilateral pattern, the side length of the quadrilateral should be 30–150 mm.

[0013] The diameter of the hydrogen filling / discharging liner should preferably be 0.6 to 0.9 times the diameter of the vertical tank. The expansion joints on the liner wall can extend or contract axially to change the axial length of the liner and adjust its storage volume, accommodating volume changes caused by the solid hydrogen storage material during filling and discharging. When expansion joints are manufactured as a single layer, elastic alloys should be used to give them good resilience. Copper-based, iron-based, and nickel-based high-elasticity alloys are suitable, utilizing their low elastic modulus and high elastic limit to provide high resilience. When expansion joints are made of multiple layers through stamping, they can be constructed with separate pressure-bearing and resilience layers. The pressure-bearing layer bears the pressure of the hydrogen storage system, while the resilience layer provides the resilience. The resilience layer should preferably be made of an elastic alloy, ensuring that the material maintains a certain tensile stress after stamping, creating a spring-like effect that allows the expansion joint to maintain its original shape and rebound when the external force is removed. When expansion joints are made of multiple layers, springs can be added between the layers to enhance their resilience. In short, the goal is to ensure the expansion joint has optimal resilience. An expansion joint can consist of one or more expansion waves, with a wave height of 30–300 mm and a wave spacing of 50–200 mm. When multiple expansion joints are set in the inner wall of the hydrogen filling and discharging liner, the multiple expansion joints are evenly distributed on the axis of the hydrogen filling and discharging liner to ensure that the volume expansion at different positions on the axis of the hydrogen filling and discharging liner can be better absorbed.

[0014] The hydrogen vents on the inner wall of the hydrogen filling / discharging liner allow hydrogen to enter and exit. To ensure uniform absorption and release of hydrogen by the solid hydrogen storage material within the liner, the vents should be evenly distributed on the inner wall, with a spacing of 20–100 mm. The vents should preferably be round, with a diameter of 30%–80% of the smallest particle size of the solid hydrogen storage material. Smaller vents prevent the solid hydrogen storage material from entering the gap between the vertical tank and the inner liner through the vents.

[0015] As a preferred solution, to ensure that all solid hydrogen storage material is filled within the expandable hydrogen filling / discharging liner and to prevent the solid hydrogen storage material from expanding and clogging the hydrogen storage material outlet pipe during hydrogen filling, a hydrogen storage material outlet plug can be installed inside the outlet pipe. The outlet plug consists of a baffle, a packing seal, a baffle cylinder, a handle, and an installation ring. The baffle cylinder is a cylindrical tube with an outer diameter smaller than the inner diameter of the hydrogen storage material outlet pipe, typically 4-10 mm smaller. One end of the baffle cylinder is closed by the baffle, while the other end is open. The baffle end is inserted into the hydrogen storage material outlet pipe to prevent solid hydrogen storage material from entering the outlet pipe when not unloading. The baffle has the same shape as the bottom of the filling / discharging liner. A handle, which can be made of round steel or angle steel, is provided at the open end for easy installation and removal of the hydrogen storage material outlet plug. The gap between the hydrogen storage material outlet pipe and the hydrogen storage material outlet plug is sealed with filler such as ceramic fiber rope to prevent solid hydrogen storage material from entering the gap between them. The diameter of the ceramic fiber rope should be 5-11 mm. To ensure that the hydrogen storage material outlet plug is fixed inside the hydrogen storage material outlet pipe, an installation ring is set at the open end. The installation ring is a circular ring that is fitted over the baffle. A circular hole is made on the installation ring, and a threaded hole is made at the same position on the hydrogen storage material outlet pipe so that the installation ring can be fixed to the hydrogen storage material outlet pipe with screws.

[0016] As a preferred option, the expansion wave of the expansion joint should be set to be concave towards the inner side of the hydrogen filling and discharging liner. This has the advantage that it can not only extend along the axial direction of the tank to increase the internal volume, but also expand outward from the expansion wave to release the axial space here, so as to better cope with the volume expansion of the solid hydrogen storage material.

[0017] As a preferred option, to ensure that the solid hydrogen storage material in the hydrogen filling and discharging liner can be smoothly discharged, the lower part of the hydrogen filling and discharging liner should be set as a cone with a cone angle of 20 to 60 degrees, and the hydrogen storage material outlet pipe should be located at the top of the cone so that the solid hydrogen storage material can be discharged smoothly.

