Hybrid hydrogen storage system and method

Abstract

The present invention discloses a hybrid hydrogen storage system and method, which relates to the field of hydrogen energy equipment technology. The present invention designs a new type of hydrogen storage and supply system that is a mixture of liquid hydrogen storage and solid-state hydrogen storage, while combining the existing advantages of both, and has unique advantages such as flexible spatial layout, high utilization efficiency, and balanced hydrogen storage mass ratio and volume ratio, which greatly improves the application and promotion potential of hydrogen energy; in the hydrogen storage stage, a two-stage cooling structure is designed to use the sensible cooling of the low-temperature hydrogen continuously generated by the liquid hydrogen storage tank and the cooling capacity of the para-orthohydrogen conversion to cool the heat cycle working fluid, greatly increasing the hydrogen charging capacity of the hydrogen storage alloy; in the hydrogen release stage, the high-grade heat generated by the hydrogen power device is used to heat the hydrogen storage alloy, achieving smooth hydrogen supply and reducing additional energy input; three hydrogen sources with different hydrogen supply characteristics are designed for the hydrogen power device. By alternating and combining them, the hydrogen power device can achieve multiple operating modes and greatly extend the overall operating time of the hydrogen storage system.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen energy equipment, and in particular to a hybrid hydrogen storage system and method. Background Art

[0002] Hydrogen, a recognized low-carbon and zero-carbon energy source, is emerging as a promising candidate. As a clean energy source, hydrogen boasts high compression ratios, large-scale storage, no energy decay, and widespread availability. It can effectively reduce the proportion of fossil fuels and enhance clean development. Therefore, developing hydrogen is a crucial component of building a "multi-energy complementary" energy supply system. Using hydrogen to power aviation, shipping, land transportation, and vehicles can significantly reduce carbon emissions, making it a crucial tool for achieving energy transformation and upgrading.

[0003] The mainstream hydrogen storage methods include gaseous hydrogen storage, liquid hydrogen storage, and solid hydrogen storage. From the perspective of technological development, the current high-pressure gaseous hydrogen storage technology is relatively mature. Liquid hydrogen storage technology uses cryogenic technology to cool hydrogen to liquefaction temperature and store it in a highly vacuum insulated container in liquid form. The mass hydrogen storage density is high (greater than 5%), but the cost is high, the energy efficiency is low, and there are leakage problems. In addition, the insulation system is complex and requires a large installation space. It is difficult to install it on the wing part in applications such as hydrogen-powered aircraft. Solid-state hydrogen storage refers to the storage of hydrogen in a solid hydrogen storage material medium by physical or chemical adsorption. The volume hydrogen storage density is high (90-110kg / m 3 It can be stored at room temperature and pressure, is easy to use, and has better safety, but solid-state hydrogen storage requires additional external heat input. Summary of the Invention

[0004] The purpose of the present invention is to provide a hybrid hydrogen storage system and method, which organically combines a liquid hydrogen storage device with a solid hydrogen storage device to form a new type of combined hydrogen storage system. On the basis of greatly improving the hydrogen storage capacity and hydrogen utilization rate of the device, it also has the advantages of flexible spatial layout and high overall thermal efficiency.

[0005] The present invention intends to achieve the purpose of the present invention by the following technical solutions:

[0006] In a first aspect, the present invention provides a hybrid hydrogen storage system comprising a solid-state hydrogen storage bottle, a hydrogen storage alloy, a para-orthohydrogen conversion cooler, a hydrogen cooler, a hydrogen regenerator, a hydrogen power unit, a liquid hydrogen storage tank, and a high-grade heat pipeline;

[0007] The hydrogen regenerator, the ortho-hydrogen conversion cooler and the hydrogen cooler are each provided with a first channel and a second channel capable of forming heat exchange contact;

[0008] The solid-state hydrogen storage bottle is provided with a hydrogen storage alloy for storing hydrogen medium; the rear end of the hydrogen storage alloy is connected to a heat circulation pipeline for regulating the temperature of the hydrogen storage alloy, and the front end is connected to a hydrogen filling pipeline and a hydrogen supply pipeline; the hydrogen filling pipeline is installed with a hydrogen filling valve for controlling the flow of hydrogen during the filling phase, and the hydrogen supply pipeline is sequentially connected to the hydrogen storage alloy, the hydrogen supply valve, the second channel of the hydrogen regenerator and the hydrogen power device. The hydrogen supply pipeline is used to transport the hydrogen inside the hydrogen storage alloy to the hydrogen power device for reaction during the hydrogen release phase;

[0009] The heat circulation pipeline is connected in sequence to the hydrogen storage alloy, the heat circulation pump, the cooling control valve, the first channel of the secondary orthohydrogen conversion cooler, the first channel of the hydrogen cooler, the heating control valve, the first channel of the hydrogen regenerator, the high-grade heater and the hydrogen storage alloy to form a circulation loop for the circulation of the heat circulation working medium; at the same time, the heat circulation pipeline is also connected to a first branch provided with a first bypass valve and a second branch provided with a second bypass valve, the first branch is connected in parallel with the heat circulation pipeline section where the cooling control valve, the first channel of the secondary orthohydrogen conversion cooler and the first channel of the hydrogen cooler are located, and the second branch is connected in parallel with the heat circulation pipeline section where the heating control valve, the first channel of the hydrogen regenerator and the high-grade heater are located; the heat circulation pipeline, the first branch and the second branch operate in coordination to achieve heating or cooling of the hydrogen storage alloy;

[0010] The gas phase space at the top of the liquid hydrogen storage tank is externally connected to a hydrogen discharge pipeline, which is sequentially connected to a hydrogen discharge valve, a second channel of the hydrogen cooler, a second channel of the ortho-hydrogen conversion cooler, and a hydrogen power device. At the same time, a branch with a hydrogen vent valve is also provided on the hydrogen discharge pipeline. The hydrogen discharge pipeline is used to discharge low-temperature hydrogen generated by heat leakage from the liquid hydrogen storage tank, and to cool the hydrogen storage alloy during hydrogen filling to increase the hydrogen storage capacity of the hydrogen storage alloy, and finally to transport the hydrogen to the hydrogen power device for reaction.

