Purified hydrogen storage device and purified hydrogen storage method

Abstract

The present invention provides a purified hydrogen storage device and a purified hydrogen storage method, which can improve hydrogen storage density and stability and reduce energy consumption. The purified hydrogen storage device includes a hydrogen transmission pipeline, a purified hydrogen storage unit, and a circulating liquid bath unit. The purified hydrogen storage unit includes a hydrogen purification tank group filled with a first metal hydride hydrogen storage material and a hydrogen storage and release tank group filled with a second metal hydride hydrogen storage material. The hydrogen purification tank group and the hydrogen storage and release tank group are sequentially installed in series along the hydrogen transmission direction on the hydrogen transmission pipeline. The circulating liquid bath unit includes a first liquid bath chamber for accommodating the hydrogen purification tank group, a second liquid bath chamber for accommodating the hydrogen storage and release tank group, and a circulating liquid infusion tank. The second liquid bath chamber and the first liquid bath chamber are sequentially installed in series along the liquid infusion direction on the circulating liquid infusion pipeline of the circulating liquid infusion tank, for circulating liquid from the circulating liquid infusion tank to the second liquid bath chamber and the first liquid bath chamber.

Description

Technical Field

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

[0002] As a clean energy source with a high calorific value and no carbon dioxide production during combustion, hydrogen has enormous potential to replace energy sources such as oil, natural gas, and coal. Furthermore, hydrogen's high calorific value, renewability, and environmental friendliness hold broad application prospects in the automotive, marine, industrial heat, and power sectors. Furthermore, the use of hydrogen as both an energy source and an industrial raw material is an essential path to achieving deep decarbonization and emission reductions in industries such as the chemical and metallurgical industries.

[0003] However, the storage and transportation of hydrogen are major obstacles to the popularization of hydrogen energy. Currently, one of the common ways to store hydrogen is to use high-pressure gas cylinders to store hydrogen. However, this gaseous hydrogen storage method has a low volumetric hydrogen storage density and is not suitable for large-scale fixed hydrogen storage. It also requires specially designed expensive tanks to withstand the hydrogen pressure, which increases costs. Another liquid hydrogen storage method requires storing liquid hydrogen at extremely low temperatures, which is difficult to transport and expensive. Solid-state hydrogen storage technology, on the other hand, mainly stores hydrogen in solid materials. It generally has the advantages of high volumetric hydrogen storage density and high safety. In addition, the use of metal hydride hydrogen storage materials can achieve fixed high-density, high-stability and fast-response solid-state hydrogen storage, meeting the hydrogen storage requirements of hydrogen facilities.

[0004] In addition, although pipeline hydrogen transportation, as one of the modes of hydrogen transportation, has the advantages of low transportation costs and low energy consumption, and can realize the continuous, large-scale, and long-distance transportation of hydrogen energy, the current hydrogen transportation through pipelines cannot meet the diverse demands of chemical, metallurgical and other industries for hydrogen pressure and flow. Therefore, the direct coupling of medium and low pressure hydrogen pipelines to solid-state hydrogen storage systems can not only achieve efficient storage of pipeline hydrogen, but also adjust the hydrogen pressure and flow according to the needs of the application backend, so as to match the hydrogen supply of pipeline hydrogen with that of industrial applications, and achieve the goal of significantly reducing carbon emissions. However, the existing solid-state hydrogen storage system not only has poor hydrogen storage density and stability, but also requires cooling and heating when absorbing and releasing hydrogen, resulting in serious energy consumption. Summary of the Invention

[0005] One advantage of the present invention is that it provides a purified hydrogen storage device and a purified hydrogen storage method, which can improve hydrogen storage density and stability and reduce energy consumption.

[0006] Another advantage of the present invention is that it provides a purified hydrogen storage device and a purified hydrogen storage method. In one embodiment of the present invention, the purified hydrogen storage device can achieve the purpose of saving energy and simplifying equipment manufacturing, operation and control without affecting the normal operation of the hydrogen transmission system.

[0007] Another advantage of the present invention is that it provides a purified hydrogen storage device and a purified hydrogen storage method, wherein in order to achieve the above-mentioned objectives, the present invention does not require the use of a complex system. Therefore, the present invention successfully and effectively provides a solution that not only provides a simple purified hydrogen storage device and a purified hydrogen storage method, but also increases the practicality and reliability of the purified hydrogen storage device and the purified hydrogen storage method.

