A high-temperature solid-state hydrogen storage device without external heat source and its operating method

Abstract

The application discloses a high-temperature solid-state hydrogen storage device without external heat source starting, which is composed of a hydrogen storage unit 1, an initiation structure 2, a gas supply system 3, a shell 4 and a temperature control device 5; the hydrogen storage unit is composed of a solid-state hydrogen storage material bed layer triggering area and a solid-state hydrogen storage material bed layer wave area; the initiation structure is composed of a solid-state hydrogen storage initiation material, a bed layer support and a fixing rod; the gas supply system is composed of a gas inlet and outlet, a filter screen, a gap space and a communication pore; the shell is composed of a hydrogen storage tank cylinder, a hydrogen storage tank end cover and a sealing gasket; and the temperature control device adopts heat exchange of a heat exchange fluid.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen energy storage and transportation, specifically relating to a high-temperature solid hydrogen storage device that can be started without an external heat source and its operation method. Background Technology

[0002] In laboratory applications of solid-state hydrogen storage materials, only a small amount of the material is used, and the solid-state hydrogen storage bed can be heated quickly and easily. However, in practical applications, due to the large mass and low thermal conductivity of solid-state hydrogen storage materials, conventional high-temperature solid-state hydrogen storage devices face the problem of difficulty and long heating time for the solid-state hydrogen storage bed. This is because existing solid-state hydrogen storage devices use a traditional heat exchange fluid start-up method, which involves heating the entire medium-to-high temperature solid-state hydrogen storage bed to a relatively high temperature using a heat exchange fluid before introducing hydrogen gas for the hydrogen absorption reaction. For example, existing literature 1 (Large scale magnesiumhydride tank coupled with an external heat source, International Journal of Hydrogen Energy, 2012, 37: 9103-9111) uses high-temperature heat transfer oil to heat the MgH2 bed to approximately 240°C before performing the hydrogen absorption operation. Furthermore, during the subsequent hydrogen absorption reaction, the temperature of the heat transfer oil is also maintained at approximately 240°C to remove the large amount of heat generated by the hydrogen absorption reaction. However, this type of start-up method based on heat exchange fluid has the following two technical problems:

[0003] 1. Since the heat exchange fluid is used, the required heat exchange fluid has the basic characteristics of large specific heat capacity and large volume. Therefore, in the process of heating up, there are problems of high energy consumption and long heating time, which is referred to as the energy consumption-time problem. Specifically, in existing literature 1, the start-up time of hydrogen absorption reaction of solid hydrogen storage material bed is 2 hours.

[0004] 2. Because a heat exchange fluid is used, the thermal management system needs to simultaneously perform heating and cooling functions. Therefore, after the start-up process is completed, the heat exchange fluid is at a high temperature. At the same time, due to the large specific heat capacity of the heat exchange fluid, the temperature of the heat exchange fluid drops slowly. This directly leads to low heat exchange efficiency of the heat exchange fluid in the subsequent hydrogen absorption reaction process, ultimately resulting in low cooling efficiency and the inability to control the reaction temperature in a timely manner, which is referred to as the temperature control problem.

[0005] To address the energy-time issue mentioned above, the thermal management system can employ electric heating. For example, existing literature 2 (Experimental and numerical study of a magnesium hydride tank, International Journal of Hydrogen Energy, 2010, 35: 6311-6322) uses heating coils wound around the outer wall of a hydrogen storage tank filled with MgH2 material. The material bed is heated to 300°C by the heating coils before the hydrogen absorption operation is performed.

[0006] However, the problems with this technical solution consist of two aspects:

[0007] 1. The electric heating coil is located outside the hydrogen storage device, which directly results in a long heating distance between the electric heating coil and the center of the solid hydrogen storage material bed. In addition, an insulation device needs to be installed outside the heating coil.

[0008] 2. The electric heating coil needs to heat the entire medium-high temperature solid hydrogen storage material bed, and the energy consumption required for heating increases proportionally with the mass of the solid hydrogen storage material being heated.

[0009] The combined consequence of the above two problems is that startup time and energy consumption cannot be effectively reduced. Specifically, the startup time of existing literature 2 still exceeds 1 hour.