[0011] The liquid phase space at the bottom of the liquid hydrogen storage tank is externally connected to a liquid hydrogen pipeline; the liquid hydrogen pipeline is sequentially connected to a liquid hydrogen valve, a liquid hydrogen pump, a liquid hydrogen vaporizer and a hydrogen power device, and is used to vaporize the liquid hydrogen and transport it to the hydrogen power device for reaction; at the same time, the liquid phase space at the bottom of the liquid hydrogen storage tank is also externally connected to a liquid hydrogen filling pipeline provided with a liquid hydrogen filling valve, and the liquid hydrogen filling pipeline is used for filling or replenishing liquid hydrogen;

[0012] The high-grade heat pipeline connects the hydrogen power device and the high-grade heater, and is used to transmit the high-grade energy of the hydrogen power device to the high-grade heater.

[0013] Preferably, the heat cycle pipeline is filled with high-pressure nitrogen or high-pressure helium as the heat cycle working fluid.

[0014] Preferably, the outer wall of the solid-state hydrogen storage bottle is made of insulating material.

[0015] Preferably, the hydrogen storage alloy is a magnesium-based hydrogen storage alloy.

[0016] Preferably, the heat circulation pipeline is arranged in the form of a coil inside the hydrogen storage alloy.

[0017] Preferably, when the hydrogen power device is a hydrogen-oxygen fuel cell, the high-grade heat pipeline transmits electrical energy to the high-grade heater; when the hydrogen power device is a hydrogen fuel engine, the high-grade heat pipeline transmits the reaction waste heat of the hydrogen fuel engine to the high-grade heater to meet the temperature required for the hydrogen storage alloy to supply hydrogen.

[0018] Preferably, the para-ortho-hydrogen conversion cooler is filled with a para-ortho-hydrogen conversion catalyst, which is used to perform para-ortho-conversion on the heated hydrogen and generate cooling capacity.

[0019] In a second aspect, the present invention provides an operating method using any of the hybrid hydrogen storage systems described in the first aspect, the method mainly comprising a hydrogen filling stage and a hydrogen supply stage, specifically as follows:

[0020] The hydrogen filling stage is specifically as follows:

[0021] S101. Open the liquid hydrogen filling valve, hydrogen discharge valve, and hydrogen vent valve; external liquid hydrogen enters the liquid hydrogen storage tank through the liquid hydrogen filling pipeline. The low-temperature hydrogen generated due to pre-cooling and heat leakage first enters the second channel of the hydrogen cooler through the hydrogen discharge valve, absorbs the heat of the heat cycle working fluid to increase the temperature; then enters the second channel of the para-ortho-hydrogen conversion cooler, undergoes para-ortho-hydrogen conversion under the action of the catalyst to generate cold energy, and finally is directly discharged through the hydrogen vent valve, thereby completing the liquid hydrogen filling process of the liquid hydrogen storage tank;

[0022] S102, open the hydrogen filling valve; external hydrogen enters the hydrogen storage alloy through the hydrogen filling pipeline, stores hydrogen in the form of a compound, and releases reaction heat at the same time; open the cooling control valve and the second bypass valve, and start the heat circulation pump; the hot circulating working medium enters the first channel of the para-orthohydrogen conversion cooler through the heat circulation pump and the cooling control valve, absorbs the para-orthohydrogen conversion cooling capacity for primary cooling, and then enters the first channel of the hydrogen cooler, absorbs the sensible cooling capacity of the low-temperature hydrogen for secondary cooling, and after reaching the set temperature, passes through the second bypass valve and cools the hydrogen storage alloy, absorbs the reaction heat generated by the hydrogen storage alloy during hydrogen filling, so as to increase the hydrogen filling amount of the hydrogen storage alloy, thereby completing the hydrogen filling process of the hydrogen storage alloy;

[0023] When the liquid hydrogen in the liquid hydrogen storage tank reaches the set liquid level, the liquid hydrogen filling valve is closed; when the hydrogen storage alloy is completely filled with hydrogen, the hydrogen filling valve, the cooling control valve and the second bypass valve are closed, the heat circulation pump is turned off, and then the hydrogen supply stage is entered;

[0024] In the hydrogen supply stage, there are three hydrogen supply modes: small-scale, medium-scale and large-scale, depending on the amount of hydrogen used. The details are as follows:

[0025] S201, the small-scale hydrogen supply mode is as follows:

[0026] The hydrogen vent valve is closed, and a small amount of hydrogen in the hydrogen discharge pipeline is transported to the hydrogen power unit. The hydrogen power unit starts to operate and generates high-grade heat, and the high-grade heat enters the high-grade heater through the high-grade heat pipeline; the first bypass valve, the heating control valve and the hydrogen supply valve are opened, and the heat circulation pump is started; the heat circulation working fluid in the heat circulation pipeline enters the first channel of the hydrogen regenerator through the heat circulation pump, the first bypass valve and the heating control valve in sequence, absorbs the heat of the high-temperature hydrogen for preheating, and then enters the high-grade heater for secondary heating. After reaching the set temperature, the hydrogen storage alloy is heated; after absorbing the heat, the hydrogen storage alloy begins to heat up and release hydrogen, and the released high-temperature hydrogen enters the hydrogen supply pipeline through the hydrogen supply valve; the high-temperature hydrogen first enters the second channel of the hydrogen regenerator to release sensible heat, and then mixes with the hydrogen in the hydrogen discharge pipeline, and the two enter the hydrogen power unit together to react;

[0027] S202: The medium-scale hydrogen supply mode is as follows:

[0028] Open the liquid hydrogen valve, start the liquid hydrogen pump, and close the hydrogen vent valve. Under the action of the liquid hydrogen pump, the liquid hydrogen in the liquid hydrogen storage tank enters the liquid hydrogen pipeline, passes through the liquid hydrogen valve and the liquid hydrogen pump in sequence, and then enters the liquid hydrogen vaporizer, absorbs heat and vaporizes. It is then mixed with the exhaust hydrogen in the hydrogen discharge pipeline, and the two enter the hydrogen power device together to react.