[0008] In order to achieve at least one of the above advantages or other advantages and purposes of the present invention, the present invention provides a purified hydrogen storage device, comprising:

[0009] Hydrogen transmission pipeline;

[0010] A purified hydrogen storage unit, comprising a hydrogen purification tank group filled with a first metal hydride hydrogen storage material and a hydrogen storage tank group filled with a second metal hydride hydrogen storage material, wherein the hydrogen purification tank group and the hydrogen storage tank group are sequentially installed in series on the hydrogen transmission pipeline along the hydrogen transmission direction; and

[0011] A circulating liquid bath unit, comprising a first liquid bath chamber accommodating the hydrogen purification tank group, a second liquid bath chamber accommodating the hydrogen storage tank group, and a circulating liquid infusion tank having a circulating liquid infusion pipeline; the second liquid bath chamber and the first liquid bath chamber are sequentially installed in series on the circulating liquid infusion pipeline along the infusion direction, and are used to circulate liquid to the second liquid bath chamber and the first liquid bath chamber through the circulating liquid infusion tank, so that the hydrogen storage tank group and the hydrogen purification tank group absorb and release hydrogen respectively under the liquid bath.

[0012] According to one embodiment of the present application, the first metal hydride hydrogen storage material is a Ti-based Laves phase hydrogen storage material having a platform pressure between 1 MPa and 3 MPa at room temperature; the second metal hydride hydrogen storage material is a Ti-based Laves phase hydrogen storage material or a rare earth AB5 type hydrogen storage material having a platform pressure between 2 MPa and 6 MPa at room temperature.

[0013] According to one embodiment of the present application, the first metal hydride hydrogen storage material is Ti 0.95 Zr 0.05 Mn 0.9 Cr 0.9 V 0.2 alloy; the second metal hydride hydrogen storage material is Ti 0.85 Zr 0.17 Cr 0.9 Mn 0.2 Fe 0.8 V 0.1 alloy.

[0014] According to one embodiment of the present application, the hydrogen purification tank group includes at least one purification tank body installed in the hydrogen transmission pipeline, and the first metal hydride hydrogen storage material is filled in the form of tablets or powder inside the purification tank body.

[0015] According to one embodiment of the present application, the hydrogen storage tank group includes a plurality of hydrogen storage tank bodies and a plurality of porous tube bodies installed one-to-one in the hydrogen storage tank bodies; the plurality of hydrogen storage tank bodies are installed side by side in the hydrogen transmission pipeline, the porous tube body extends from the air inlet of the hydrogen storage tank body toward the air outlet of the hydrogen storage tank body, and the second metal hydride hydrogen storage material is filled between the hydrogen storage tank body and the porous tube body.

[0016] According to one embodiment of the present application, the hydrogen transmission pipeline includes a series main pipe, a parallel branch pipe, an air inlet valve, an air outlet valve and a one-way gas valve; one end of each of the parallel branch pipes is connected to the air inlet or air outlet of the hydrogen storage tank body, and the other end of each of the parallel branch pipes is connected to the series main pipe; the air inlet valve is installed on the parallel branch pipe connected to the air inlet of the hydrogen storage tank body, and the air outlet valve is installed on the parallel branch pipe connected to the air outlet of the hydrogen storage tank body; the purification tank body and the one-way gas valve are respectively installed on the series main pipe, and the one-way gas valve is located in the pipeline between the hydrogen purification tank group and the hydrogen storage tank group.

[0017] According to one embodiment of the present application, the left inflection point pressure of the PCT curve of the second metal hydride hydrogen storage material at room temperature is higher than the filling pressure of the hydrogenation load; and the gas outlet valve is a pressure reducing valve.

[0018] According to one embodiment of the present application, the circulating infusion tank includes a liquid storage tank body and a one-way liquid valve installed in the circulating infusion pipeline, and the one-way liquid valve is located in the pipeline between the second liquid flow chamber and the first liquid flow chamber.

[0019] According to one embodiment of the present application, the purified hydrogen storage device further includes a control unit, which includes a controller controllably connected to the purified hydrogen storage unit and the circulating liquid bath unit, a flow sensor installed on the parallel branch pipe, a pressure sensor installed on the hydrogen storage tank body, and temperature sensors installed on the purified tank body and the hydrogen storage tank body, respectively; the controller is communicatively connected to the flow sensor, the pressure sensor, and the temperature sensor, and is used to control the purified hydrogen storage unit and the circulating liquid bath unit to perform corresponding operations based on information collected via the flow sensor, the pressure sensor, and the temperature sensor.

[0020] According to one embodiment of the present application, the circulating infusion tank further includes a thermostat installed in the liquid storage tank body, which is used to adjust the temperature of the liquid in the liquid storage tank body; the controller includes a hydrogen transmission controller and a liquid bath controller, the hydrogen transmission controller is communicatively connected to the flow sensor and the pressure sensor, and the hydrogen transmission controller is controllably connected to the air inlet valve and the air outlet valve, which is used to independently control the opening and closing of the air inlet valve and the air outlet valve in groups; the liquid bath controller is communicatively connected to the temperature sensor, and the liquid bath controller is controllably connected to the circulating infusion tank, which is used to control the circulating infusion tank to circulate liquid of a predetermined temperature to the first liquid bath chamber and the second liquid bath chamber.