[0010] Furthermore, existing literature 2 still cannot effectively solve the temperature control problem of existing literature 1. The reason is that existing literature 2 uses an electric heating coil as the heating system, which means that there is no need to use a heat exchange fluid. Instead, it uses a technical solution of setting cooling air inside the hydrogen storage device for cooling. However, since the cooling air is set inside the hydrogen storage device, there is a problem of small heat exchange area, which directly leads to the inability to quickly remove the heat generated by the hydrogen absorption reaction, that is, poor heat exchange effect. At the same time, since the heating coil of existing literature 2 is arranged on the outer wall of the hydrogen storage device, it directly hinders the contact between the hydrogen storage device and the external low-temperature environment, that is, there is a problem of large resistance to heat dissipation from the hydrogen storage device to the external low-temperature environment.

[0011] Furthermore, based on the above analysis of existing technologies, even if the energy consumption-time problem (Problem 1) and the temperature control problem (Problem 2) are solved, the fundamental principle of the technical solution is to initiate the hydrogen storage reaction based on external energy supply, meaning that the necessary technical feature includes an additional energy supply device. This technical feature directly leads to an increase in the structural complexity of the hydrogen storage device. Summary of the Invention

[0012] The purpose of this invention is to provide a high-temperature solid-state hydrogen storage device and its operating method that can be started without an external heat source. To solve the technical problems caused by the need for an additional power supply device in existing technologies, a completely different initiation principle must be adopted. Therefore, to achieve a high-temperature solid-state hydrogen storage device that can be started without an external heat source, the inventive principle of this invention is as follows:

[0013] 1. A solid hydrogen storage initiation material is used to make an initiation structure to activate the solid hydrogen storage functional material. The two types of solid hydrogen storage materials absorb hydrogen and release heat in stages in the hydrogen storage device, achieving the technical effect of not needing external power supply, thereby reducing the need for external power supply devices, and ultimately achieving the technical effect of simplifying the system structure and reducing the system volume.

[0014] 2. Based on the technical principle of no external heat source, the heat exchange fluid does not need to achieve active heating. It only needs to remove the heat of hydrogen absorption reaction of the solid hydrogen storage material. Therefore, it has the characteristic of low temperature of heat exchange fluid, that is, it has the characteristic of large heat exchange temperature difference with the solid hydrogen storage material bed, which directly leads to the technical effect of fast heat transfer rate.

[0015] 3. By placing the initiation structure inside the hydrogen storage device, the heat transfer distance between the initiation structure and the solid hydrogen storage material bed is shortened. At the same time, the heat dissipation to the external environment during the start-up process can be reduced by cutting the insulation structure.

[0016] 4. A method is adopted to trigger the reaction of the remaining hydrogen storage materials by heating a portion of the solid hydrogen storage material, thereby reducing the energy consumption required to start the hydrogen absorption reaction and reducing the amount of solid hydrogen storage initiating material used. The principle is as follows: First, the solid hydrogen storage initiating material reacts with hydrogen at room temperature and releases heat, raising the temperature of the solid hydrogen storage initiating material to the temperature required for the reaction of the solid hydrogen storage functional material; then, the solid hydrogen storage initiating material heats a portion of the solid hydrogen storage functional material near the bed support, initiating the hydrogen absorption reaction of that portion of the solid hydrogen storage functional material; then, after the reaction of the solid hydrogen storage initiating material is completed, the remaining portion of the solid hydrogen storage functional material can be used to trigger subsequent reactions through the heat released from the hydrogen absorption reaction of the already reacted portion of the solid hydrogen storage material, until the entire solid hydrogen storage functional material bed has completed hydrogen absorption.

[0017] To achieve the above objectives, the present invention employs the following technical solution:

[0018] A high-temperature solid hydrogen storage device that can be started without an external heat source consists of a hydrogen storage unit, an initiation structure, a gas supply system, a shell, and a temperature control device.

[0019] The hydrogen storage unit consists of a triggering zone of the solid hydrogen storage material bed and a sweeping zone of the solid hydrogen storage material bed;

[0020] In the hydrogen storage unit, both the triggering zone and the susceptibility zone of the solid hydrogen storage material bed are composed of solid hydrogen storage functional material particles and pores; the solid hydrogen storage functional material is a large-capacity solid hydrogen storage material.

[0021] The trigger zone of the solid hydrogen storage material bed is connected to the bed support in the initiation structure on one side and to the swarming zone of the solid hydrogen storage material bed on the other side; the distance from the trigger zone of the solid hydrogen storage material bed to the bed support is 0-15mm.

[0022] There are gaps between the hydrogen storage unit and the side wall of the hydrogen storage tank in the outer shell, as well as between the upper and lower walls of the hydrogen storage tank.

[0023] The initiation structure consists of a solid hydrogen storage initiation material, a bed support, and a fixing rod.