[0029] S203, the large-scale hydrogen supply mode is as follows:

[0030] Close the hydrogen vent valve, and a small amount of hydrogen in the hydrogen discharge pipeline is transported to the hydrogen power device. The hydrogen power device starts to operate and generates high-grade heat. The high-grade heat enters the high-grade heater through the high-grade heat pipeline; open the first bypass valve, heating control valve, and hydrogen supply valve, and start the heat circulation pump; the heat circulation working fluid in the heat circulation pipeline passes through the heat circulation pump, the first bypass valve, and the heating control valve in sequence and enters the first channel of the hydrogen regenerator, absorbs the heat of the high-temperature hydrogen for preheating, and then enters the high-grade heater for secondary heating. After reaching the set temperature, the hydrogen storage The alloy is heated, and the hydrogen storage alloy absorbs heat and begins to heat up and release hydrogen. The released high-temperature hydrogen enters the hydrogen supply pipeline through the hydrogen supply valve, first enters the second channel of the hydrogen regenerator to release sensible heat, and then mixes with the hydrogen in the hydrogen discharge pipeline. The liquid hydrogen valve is opened, the liquid hydrogen pump is started, and the hydrogen vent valve is closed. Under the action of the liquid hydrogen pump, the liquid hydrogen in the liquid hydrogen storage tank enters the liquid hydrogen pipeline, passes through the liquid hydrogen valve and liquid hydrogen pump in sequence, and then enters the liquid hydrogen vaporizer to absorb heat and vaporize, and then mixes with the hydrogen in the hydrogen discharge pipeline. The three together enter the hydrogen power device to react.

[0031] When all the hydrogen in the hydrogen storage alloy and liquid hydrogen storage tank is consumed, the hydrogen supply phase ends, all valves and moving equipment are closed, and the hydrogen filling phase is re-entered. The system operates back and forth between the hydrogen filling phase and the hydrogen supply phase to achieve continuous operation of the hybrid hydrogen storage system.

[0032] Compared with the existing technology, the present invention has the following outstanding and beneficial technical effects: a new type of hydrogen storage and supply system that is a mixture of liquid hydrogen storage and solid-state hydrogen storage is designed, which combines the existing advantages of both, and has unique advantages such as flexible spatial layout, high utilization efficiency, and balanced hydrogen storage mass ratio and volume ratio, which greatly improves the application and promotion potential of hydrogen energy; in the hydrogen storage stage, a two-stage cooling structure is designed, and the sensible cooling of the low-temperature hydrogen continuously generated by the liquid hydrogen storage tank and the cooling capacity of the para-orthohydrogen conversion are used to cool the thermal cycle working fluid, thereby greatly increasing the hydrogen charging capacity of the hydrogen storage alloy; in the hydrogen release stage, the high-grade heat generated by the hydrogen power device is used to heat the hydrogen storage alloy, thereby achieving smooth hydrogen supply and reducing additional energy input; three hydrogen sources with different hydrogen supply characteristics are designed for the hydrogen power device. By using them in alternating combination, the hydrogen power device can achieve multiple operating modes and greatly extend the overall operating time of the hydrogen storage system.

[0033] The concept, specific structure and technical effects of the present invention will be further described below in conjunction with the accompanying drawings to fully understand the purpose, characteristics and effects of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a structural schematic diagram of a hybrid hydrogen storage system of the present invention.

[0035] Figure 1 Middle: hydrogen filling pipeline 1, hydrogen filling valve 2, solid hydrogen storage bottle 3, hydrogen storage alloy 4, heat circulation pipeline 5, heat circulation pump 6, cooling control valve 7, secondary hydrogen conversion cooler 8, hydrogen cooler 9, heating control valve 10, hydrogen regenerator 11, high-grade heater 12, first branch 13, first bypass valve 14, second branch 15, second bypass valve 16, hydrogen supply pipeline 17, hydrogen supply valve 18, hydrogen power unit 19, hydrogen discharge pipeline 20, liquid hydrogen storage tank 21, hydrogen discharge valve 22, liquid hydrogen pipeline 23, liquid hydrogen valve 24, liquid hydrogen pump 25, liquid hydrogen vaporizer 26, liquid hydrogen filling pipeline 27, liquid hydrogen filling valve 28, high-grade heat pipeline 29, hydrogen vent valve 30. DETAILED DESCRIPTION

[0036] In order to make the above-mentioned objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below. The technical features in the various embodiments of the present invention can be combined accordingly without conflicting with each other.

[0037] In the description of the present invention, it should be understood that when an element is considered to be "connected" to another element, it can be directly connected to the other element or indirectly connected, that is, there are intermediate elements. On the contrary, when an element is said to be "directly" connected to another element, there are no intermediate elements.

[0038] In the description of the present invention, it should be understood that the terms "first" and "second" are used solely for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly specifying the number of technical features being described. Therefore, features defined as "first" or "second" may explicitly or implicitly include at least one of such features.

[0039] In the description of the present invention, it should be understood that the terms "low temperature" and "high temperature" (such as "low temperature hydrogen" and "high temperature hydrogen") refer to relatively high or low temperatures compared to the temperature of the same medium in the same path, and cannot be understood as indicating or implying relative importance or implicitly indicating the absolute temperature value of the indicated technical characteristics.

[0040] See also Figure 1 In a preferred embodiment of the present invention, a hybrid hydrogen storage system is provided. The system's components primarily include a solid-state hydrogen storage bottle 3, a hydrogen storage alloy 4, a para-ortho-hydrogen conversion cooler 8, a hydrogen cooler 9, a hydrogen regenerator 11, a hydrogen power unit 19, a liquid hydrogen storage tank 21, and a high-grade heat pipe 29. The following describes in detail the coordination and interaction between these components.