[0021] According to another aspect of the present application, the present application further provides a method for purifying hydrogen storage, comprising the steps of:

[0022] Controlling the circulating infusion tank to circulate liquid with a predetermined temperature to a second liquid-transfer chamber and a first liquid-transfer chamber which are sequentially installed in series in the circulating infusion pipeline along the infusion direction;

[0023] When the hydrogenation load requires hydrogen filling, controlling the hydrogen storage tank group filled with the second metal hydride hydrogen storage material to release hydrogen under the liquid bath provided by the second liquid bath; and

[0024] When the hydrogenation load is completed, the hydrogen purification tank group filled with the first metal hydride hydrogen storage material is controlled to release hydrogen under the liquid bath provided by the first liquid bath chamber, and the hydrogen storage tank group is controlled to absorb the hydrogen released through the hydrogen purification tank under the liquid bath provided by the second liquid bath chamber.

[0025] According to one embodiment of the present application, the purified hydrogen storage method further comprises the steps of:

[0026] While the hydrogen storage tank group releases hydrogen, the hydrogen purification tank group is controlled to absorb hydrogen from the hydrogen transmission pipeline under the liquid bath provided by the first liquid transition chamber.

[0027] In summary, compared with the prior art, the present invention has but is not limited to the following advantages:

[0028] 1) The present application can utilize the same liquid bath system to simultaneously regulate the temperature of the hydrogen storage tank group and the hydrogen purification tank group, which not only saves energy but also simplifies equipment manufacturing and operation processes.

[0029] 2) When the hydrogen storage and discharge tank group absorbs hydrogen, the hydrogen storage and discharge tank group will release heat to heat the liquid flowing through the second liquid bath, so that the temperature of the liquid flowing through the first liquid bath is increased, which is convenient for the hydrogen purification tank group to absorb heat and discharge hydrogen in the liquid bath with increased temperature, that is, the hydrogen purification tank group can use the heat released by the hydrogen storage and discharge tank group to discharge hydrogen, thereby avoiding energy consumption; when the hydrogen storage tank group discharges hydrogen, the hydrogen storage tank group will release cold energy (that is, absorb heat) to cool the liquid flowing through the second liquid bath, so that the temperature of the liquid flowing through the first liquid bath is reduced, thereby facilitating the hydrogen purification tank group to release heat and absorb hydrogen in the liquid bath with reduced temperature, that is, the hydrogen purification tank group can use the cold energy released by the hydrogen storage tank group to absorb hydrogen, thereby avoiding energy consumption.

[0030] 3) When the input hydrogen volume and the output hydrogen volume of the purified hydrogen storage device are substantially the same, the net value of the hydrogen absorption and desorption reactions between the first metal hydride hydrogen storage material and the second metal hydride hydrogen storage material is zero, so that the outflow liquid temperature and the return liquid temperature of the circulating infusion tank remain substantially unchanged, realizing a circulating liquid bath without thermal effect, which helps to save energy. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a schematic structural diagram of a purified hydrogen storage device according to an embodiment of the present application;

[0032] Figure 2 A longitudinal cross-sectional schematic diagram of a hydrogen storage tank in a purified hydrogen storage device according to the above embodiment of the present application is shown;

[0033] Figure 3 A schematic transverse cross-sectional view of a hydrogen storage tank according to the above embodiment of the present application is shown;

[0034] Figure 4 It is a schematic flow chart of a method for purifying hydrogen storage according to an embodiment of the present application.

[0035] Explanation of the main component symbols: 10, purified hydrogen storage device; 11, hydrogen transmission pipeline; 111, series main pipe; 112, parallel branch pipe; 113, air inlet valve; 114, air outlet valve; 115, one-way gas valve; 12, purified hydrogen storage unit; 121, hydrogen purification tank group; 1210, first metal hydride hydrogen storage material; 1211, purification tank body; 122, hydrogen storage tank group; 1220, second metal hydride hydrogen storage material; 1221, hydrogen storage tank body; 1222, porous tube body ; 13. Circulating liquid bath unit; 131. First liquid bath chamber; 132. Second liquid bath chamber; 133. Circulating infusion tank; 1330. Circulating infusion pipeline; 1331. Liquid storage tank body; 1332. One-way liquid valve; 1333. Thermostat; 14. Control unit; 141. Controller; 1411. Hydrogen transmission controller; 1412. Liquid bath controller; 142. Flow sensor; 143. Pressure sensor; 144. Temperature sensor; 2. Hydrogen transmission pipeline; 3. Hydrogenation load.

[0036] The above description of the main component symbols is combined with the accompanying drawings and specific embodiments to further illustrate the present invention in detail. DETAILED DESCRIPTION

[0037] The following description is intended to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are for illustrative purposes only, and those skilled in the art will readily appreciate other obvious variations. The basic principles of the present invention defined in the following description may be applied to other embodiments, variations, improvements, equivalents, and other technical solutions that do not depart from the spirit and scope of the present invention.