[0018] As a preferred solution, to avoid problems such as caking or poor flowability of the solid hydrogen storage material in the hydrogen filling and discharging liner, which may cause difficulties in unloading, a loosening air inlet can be installed on the wall of the hydrogen filling and discharging liner. During the unloading process of the solid hydrogen storage material, inert gases such as high-pressure nitrogen and carbon dioxide can be introduced to allow the solid hydrogen storage material to be discharged more smoothly.

[0019] As a preferred option, a filter screen, such as a wire mesh, can be installed on the hydrogen vent to prevent fine, broken solid hydrogen storage material particles from entering the gap between the vertical tank and the hydrogen filling / draining liner. The pore size of the filter screen should preferably be 10% to 30% of the minimum particle size of the solid hydrogen storage material. To reduce potential damage to the filter screen caused by adding and discharging solid hydrogen storage material, the filter screen should preferably be installed on the outside of the hydrogen filling / draining liner, i.e., between the vertical tank and the hydrogen filling / draining liner.

[0020] As a better solution, a hydrogen conduit can be installed inside the hydrogen inlet. The shape of the hydrogen conduit is consistent with that of the hydrogen inlet, and the outer diameter of the hydrogen conduit is consistent with the inner diameter of the hydrogen inlet. The hydrogen conduit is a round tube with open ends. Filter screens are installed inside the hydrogen conduit, near the outlet and inlet ends, to improve the reliability of the filter screens. This ensures that the solid hydrogen storage material is stored in the hydrogen filling / discharging liner and does not enter the gap between the hydrogen filling / discharging liner and the vertical tank with the hydrogen, nor does it leave the hydrogen storage device with the hydrogen.

[0021] As a preferred solution, a limiting hinge can be installed on the wall of the hydrogen filling / discharging liner. The limiting hinge consists of a connecting rod and a connecting hinge. The connecting rod is connected via the connecting hinge and can rotate around the hinge. The initial position of the limiting hinge installation is when the connecting rods are at a certain angle, preferably 30–60 degrees. The limiting hinge moves downwards as the hydrogen filling / discharging liner expands and elongates. When the connecting rods overlap and form a straight line, i.e., the angle between the two connected rods is 0 degrees, the limiting hinge reaches its limiting termination position and restricts further downward movement and elongation of the hydrogen filling / discharging liner. It is preferable to have two or more limiting hinges evenly distributed around the circumference of the hydrogen filling / discharging liner to ensure the liner is in a uniformly limited state.

[0022] As a preferred embodiment, a rebound device is installed inside the vertical tank, below the hydrogen filling / discharging liner. The rebound device consists of a mounting top plate, a rebound spring, and a mounting base plate from top to bottom. The mounting top plate is fixed below the hydrogen filling / discharging liner, and the mounting base plate is mounted on the bottom plate of the vertical tank. The upper and lower ends of the rebound spring are connected to the mounting top plate and the mounting base plate, respectively. When one rebound device is installed, it is located at the bottom center of the hydrogen filling / discharging liner, with the hydrogen storage material outlet pipe fitted inside. If two or more rebound devices are installed, they are evenly distributed along the lower edge of the hydrogen filling / discharging liner. The function of the rebound device is to assist the expansion joint in rebounding, ensuring that after the solid hydrogen storage material releases hydrogen, the expansion joint is in a contracted state, allowing it to expand during the next hydrogen filling. When the hydrogen storage device is not storing hydrogen, the return spring is in a natural or appropriately compressed state. When the solid hydrogen storage material begins to absorb hydrogen, its volume expands, causing the expansion joint to extend downwards. This increases the storage volume of the hydrogen filling / discharging liner while simultaneously compressing the return spring, allowing the spring to accumulate elastic potential energy. When the solid hydrogen storage material in the filling / discharging liner begins to release hydrogen, its volume decreases, and it no longer exerts a downward force on the return spring. At this point, the elastic potential energy accumulated in the spring begins to be released, applying a force to the filling / discharging liner. The expansion joint of the filling / discharging liner absorbs the compressive stress, causing the expansion joint to contract in preparation for the next hydrogen storage and release cycle.