[0024] In the initiation structure, the solid hydrogen storage initiation material is a low-temperature solid hydrogen storage material;

[0025] The bed support consists of partitions and sleeves;

[0026] The separator plate is fixed at the bottom of the sleeve, and the upper part of the separator plate is in contact with the trigger area of ​​the solid hydrogen storage material bed.

[0027] The outer surface of the sleeve contacts the hydrogen storage unit, and the inner surface of the sleeve mates with the fixing rod;

[0028] At least one of the partition plates of the fixing rod and the bed support is a hollow structure for filling with solid hydrogen storage initiating material; when the fixing rod or the bed support is filled with solid hydrogen storage initiating material, the fixing rod or the bed support is provided with communicating pores for hydrogen to enter the fixing rod or the bed support and react with the solid hydrogen storage initiating material; the mass of the solid hydrogen storage initiating material bed does not exceed 1 / 2 of the mass of the solid hydrogen storage functional material in the hydrogen storage unit;

[0029] Multiple bed supports are connected in series and fixed to a fixed rod, with gaps between the bed supports;

[0030] The gas supply system consists of gas inlet and outlet, filter screen, gap space and connecting pores;

[0031] In the gas supply system, a filter screen is installed on the lower side of the gas inlet and outlet to filter the gas entering and exiting the hydrogen storage tank.

[0032] The outer shell consists of a hydrogen storage tank body, a hydrogen storage tank end cap, and a sealing gasket;

[0033] Within the outer shell, the internal cavity of the hydrogen storage tank contains a hydrogen storage unit, an initiation structure, and a gas supply system; a flange connection hole is provided on the upper edge of the hydrogen storage tank; and a fixing rod is fixed to the bottom of the hydrogen storage tank.

[0034] The hydrogen storage tank end cap is provided with an end cap flange connection hole on its edge; the hydrogen storage tank end cap is provided with a gas inlet and outlet.

[0035] The flange connection hole of the cylinder body and the flange connection hole of the end cover are connected by bolts; when the hydrogen storage tank body is connected to the hydrogen storage tank end cover, a sealing gasket is provided between the hydrogen storage tank body and the hydrogen storage tank end cover.

[0036] The temperature control device uses heat exchange fluid for heat exchange;

[0037] The temperature control device is located on the outside of the hydrogen storage tank and is used to remove the heat generated by the hydrogen absorption reaction of the solid hydrogen storage material.

[0038] A method for operating a high-temperature solid hydrogen storage tank without an external heat source includes the following steps:

[0039] Step 1, preparations before hydrogen absorption: First, fill the hydrogen storage tank with hydrogen storage units and fill the initiation structure with solid hydrogen storage initiation material. Then, after sealing the hydrogen storage tank, perform a vacuum operation to remove impurity gases from the hydrogen storage tank. Finally, start the temperature control device to control the temperature of the hydrogen storage tank.

[0040] Step 2, initiation of the hydrogen absorption process: First, hydrogen gas is introduced into the hydrogen storage tank through the gas supply system to bring the hydrogen pressure to the operating pressure. The hydrogen gas first reacts with the solid hydrogen storage initiating material to generate heat, raising the temperature of the solid hydrogen storage initiating material. Then, the heat generated by the hydrogen absorption reaction of the solid hydrogen storage initiating material is transferred to the hydrogen storage unit, heating the trigger zone of the solid hydrogen storage material bed. Finally, the reaction in the trigger zone of the solid hydrogen storage material bed releases a large amount of heat, driving the continuous reaction in the ripple zone of the solid hydrogen storage material bed.

[0041] Step 3, controlling the hydrogen absorption process, involves adjusting the speed of the heat exchange fluid in the temperature control device to control the progress of the hydrogen absorption reaction in the trigger zone and the spur zone of the solid hydrogen storage material bed; after the hydrogen absorption reaction ends or the control is completed, the gas supply system stops supplying gas, and at the same time, the temperature control device lowers the temperature of the hydrogen storage tank to room temperature.

[0042] When the solid-state hydrogen storage material is Mg2Ni and the solid-state hydrogen storage initiation material is LaNi5

[0043] In step 1, the hydrogen storage unit is cylindrical with a diameter of 15cm, a height of 5cm, and a porosity of 0.3.

[0044] Within the initiation structure, solid hydrogen storage initiation material is placed in a cylindrical partition plate; the partition plate has a diameter of 14 cm and a height of 0.5 cm, and the porosity of the solid hydrogen storage initiation material bed is 0.63.