[0038] Those skilled in the art should understand that, in the disclosure of the present invention, the terms "longitudinal", "transverse", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like to indicate orientations or positional relationships are based on the orientations or positional relationships shown in the accompanying drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, the above terms should not be understood as limiting the present invention.

[0039] In the present invention, the term "a" or "an" in the claims and the specification should be understood as "one or more." That is, in one embodiment, the number of an element may be one, while in another embodiment, the number of the element may be multiple. Unless the disclosure of the present invention clearly indicates that the number of the element is only one, the term "a" or "an" should not be understood as a unique or singular element, and the term "a" or "an" should not be understood as a limitation on the quantity.

[0040] In the description of the present invention, it should be understood that the terms "first", "second", etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance. In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "connected" and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through a medium. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0041] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0042] Considering that existing solid-state hydrogen storage systems not only have poor hydrogen storage density and stability, but also require cooling and heating during hydrogen absorption and desorption, respectively, resulting in severe energy consumption, this application designs a purified hydrogen storage device and purified hydrogen storage method that can improve hydrogen storage density and stability and reduce energy consumption.

[0043] Specifically, refer to the accompanying drawings of the present application. Figures 1 to 3 According to one embodiment of the present application, a purified hydrogen storage device 10 is provided. The purified hydrogen storage device 10 is used to connect a hydrogen transmission pipeline 2 with a hydrogenation load 3 so that hydrogen can be transferred. The purified hydrogen storage device 10 purifies, filters, and stores the low- and medium-pressure hydrogen delivered through the hydrogen transmission pipeline 2 before it is added to the hydrogenation load 3, thereby improving hydrogen storage density and hydrogen transmission stability. It is understood that the hydrogen transmission pipeline 2 mentioned in this application is preferably implemented as a low- and medium-pressure pipeline; the hydrogenation load 3 mentioned in this application can be implemented, but is not limited to, as a hydrogenation machine, a hydrogen vehicle, or other hydrogen storage tank.

[0044] More specifically, if Figure 1As shown, the purified hydrogen storage device 10 may include a hydrogen transmission pipeline 11, a purified hydrogen storage unit 12, and a circulating liquid bath unit 13. The input end of the hydrogen transmission pipeline 11 is used to connect to the hydrogen transmission pipeline 2, and the output end of the hydrogen transmission pipeline 11 is used to connect to the hydrogenation load 3. The purified hydrogen storage unit 12 includes a hydrogen purification tank group 121 filled with a first metal hydride hydrogen storage material 1210 and a hydrogen storage tank group 122 filled with a second metal hydride hydrogen storage material 1220. The hydrogen purification tank group 121 and the hydrogen storage tank group 122 are sequentially installed in series on the hydrogen transmission pipeline 11 along the hydrogen transmission direction. The circulating liquid bath unit 13 includes a first liquid bath 131 for accommodating the hydrogen purification tank group 121, a second liquid bath 132 for accommodating the hydrogen storage tank group 122, and a circulating liquid infusion tank 133 having a circulating liquid infusion pipeline 1330. The second liquid bath 132 and the first liquid bath 131 are sequentially installed in series along the liquid infusion direction on the circulating liquid infusion pipeline 1330, and are used to circulate liquid to the second liquid bath 132 and the first liquid bath 131 through the circulating liquid infusion tank 133, so that the hydrogen storage tank group 122 and the hydrogen purification tank group 121 absorb and release hydrogen under the liquid bath. It is understood that the liquid bath mentioned in this application can be, but is not limited to, a water bath, and can also be implemented as other fluid baths such as an oil bath; the first liquid bath 131 and the second liquid bath 132 mentioned in this application can be, but are not limited to, a water bath.

[0045] It is worth noting that since the hydrogen purification tank group 121 and the hydrogen storage tank group 122 are installed in series on the hydrogen transmission pipeline 11 along the hydrogen transmission direction, the hydrogen transmitted through the hydrogen transmission pipeline 11 first flows through the hydrogen purification tank group 121 to be purified and filtered, and then flows through the hydrogen storage tank group 122 to be pressure-regulated and stored, which helps to improve the hydrogen storage density and hydrogen transmission stability, so that the medium and low pressure hydrogen transmitted through the hydrogen transmission pipeline 2 can meet the refueling needs of the hydrogenation load 3 after purification and storage by the purified hydrogen storage device 10.

[0046] At the same time, since the second liquid bath chamber 132 and the first liquid bath chamber 131 are installed in series in the circulating infusion pipeline 1330 along the infusion direction, the liquid transported by the circulating infusion tank 133 flows through the hydrogen storage tank group 122 and the hydrogen purification tank group 121 in sequence, so that the temperature of the hydrogen storage tank group 122 and the hydrogen purification tank group 121 can be simultaneously adjusted using the same liquid bath system, which not only saves energy but also simplifies equipment manufacturing and operation processes.

