A solid hydrogen storage device

Abstract

This invention discloses a solid hydrogen storage device, comprising a heat exchange medium distribution and collection box, a hydrogen distribution and collection box, and a hydrogen filling and discharging box arranged from top to bottom; the heat exchange medium distribution and collection box or the hydrogen distribution and collection box has two or more lug-type supports on its circumference; the hydrogen filling and discharging box has a hydrogen storage material inlet pipe and a hydrogen storage material outlet pipe respectively installed at the top and bottom; the hydrogen filling and discharging box has an expansion joint on its cylindrical wall; the hydrogen filling and discharging box is filled with solid hydrogen storage material; the heat exchange medium distribution and collection box is provided with two partition plates, dividing the heat exchange medium distribution and collection box into a heat exchange medium inlet box and a heat exchange medium outlet box, which are connected by a U-shaped heat exchange pipe installed inside the hydrogen filling and discharging box; the bottom plate of the hydrogen distribution and collection box has a connecting hole that connects to the hydrogen filling and discharging box. This invention simultaneously solves the problem of heat and volume compensation during hydrogen filling and discharging, improving the reliability of the system.

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, which is cylindrical in shape and includes a heat exchange medium distribution and collection box, a hydrogen distribution and collection box, and a hydrogen filling and discharging box suspended below the hydrogen distribution and collection box, arranged coaxially from top to bottom. The heat exchange medium distribution and collection box and the hydrogen distribution and collection box share the same bottom plate, and the hydrogen distribution and collection box and the hydrogen filling and discharging box also share the same bottom plate. Two or more lug-type supports are provided on the circumference of either the heat exchange medium distribution and collection box or the hydrogen distribution and collection box.

[0007] A hydrogen storage material inlet pipe is set at the center of the top of the hydrogen filling and discharging tank and is connected to the hydrogen filling and discharging tank. The hydrogen storage material inlet pipe passes through the hydrogen distribution and collection tank and the heat exchange medium distribution and collection tank and extends to the outside of the top plate of the heat exchange medium distribution and collection tank. A hydrogen storage material outlet pipe is set at the center of the bottom of the hydrogen filling and discharging tank and is connected to the hydrogen filling and discharging tank. There is one or more expansion joints on the cylindrical wall of the hydrogen filling and discharging tank. The expansion joints can extend or contract along the axial direction. The hydrogen filling and discharging tank is filled with solid hydrogen storage material.

[0008] The hydrogen distribution and collection box has a hydrogen inlet and a hydrogen outlet on its cylindrical wall. The hydrogen distribution and collection box is connected to the hydrogen filling and discharging box through a connecting hole on its bottom plate. The connecting hole ensures that hydrogen can enter or leave the hydrogen filling and discharging box evenly.

[0009] Two partition plates are symmetrically arranged perpendicular to the bottom plate of the heat exchange medium distribution and collection box, along the diameter direction of 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, which are symmetrically arranged on 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 U-shaped heat exchange tubes extend downward through the hydrogen distribution and collection box body and into the hydrogen filling and discharging box and are buried in the solid hydrogen storage material. The heat exchange medium inlet box and the heat exchange medium outlet box are connected by the U-shaped heat exchange tubes. The cylinder wall corresponding to the heat exchange medium inlet box is provided with a heat exchange medium inlet, and the cylinder wall corresponding to the heat exchange medium outlet box is provided with 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 box or to replenish heat to the solid hydrogen storage material.

[0010] The heat exchange medium distribution and collection box and the hydrogen distribution and collection box are isolated from each other and do not communicate with each other; the heat exchange medium distribution and collection box and the hydrogen charging and discharging box are isolated from each other and do not communicate with each other.

[0011] The lug supports are used to support and fix the solid hydrogen storage equipment. By setting two or more lug supports on the circumference of the heat exchange medium distribution and collection box or the hydrogen distribution and collection box, and suspending the solid hydrogen storage equipment on the steel structure or concrete foundation by means of bolts or welding, the hydrogen filling and discharging box is in a free expansion and contraction state. Generally, 2 to 8 lug supports can be set.