[0045] The temperature control device uses heat exchange fluid, specifically heat transfer oil, with a heat transfer coefficient of 200-5000 W / m. 2The heat exchange fluid temperature is 288.15-308.15 K;

[0046] In step 2, the operating pressure inside the hydrogen storage tank is 1-5 MPa.

[0047] After experimental testing, the technical effects of the present invention were compared with those of the traditional heat exchange fluid start-up method. It can be seen that the start-up time of the hydrogen storage device of the present invention is only 5.3% of that of the traditional method, no external power supply is required, and the hydrogen absorption reaction completion time of the hydrogen storage device is shortened by 55.4%.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] 1. This invention proposes a high-temperature solid hydrogen storage device and its operation method that can be started without an external heat source. By combining the working temperature range of solid hydrogen storage initiating materials with low start-up temperature and solid hydrogen storage functional materials with high start-up temperature, the hydrogen absorption reaction of solid hydrogen storage initiating materials and solid hydrogen storage functional materials is triggered in stages under the condition of no external power supply, thereby reducing the dependence of the hydrogen absorption reaction of the hydrogen storage device on external power supply.

[0050] 2. By placing the initiation structure inside the hydrogen storage device, the distance between the initiation structure and the solid hydrogen storage functional material bed is shortened, the heat transfer rate is improved, and only a part of the solid hydrogen storage functional material is heated, which improves the start-up speed of the hydrogen storage device.

[0051] 3. By placing the initiation structure inside the hydrogen storage device, less heat is lost to the surrounding low-temperature environment. Furthermore, heating only a portion of the solid hydrogen storage functional material can trigger the continuous hydrogen absorption of the solid hydrogen storage functional material bed, reducing the energy consumption required to start the hydrogen absorption reaction and minimizing the impact of the solid hydrogen storage initiation material with a low hydrogen storage capacity on the capacity of the hydrogen storage device.

[0052] 4. The heat transfer performance between the external temperature control system of the hydrogen storage device and the solid hydrogen storage material bed is improved. Compared with the traditional heat exchange fluid start-up method, the initial temperature of the fluid is low, the heat transfer temperature difference is large, the cooling rate of the temperature control device is fast, the heat load is small, and the hydrogen absorption reaction of the hydrogen storage device is completed in a short time.

[0053] 5. The initiation structure and temperature control device in the thermal management system of the hydrogen storage device do not affect each other. The structure of the thermal management system and the internal heat flow are simple and clear, and the operation and control methods are simple. Attached image description:

[0054] Figure 1This is a schematic diagram of a high-temperature solid hydrogen storage device that can be started without an external heat source, as shown in Example 1. In this diagram, 1 is the hydrogen storage unit, 1-1 is the triggering zone of the solid hydrogen storage material bed, 1-2 is the ripple zone of the solid hydrogen storage material bed, 2 is the initiation structure, 2-1 is the bed support, 2-2 is the fixing rod, 3 is the gas supply system, 3-1 is the gas inlet / outlet, 3-2 is the filter screen, 4 is the outer shell, 4-1 is the hydrogen storage tank body, 4-1-1 is the flange connection hole of the body, 4-2 is the hydrogen storage tank end cap, 4-2-1 is the flange connection hole of the end cap, 4-3 is the sealing gasket, and 5 is the temperature control device.

[0055] Figure 2 This is a schematic diagram of the bed support structure in Example 1, where 2-1-1 is a sleeve and 2-1-2 is a partition plate;

[0056] Figure 3 This is a graph showing the change in bed reaction fraction over time during the startup process of Example 1;

[0057] Figure 4 This is a schematic diagram of a high-temperature solid hydrogen storage device without an external heat source, in which the function of the initiation structure is realized by a fixed rod, as described in Example 2. Detailed Implementation

[0058] The present invention will be further described in detail through embodiments and with reference to the accompanying drawings, but this is not intended to limit the scope of the invention.

[0059] Example 1

[0060] A high-temperature solid-state hydrogen storage device that can be started without an external heat source, such as Figure 1 As shown, it consists of a hydrogen storage unit 1, an initiation structure 2, a gas supply system 3, an outer shell 4, and a temperature control device 5.

[0061] The specific location and structural relationship of the hydrogen storage unit 1 are as follows: Figure 1 As shown, it consists of a solid hydrogen storage material bed triggering region 1-1 and a solid hydrogen storage material bed scalability region 1-2.