[0041] In the system of the present invention, the interior of the hydrogen regenerator 11 has a first channel and a second channel that can form heat exchange contact. The first channel is used to pass the hot cycle working fluid from the heat cycle pipeline 5, and the second channel is used to pass the high-temperature hydrogen released from the hydrogen storage alloy 4. The hot cycle working fluid absorbs the heat of the high-temperature hydrogen to heat up and preheat it so that the hydrogen storage alloy 4 begins to heat up and release hydrogen after absorbing the heat. The hydrogen absorbs the coldness of the hot cycle working fluid to cool down and enter the hydrogen power device 19 for reaction.

[0042] In the system of the present invention, the interior of the secondary orthohydrogen conversion cooler 8 has a first channel and a second channel capable of forming heat exchange contact. The first channel is used to pass the heat cycle working medium from the heat cycle pipeline 5, and the second channel is used to pass the hydrogen from the liquid hydrogen storage tank 21. The interior of the hydrogen cooler 9 has a first channel and a second channel capable of forming heat exchange contact. The first channel is used to pass the heat cycle working medium from the heat cycle pipeline 5, and the second channel is used to pass the hydrogen from the liquid hydrogen storage tank 21. The secondary orthohydrogen conversion cooler 8 and the hydrogen cooler 9 cooperate with each other in actual use, and the first channels of both are only used in the hydrogen (hydrogen and liquid hydrogen) filling stage, specifically as follows: the high-temperature hydrogen flowing out of the liquid hydrogen storage tank 21 first enters the second channel of the hydrogen cooler 9, absorbs the heat of the heat cycle working medium to increase the temperature, and then enters the second channel of the secondary orthohydrogen conversion cooler 8, and performs secondary ortho conversion under the action of the catalyst to generate cold energy; in this process, the heat cycle medium first enters the first channel of the secondary orthohydrogen conversion cooler 8, absorbs the secondary orthohydrogen conversion cold energy for primary cooling, and then enters the first channel of the hydrogen cooler 9, absorbs the low-temperature hydrogen sensible cold energy for secondary cooling, and after reaching the set temperature, the hydrogen storage alloy 4 is cooled through the second bypass valve 16, absorbing the reaction heat generated during the hydrogen filling, and increasing the hydrogen filling amount of the hydrogen storage alloy 4.

[0043] In the system of the present invention, the solid-state hydrogen storage bottle 3 is a container structure that is relatively closed to the outside. A hydrogen storage alloy 4 is provided inside the bottle for storing hydrogen. The rear end of the hydrogen storage alloy 4 is connected to a heat circulation pipeline 5, which is used to control the temperature of the hydrogen storage alloy 4. The front end of the hydrogen storage alloy 4 is connected to a hydrogen filling pipeline 1 and a hydrogen supply pipeline 17. The hydrogen filling pipeline 1 is equipped with a hydrogen filling valve 2 for controlling the flow of hydrogen during the filling phase. The hydrogen supply pipeline 17 is sequentially connected to the hydrogen storage alloy 4, the hydrogen supply valve 18, the second channel of the hydrogen regenerator 11, and the hydrogen power device 19. It is used to transport the hydrogen inside the hydrogen storage alloy 4 to the hydrogen power device 19 for reaction during the hydrogen release phase.

[0044] That is, along the direction of medium flow, the hydrogen filling line 1 is connected to the external hydrogen source at its head end and to the hydrogen storage alloy 4 at its tail end. The hydrogen supply line 17 is connected to the hydrogen storage alloy 4 at its head end and to the hydrogen power device 19 at its tail end. In actual use, the hydrogen filling line 1 and the hydrogen supply line 17 are not opened at the same time. During the hydrogen filling phase, the hydrogen filling line 1 is opened while the hydrogen supply line 17 is closed. During the hydrogen supply phase, the hydrogen supply line 17 is selectively opened based on the amount of hydrogen supplied, while the hydrogen filling line 1 is always closed.

[0045] In a preferred embodiment of the system of the present invention, the hydrogen storage alloy can be a magnesium-based hydrogen storage alloy. The exterior of the solid hydrogen storage bottle can be made of high-strength thermal insulation material to prevent the ambient temperature from affecting the hydrogen storage alloy inside.

[0046] In the system of the present invention, a heat circulation pipeline 5 sequentially connects the hydrogen storage alloy 4, a heat circulation pump 6, a cooling control valve 7, the first channel of the para-orthohydrogen conversion cooler 8, the first channel of the hydrogen cooler 9, a heating control valve 10, the first channel of the hydrogen regenerator 11, a high-grade heater 12, and the hydrogen storage alloy 4 to form a circulation loop. The heat circulation pipeline 5 is filled with a heat circulation medium for its circulation. Furthermore, the heat circulation pipeline 5 is also connected to a first branch 13 equipped with a first bypass valve 14 and a second branch 15 equipped with a second bypass valve 16. In actual use, the heat circulation pipeline 5, the first branch 13, and the second branch 15 operate in coordination to achieve the purposes of heating and cooling the hydrogen storage alloy 4.

[0047] Specifically, along the medium flow direction, the head end of the first branch 13 communicates with the heat circulation pipeline 5 located between the heat circulation pump 6 and the cooling control valve 7, and the terminal end communicates with the heat circulation pipeline 5 located between the hydrogen cooler 9 and the heating control valve 10. That is, the first branch 13 is connected in parallel with the heat circulation pipeline 5 section containing the cooling control valve 7, the first channel of the secondary ortho-hydrogen conversion cooler 8, and the first channel of the hydrogen cooler 9, and in actual use, one of the two parallel pipelines is selectively opened. Similarly, along the medium flow direction, the head end of the second branch 15 communicates with the heat circulation pipeline 5 located between the hydrogen cooler 9 and the heating control valve 10, and the terminal end communicates with the heat circulation pipeline 5 located between the high-grade heater 12 and the hydrogen storage alloy 4. That is, the second branch 15 is connected in parallel with the heat circulation pipeline 5 section containing the heating control valve 10, the first channel of the hydrogen regenerator 11, and the high-grade heater 12, and in actual use, one of the two parallel pipelines is selectively opened.

[0048] In a preferred embodiment of the system of the present invention, the heat circulation piping can be filled with an inert gas such as high-pressure nitrogen or high-pressure helium as the heat circulation working fluid. The heat circulation piping preferably utilizes a high-efficiency heat exchange method such as coils within the hydrogen storage alloy to increase the heat exchange area between the heat circulation piping and the hydrogen storage alloy.