[0012] The hydrogen inlet and outlet serve as the channels for hydrogen to enter and exit the hydrogen distribution and collection box, respectively. Alternatively, the hydrogen inlet and outlet can be combined into one, with only one hydrogen inlet and outlet serving as both.

[0013] The connecting holes are arranged in a ring, equilateral triangle, or regular quadrilateral pattern on the bottom plate of the hydrogen distribution and collection tank. The connecting holes are preferably circular, with a diameter of 19–60 mm. When the connecting holes are evenly distributed in a ring, the circumferential spacing between the holes should be 30–80 mm, and the radial spacing should be 40–60 mm. When the connecting holes are evenly distributed in equilateral triangles, the side length of the equilateral triangles should be 20–60 mm; when the connecting holes are evenly distributed in regular quadrilaterals, the side length of the regular quadrilaterals should be 20–100 mm.

[0014] When loading solid hydrogen storage material, the outlet pipe of the hydrogen storage material is closed, and the inlet pipe is open. Under gravity, the hydrogen storage material enters the hydrogen filling and discharging tank through the inlet pipe and is stored there. When the hydrogen storage material needs to be replaced due to its lifespan decline, the outlet pipe is opened, and under gravity, the hydrogen storage material in the hydrogen filling and discharging tank exits the hydrogen storage equipment through the outlet pipe. The inlet and outlet pipes of the hydrogen storage material should preferably be cylindrical, with a diameter of 50–400 mm.

[0015] Depending on the different needs of hydrogen filling and discharging, during hydrogen filling, a 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 tank. 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 hydrogen needs to be released from the solid hydrogen storage material, a 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 tank. 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 release process is ensured to proceed at a high rate. Fluids such as water, nitrogen, and air can be used as the heat exchange medium.

[0016] The U-shaped heat exchange tubes are arranged in a ring, equilateral triangle, or regular quadrilateral pattern on the cross-section of the heat exchange medium inlet and outlet boxes to ensure that heat can be uniformly released or replenished throughout the hydrogen charging and discharging box. 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 heat exchange 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 equilateral 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 regular quadrilateral should be 30–150 mm.

[0017] The expansion joints installed on the wall of the hydrogen filling and discharging tank can extend or contract axially to adjust the storage volume of the hydrogen filling and discharging tank by changing its axial length, thus accommodating the volume changes of the solid hydrogen storage material during the filling and discharging process. When the expansion joint is manufactured as a single layer, an elastic alloy is preferable to give it good resilience. Copper-based high-elasticity alloys, iron-based high-elasticity alloys, and nickel-based high-elasticity alloys can be used, taking advantage of their low elastic modulus and high elastic limit to give the expansion joint high resilience. When the expansion joint is made of multiple layers of materials through stamping, it can be constructed by separating the pressure-bearing layer and the resilience layer. The pressure-bearing layer bears the pressure of the hydrogen storage equipment, 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, forming a spring-like effect that allows the expansion joint to maintain its original shape and rebound when the external force is removed. When the expansion joint is made of multiple layers, springs can also be added between the layers to give the expansion joint resilience. In summary, the goal is to ensure that the expansion joint has the best possible 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 installed on the wall of the hydrogen filling and discharging tank, they are evenly distributed along the axis of the tank to ensure that volume expansion at different locations along the axis can be effectively absorbed.

[0018] As a preferred option, a filter screen, such as a wire mesh, can be installed in the perforated area of ​​the bottom plate of the hydrogen distribution and collection tank to prevent small, broken solid hydrogen storage material particles from leaving the hydrogen filling and discharging tank with the hydrogen. The pore size of the filter screen should be smaller than the minimum particle size of the solid hydrogen storage material, preferably 10% to 30% of the minimum particle size of the solid hydrogen storage material.