[0062] Both the triggering zone 1-1 and the ripple zone 1-2 of the solid hydrogen storage material bed are composed of solid hydrogen storage functional material particles and pores; the solid hydrogen storage functional material is a large-capacity solid hydrogen storage material.

[0063] The solid hydrogen storage material bed triggering zone 1-1 is connected to the bed support 2-1 in the initiation structure 2 on one side, and to the solid hydrogen storage material bed swarming zone 1-2 on the other side; the distance from the solid hydrogen storage material bed triggering zone 1-1 to the bed support 2-1 is 0-15mm;

[0064] There is a gap between the hydrogen storage unit 1 and the side wall of the hydrogen storage tank 4-1 in the outer shell 4, and between the upper and lower walls of the hydrogen storage tank.

[0065] The specific location and structural relationship of the triggering structure 2 are as follows: Figure 1 As shown, it consists of a solid hydrogen storage initiation material, a bed support 2-1, and a fixing rod 2-2; it is used to provide heat for the start-up of the hydrogen storage tank and to support the hydrogen storage unit.

[0066] The solid hydrogen storage initiation material is a low-temperature solid hydrogen storage material;

[0067] The specific location and structural relationship of the bed support 2-1 are as follows: Figure 2 As shown, it consists of a partition plate 2-1-1 and a sleeve 2-1-2;

[0068] The separator 2-1-1 is fixed at the bottom of the sleeve 2-1-2, and the upper side of the separator 2-1-1 is in contact with the trigger area 1-1 of the solid hydrogen storage material bed.

[0069] The partition plate 2-1-1 is a hollow structure used to fill solid hydrogen storage initiation material; the partition plate 2-1-1 is provided with connecting pores for hydrogen to enter the partition plate 2-1-1 and react with the solid hydrogen storage initiation material; the mass of the solid hydrogen storage initiation material does not exceed 1 / 2 of the mass of the solid hydrogen storage functional material in hydrogen storage unit 1.

[0070] The outer surface of sleeve 2-1-2 contacts hydrogen storage unit 1, and the inner surface of sleeve 2-1-2 mates with fixing rod 2-2;

[0071] Multiple bed supports 2-1 are connected in series and fixed to the fixed rod 2-2, with gaps between the bed supports 2-1.

[0072] The gas supply system 3 consists of a gas inlet / outlet 3-1, a filter 3-2, a gap space, and connecting pores; the gas supply system 3 is used to realize the gas exchange between the solid hydrogen storage material bed trigger zone 1-1, the solid hydrogen storage material bed scalability zone 1-2, and the solid hydrogen storage initiating material and the outside.

[0073] A filter screen 3-2 is installed on the lower side of the gas inlet / outlet 3-1 to filter the gas entering and exiting the hydrogen storage tank.

[0074] The specific positional and structural relationships of the outer shell 4 are as follows: Figure 1 As shown, it consists of a hydrogen storage tank body 4-1, a hydrogen storage tank end cap 4-2, and a sealing gasket 4-3.

[0075] The internal cavity of the hydrogen storage tank body 4-1 accommodates the hydrogen storage unit 1, the initiation structure 2, and the gas supply system 3; the upper edge of the hydrogen storage tank body 4-1 is provided with a cylinder flange connection hole 4-1-1; a fixing rod 2-2 is fixed at the bottom of the hydrogen storage tank body 4-1.

[0076] The edge of the hydrogen storage tank end cover 4-2 is provided with an end cover flange connection hole 4-2-1; the hydrogen storage tank end cover 4-2 is provided with a gas inlet / outlet 3-1;

[0077] The flange connection hole 4-1-1 of the cylinder body and the flange connection hole 4-2-1 of the end cover are connected by bolts; when the cylinder body 4-1 of the hydrogen storage tank is connected to the end cover 4-2 of the hydrogen storage tank, a sealing gasket 4-3 is provided between the cylinder body 4-1 of the hydrogen storage tank and the end cover 4-2 of the hydrogen storage tank.

[0078] The temperature control device 5 is arranged on the outside of the hydrogen storage tank body 4-1 and uses heat exchange fluid for heat exchange; the temperature control device 5 is used to remove the heat generated by the hydrogen absorption reaction of the solid hydrogen storage material.

[0079] Taking commercially available Mg2Ni as a solid-state hydrogen storage functional material and commercially available LaNi5 as a solid-state hydrogen storage initiation material as an example, an operation method for a high-temperature solid-state hydrogen storage device that can be started without an external heat source includes the following steps:

[0080] Step 1, preparations before hydrogen absorption: First, fill the hydrogen storage tank with hydrogen storage units and fill the initiation structure with solid hydrogen storage initiation material. Then, after sealing the hydrogen storage tank, perform a vacuum operation to remove impurity gases from the hydrogen storage tank. Finally, start the temperature control device to control the temperature of the hydrogen storage tank.