[0047] In other words, when the hydrogen storage tank group 122 absorbs hydrogen, the hydrogen storage tank group 122 will release heat to heat the liquid flowing through the second liquid-transfer chamber 132, so that the temperature of the liquid flowing through the first liquid-transfer chamber 131 is increased, which facilitates the hydrogen purification tank group 121 to absorb heat and release hydrogen in the liquid bath with increased temperature, that is, the hydrogen purification tank group 121 can use the heat released by the hydrogen storage tank group 122 to release hydrogen, thereby avoiding energy consumption; when the hydrogen storage tank group 122 releases hydrogen, the hydrogen storage tank group 122 will release cold energy (that is, absorb heat) to cool the liquid flowing through the second liquid-transfer chamber 132, so that the temperature of the liquid flowing through the first liquid-transfer chamber 131 is reduced, which facilitates the hydrogen purification tank group 121 to release heat and absorb hydrogen in the liquid bath with reduced temperature, that is, the hydrogen purification tank group 121 can use the cold energy released by the hydrogen storage tank group 122 to absorb hydrogen, thereby avoiding energy consumption.

[0048] It is understood that when the hydrogen input and output volumes of the purified hydrogen storage device 10 are substantially the same, the net value of the hydrogen absorption and desorption reactions occurring between the first metal hydride hydrogen storage material 1210 and the second metal hydride hydrogen storage material 1220 is zero, maintaining substantially constant the temperature of the liquid outflowing from the circulating infusion tank 133 and the temperature of the liquid returning thereto, thereby achieving a circulating liquid bath without a heat effect and contributing to energy conservation. Furthermore, when the hydrogen input and output volumes of the purified hydrogen storage device 10 are different, the operating state of the purified hydrogen storage device 10 can be considered a combination of two operating conditions: one with only hydrogen input and one with only hydrogen output. The circulating infusion tank 133 of the present application can still function normally to provide the required liquid bath, without affecting the normal operation of the system.

[0049] Alternatively, the first metal hydride hydrogen storage material 1210 may be a Ti-based Laves-phase hydrogen storage material having a plateau pressure between 1 MPa and 3 MPa at room temperature; and the second metal hydride hydrogen storage material 1220 may be a Ti-based Laves-phase hydrogen storage material or a rare earth AB5-type hydrogen storage material having a plateau pressure between 2 MPa and 6 MPa at room temperature. It is understood that the room temperature referred to herein may refer to 20°C.

[0050] Preferably, the platform pressure of the first metal hydride hydrogen storage material 1210 at room temperature is lower than the platform pressure of the second metal hydride hydrogen storage material 1220 at room temperature. In this way, the hydrogen transported via the hydrogen transmission pipeline 2 can first be purified and filtered by the first metal hydride hydrogen storage material 1210 in the hydrogen purification tank group 121, and then pressurized and stored by the second metal hydride hydrogen storage material 1220 in the hydrogen storage tank group 122, so as to meet the hydrogen filling pressure required by the hydrogenation load 3.

[0051] For example, the first metal hydride hydrogen storage material 1210 may be, but is not limited to, Ti0.95 Zr 0.05 Mn 0.9 Cr 0.9 V 0.2 alloy, the hydrogen absorption platform pressure at 20°C is 2.04 MPa, and the hydrogen release platform pressure at 20°C is 1.68 MPa; the second metal hydride hydrogen storage material 1220 can be, but is not limited to, implemented as Ti 0.85 Zr 0.17 Cr 0.9 Mn 0.2 Fe 0.8 V 0.1 alloy, the hydrogen absorption platform pressure at 20° C. is 2.99 MPa, and the hydrogen desorption platform pressure at 20° C. is 2.71 MPa. It is understood that in other examples of the present application, the second metal hydride hydrogen storage material 1220 can also be implemented as La 0.25 Ce 0.55 Ca 0.2 Ni 4.5 Co 0.5 Rare earth AB5 type hydrogen storage materials and materials such as Ti 0.95 Zr 0.05 Mn 0.9 Cr 0.9 V 0.2 or Ti 0.95 Zr 0.07 Mn 1.15 Cr 0.7 V 0.15 One of the Ti-based AB2-type Laves phase hydrogen storage materials.