[0023] As a better solution, when the limiting hinge is not used, a limiting rod can be installed inside the spring of the rebound device. The limiting rod is fixed to the mounting base and kept vertical. The limiting rod can be cylindrical, square, or angle iron, with an outer diameter smaller than the inner diameter of the spring so that it can be installed inside the spring. After installation, the height difference between the spring and the limiting rod should be 60% to 90% of the maximum downward displacement of the hydrogen filling / discharging liner. The purpose of the limiting rod is to restrict the downward movement of the hydrogen filling / discharging liner. Once the liner reaches the limiting rod, it will stop moving downward. At this point, a stress sensor or contact sensor can be installed on the limiting rod. When the limiting rod begins to generate stress or contact with the liner is detected, an alarm is triggered or the process settings stop the storage of hydrogen in the hydrogen storage device. The advantage of the limiting rod is that it ensures that the hydrogen storage device will not be damaged by overfilling or excessive expansion of the solid hydrogen storage material.

[0024] When filling the hydrogen storage device with solid hydrogen storage material, open the hydrogen storage material inlet pipe and close the hydrogen storage material outlet pipe to fill the charging / discharging liner with solid hydrogen storage material. Keep the hydrogen storage material inlet and outlet pipes closed during the charging / discharging process. When unloading the solid hydrogen storage material from the hydrogen storage device, open the hydrogen storage material outlet pipe to unload the solid hydrogen storage material from the charging / discharging liner. When unloading the solid hydrogen storage material, the hydrogen storage material inlet pipe can also be opened as a vent. The purpose of opening the hydrogen storage material inlet pipe is to maintain the pressure balance of the liner and prevent the formation of negative pressure in the charging / discharging liner when the solid hydrogen storage material is rapidly unloaded, which would make it difficult to unload the solid hydrogen storage material or cause the charging / discharging liner to collapse. If the solid hydrogen storage material has poor flowability and cannot be unloaded due to caking, compression, or other reasons, the loosening air inlet can be opened and inert gas such as nitrogen can be introduced to loosen the solid hydrogen storage material and unload it more smoothly from the charging / discharging liner.

[0025] During hydrogen filling, the hydrogen inlet of this solid hydrogen storage device is opened and the hydrogen outlet is closed, forming a sealed cavity where hydrogen can only enter and not exit. Hydrogen enters from the hydrogen inlet into the gap between the filling / discharging liner and the vertical tank, and then enters the filling / discharging liner through hydrogen vents. Under pressure, the hydrogen is stored in the solid hydrogen storage material within the filling / discharging liner. During filling, the volume of the solid hydrogen storage material increases, causing the expansion joint to extend towards the outlet pipe of the hydrogen storage material. This increase in the volume of the filling / discharging liner compensates for the increase in the volume of the solid hydrogen storage material, preventing the filling / discharging liner from bulging. Because the solid hydrogen storage material releases heat during the absorption of hydrogen, once the heat released during hydrogen filling reaches a certain level, the temperature inside the hydrogen filling / discharging tank rises. At this point, a low-temperature medium is introduced into the heat exchange medium inlet box from the heat exchange medium inlet box, and then enters the U-shaped heat exchange tube from the heat exchange medium inlet box. The heat released during the hydrogen filling process is absorbed by the U-shaped heat exchange tube, the temperature of the solid hydrogen storage material is reduced, and the temperature of the low-temperature medium rises. The medium then collects through the U-shaped heat exchange tube into the heat exchange medium outlet box, and then leaves the hydrogen storage device through the heat exchange medium outlet.

[0026] When releasing hydrogen, this solid hydrogen storage device opens the hydrogen outlet and closes the hydrogen inlet, creating a sealed cavity that allows only outflow. Hydrogen is released from the solid hydrogen storage material, exits through the hydrogen pores into the hydrogen filling / discharging liner, and fills the gap between the liner and the vertical tank. Once a certain pressure is established, the hydrogen exits through the outlet, supplying downstream devices or external equipment. After releasing hydrogen, the solid hydrogen storage material decreases in volume, and the expansion joint contracts due to its resilience, restoring the liner to its pre-filling state. Since the solid hydrogen storage material needs to absorb heat to release the stored hydrogen, a high-temperature heat exchange medium enters the heat exchange medium inlet box through the inlet, then flows into the U-shaped heat exchange tube. This U-shaped tube transfers heat to the solid hydrogen storage material within the liner, causing it to absorb heat, heat up, and release hydrogen. The released heat is collected in the outlet box through the U-shaped heat exchange tube and then exits the solid hydrogen storage device through the outlet.