[0081] The hydrogen storage unit is cylindrical, with a diameter of 15cm and a height of 5cm; the solid hydrogen storage material is commercially available Mg2Ni, and the porosity of the hydrogen storage unit is 0.3.

[0082] Within the initiation structure, a solid hydrogen storage initiation material is placed in a cylindrical partition plate; the partition plate has a diameter of 14 cm and a height of 0.5 cm; the solid hydrogen storage initiation material is commercially available LaNi5, and the porosity of the solid hydrogen storage initiation material bed is 0.63.

[0083] The temperature control device uses heat exchange fluid, specifically heat transfer oil, with a heat transfer coefficient of 2000 W / m. 2 The temperature of the heat exchange fluid is 298.15 K.

[0084] Step 2, initiation of the hydrogen absorption process: First, hydrogen gas is introduced into the hydrogen storage tank through the gas supply system to bring the hydrogen pressure to the operating pressure. The hydrogen gas first reacts with the solid hydrogen storage initiating material to generate heat, raising the temperature of the solid hydrogen storage initiating material. Then, the heat generated by the hydrogen absorption reaction of the solid hydrogen storage initiating material is transferred to the hydrogen storage unit, heating the trigger zone of the solid hydrogen storage material bed. Finally, the reaction in the trigger zone of the solid hydrogen storage material bed releases a large amount of heat, driving the continuous reaction in the ripple zone of the solid hydrogen storage material bed.

[0085] The operating pressure inside the hydrogen storage tank is 4 MPa;

[0086] Step 3, controlling the hydrogen absorption process, involves adjusting the speed of the heat exchange fluid in the temperature control device to control the progress of the hydrogen absorption reaction in the trigger zone and the spur zone of the solid hydrogen storage material bed; after the hydrogen absorption reaction ends or the control is completed, the gas supply system stops supplying gas, and at the same time, the temperature control device lowers the temperature of the hydrogen storage tank to room temperature.

[0087] To demonstrate that the hydrogen storage device of this invention can start up and complete the hydrogen absorption process, a hydrogen storage tank start-up and hydrogen absorption test was conducted. The test results are as follows: Figure 3 As shown,

[0088] When the start-up time is 25 seconds, the reaction fraction of the solid hydrogen storage functional material in the hydrogen storage tank increases rapidly, that is, the solid hydrogen storage functional material bed enters the continuous rapid reaction stage, which indicates that the hydrogen storage tank has been successfully started up.

[0089] The time required for the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank to reach 0.9 is 870s.

[0090] During startup, the high-temperature solid-state hydrogen storage and absorption process startup method of the present invention does not require external power supply.

[0091] To demonstrate that the apparatus and method described in this invention can achieve rapid start-up and accelerated hydrogen absorption reaction, Comparative Example 1 is provided, a conventional heat exchange fluid start-up method.

[0092] Comparative Example 1

[0093] A control method for a solid-state hydrogen storage device based on conventional heat exchange fluid start-up, referred to as the conventional heat exchange fluid start-up method, is disclosed. Unless otherwise specified, the steps are the same as in Example 1, except that the initiation structure within the hydrogen storage tank is not used. Instead, the heat exchange fluid in a temperature control device is used to heat the solid-state hydrogen storage material. Specifically, firstly, the temperature of the heat exchange fluid in the temperature control device is raised to 393.15 K by activating the temperature control device. Then, the heat exchange fluid is transported to the outer wall of the hydrogen storage tank via the temperature control device to heat the tank, i.e., to activate the device. After the hydrogen storage tank is activated, the temperature of the heat exchange fluid is maintained at 393.15 K to remove the heat generated during the hydrogen absorption process.

[0094] This indicates that, due to the thermal resistance between the heat exchange fluid and the solid hydrogen storage material bed inside the hydrogen storage tank, the temperature of the heat exchange fluid needs to be raised to 393.15K to meet the requirements for triggering the reaction; furthermore, the temperature of the heat exchange fluid in the temperature control device needs to be maintained at 393.15K.