[0052] It is worth noting that according to the temperature-pressure relationship characteristics of the metal hydride hydrogen storage material, the platform pressure of the metal hydride hydrogen storage material increases with increasing temperature, that is, the platform pressure of the first metal hydride hydrogen storage material 1210 in a liquid bath with increasing temperature is greater than its platform pressure in a liquid bath with decreasing temperature. Therefore, when the hydrogen storage tank group 122 absorbs hydrogen and releases heat, the liquid flowing through the second liquid exchange chamber 132 is heated and heated to flow into the first liquid exchange chamber 131, so that the hydrogen purification tank group 121 releases hydrogen at a higher pressure in the liquid bath with increased temperature, that is, the hydrogen release platform pressure of the hydrogen purification tank group 121 is increased, which helps to improve the hydrogen absorption efficiency of the hydrogen storage tank group 122; when the hydrogen storage tank group 122 releases hydrogen and absorbs heat, the liquid flowing through the second liquid exchange chamber 132 is cooled and cooled to flow into the first liquid exchange chamber 131, so that the hydrogen purification tank group 121 absorbs hydrogen in the liquid bath with reduced temperature, that is, the hydrogen absorption platform pressure of the hydrogen purification tank group 121 is reduced, which helps to improve the hydrogen absorption efficiency of the hydrogen purification tank group 121.

[0053] Alternatively, as Figure 1 As shown, the hydrogen purification tank group 121 may include at least one purification tank body 1211 installed in the hydrogen transmission pipeline 11 , and the first metal hydride hydrogen storage material 1210 is filled in the purification tank body 1211 with tablets or powder.

[0054] For example, Figure 1 As shown, the hydrogen purification tank group 121 may include a purification tank body 1211, the first metal hydride hydrogen storage material 1210, a binder (not shown in the figure) and a thermal conductor (not shown in the figure). The first metal hydride hydrogen storage material 1210 is fully mixed with the binder and the thermal conductor and then pressed into tablets and filled into the purification tank body 1211 to purify and filter the hydrogen transported through the hydrogen transmission pipeline 2.

[0055] It is understood that the binder mentioned in this application can be, but is not limited to, a combination of one or more of epoxy resin, phenolic resin, and silicone resin; the thermal conductor mentioned in this application can be a combination of one or more of flake graphite, expanded graphite, metal oxide, and metal powder. In addition, in other examples of this application, the first metal hydride hydrogen storage material 1210 can also be filled with powder, that is, the first metal hydride hydrogen storage material 1210 is thoroughly mixed with the thermal conductor and then filled into the purification tank 1211.

[0056] Optionally, the specific filling method of the first metal hydride hydrogen storage material 1210 of the present application can be implemented as epoxy resin adhesive block filling, and the added amount of epoxy resin is 5 wt.%.

[0057] Alternatively, as Figure 1 and Figure 2As shown, the hydrogen storage tank group 122 may include a plurality of hydrogen storage tank bodies 1221 and a plurality of porous tube bodies 1222 installed one-to-one in the hydrogen storage tank bodies 1221; the plurality of hydrogen storage tank bodies 1221 are installed in parallel in the hydrogen transmission pipeline 11, and the porous tube body 1222 extends from the air inlet of the hydrogen storage tank body 1221 toward the air outlet of the hydrogen storage tank body 1221, and the second metal hydride hydrogen storage material 1220 is filled between the hydrogen storage tank body 1221 and the porous tube body 1222. Thus, when the hydrogen purification tank group 121 is discharging hydrogen, the porous tube 1222 can transport the hydrogen from the hydrogen purification tank group 121 to the second metal hydride hydrogen storage material 1220 for hydrogen absorption and storage. Furthermore, when the hydrogen purification tank group 121 stops discharging hydrogen, the porous tube 1222 can collect the hydrogen released from the second metal hydride hydrogen storage material 1220 and transport it to the gas outlet of the hydrogen storage tank 1221 to replenish the hydrogenation load 3. It will be understood that the porous tube 1222 mentioned in this application refers to a hollow tube with multiple through-holes in the tube wall: one end opening of the hollow tube corresponds to the gas inlet of the hydrogen storage tank 1221, the other end opening of the hollow tube corresponds to the gas outlet of the hydrogen storage tank 1221, and the through-holes in the tube wall of the hollow tube correspond to the second metal hydride hydrogen storage material 1220.

[0058] Alternatively, as Figure 2 As shown, the porous tube 1222 has a connection end connected to the air inlet of the hydrogen storage tank 1221 and a free end adjacent to the air outlet of the hydrogen storage tank 1221. This leaves a buffer space between the free end of the porous tube 1222 and the air outlet of the hydrogen storage tank 1221 for buffering hydrogen gas output through the free end opening of the porous tube 1222. This allows this hydrogen gas to be output through the air outlet of the hydrogen storage tank 1221 to refill the hydrogenation load 3 and also to contact the second metal hydride hydrogen storage material 1220 for hydrogen absorption and storage. At the same time, hydrogen gas released by the second metal hydride hydrogen storage material 1220 can also enter the buffer space directly without being collected by the porous tube 1222, and be output through the air outlet of the hydrogen storage tank 1221 to refill the hydrogenation load 3.