[0019] As a preferred option, a hydrogen distribution and collection pipe can be installed within the connecting hole on the bottom plate of the hydrogen distribution and collection tank. This pipe suspends inside the hydrogen filling and discharging tank and is embedded in the solid hydrogen storage material. The length of the hydrogen distribution and collection pipe should preferably be 80-95% of the initial length of the hydrogen filling and discharging tank. The lower end of the hydrogen distribution and collection pipe is sealed with a plate, and one or more layers of hydrogen pores are formed on the pipe wall. Each layer typically has 2-6 pores, and the spacing between layers should preferably be 50-150 mm. The diameter of the hydrogen pores is smaller than the minimum particle size of the solid hydrogen storage material. Alternatively, hydrogen pores can also be formed on the sealing plate at the lower end of the hydrogen distribution and collection pipe, in which case no hydrogen pores are required on the pipe wall. The advantage of the hydrogen distribution and collection pipe is that it allows for better introduction and extraction of hydrogen along the axis of the hydrogen filling and discharging tank.

[0020] As a preferred solution, to ensure that all solid hydrogen storage material is filled within an expandable hydrogen filling and discharging tank, and to prevent the solid hydrogen storage material from expanding and clogging the 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 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 outlet pipe to prevent solid hydrogen storage material from entering the outlet pipe during non-discharging operations. The baffle has the same shape as the bottom of the hydrogen filling and discharging tank. 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. 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.

[0021] As a preferred option, the expansion wave of the expansion joint should be set to be concave towards the inside of the hydrogen filling and discharging tank. This has the advantage that it can not only extend along the axial direction of the hydrogen filling and discharging tank to increase the volume inside the tank, 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.

[0022] As a preferred option, to ensure that the solid hydrogen storage material in the hydrogen filling and discharging tank can be smoothly discharged, the lower part of the hydrogen filling and discharging tank should be set in a cone shape 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.

[0023] As a preferred solution, to avoid problems such as caking or poor flowability of solid hydrogen storage material in the hydrogen filling and discharging tank, which may cause difficulties in unloading, a loosening air inlet can be installed on the wall of the hydrogen filling and discharging tank. During the unloading process of 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.

[0024] As a preferred option, limiting hinges can be installed on the wall of the hydrogen filling and discharging tank. The limiting hinge consists of a connecting rod and a connecting hinge, with the connecting rod connected via the hinge and able to rotate around it. 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 and discharging tank wall expands and elongates. When the connecting rods overlap and form a straight line, i.e., when the angle between the two connected rods is 0 degrees, the limiting hinge reaches its limiting termination position, restricting further downward movement and elongation of the hydrogen filling and discharging tank. It is preferable to have two or more limiting hinges, evenly distributed around the circumference of the hydrogen filling and discharging tank, to ensure the tank is in a uniformly limited state.

[0025] As a preferred embodiment, a rebound device is installed below the hydrogen filling and discharging tank. The rebound device consists of a top mounting plate, a rebound spring, and a bottom mounting plate from top to bottom. The top mounting plate is fixed below the hydrogen filling and discharging tank, and the bottom mounting plate is fixed to a steel structure or concrete foundation. The upper and lower ends of the rebound spring are connected to the top and bottom mounting plates, respectively. When one rebound device is installed, it is located at the bottom center of the hydrogen filling and discharging tank, with the hydrogen storage material outlet pipe housed within it. If two or more rebound devices are installed, they are evenly distributed along the lower edge of the hydrogen filling and discharging tank. The function of the rebound device is to assist the expansion joint in rebounding, ensuring that the expansion joint is in a contracted state after the solid hydrogen storage material releases hydrogen, 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 and discharging tank while simultaneously compressing the return spring, allowing the spring to accumulate elastic potential energy. When the solid hydrogen storage material in the hydrogen filling and discharging tank 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 hydrogen filling and discharging tank. The expansion joint of the hydrogen filling and discharging tank absorbs the compressive stress, causing the expansion joint to contract in preparation for the next hydrogen storage and release cycle.