[0027] The same medium can be used during hydrogen charging and discharging. By setting up external heaters or coolers, the heat exchange medium is cooled during hydrogen charging and heated during hydrogen discharging, so as to achieve the purpose of recycling.

[0028] The present invention has the following beneficial effects:

[0029] 1) By storing hydrogen in solid hydrogen storage materials, there is no need for harsh conditions such as high pressure or low temperature. The hydrogen storage process does not require excessive energy consumption, and it is safe, efficient and has a stable hydrogen release rate.

[0030] 2) By setting expansion elements and heat exchange elements, the heat and volume compensation problems in the hydrogen charging and discharging process are solved at the same time, so that the hydrogen charging and discharging can be carried out at a higher rate; the expansion elements reduce the mutual expansion and compression of solid hydrogen storage alloy materials, and the internal lattice of solid hydrogen storage alloy materials can still maintain a good morphology after more hydrogen charging and discharging cycles, resulting in slower decay of hydrogen storage capacity and longer life of solid hydrogen storage materials.

[0031] 3) By creating an internal volume change through expansion elements, the stress applied to the hydrogen storage shell caused by volume expansion is greatly reduced, avoiding risks such as bulging and cracking of the solid hydrogen storage shell. Furthermore, by setting a limiting device, the safety and reliability of solid hydrogen storage are improved, and the cost of solid hydrogen storage is reduced. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the solid hydrogen storage device of the present invention;

[0033] Figure 2 yes Figure 1 A top view of the structure along the central AA direction;

[0034] Figure 3 yes Figure 1 A schematic diagram of a structure for plugging the outlet of hydrogen storage material;

[0035] Figure 4 yes Figure 1 A schematic diagram of a type of mid-limit hinge;

[0036] Figure 5 yes Figure 1 A schematic diagram of a rebound device;

[0037] Figure 6 yes Figure 1 A schematic diagram of a hydrogen gas conduit.

[0038] In the diagram: 1-Hydrogen storage material inlet pipe, 2-Heat exchange medium distribution and collection box, 3-Heat exchange medium inlet, 4-Heat exchange medium outlet, 5-Hydrogen inlet, 6-Hydrogen outlet, 7-Vertical tank, 8-Hydrogen vent, 9-Hydrogen filling / discharging inner liner, 10-Hydrogen conduit, 11-Sliding seal, 12-Hydrogen storage material outlet pipe, 13-Hydrogen storage material outlet plug, 14-Solid hydrogen storage material, 15-Rebound device, 16-Loosening air inlet, 17-U-shaped heat exchanger Pipe, 18-Filter screen, 19-Limit hinge, 20-Expansion joint, 21-Heat exchange medium inlet box, 22-Heat exchange medium outlet box, 23-Divider plate, 24-Divider plate, 25-Baffle, 26-Stuffing seal, 27-Baffle cylinder, 28-Handle, 29-Mounting ring, 30-Connecting rod, 31-Connecting hinge, 32-Mounting top plate, 33-Limit rod, 34-Rebound spring, 35-Mounting base plate, 36-Filter screen, 37-Filter screen. Detailed Implementation

[0039] The present invention will now be described in detail with reference to the accompanying drawings.

[0040] like Figure 1 and Figure 2 As shown, the solid hydrogen storage device of the present invention includes a vertical tank 7, a heat exchange medium distribution and collection box 2 and a hydrogen filling and discharging liner 9 arranged coaxially with the vertical tank from top to bottom inside the vertical tank; the heat exchange medium distribution and collection box 2 is cylindrical and is formed by the inner wall of the vertical tank 7, the top plate of the vertical tank 7 and the bottom plate of the heat exchange medium distribution and collection box 2; the hydrogen filling and discharging liner 9 is cylindrical and suspended below the bottom plate of the heat exchange medium distribution and collection box 2. The bottom plate of the heat exchange medium distribution and collection box 2 and the inner wall of the hydrogen filling and discharging liner 9 form a closed space, and a teacup-shaped gap is formed between the outer wall of the hydrogen filling and discharging liner 9 and the inner wall of the vertical tank 7; a hydrogen inlet 5 and a hydrogen outlet 6 are provided on the tank wall of the vertical tank 7 corresponding to the teacup-shaped gap;