[0059] Optionally, the filling method of the second metal hydride hydrogen storage material 1220 mentioned in the present application can be, but is not limited to, filling a mixed block of epoxy resin adhesive and flake graphite thermal conductor, with the added amount of epoxy resin and flake graphite being 5wt.%; after the filling is completed to form a block, a hole can be punched in the middle of the block to allow the porous tube body 1222 to pass through.

[0060] It is worth noting that both the purification tank 1211 and the hydrogen storage tank 1221 of the present application can be implemented as cylindrical stainless steel tanks to achieve higher pressure-bearing capacity while also having better thermal conductivity, allowing the metal hydride hydrogen storage material to better dissipate heat to the outside during hydrogen absorption and better absorb heat from the outside during hydrogen release. Furthermore, the hydrogen transmission pipeline 11 mentioned in the present application can be, but is not limited to, made of stainless steel pipe.

[0061] According to the above embodiments of the present application, Figure 1 As shown, the hydrogen transmission pipeline 11 may include a series main pipe 111, a parallel branch pipe 112, an air inlet valve 113, and an air outlet valve 114. One end of each parallel branch pipe 112 is connected to the air inlet or air outlet of the hydrogen storage tank 1221, and the other end of each parallel branch pipe 112 is connected to the series main pipe 111. The air inlet valve 113 is installed on the parallel branch pipe 112 connected to the air inlet of the hydrogen storage tank 1221. The air outlet valve 114 is installed on the parallel branch pipe 112 connected to the air outlet of the hydrogen storage tank 1221. The purification tank 1211 is installed on the series main pipe 111.

[0062] Optionally, the left inflection point pressure of the PCT curve of the second metal hydride hydrogen storage material 1220 at room temperature is higher than the filling pressure of the hydrogenation load 3; the outlet valve 114 is implemented as a pressure reducing valve so as to realize constant pressure hydrogen supply by using the pressure reducing valve.

[0063] Alternatively, as Figure 1 As shown, the hydrogen transmission pipeline 11 may further include a one-way gas valve 115 installed on the series main pipe 111. The one-way gas valve 115 is located in the pipeline between the hydrogen purification tank group 121 and the hydrogen storage tank group 122, and is used to allow hydrogen to flow from the hydrogen purification tank group 121 to the hydrogen storage tank group 122, and prevent hydrogen from flowing from the hydrogen storage tank group 122 to the hydrogen purification tank group 121. In this way, when the hydrogen storage tank group 122 releases high-pressure hydrogen, the high-pressure hydrogen is prevented from flowing back into the hydrogen purification tank group 121, ensuring the normal operation of the hydrogen transmission system.

[0064] Alternatively, as Figure 1 As shown, the circulating infusion tank 133 may include a liquid storage tank body 1331 and a one-way liquid valve 1332 installed in the circulating infusion pipeline 1330. The one-way liquid valve 1332 is located in the pipeline between the second liquid-transfer chamber 132 and the first liquid-transfer chamber 131, and is used to allow liquid to flow from the second liquid-transfer chamber 132 to the first liquid-transfer chamber 131 and prevent liquid from flowing from the first liquid-transfer chamber 131 to the second liquid-transfer chamber 132, thereby ensuring the normal operation of the liquid bath system. It is understood that the circulating infusion pipeline 1330 mentioned in this application can be composed of an infusion tube body and an infusion pump, and this application will not repeat them in detail.

[0065] It is worth noting that in order to realize the automatic control of the purified hydrogen storage device 10, as Figure 1 As shown, the purified hydrogen storage device 10 of the present application may further include a control unit 14, which includes a controller 141 controllably connected to the purified hydrogen storage unit 12 and the circulating liquid bath unit 13, a flow sensor 142 installed on the parallel branch pipe 112, a pressure sensor 143 installed on the hydrogen storage tank body 1221, and a temperature sensor 144 installed on the purification tank body 1211 and the hydrogen storage tank body 1221, respectively; the controller 141 is communicatively connected to the flow sensor 142, the pressure sensor 143 and the temperature sensor 144, and is used to control the purified hydrogen storage unit 12 and the circulating liquid bath unit 13 to perform corresponding operations according to the information collected by the flow sensor 142, the pressure sensor 143 and the temperature sensor 144.

[0066] Optionally, the flow sensor 142 may be, but is not limited to, implemented as a flow meter adjacent to the air outlet of the hydrogen storage tank body 1221, so that a certain degree of adjustment can be made using the flow meter according to user needs; the pressure sensor 143 may be, but is not limited to, implemented as a pressure gauge adjacent to the air outlet of the hydrogen storage tank body 1221; the temperature sensor 144 may be, but is not limited to, implemented as a temperature-sensing thermocouple inserted into the purification tank body 1211 or the hydrogen storage tank body 1221, so as to measure the temperature inside the tank body in real time.