[0026] 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 made of angle steel, 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 and discharging tank. The purpose of the limiting rod is to restrict the downward movement of the hydrogen filling and discharging tank. When the hydrogen filling and discharging tank moves down to contact the limiting rod, it will no longer move downward. At this time, a stress sensor or contact sensor can be installed on the limiting rod. When the limiting rod begins to generate stress or contact between the limiting rod and the hydrogen filling and discharging tank is detected, an alarm is issued or the process settings are used to stop the storage of hydrogen in the hydrogen storage equipment. The advantage of setting a limiting rod is that it can ensure that the hydrogen storage equipment will not be damaged by overfilling or excessive expansion of the solid hydrogen storage material.

[0027] 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 hydrogen charging and discharging tank with the solid hydrogen storage material. Keep both the hydrogen storage material inlet and outlet pipes closed during the charging and 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 hydrogen charging and discharging tank. 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 inside the hydrogen charging and discharging tank and prevent the formation of negative pressure inside the hydrogen charging and discharging tank when the solid hydrogen storage material is rapidly unloaded, which would make it difficult to unload the solid hydrogen storage material or cause the hydrogen charging and discharging tank to collapse due to negative pressure. 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 gases such as nitrogen can be introduced to loosen the solid hydrogen storage material and unload it more smoothly from the hydrogen charging and discharging tank.

[0028] During hydrogen charging, the hydrogen inlet is opened and the hydrogen outlet is closed. Hydrogen enters the hydrogen distribution and collection box from the hydrogen inlet and then flows into the hydrogen charging and discharging box through the connecting hole on the bottom plate of the hydrogen distribution and collection box. Under pressure, the hydrogen is stored in the solid hydrogen storage material in the hydrogen charging and discharging box. During the charging process, the volume of the solid hydrogen storage material increases, causing the expansion joint to extend towards the hydrogen storage material outlet pipe, thus increasing the volume of the hydrogen charging and discharging box. This increases the volume of the solid hydrogen storage material, preventing the hydrogen charging and discharging box from bulging. Since the solid hydrogen storage material releases heat during hydrogen absorption, the temperature inside the hydrogen charging and discharging box rises after the heat released during charging reaches a certain level. 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 U-shaped heat exchange tube absorbs the heat released during the hydrogen charging process, lowering the temperature of the solid hydrogen storage material and raising the temperature of the low-temperature medium. The medium then collects through the U-shaped heat exchange tube and flows into the heat exchange medium outlet box, and finally leaves the hydrogen storage device through the heat exchange medium outlet.

[0029] When releasing hydrogen, this solid hydrogen storage device opens the hydrogen outlet and closes the hydrogen inlet. Hydrogen is released from the solid hydrogen storage material, enters through the connecting holes, and fills the hydrogen distribution and collection tank. After reaching a certain pressure, it leaves the hydrogen storage device through the hydrogen outlet, supplying downstream units or external equipment. After releasing hydrogen, the solid hydrogen storage material reduces in volume, and the expansion joint contracts under its resilience, restoring the hydrogen filling and discharging tank 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 tank through the heat exchange medium inlet, then enters the U-shaped heat exchange tube. The U-shaped heat exchange tube transfers heat to the solid hydrogen storage material in the hydrogen filling and discharging tank, causing it to absorb heat, heat up, and release hydrogen. After releasing heat, the high-temperature heat exchange medium collects through the U-shaped heat exchange tube into the heat exchange medium outlet tank and then leaves the solid hydrogen storage device through the heat exchange medium outlet.

[0030] 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.

[0031] The present invention has the following beneficial effects:

[0032] 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.

[0033] 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.