[0041] A hydrogen storage material inlet pipe 1 is located at the top center of the hydrogen filling / discharging inner liner 9, communicating with the inner liner 9. The hydrogen storage material inlet pipe 1 passes through the heat exchange medium distribution and collection box 2 and extends to the outside of the top plate of the vertical tank 7. A hydrogen storage material outlet pipe 12 is located at the bottom center of the hydrogen filling / discharging inner liner 9, communicating with the inner liner 7. The hydrogen storage material outlet pipe 12 passes through the bottom of the teacup-shaped gap and extends to the outside of the bottom plate of the vertical tank 7. A sliding seal 11 that moves axially along the vertical tank 7 is provided between the outer wall of the hydrogen storage material outlet pipe 12 and the bottom plate of the vertical tank 7. A hydrogen storage material outlet plug 13 is provided inside the hydrogen storage material outlet pipe 12. One or more... Expansion joint 20, which can extend or contract axially; the hydrogen filling / discharging liner 9 is filled with solid hydrogen storage material 14; hydrogen pores 8 are opened on the wall of the hydrogen filling / discharging liner 9 to allow hydrogen to enter and exit the hydrogen filling / discharging liner 9, and the pore diameter of the hydrogen pores 8 is smaller than the minimum particle size of the solid hydrogen storage material 14; a hydrogen conduit 10 can be installed on the hydrogen pores, or a filter screen 18 can be installed on the outside of the hydrogen pores, i.e., on the outside of the wall of the hydrogen filling / discharging liner 9; a limiting hinge 19 is provided on the outside of the wall of the hydrogen filling / discharging liner 9 along the axial direction; a rebound device 15 is provided inside the vertical tank body 7 and below the hydrogen filling / discharging liner 9; a loosening air inlet 16 is provided on the wall of the hydrogen filling / discharging liner 9.

[0042] like Figure 2 As shown, partition plates 23 and 24 are symmetrically arranged along the diameter of the vertical tank 7 inside the heat exchange medium distribution and collection box 2 and outside the hydrogen storage material inlet pipe 1. Partition plates 23 and 24 divide the heat exchange medium distribution and collection box 2 into a symmetrically arranged heat exchange medium inlet box 21 and heat exchange medium outlet box 22. Figure 1U-shaped heat exchange tubes 17 are symmetrically arranged inside the hydrogen filling and discharging liner 9 below the bottom plate of the heat exchange medium distribution and collection box 2 corresponding to the heat exchange medium inlet box 21 and the heat exchange medium outlet box 22. The U-shaped heat exchange tubes 17 are embedded in the solid hydrogen storage material 14. The heat exchange medium inlet box 21 and the heat exchange medium outlet box 22 are connected through the U-shaped heat exchange tubes 17. The vertical tank 7 corresponding to the heat exchange medium inlet box 21 has a heat exchange medium inlet 3 on its tank wall, and the vertical tank 7 corresponding to the heat exchange medium outlet box 22 has a heat exchange medium outlet 4 on its tank wall. The heat exchange medium inlet 3, the heat exchange medium inlet box 21, the U-shaped heat exchange tubes 17, the heat exchange medium outlet box 22 and the heat exchange medium outlet 4 form a closed and connected cavity, which allows the heat exchange medium to remove heat from the solid hydrogen storage material 14 filled in the hydrogen filling and discharging liner 9 or to replenish heat to the solid hydrogen storage material 14.

[0043] Figure 3 yes Figure 1 A schematic diagram of a structure for a hydrogen storage material outlet plug. As shown in the figure, the hydrogen storage material outlet plug includes a baffle 25, a packing seal 26, a baffle cylinder 27, a handle 28, and a mounting ring 29. The baffle cylinder 27 is a cylindrical shape, with an outer diameter smaller than the inner diameter of the hydrogen storage material outlet pipe 12, typically 4-10 mm smaller. One end of the baffle cylinder 27 is closed by the baffle 25, while the other end is open. The baffle end is inserted into the hydrogen storage material outlet pipe 12 to prevent solid hydrogen storage material from entering the outlet pipe 12 when not unloading. The baffle 25 is aligned with the bottom of the hydrogen filling / discharging inner liner 9. The shape is consistent; a handle 28 is provided at the open end of the baffle 27, which can be round steel or angle steel, etc.; the gap between the hydrogen storage material outlet pipe 12 and the hydrogen storage material outlet plug is filled with filler such as ceramic fiber rope and sealed 26, the diameter of the ceramic fiber rope should be 5-11mm; the mounting ring 29 is a circular ring, which is fitted outside the baffle 27, and a circular hole is opened on the mounting ring 29. A threaded hole is opened at the same position on the hydrogen storage material outlet pipe 12 so that the mounting ring 29 can be fixed on the hydrogen storage material outlet pipe 12 with screws.