[0049] In the system of the present invention, the liquid hydrogen storage tank 21 should be a relatively closed container structure, the interior of which is used to hold liquid hydrogen. A hydrogen discharge pipeline 20 is provided in the gaseous space at the top of the liquid hydrogen storage tank 21. The hydrogen discharge pipeline 20 located outside the liquid hydrogen storage tank 21 is connected in sequence to the hydrogen discharge valve 22, the second channel of the hydrogen cooler 9, the second channel of the para-orthohydrogen conversion cooler 8, and the hydrogen power device 19. At the same time, a branch of the hydrogen vent valve 30 is also provided on the hydrogen discharge pipeline 20. The hydrogen discharge pipeline 20 and its branches can discharge the low-temperature hydrogen generated by heat leakage from the liquid hydrogen storage tank 21, and cool the hydrogen storage alloy 4 during hydrogen charging to increase its hydrogen storage capacity, and finally transport it to the hydrogen power device 19 for reaction.

[0050] In a preferred embodiment of the system of the present invention, the branch of hydrogen discharge line 20 can be located between the orthohydrogen conversion cooler 8 and the hydrogen power unit 19, with the terminal end connected to the outside atmosphere. The orthohydrogen conversion cooler is filled with a orthohydrogen conversion catalyst, which converts the heated hydrogen into orthohydrogen and generates cooling energy.

[0051] In the system of the present invention, a liquid hydrogen pipeline 23 is provided in the liquid phase space at the bottom of the liquid hydrogen storage tank 21. The liquid hydrogen pipeline 23 located outside the liquid hydrogen storage tank 21 is connected to a liquid hydrogen valve 24, a liquid hydrogen pump 25, a liquid hydrogen vaporizer 26 and a hydrogen power device 19 in sequence. The liquid hydrogen pipeline 23 is used to vaporize the liquid hydrogen and transport it to the hydrogen power device 19 for reaction; at the same time, a liquid hydrogen filling pipeline 27 with a liquid hydrogen filling valve 28 installed at the bottom of the liquid hydrogen storage tank 21 is also provided for filling or replenishing liquid hydrogen.

[0052] In a preferred embodiment of the system of the present invention, liquid hydrogen refilling line 27 and liquid hydrogen line 23 do not interfere with each other and have no shared pipeline sections. Two holes can be opened at the bottom of liquid hydrogen storage tank 21, one for securing liquid hydrogen refilling line 27 and the other for securing liquid hydrogen line 23. The cooling energy generated by the liquid hydrogen vaporizer can be used in scenarios or devices requiring high cooling quality, thus avoiding energy waste.

[0053] In the system of the present invention, the high-grade heat pipeline 29 connects the hydrogen power device 19 and the high-grade heater 12 to transmit the high-grade energy of the hydrogen power device 19 to the high-grade heater 12 .

[0054] In a preferred embodiment of the system of the present invention, when the hydrogen power device is a hydrogen-oxygen fuel cell, the high-grade heat pipeline transmits electrical energy to the high-grade heater; when the hydrogen power device is a hydrogen fuel engine, the high-grade heat pipeline transmits the reaction waste heat of the hydrogen fuel engine to the high-grade heater to meet the temperature required for hydrogen supply by the hydrogen storage alloy.

[0055] In another embodiment of the present invention, based on the above Figure 1The hybrid hydrogen storage system shown also provides an operating method for a liquid hydrogen storage and supply system, and the operating process of the method is mainly divided into two stages, one stage is the hydrogen filling stage, and the other stage is the hydrogen supply stage. The two stages can be selected in a priority order according to the situation of hydrogen gas inside the solid-state hydrogen storage bottle 3 and liquid hydrogen inside the liquid hydrogen storage tank 21. For example, when the hydrogen gas inside the solid-state hydrogen storage bottle 3 and the liquid hydrogen inside the liquid hydrogen storage tank 21 have reached the required filling amount, the hydrogen supply stage can be carried out first. When the hydrogen gas inside the solid-state hydrogen storage bottle 3 and the liquid hydrogen inside the liquid hydrogen storage tank 21 are continuously consumed and fall below the threshold during the hydrogen supply stage, the hydrogen filling stage can be carried out again, and the cycle repeats. Of course, when the hydrogen gas inside the solid-state hydrogen storage bottle 3 and the liquid hydrogen inside the liquid hydrogen storage tank 21 are insufficient, the hydrogen filling stage can be carried out first and then the hydrogen supply stage. The following will take the situation where there is no hydrogen gas inside the solid-state hydrogen storage bottle 3 and no liquid hydrogen inside the liquid hydrogen storage tank 21 in the initial state as an example to explain each stage in detail:

[0056] It should be noted that this method first controls all valves to be in a closed state, and the heat circulation pump 6, liquid hydrogen pump 25, hydrogen power device 19 and other dynamic equipment are in a stopped state.

[0057] First, hydrogen (hydrogen gas and liquid hydrogen) filling stage:

[0058] S101, liquid hydrogen filling: open the liquid hydrogen filling valve 28, hydrogen discharge valve 22 and hydrogen vent valve 30, and external liquid hydrogen enters the liquid hydrogen storage tank 21 through the liquid hydrogen filling pipeline 27. The low-temperature hydrogen generated due to pre-cooling and heat leakage first enters the second channel of the hydrogen cooler 9 through the hydrogen discharge valve 22, absorbs the heat of the heat cycle working medium to increase the temperature, and then enters the second channel of the para-ortho-hydrogen conversion cooler 8, undergoes para-ortho-hydrogen conversion under the action of the catalyst to generate cold energy, and finally is directly discharged through the hydrogen vent valve 30.