[0034] 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

[0035] Figure 1 This is a schematic diagram of a solid hydrogen storage device according to the present invention;

[0036] Figure 2 yes Figure 1 A top view of the structure along the AA direction;

[0037] Figure 3 yes Figure 1A top view of the structure in the middle BB direction;

[0038] Figure 4 yes Figure 1 A schematic diagram of a structure for plugging the outlet of hydrogen storage material;

[0039] Figure 5 yes Figure 1 A schematic diagram of a type of mid-limit hinge;

[0040] Figure 6 yes Figure 1 A schematic diagram of a rebound device.

[0041] 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 distribution and collection box, 6-Hydrogen inlet, 7-Hydrogen outlet, 8-Awl-type support, 9-Connecting hole, 10-U-shaped heat exchange tube, 11-Hydrogen distribution and collection pipe, 12-Hydrogen hole, 13-Hydrogen charging and discharging box, 14-Hydrogen storage material outlet pipe, 15-Hydrogen storage material outlet plug, 16-Solid hydrogen storage material 17-Concrete foundation, 18-Rebound device, 19-Loosening air inlet, 20-Limit hinge, 21-Expansion joint, 22-Heat exchange medium inlet box, 23-Heat exchange medium outlet box, 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. Detailed Implementation

[0042] The present invention will now be described in detail with reference to the accompanying drawings.

[0043] Figures 1-3 One embodiment of the solid hydrogen storage device of the present invention is given. The solid hydrogen storage device shown in the figure is generally cylindrical.

[0044] It includes a heat exchange medium distribution and collection box 2, a hydrogen distribution and collection box 5, and a hydrogen charging and discharging box 13 suspended below the hydrogen distribution and collection box 5, arranged coaxially from top to bottom; the heat exchange medium distribution and collection box 2 and the hydrogen distribution and collection box 5 share the same bottom plate, and the hydrogen distribution and collection box 5 and the hydrogen charging and discharging box 13 share the same bottom plate; four lug-type supports 8 are provided on the circumference of the heat exchange medium distribution and collection box 2 or the hydrogen distribution and collection box 5.

[0045] A hydrogen storage material inlet pipe 1 is provided at the center of the top of the hydrogen filling and discharging tank 13, which is connected to the hydrogen filling and discharging tank 13. The hydrogen storage material inlet pipe 1 passes through the body of the hydrogen distribution and collection tank 5 and the heat exchange medium distribution and collection tank 2 and extends to the outside of the top plate of the heat exchange medium distribution and collection tank 2. A hydrogen storage material outlet pipe 14 is provided at the center of the bottom of the hydrogen filling and discharging tank 13, which is connected to the hydrogen filling and discharging tank 13. Two or more expansion joints 21 are provided on the cylindrical wall of the hydrogen filling and discharging tank 13. The expansion joints 21 can extend or contract along the axial direction. The hydrogen filling and discharging tank 13 is filled with solid hydrogen storage material 16.

[0046] The hydrogen distribution and collection box 5 has a hydrogen inlet 6 and a hydrogen outlet 7 on its corresponding cylinder wall. A hydrogen distribution and collection pipe 11 is installed on the connecting hole 9 on the bottom plate of the hydrogen distribution and collection box 5. The bottom end of the hydrogen distribution and collection pipe 11 is closed, and hydrogen holes 12 are opened on its pipe wall. The hydrogen distribution and collection box 5 is connected to the hydrogen filling and discharging box 13 through the connecting hole 9, the hydrogen distribution and collection pipe 11 and the hydrogen holes 12, so as to ensure that hydrogen can enter or leave the hydrogen filling and discharging box 13 evenly. The diameter of the hydrogen holes 12 is smaller than the minimum particle size of the solid hydrogen storage material 16.