[0044] Figure 4 yes Figure 1 A schematic diagram of a limiting hinge structure. As shown in the figure, the limiting hinge consists of connecting rods 30 and connecting hinges 31, with the connecting rods 30 connected via the connecting hinges 31. The initial installation position of the limiting hinge is such that the connecting rods 30 are at a certain angle, with the included angle between the connected rods preferably being 30 to 60 degrees. It is preferable to have two or more limiting hinges, evenly distributed around the circumference of the hydrogen filling / discharging liner, to ensure that the hydrogen filling / discharging liner is in a uniformly limited position.

[0045] Figure 5 yes Figure 1A schematic diagram of the rebound device. As shown in the figure, the rebound device consists of a mounting top plate 32, a rebound spring 34, and a mounting base plate 35 from top to bottom. When one rebound device is installed, it is located at the bottom center of the hydrogen filling / discharging liner, with the hydrogen storage material outlet pipe fitted inside it. If two or more rebound devices are installed, they are evenly distributed along the lower edge of the hydrogen filling / discharging liner. When no limiting hinge is installed, a limiting rod 33 can be installed inside the rebound spring. The purpose of the limiting rod is to restrict the downward movement of the hydrogen filling / discharging liner. Once the hydrogen filling / discharging liner moves down to contact the limiting rod 33, it will no longer move downward.

[0046] Figure 6 yes Figure 1 A schematic diagram of a hydrogen conduit. As shown in the figure, the hydrogen conduit is a circular tube open at both ends. Filter screens 36 and 37 are installed inside the hydrogen conduit, near the outlet and inlet ends, to improve the reliability of the filters and ensure that the solid hydrogen storage material is stored in the hydrogen filling / discharging liner and does not enter the gap between the hydrogen filling / discharging liner and the vertical tank with the hydrogen, nor does it leave the hydrogen storage device with the hydrogen.

[0047] The operation process of the present invention will be described below with reference to the accompanying drawings:

[0048] 1) Loading and unloading of solid hydrogen storage materials

[0049] Close the hydrogen storage material outlet pipe 12 and open the hydrogen storage material inlet pipe 1. Under the influence of gravity, the solid hydrogen storage material 14 enters the hydrogen filling / discharging liner 9 from the hydrogen storage material inlet pipe 1 and is stored in the hydrogen filling / discharging liner. When the solid hydrogen storage material 14 needs to be replaced due to its lifespan decline, open the hydrogen storage material outlet pipe 12. Under the influence of gravity, the solid hydrogen storage material 14 in the hydrogen filling / discharging liner 9 leaves the hydrogen storage device from the hydrogen storage material outlet pipe 12. If the solid hydrogen storage material 14 cannot be discharged due to poor flowability caused by caking, compression, etc., the loosening air inlet 17 can be opened and inert gases such as nitrogen can be introduced to loosen the solid hydrogen storage material 14 and discharge it more smoothly from the hydrogen filling / discharging liner 9.