[0059] S102, hydrogen filling: open the hydrogen filling valve 2, and external hydrogen enters the hydrogen storage alloy 4 through the hydrogen filling pipeline 1, and is stored in the hydrogen storage alloy 4 in the form of a compound, while releasing reaction heat; open the cooling control valve 7 and the second bypass valve 16, start the heat circulation pump 6, and the heat circulation working medium enters the first channel of the para-orthohydrogen conversion cooler 8 through the heat circulation pump 6 and the cooling control valve 7, absorbs the para-orthohydrogen conversion cooling energy for primary cooling, and then enters the first channel of the hydrogen cooler 9, absorbs the sensible cooling energy of the low-temperature hydrogen for secondary cooling, and after reaching the set temperature, the hydrogen storage alloy 4 is cooled through the second bypass valve 16, and the reaction heat generated during the hydrogen filling is absorbed, thereby increasing the hydrogen filling amount of the hydrogen storage alloy 4.

[0060] When the liquid hydrogen inside the liquid hydrogen storage tank 21 reaches the set liquid level, the liquid hydrogen filling valve 28 is closed; when the hydrogen storage alloy 4 is completely filled with hydrogen, the hydrogen filling valve 2, the cooling control valve 7 and the second bypass valve 16 are closed, the heat circulation pump 6 is turned off, and the next stage is entered.

[0061] Second, during the hydrogen supply phase, there are three hydrogen supply modes depending on the amount of hydrogen used:

[0062] S201. Small-scale hydrogen supply mode: solid hydrogen storage + liquid hydrogen storage tank evaporation hydrogen, as follows:

[0063] The hydrogen vent valve 30 is closed, and a small amount of hydrogen in the hydrogen discharge pipeline 20 is transported to the hydrogen power device 19. The hydrogen power device 19 starts to operate and generates high-grade heat. The high-grade heat enters the high-grade heater 12 through the high-grade heat pipeline 29; the first bypass valve 14, the heating control valve 10, and the hydrogen supply valve 18 are opened, and the heat circulation pump 6 is started. The heat circulation working medium in the heat circulation pipeline 5 passes through the heat circulation pump 6, the first bypass valve 14, and the heating control valve 10 in sequence and enters the first channel of the hydrogen regenerator 11, absorbs the heat of the high-temperature hydrogen for preheating, and then enters the high-grade heater 12 for secondary heating. After reaching the set temperature, the hydrogen storage alloy 4 is heated. After absorbing the heat, the hydrogen storage alloy 4 begins to heat up and releases hydrogen. The high-temperature hydrogen enters the hydrogen supply pipeline 17 through the hydrogen supply valve 18, first enters the second channel of the hydrogen regenerator 11 to release sensible heat, and then mixes with the hydrogen in the hydrogen discharge pipeline 20. The two enter the hydrogen power device 19 together to react.

[0064] S202, medium-scale hydrogen supply mode: liquid hydrogen + hydrogen evaporation from liquid hydrogen storage tanks, details as follows:

[0065] Open the liquid hydrogen valve 24, start the liquid hydrogen pump 25, and close the hydrogen vent valve 30. Under the action of the liquid hydrogen pump 25, the liquid hydrogen in the liquid hydrogen storage tank 21 enters the liquid hydrogen pipeline 23, and enters the liquid hydrogen vaporizer 26 through the liquid hydrogen valve 24 and the liquid hydrogen pump 25 in turn, absorbs heat and vaporizes, and mixes with the exhaust hydrogen in the hydrogen exhaust pipeline 20. The two enter the hydrogen power device 19 together to react.

[0066] S203, large-scale hydrogen supply mode: solid hydrogen storage + liquid hydrogen + hydrogen evaporation from liquid hydrogen storage tanks, specifically as follows:

[0067] The hydrogen vent valve 30 is closed, and a small amount of hydrogen in the hydrogen discharge pipeline 20 is transported to the hydrogen power device 19. The hydrogen power device 19 starts to operate and generates high-grade heat. The high-grade heat enters the high-grade heater 12 through the high-grade heat pipeline 29; the first bypass valve 14, the heating control valve 10, and the hydrogen supply valve 18 are opened, and the heat circulation pump 6 is started. The heat circulation working medium in the heat circulation pipeline 5 passes through the heat circulation pump 6, the first bypass valve 14, and the heating control valve 10 in sequence and enters the first channel of the hydrogen regenerator 11, absorbs the heat of the high-temperature hydrogen for preheating, and then enters the high-grade heater 12 for secondary heating. After reaching the set temperature, the hydrogen storage Alloy 4 is heated, and the hydrogen storage alloy 4 begins to heat up and release hydrogen after absorbing heat. The high-temperature hydrogen enters the hydrogen supply pipeline 17 through the hydrogen supply valve 18, first enters the second channel of the hydrogen regenerator 11 to release sensible heat, and then mixes with the hydrogen in the hydrogen discharge pipeline 20; the liquid hydrogen valve 24 is opened, the liquid hydrogen pump 25 is started, and the hydrogen vent valve 30 is closed. Under the action of the liquid hydrogen pump 25, the liquid hydrogen in the liquid hydrogen storage tank 21 enters the liquid hydrogen pipeline 23, and enters the liquid hydrogen vaporizer 26 through the liquid hydrogen valve 24 and the liquid hydrogen pump 25 in turn, absorbs heat and vaporizes, and then mixes with the hydrogen in the hydrogen discharge pipeline 20. The three enter the hydrogen power device 19 together to react.

[0068] When all the hydrogen in the hydrogen storage alloy 4 and the liquid hydrogen storage tank 21 is consumed, the hydrogen supply phase ends, all valves and moving equipment are closed, and the hydrogen (hydrogen gas and liquid hydrogen) filling phase is re-entered, and the system operates reciprocatingly, forming an overall operating process of a hybrid hydrogen storage system.

[0069] It should be noted that the "small scale, medium scale and large scale" in the above three hydrogen supply modes are all relative hydrogen quantities, and the specific thresholds can be formulated according to actual conditions.

[0070] It should be noted that the numbers in the above steps (such as S101~S102, S201~S203, etc.) do not specifically refer to the order of operations in actual use, but are only used to distinguish the implementation of a certain path or a certain function. In actual operation, several or single steps can be performed simultaneously, separately or sequentially as needed.