[0047] Two partition plates 24 are symmetrically arranged inside the heat exchange medium distribution and collection box 2 and outside the hydrogen storage material inlet pipe 1, perpendicular to the diameter direction of the heat exchange medium distribution and collection box 2 and perpendicular to the bottom plate of the heat exchange medium distribution and collection box 2. The partition plates 24 divide the heat exchange medium distribution and collection box 2 into a heat exchange medium inlet box 22 and a heat exchange medium outlet box 23 that are symmetrically arranged on the bottom plate of the heat exchange medium distribution and collection box corresponding to the heat exchange medium inlet box 22 and the heat exchange medium outlet box 23. The U-shaped heat exchange pipes 10 extend downward through the box body of the hydrogen distribution and collection box 5 and into the hydrogen filling and discharging box 13. Buried within the solid hydrogen storage material 16, the heat exchange medium inlet box 22 and the heat exchange medium outlet box 23 are connected by a U-shaped heat exchange tube 10. The heat exchange medium inlet 3 is provided on the cylinder wall corresponding to the heat exchange medium inlet box 22, and the heat exchange medium outlet 4 is provided on the cylinder wall corresponding to the heat exchange medium outlet box 23. The heat exchange medium inlet 3, the heat exchange medium inlet box 22, the U-shaped heat exchange tube 10, the heat exchange medium outlet box 23, and the heat exchange medium outlet 4 form a closed and interconnected cavity, which allows the heat exchange medium to remove heat from the solid hydrogen storage material 16 filled in the hydrogen filling and discharging box 13 or to replenish heat to the solid hydrogen storage material 16.

[0048] The heat exchange medium distribution and collection box 2 and the hydrogen distribution and collection box 5 are isolated from each other and are not connected to each other; the heat exchange medium distribution and collection box 2 and the hydrogen charging and discharging box 13 are isolated from each other and are not connected to each other.

[0049] A limiting hinge 20 is provided on the outer side of the hydrogen filling and discharging box 13 along the axial direction. A rebound device 18 is provided below the hydrogen filling and discharging box 13 and is fixed on the concrete foundation 17. A loosening air inlet 19 is provided on the wall of the hydrogen filling and discharging box 13.

[0050] Figure 4 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 14, typically 4–11 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 14 to prevent solid hydrogen storage material 16 from entering the outlet pipe 14 during non-discharge operations. The baffle 25 is located at the bottom of the hydrogen filling and discharging tank 13. The shapes are 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 14 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 14 so that the mounting ring 29 can be fixed on the hydrogen storage material outlet pipe 14 with screws.

[0051] Figure 5 yes Figure 1 A schematic diagram of a limiting hinge structure is shown. As illustrated, 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 hinges is such that the connecting rods 30 are at a certain angle, with the included angle between the connected rods preferably between 30 and 60 degrees. It is preferable to have two or more limiting hinges, evenly distributed around the circumference of the hydrogen filling and discharging tank, to ensure the hydrogen filling and discharging tank is in a uniformly limited position.

[0052] Figure 6 yes Figure 1 A 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 a single rebound device is installed, it is located at the bottom center of the hydrogen filling and discharging tank, 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 and discharging tank. When no limiting hinge is installed, a limiting rod 33 can be installed inside the rebound spring 34. The purpose of the limiting rod is to restrict the downward movement of the hydrogen filling and discharging tank. Once the hydrogen filling and discharging tank moves down to contact the limiting rod 33, it will no longer move downward.

[0053] The operation process of the present invention will be described below with reference to the accompanying drawings:

[0054] 1) Loading and unloading of solid hydrogen storage materials

[0055] Close the hydrogen storage material outlet pipe 14 and open the hydrogen storage material inlet pipe 1. Under gravity, the solid hydrogen storage material 16 enters the hydrogen filling and discharging tank 13 from the inlet pipe 1 and is stored there. When the solid hydrogen storage material 16 needs replacement due to its declining lifespan, open the hydrogen storage material outlet pipe 14. Under gravity, the solid hydrogen storage material 16 in the hydrogen filling and discharging tank 13 leaves the hydrogen storage device through the outlet pipe 14. If the solid hydrogen storage material 16 has poor flowability and cannot be discharged due to caking, compression, or other reasons, the loosening air inlet 19 can be opened and inert gases such as nitrogen can be introduced to loosen the solid hydrogen storage material 16, allowing it to be discharged more smoothly from the hydrogen filling and discharging tank 13.