[0050] 2) Hydrogen charging of solid hydrogen storage materials

[0051] Simultaneously close hydrogen outlet 6, hydrogen storage material inlet pipe 1, hydrogen storage material outlet pipe 12, and loosening air inlet 16, and open hydrogen inlet 5. Hydrogen enters through hydrogen inlet 5 and fills the gap between the inner wall of the hydrogen filling / discharging liner 9 and the vertical tank 7, then enters the hydrogen filling / discharging liner 9 through hydrogen inlet 8 and is absorbed and stored by the solid hydrogen storage material 14. During the hydrogen filling process, the low-temperature heat exchange medium enters the heat exchange medium inlet box 21 from the heat exchange medium inlet 3, and enters the U-shaped heat exchange tube 17 through the distribution action of the heat exchange medium inlet box 21. After absorbing the heat released by the solid hydrogen storage material 14 in the hydrogen filling / discharging liner 9, it is collected in the heat exchange medium outlet box 22 and leaves the hydrogen storage device through the heat exchange medium outlet 4. During the hydrogen filling process, the volume of the solid hydrogen storage material 14 increases, causing the expansion joint 20 to extend towards the hydrogen storage material outlet pipe 12. The volume of the hydrogen filling / discharging liner 9 increases, compensating for the increase in the volume of the solid hydrogen storage material 14, and the hydrogen filling / discharging liner 9 avoids the risk of bulging.

[0052] 3) Hydrogen release from solid hydrogen storage materials

[0053] Simultaneously close the hydrogen inlet 5, hydrogen storage material inlet pipe 1, hydrogen storage material outlet pipe 12, and loosening air inlet 16, and open the hydrogen outlet 6. The high-temperature heat exchange medium enters the heat exchange medium inlet box 21 from the heat exchange medium inlet 3, and through the distribution action of the heat exchange medium inlet box 21, enters the U-shaped heat exchange tube 17, providing heat to the solid hydrogen storage material 14 in the hydrogen filling / discharging liner 9. The solid hydrogen storage material 14 absorbs heat and releases hydrogen gas, which leaves the hydrogen storage device through the hydrogen outlet 6. The heat exchange medium, after releasing heat, collects in the heat exchange medium outlet box 22 and leaves the hydrogen storage device through the heat exchange medium outlet 4. The heat exchange medium can be water, nitrogen, air, or other fluids. After the solid hydrogen storage material 14 releases hydrogen, its volume decreases, and the expansion joint 20 contracts under the action of elastic force, allowing the hydrogen filling / discharging liner 9 to return to its pre-filling state as much as possible. Of course, to ensure the contraction of the hydrogen filling / discharging liner 9, a limiting hinge 19 can be used to prevent excessive deformation of the expansion joint 20, and a springback device 15 can be used to assist the contraction of the expansion joint 20. Alternatively, without setting a limiting hinge, a limiting rod 33 can be set inside the spring spring of the rebound device to prevent excessive deformation of the expansion joint 20.

Claims

1. A solid hydrogen storage device, characterized in that: The system includes a vertical tank, a heat exchange medium distribution and collection box coaxially arranged from top to bottom within the vertical tank, and a hydrogen filling and discharging liner. The heat exchange medium distribution and collection box is cylindrical and is formed by the inner wall of the vertical tank, the top plate of the vertical tank, and the bottom plate of the heat exchange medium distribution and collection box. The hydrogen filling and discharging liner is cylindrical and suspended below the bottom plate of the heat exchange medium distribution and collection box. The bottom plate of the heat exchange medium distribution and collection box and the inner wall of the hydrogen filling and discharging liner form a closed space, and a teacup-shaped gap is formed between the outer wall of the hydrogen filling and discharging liner and the inner wall of the vertical tank. A hydrogen inlet and a hydrogen outlet are provided on the vertical tank wall corresponding to the teacup-shaped gap. A hydrogen storage material inlet pipe is located at the top center of the hydrogen filling / discharging inner liner, connecting to the inner liner. This inlet pipe passes through the heat exchange medium distribution and collection box and extends to the outside of the top plate of the vertical tank. A hydrogen storage material outlet pipe is located at the bottom center of the inner liner, connecting to the inner liner. This outlet pipe passes through the bottom of a teacup-shaped gap and extends to the outside of the bottom plate of the vertical tank. A sliding seal, movable axially along the vertical tank, is provided between the outer wall of the outlet pipe and the bottom plate of the outlet pipe. One or more expansion joints are provided on the cylindrical wall of the inner liner, which can extend or contract axially. The inner liner is filled with solid hydrogen storage material. Hydrogen pores are opened on the wall of the inner liner to allow hydrogen to enter and exit. The pore size of the hydrogen pores is smaller than the minimum particle size of the solid hydrogen storage material. Two partition plates are symmetrically arranged along the diameter of the vertical tank inside the heat exchange medium distribution and collection box and outside the hydrogen storage material inlet pipe. The partition plates divide the heat exchange medium distribution and collection box into a heat exchange medium inlet box and a heat exchange medium outlet box that are symmetrically arranged on the left and right sides. U-shaped heat exchange tubes are symmetrically arranged in the hydrogen filling and discharging liner below the bottom plate of the heat exchange medium distribution and collection box corresponding to the heat exchange medium inlet box and the heat exchange medium outlet box. The vertical tank wall corresponding to the heat exchange medium inlet box has a heat exchange medium inlet, and the vertical tank wall corresponding to the heat exchange medium outlet box has a heat exchange medium outlet. The heat exchange medium inlet, heat exchange medium inlet box, U-shaped heat exchange tube, heat exchange medium outlet box and heat exchange medium outlet form a closed and connected cavity, which allows the heat exchange medium to remove heat from the solid hydrogen storage material filled in the hydrogen filling and discharging liner or to replenish heat to the solid hydrogen storage material.