[0095] The test results for the startup and hydrogen absorption of traditional hydrogen storage tanks, i.e., the startup method using traditional heat exchange fluids, are as follows: Figure 3 As shown,

[0096] At a startup time of 13 seconds, the reaction fraction of the solid hydrogen storage material bed inside the hydrogen storage tank rapidly increases, indicating that the solid hydrogen storage material bed has entered a sustained rapid reaction stage. This phenomenon indicates that the hydrogen storage tank has started successfully. However, since the temperature of the heat exchange fluid has already reached 393.15 K at a startup time of 0 seconds, the actual startup time of the hydrogen storage tank should be... Figure 3 The start-up time shown is 460s, which includes the heating time of the heat exchange fluid. Therefore, the start-up time of the hydrogen storage tank under the traditional heat exchange fluid start-up method is 473s. Compared with Example 1, the start-up time has increased by 1792%.

[0097] When the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank reaches 0.9, the time required is 1950s. Compared with Example 1, the time required increases by 114%. The reason is that the temperature of the heat exchange fluid is maintained at 393.15K, which results in a small temperature difference between the heat exchange fluid and the solid hydrogen storage functional material bed and a slow heat transfer rate.

[0098] During startup, the energy consumption of the traditional heat exchange fluid startup method is 460 kJ, and this data does not take into account the energy dissipation during fluid flow. Compared with the startup method of the high-temperature solid-state hydrogen storage and absorption process of this invention, it can be seen that the traditional heat exchange fluid startup method requires external power supply.

[0099] To demonstrate the universality of the external heat source-free start-up method of the present invention, Embodiment 2 is provided, which is a high-temperature solid hydrogen storage device with external heat source-free start-up where the function of the initiation structure is realized by a fixed rod.

[0100] Example 2

[0101] A high-temperature solid-state hydrogen storage device that can be started without an external heat source, such as Figure 4 As shown, the parts not specifically described are the same as in Example 1, except that: the fixing rod 2-2 replaces the partition plate 2-1-2 as a hollow structure for filling solid hydrogen storage initiation material; correspondingly, the fixing rod is provided with connecting holes for hydrogen to enter the fixing rod and react with the solid hydrogen storage initiation material.

[0102] To demonstrate that the hydrogen storage device in Embodiment 2 of this invention can start and complete the hydrogen absorption process, a hydrogen storage tank start-up and hydrogen absorption test was conducted. The test results show that...

[0103] When the startup time is 29 seconds, the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank increases rapidly, that is, the solid hydrogen storage functional material bed enters the continuous rapid reaction stage. This phenomenon indicates that the hydrogen storage tank has been successfully started.

[0104] The time required for the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank to reach 0.9 is 912 seconds.

[0105] During startup, the high-temperature solid-state hydrogen storage and absorption process startup method of the present invention does not require external power supply.

[0106] Example 2 shows that using a hollow fixed rod filled with solid hydrogen storage initiation material as the initiation structure can also achieve the effect of starting without an external heat source.

Claims

1. A high-temperature solid hydrogen storage tank that can be started without an external heat source, characterized in that: It consists of a hydrogen storage unit, an initiation structure, a gas supply system, an outer shell, and a temperature control device; The hydrogen storage unit consists of a solid hydrogen storage material bed triggering zone and a solid hydrogen storage material bed scalability zone. Both the solid hydrogen storage material bed triggering zone and the solid hydrogen storage material scalability zone are composed of solid hydrogen storage functional material particles and pores. The solid hydrogen storage functional material is a high-capacity solid hydrogen storage material. One side of the solid hydrogen storage material bed triggering zone is connected to the bed support in the initiation structure, and the other side is connected to the solid hydrogen storage material bed scalability zone. A gap is left between the hydrogen storage unit and the side wall of the hydrogen storage tank in the outer shell, as well as the upper and lower walls of the hydrogen storage tank. The initiation structure consists of a solid hydrogen storage initiation material, a bed support, and a fixing rod; the solid hydrogen storage initiation material in the initiation structure is a low-temperature solid hydrogen storage material. The bed support consists of partitions and sleeves; The separator plate is fixed at the bottom of the sleeve, and the upper part of the separator plate is in contact with the trigger area of ​​the solid hydrogen storage material bed. The outer surface of the sleeve contacts the hydrogen storage unit, and the inner surface of the sleeve mates with the fixing rod; At least one of the partition plates of the fixed rod and the bed support is a hollow structure for filling with solid hydrogen storage initiating material; when the fixed rod or the bed support is filled with solid hydrogen storage initiating material, the fixed rod or the bed support is provided with communicating pores for hydrogen to enter the fixed rod or the bed support and react with the solid hydrogen storage initiating material. The gas supply system consists of gas inlet and outlet, filter screen, gap space and connecting pores; The outer shell consists of a hydrogen storage tank body, a hydrogen storage tank end cap, and a sealing gasket; the inner cavity of the hydrogen storage tank body houses the hydrogen storage unit, the initiation structure, and the gas supply system. The temperature control device uses heat exchange fluid for heat exchange.