[0056] 2) Hydrogen charging of solid hydrogen storage materials

[0057] Simultaneously close hydrogen outlet 7, hydrogen storage material inlet pipe 1, hydrogen storage material outlet pipe 14, and loosening air inlet 19, and open hydrogen inlet 6. Hydrogen enters hydrogen distribution and collection box 5 through hydrogen inlet 6, and then enters hydrogen filling and discharging box 13 through connecting hole 9, hydrogen distribution and collection pipe 11, and hydrogen hole 12 on the bottom plate of hydrogen distribution and collection box 5, where it is absorbed and stored by solid hydrogen storage material 16. During hydrogen charging, low-temperature heat exchange medium enters from heat exchange medium inlet 3 and fills heat exchange medium inlet box 22, then flows through U-shaped heat exchange pipe 10. After absorbing the heat released by solid hydrogen storage material 16 in hydrogen filling and discharging box 13 due to hydrogen absorption, it flows into heat exchange medium outlet box 23 and leaves the hydrogen storage equipment through heat exchange medium outlet 4. During hydrogen charging, the volume of solid hydrogen storage material 16 increases, causing expansion joint 21 to extend towards hydrogen storage material outlet pipe 14. The volume of hydrogen filling and discharging box 13 increases, compensating for the increase in the volume of solid hydrogen storage material 16, thus avoiding the risk of bulging in hydrogen filling and discharging box 13.

[0058] 3) Hydrogen release from solid hydrogen storage materials

[0059] Simultaneously close the hydrogen inlet 6, hydrogen storage material inlet pipe 1, hydrogen storage material outlet pipe 14, and loosening air inlet 19, and open the hydrogen outlet 7. High-temperature heat exchange medium enters from heat exchange medium inlet 3 and fills the heat exchange medium inlet box 22, then flows through the U-shaped heat exchange tube 10, providing heat to the solid hydrogen storage material 16 in the hydrogen filling and discharging box 13. The solid hydrogen storage material 16 absorbs heat and releases hydrogen. The released hydrogen enters the hydrogen distribution and collection pipe 11 through the hydrogen holes 12 on the pipe wall, then flows through the hydrogen distribution and collection pipe 11 and the connecting hole 9 into the hydrogen distribution and collection box 5, and finally leaves the hydrogen storage device through the hydrogen outlet 7. The heat exchange medium, after releasing heat, flows into the heat exchange medium outlet box 23 and leaves the hydrogen storage device through the heat exchange medium outlet 4. After the solid hydrogen storage material 16 releases hydrogen, its volume decreases, and the expansion joint 21 contracts under the action of elastic force, allowing the hydrogen filling and discharging box 13 to return to its state before hydrogen filling as much as possible. Of course, to ensure the retraction of the hydrogen filling and discharging tank 13, the expansion joint 21 can be prevented from excessive deformation by the limiting hinge 20, and the retraction of the expansion joint 21 can be assisted by the spring-loaded device 18. Alternatively, without the limiting hinge, a limiting rod 33 can be provided inside the spring-loaded spring 34 of the spring-loaded device to prevent excessive deformation of the expansion joint 21.