2. The solid hydrogen storage device according to claim 1, characterized in that: The outlet pipe of the hydrogen storage material is equipped with a hydrogen storage material outlet plug.

3. The solid hydrogen storage device according to claim 2, characterized in that: The hydrogen storage material outlet plug includes a baffle, a packing seal, a baffle cylinder, and a handle. The baffle cylinder is a cylindrical tube with an outer diameter smaller than the inner diameter of the hydrogen storage material outlet pipe. One end of the baffle cylinder is closed with a baffle, and the other end is open. The baffle end is inserted into the hydrogen storage material outlet pipe to prevent solid hydrogen storage material from entering the outlet pipe when not unloading. The baffle has the same shape as the bottom of the hydrogen filling / discharging liner. A handle is provided at the open end, which can be a round steel or angle steel, to facilitate the installation and removal of the hydrogen storage material outlet plug. A packing seal is provided in the gap between the hydrogen storage material outlet pipe and the hydrogen storage material outlet plug to prevent solid hydrogen storage material from entering the gap between them.

4. The solid hydrogen storage device according to claim 3, characterized in that: The baffle is provided with a mounting ring at the open end. The mounting ring is a circular ring that is fitted over the baffle. A circular hole is made on the mounting ring, and a threaded hole is made at the same position on the hydrogen storage material outlet pipe so that the mounting ring can be fixed to the hydrogen storage material outlet pipe with screws.

5. The solid hydrogen storage device according to claim 1, characterized in that: Limit hinges are installed on the inner wall of the hydrogen filling / discharging liner.

6. The solid hydrogen storage device according to claim 5, characterized in that: The limiting hinge consists of a connecting rod and a connecting hinge. The connecting rod is connected by the connecting hinge and can rotate around the connecting hinge. The initial position of the limiting hinge is when the connecting rods are at a certain angle. The limiting hinge moves downward as the inner wall of the hydrogen filling and discharging liner expands and elongates. When the connecting rods overlap and form a straight line, that is, when the included angle between the two connected connecting rods is 0 degrees, the limiting hinge reaches the limiting termination position and restricts the inner wall of the hydrogen filling and discharging liner from continuing to move downward and elongate.

7. The solid hydrogen storage device according to claim 1, characterized in that: A rebound device is installed inside the vertical tank, below the hydrogen filling / discharging liner.

8. The solid hydrogen storage device according to claim 7, characterized in that: The rebound device consists of a mounting top plate, a rebound spring, and a mounting bottom plate from top to bottom. The mounting top plate is fixed below the hydrogen filling / discharging inner liner, and the mounting bottom plate is installed on the bottom plate of the vertical tank. The upper and lower ends of the rebound spring are connected to the mounting top plate and the mounting bottom plate, respectively.

9. The solid hydrogen storage device according to claim 8, characterized in that: A limiting rod is installed inside the rebound spring of the rebound device. The limiting rod is fixed to the mounting base plate and kept vertical. The limiting rod is cylindrical or square. The outer diameter of the limiting rod is smaller than the inner diameter of the rebound spring. The height of the limiting rod is lower than the height of the rebound spring in its natural state. The limiting rod restricts the downward movement of the hydrogen filling / discharging liner. When the hydrogen filling / discharging liner moves down to contact the limiting rod, it will no longer move downward.

10. The solid hydrogen storage device according to claim 5, characterized in that: A rebound device is installed inside the vertical tank, below the hydrogen filling / discharging liner.

Images