2. The high-temperature solid hydrogen storage tank as described in claim 1, characterized in that: The distance from the trigger area of ​​the solid hydrogen storage material bed to the bed support is 0-15 mm.

3. The high-temperature solid hydrogen storage tank as described in claim 1, characterized in that: The mass of the solid hydrogen storage initiation material bed shall not exceed 1 / 2 of the mass of the solid hydrogen storage functional material in the hydrogen storage unit; Multiple bed supports are connected in series and fixed to a fixed rod, with gaps between the bed supports.

4. The high-temperature solid hydrogen storage tank as described in claim 1, characterized in that: In the gas supply system, a filter screen is installed on the lower side of the gas inlet and outlet to filter the gas entering and exiting the hydrogen storage tank.

5. The high-temperature solid hydrogen storage tank as described in claim 1, characterized in that: The upper edge of the hydrogen storage tank body is provided with a flange connection hole; a fixing rod is fixed to the bottom of the hydrogen storage tank body. The hydrogen storage tank end cap is provided with an end cap flange connection hole on its edge; the hydrogen storage tank end cap is provided with a gas inlet and outlet. The flange connection hole of the cylinder body and the flange connection hole of the end cover are connected by bolts; when the hydrogen storage tank body is connected to the hydrogen storage tank end cover, a sealing gasket is provided between the hydrogen storage tank body and the hydrogen storage tank end cover.

6. The high-temperature solid hydrogen storage tank as described in claim 1, characterized in that: The temperature control device is located on the outside of the hydrogen storage tank and is used to remove the heat generated by the hydrogen absorption reaction of the solid hydrogen storage material.

7. A method for operating a high-temperature solid hydrogen storage tank without an external heat source, comprising the high-temperature solid hydrogen storage tank without an external heat source as described in any one of claims 1-6, characterized in that, The operation method includes the following steps: Step 1, preparations before hydrogen absorption: First, fill the hydrogen storage tank with hydrogen storage units and fill the initiation structure with solid hydrogen storage initiation material. Then, after sealing the hydrogen storage tank, perform a vacuum operation to remove impurity gases from the hydrogen storage tank. Finally, start the temperature control device to control the temperature of the hydrogen storage tank. Step 2, initiation of the hydrogen absorption process: First, hydrogen gas is introduced into the hydrogen storage tank through the gas supply system to bring the hydrogen pressure to the operating pressure. The hydrogen gas first reacts with the solid hydrogen storage initiating material to generate heat, raising the temperature of the solid hydrogen storage initiating material. Then, the heat generated by the hydrogen absorption reaction of the solid hydrogen storage initiating material is transferred to the hydrogen storage unit, heating the trigger zone of the solid hydrogen storage material bed. Finally, the reaction in the trigger zone of the solid hydrogen storage material bed releases a large amount of heat, driving the continuous reaction in the ripple zone of the solid hydrogen storage material bed. Step 3, controlling the hydrogen absorption process, involves adjusting the speed of the heat exchange fluid in the temperature control device to control the progress of the hydrogen absorption reaction in the trigger zone and the spur zone of the solid hydrogen storage material bed; after the hydrogen absorption reaction ends or the control is completed, the gas supply system stops supplying gas, and at the same time, the temperature control device lowers the temperature of the hydrogen storage tank to room temperature.

8. The operating method of the high-temperature solid hydrogen storage tank as described in claim 7, characterized in that: When the solid-state hydrogen storage material is Mg2Ni and the solid-state hydrogen storage initiation material is LaNi5 In step 1, the hydrogen storage unit is cylindrical with a diameter of 15 cm, a height of 5 cm, and a porosity of 0.

3. Within the initiation structure, solid hydrogen storage initiation material is placed in a cylindrical partition plate; the partition plate has a diameter of 14 cm and a height of 0.5 cm, and the porosity of the solid hydrogen storage initiation material bed is 0.

63. The temperature control device uses heat exchange fluid, specifically heat transfer oil, with a heat transfer coefficient of 200-5000 W / m. 2 The temperature of the heat exchange fluid is 288.15-308.15 K; In step 2, the operating pressure inside the hydrogen storage tank is 1-5 MPa.

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