[0071] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A hybrid hydrogen storage system, characterized in that: It includes a solid hydrogen storage bottle (3), a hydrogen storage alloy (4), a para-ortho-hydrogen conversion cooler (8), a hydrogen cooler (9), a hydrogen regenerator (11), a hydrogen power device (19), a liquid hydrogen storage tank (21) and a high-grade heat pipeline (29); The hydrogen regenerator (11), the ortho-parahydrogen conversion cooler (8) and the hydrogen cooler (9) each have a first channel and a second channel inside thereof capable of forming heat exchange contact; The solid-state hydrogen storage bottle (3) is provided with a hydrogen storage alloy (4) for storing hydrogen medium; the rear end of the hydrogen storage alloy (4) is connected to a heat circulation pipeline (5) for regulating the temperature of the hydrogen storage alloy (4), and the front end is connected to a hydrogen filling pipeline (1) and a hydrogen supply pipeline (17); the hydrogen filling pipeline (1) is installed with a hydrogen filling valve (2) for controlling the flow of hydrogen during the filling stage, and the hydrogen supply pipeline (17) is connected in sequence to the hydrogen storage alloy (4), the hydrogen supply valve (18), the second channel of the hydrogen regenerator (11) and the hydrogen power device (19), and the hydrogen supply pipeline (17) is used to transport the hydrogen inside the hydrogen storage alloy (4) to the hydrogen power device (19) for reaction during the hydrogen release stage; The heat circulation pipeline (5) is connected in sequence to the hydrogen storage alloy (4), the heat circulation pump (6), the cooling control valve (7), the first channel of the para-orthohydrogen conversion cooler (8), the first channel of the hydrogen cooler (9), the heating control valve (10), the first channel of the hydrogen regenerator (11), the high-grade heater (12) and the hydrogen storage alloy (4) to form a circulation loop for the circulation of the heat circulation working medium; at the same time, the heat circulation pipeline (5) is also connected to a first branch (13) provided with a first bypass valve (14) and a second branch (16) provided with a second bypass valve (17). The branch (15) comprises a first branch (13) connected in parallel with a heat circulation pipeline (5) section where the cooling control valve (7), the first channel of the secondary orthohydrogen conversion cooler (8) and the first channel of the hydrogen cooler (9) are located, and a second branch (15) connected in parallel with a heat circulation pipeline (5) section where the heating control valve (10), the first channel of the hydrogen regenerator (11) and the high-grade heater (12) are located; the heat circulation pipeline (5), the first branch (13) and the second branch (15) operate in coordination to achieve heating or cooling of the hydrogen storage alloy (4); The gas phase space at the top of the liquid hydrogen storage tank (21) is externally connected to a hydrogen discharge pipeline (20), which is sequentially connected to a hydrogen discharge valve (22), a second channel of a hydrogen cooler (9), a second channel of a para-orthohydrogen conversion cooler (8), and a hydrogen power device (19). At the same time, a branch with a hydrogen vent valve (30) is also provided on the hydrogen discharge pipeline (20); the hydrogen discharge pipeline (20) is used to discharge low-temperature hydrogen generated by heat leakage from the liquid hydrogen storage tank (21), and to cool the hydrogen storage alloy (4) during hydrogen charging, thereby increasing the hydrogen storage capacity of the hydrogen storage alloy (4), and finally transporting the hydrogen to the hydrogen power device (19) for reaction; The liquid phase space at the bottom of the liquid hydrogen storage tank (21) is externally connected to a liquid hydrogen pipeline (23); the liquid hydrogen pipeline (23) is sequentially connected to a liquid hydrogen valve (24), a liquid hydrogen pump (25), a liquid hydrogen vaporizer (26) and a hydrogen power device (19), and is used to vaporize the liquid hydrogen and transport it to the hydrogen power device (19) for reaction; at the same time, the liquid phase space at the bottom of the liquid hydrogen storage tank (21) is also externally connected to a liquid hydrogen filling pipeline (27) provided with a liquid hydrogen filling valve (28), and the liquid hydrogen filling pipeline (27) is used for filling or replenishing liquid hydrogen; The high-grade heat pipeline (29) connects the hydrogen power device (19) and the high-grade heater (12) and is used to transmit the high-grade energy of the hydrogen power device (19) to the high-grade heater (12).

2. A hybrid hydrogen storage system according to claim 1, characterized in that: The interior of the heat cycle pipeline (5) is filled with high-pressure nitrogen or high-pressure helium as a heat cycle working medium.

3. A hybrid hydrogen storage system according to claim 1, characterized in that: The outer wall of the solid-state hydrogen storage bottle (3) is made of thermal insulation material.

4. A hybrid hydrogen storage system according to claim 1, characterized in that: The hydrogen storage alloy (4) is a magnesium-based hydrogen storage alloy.

5. A hybrid hydrogen storage system according to claim 1, characterized in that: The heat circulation pipeline (5) is arranged in the form of a coil inside the hydrogen storage alloy (4).

6. A hybrid hydrogen storage system according to claim 1, characterized in that: When the hydrogen power device (19) is a hydrogen-oxygen fuel cell, the high-grade heat pipe (29) transmits electric energy to the high-grade heater (12); when the hydrogen power device (19) is a hydrogen fuel engine, the high-grade heat pipe (29) transmits the reaction waste heat of the hydrogen fuel engine to the high-grade heater (12) to meet the temperature required for hydrogen supply by the hydrogen storage alloy (4).

7. A hybrid hydrogen storage system according to claim 1, characterized in that: The interior of the para-ortho-hydrogen conversion cooler (8) is filled with a para-ortho-hydrogen conversion catalyst, which is used to perform para-ortho-conversion on the heated hydrogen and generate cold.