Claims

1. A solid hydrogen storage device, characterized in that: The overall shape is cylindrical, including a heat exchange medium distribution and collection box, a hydrogen distribution and collection box, and a hydrogen charging and discharging box suspended below the hydrogen distribution and collection box, arranged coaxially from top to bottom; the heat exchange medium distribution and collection box and the hydrogen distribution and collection box share the same bottom plate, and the hydrogen distribution and collection box and the hydrogen charging and discharging box share the same bottom plate; the heat exchange medium distribution and collection box or the hydrogen distribution and collection box is provided with two or more lug supports on its circumference; A hydrogen storage material inlet pipe is set at the center of the top of the hydrogen filling and discharging tank and is connected to the hydrogen filling and discharging tank. The hydrogen storage material inlet pipe passes through the hydrogen distribution and collection tank and the heat exchange medium distribution and collection tank and extends to the outside of the top plate of the heat exchange medium distribution and collection tank. A hydrogen storage material outlet pipe is set at the center of the bottom of the hydrogen filling and discharging tank and is connected to the hydrogen filling and discharging tank. There is one or more expansion joints on the cylindrical wall of the hydrogen filling and discharging tank. The expansion joints can extend or contract along the axial direction. The hydrogen filling and discharging tank is filled with solid hydrogen storage material. The hydrogen distribution and collection box has a hydrogen inlet and a hydrogen outlet on its cylindrical wall. The hydrogen distribution and collection box is connected to the hydrogen filling and discharging box through a connecting hole on its bottom plate. The connecting hole ensures that hydrogen can enter or leave the hydrogen filling and discharging box evenly. Two partition plates are symmetrically arranged perpendicular to the bottom plate of the heat exchange medium distribution and collection box, along the diameter direction of 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, which are symmetrically arranged on 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 U-shaped heat exchange tubes extend downward through the hydrogen distribution and collection box body and into the hydrogen filling and discharging box and are buried in the solid hydrogen storage material. The heat exchange medium inlet box and the heat exchange medium outlet box are connected by the U-shaped heat exchange tubes. The cylinder wall corresponding to the heat exchange medium inlet box is provided with a heat exchange medium inlet, and the cylinder wall corresponding to the heat exchange medium outlet box is provided with 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 box or to replenish heat to the solid hydrogen storage material. The heat exchange medium distribution and collection box and the hydrogen distribution and collection box are isolated from each other and do not communicate with each other; the heat exchange medium distribution and collection box and the hydrogen charging and discharging box are isolated from each other and do not communicate with each other.

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 and discharging tank. 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 cylindrical wall of the hydrogen filling and discharging box.

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 hydrogen filling and discharging tank 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 hydrogen filling and discharging tank 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 below the hydrogen filling and discharging tank.

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

9. The solid hydrogen storage device according to claim 8, characterized in that: The rebound device has a limiting rod inside the rebound spring. The limiting rod is cylindrical or square, and its outer diameter is smaller than that of the rebound spring. The height of the limiting rod is lower than that of the rebound spring in its natural state. The limiting rod restricts the downward movement of the hydrogen filling and discharging box. When the hydrogen filling and discharging box 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 below the hydrogen filling and discharging tank.

11. The solid hydrogen storage device according to claim 1, characterized in that: A hydrogen distribution and collection pipe is installed in the connecting hole on the bottom plate of the hydrogen distribution and collection box. The hydrogen distribution and collection pipe is suspended inside the hydrogen filling and discharging box and buried in the solid hydrogen storage material. The lower end of the hydrogen distribution and collection pipe is sealed with a sealing plate. Hydrogen holes are opened on the pipe wall, and the diameter of the hydrogen holes is smaller than the minimum particle size of the solid hydrogen storage material.

12. The solid hydrogen storage device according to claim 1, characterized in that: A hydrogen distribution and collection pipe is installed in the connecting hole on the bottom plate of the hydrogen distribution and collection box. The hydrogen distribution and collection pipe is suspended inside the hydrogen filling and discharging box and buried in the solid hydrogen storage material. The lower end of the hydrogen distribution and collection pipe is sealed with a sealing plate. The sealing plate has hydrogen holes with a diameter smaller than the minimum particle size of the solid hydrogen storage material.

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