8. An operating method using the hybrid hydrogen storage system according to any one of claims 1 to 7, characterized in that: It includes the hydrogen filling stage and the hydrogen supply stage, as follows: The hydrogen filling stage is specifically as follows: S101, open the liquid hydrogen filling valve (28), the hydrogen discharge valve (22) and the hydrogen vent valve (30); external liquid hydrogen enters the liquid hydrogen storage tank (21) through the liquid hydrogen filling pipeline (27), and the low-temperature hydrogen generated due to pre-cooling and heat leakage first enters the second channel of the hydrogen cooler (9) through the hydrogen discharge valve (22), absorbs the heat of the heat cycle working medium and heats up; then enters the second channel of the ortho-hydrogen conversion cooler (8), performs ortho-hydrogen conversion under the action of the catalyst to generate cold energy, and finally directly empties through the hydrogen vent valve (30), thereby completing the liquid hydrogen filling process of the liquid hydrogen storage tank (21); S102, opening the hydrogen filling valve (2); external hydrogen enters the hydrogen storage alloy (4) through the hydrogen filling pipeline (1), and is stored in the form of a compound while releasing reaction heat; The cooling control valve (7) and the second bypass valve (16) are opened, and the heat circulation pump (6) is started; the heat circulation working medium enters the first channel of the orthohydrogen conversion cooler (8) through the heat circulation pump (6) and the cooling control valve (7), absorbs the cold energy of the orthohydrogen conversion to perform a primary cooling, and then enters the first channel of the hydrogen cooler (9), absorbs the sensible cold energy of the low-temperature hydrogen to perform a secondary cooling, and after reaching the set temperature, passes through the second bypass valve (16) and cools the hydrogen storage alloy (4), absorbs the reaction heat generated by the hydrogen storage alloy (4) during hydrogen filling, so as to increase the hydrogen filling amount of the hydrogen storage alloy (4), thereby realizing the hydrogen filling process of the hydrogen storage alloy (4); When the liquid hydrogen in the liquid hydrogen storage tank (21) reaches the set liquid level, the liquid hydrogen filling valve (28) is closed; when the hydrogen storage alloy (4) is completely filled with hydrogen, the hydrogen filling valve (2), the cooling control valve (7) and the second bypass valve (16) are closed, the heat circulation pump (6) is turned off, and then the hydrogen supply stage is entered; In the hydrogen supply stage, there are three hydrogen supply modes: small-scale, medium-scale and large-scale, depending on the amount of hydrogen used. The details are as follows: S201, the small-scale hydrogen supply mode is as follows: The hydrogen vent valve (30) is closed, and a small amount of hydrogen in the hydrogen discharge pipeline (20) is transported to the hydrogen power device (19). The hydrogen power device (19) starts to operate and generates high-grade heat, and the high-grade heat enters the high-grade heater (12) through the high-grade heat pipeline (29); the first bypass valve (14), the heating control valve (10) and the hydrogen supply valve (18) are opened, and the heat circulation pump (6) is started; the heat circulation working medium in the heat circulation pipeline (5) enters the hydrogen through the heat circulation pump (6), the first bypass valve (14) and the heating control valve (10) in sequence. The first channel of the regenerator (11) absorbs the heat of the high-temperature hydrogen to be preheated, and then enters the high-grade heater (12) for secondary heating, and heats the hydrogen storage alloy (4) after reaching the set temperature; the hydrogen storage alloy (4) begins to heat up and releases hydrogen after absorbing the heat, and the released high-temperature hydrogen enters the hydrogen supply pipeline (17) through the hydrogen supply valve (18); the high-temperature hydrogen first enters the second channel of the hydrogen regenerator (11) to release sensible heat, and then mixes with the hydrogen in the hydrogen discharge pipeline (20), and the two enter the hydrogen power device (19) together to react; S202: The medium-scale hydrogen supply mode is as follows: The liquid hydrogen valve (24) is opened, the liquid hydrogen pump (25) is started, and the hydrogen vent valve (30) is closed; under the action of the liquid hydrogen pump (25), the liquid hydrogen in the liquid hydrogen storage tank (21) enters the liquid hydrogen pipeline (23), passes through the liquid hydrogen valve (24) and the liquid hydrogen pump (25) in sequence, and then enters the liquid hydrogen vaporizer (26), absorbs heat and vaporizes, and then mixes with the exhaust hydrogen in the hydrogen discharge pipeline (20), and the two enter the hydrogen power device (19) together to react; S203, the large-scale hydrogen supply mode is as follows: The hydrogen vent valve (30) is closed, and a small amount of hydrogen in the hydrogen discharge pipeline (20) is transported to the hydrogen power device (19). The hydrogen power device (19) starts to operate and generates high-grade heat, and the high-grade heat enters the high-grade heater (12) through the high-grade heat pipeline (29); the first bypass valve (14), the heating control valve (10), and the hydrogen supply valve (18) are opened, and the heat circulation pump (6) is started; the heat circulation working medium in the heat circulation pipeline (5) passes through the heat circulation pump (6), the first bypass valve (14), and the heating control valve (10) in sequence and enters the first channel of the hydrogen regenerator (11), absorbs the heat of the high-temperature hydrogen for preheating, and then enters the high-grade heater (12) for secondary heating. After reaching the set temperature, the hydrogen storage alloy ( 4) heating, the hydrogen storage alloy (4) absorbs heat and begins to heat up and release hydrogen; the released high-temperature hydrogen enters the hydrogen supply pipeline (17) through the hydrogen supply valve (18), first enters the second channel of the hydrogen regenerator (11) to release sensible heat, and then mixes with the hydrogen in the hydrogen discharge pipeline (20); the liquid hydrogen valve (24) is opened, the liquid hydrogen pump (25) is started, and the hydrogen vent valve (30) is closed; under the action of the liquid hydrogen pump (25), the liquid hydrogen in the liquid hydrogen storage tank (21) enters the liquid hydrogen pipeline (23), passes through the liquid hydrogen valve (24) and the liquid hydrogen pump (25) in sequence, and then enters the liquid hydrogen vaporizer (26) to absorb heat and vaporize, and then also mixes with the hydrogen in the hydrogen discharge pipeline (20), and the three enter the hydrogen power device (19) together to react; When all the hydrogen in the hydrogen storage alloy (4) and the liquid hydrogen storage tank (21) is consumed, the hydrogen supply phase ends, all valves and moving equipment are closed, and the system re-enters the hydrogen filling phase. The system operates back and forth between the hydrogen filling phase and the hydrogen supply phase to achieve continuous operation of the hybrid hydrogen storage system.

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