[0067] Alternatively, as Figure 1 As shown, the circulating infusion tank 133 may further include a thermostat 1333 installed in the liquid storage tank body 1331, for adjusting the temperature of the liquid in the liquid storage tank body 1331; the controller 141 may include a hydrogen transmission controller 1411 and a liquid bath controller 1412; the hydrogen transmission controller 1411 is communicatively connected to the flow sensor 142 and the pressure sensor 143, and the hydrogen transmission controller 1411 is controllably connected to the air inlet valve 113 and the air outlet valve 114, for independently controlling the opening and closing of the air inlet valve 113 and the air outlet valve 114 in groups to achieve automatic hydrogen filling; the liquid bath controller 1412 is communicatively connected to the temperature sensor 144, and the liquid bath controller 1412 is controllably connected to the circulating infusion tank 133, for controlling the circulating infusion tank 133 to circulate liquid of a predetermined temperature to the first liquid flow chamber 131 and the second liquid flow chamber 132.

[0068] It is worth noting that, according to another aspect of the present application, Figure 4 As shown, an embodiment of the present application further provides a method for purifying hydrogen storage, which may include the steps of:

[0069] S110: Controlling the circulating infusion tank to circulate liquid having a predetermined temperature to a second liquid-transfer chamber and a first liquid-transfer chamber which are sequentially installed in series in the circulating infusion pipeline along the infusion direction;

[0070] S120: When the hydrogenation load requires hydrogen filling, controlling the hydrogen storage tank group filled with the second metal hydride hydrogen storage material to release hydrogen under the liquid bath provided by the second liquid bath; and

[0071] S130: When the hydrogenation load is completed, the hydrogen purification tank group filled with the first metal hydride hydrogen storage material is controlled to release hydrogen in the liquid bath provided by the first liquid bath chamber, and the hydrogen storage tank group is controlled to absorb the hydrogen released by the hydrogen purification tank group in the liquid bath provided by the second liquid bath chamber.

[0072] It is worth noting that although the second metal hydride hydrogen storage material in the hydrogen storage tank assembly releases heat when absorbing hydrogen to heat the liquid flowing through the second liquid bath, the first metal hydride hydrogen storage material in the hydrogen purification tank absorbs heat when releasing hydrogen to cool the liquid heated by the hydrogen storage tank assembly, so that the entire liquid bath system does not experience a thermal effect, which helps save energy.

[0073] In addition, if Figure 4 As shown, the purified hydrogen storage method of the present application may further include the steps of:

[0074] S140: While the hydrogen storage tank assembly is releasing hydrogen, the hydrogen purification tank assembly is controlled to absorb hydrogen from the hydrogen transmission pipeline in a liquid bath provided by the first liquid bath. Thus, while the second metal hydride hydrogen storage material in the hydrogen storage tank assembly absorbs heat to cool the liquid flowing through the second liquid bath during hydrogen release, the first metal hydride hydrogen storage material in the hydrogen purification tank releases heat to heat the liquid cooled by the hydrogen storage tank assembly during hydrogen absorption. This prevents the liquid bath system from generating any thermal effects, thus conserving energy.

[0075] Optionally, the predetermined temperature mentioned in the present application may be, but is not limited to, implemented as room temperature, ie, 20° C., so as to reduce energy consumption of the entire system.

[0076] It is worth noting that when the hydrogen purification tank group in the purified hydrogen storage device is initially activated, or absorbs hydrogen in the absence of hydrogen output flow, since the circulating infusion tank circulates liquid to the second liquid transfer chamber and the first liquid transfer chamber through the circulating infusion pipeline, and the hydrogen storage and discharge tank group does not release or absorb heat because it does not absorb or discharge hydrogen, the first metal hydride hydrogen storage material in the hydrogen purification tank group releases heat when the hydrogen absorption reaction occurs, causing the temperature of the liquid flowing back to the liquid storage tank body to increase; at this time, the purified hydrogen storage device of the present application can control the thermostat in the liquid storage tank to fine-tune the liquid temperature to ensure that the liquid storage tank circulates and outputs constant temperature liquid.

[0077] In addition, when the purified hydrogen storage device has no hydrogen input or only needs low-pressure hydrogen input and only uses the hydrogen storage tank group to release hydrogen, since the circulating infusion tank circulates liquid to the second liquid-transfer chamber and the first liquid-transfer chamber through the circulating infusion pipeline, and the hydrogen purification tank group does not release heat or releases a small amount of heat because it does not absorb hydrogen or absorbs a small amount of hydrogen, the second metal hydride hydrogen storage material in the hydrogen storage tank group absorbs heat when the hydrogen release reaction occurs, so that the temperature of the liquid flowing back to the liquid storage tank body is reduced; at this time, the purified hydrogen storage device of the present application can still control the thermostat in the liquid storage tank to fine-tune the liquid temperature, ensuring that the liquid storage tank circulates and outputs constant temperature liquid.

[0078] For example, in the purified hydrogen storage method of the present application: since the hydrogen storage tank group is usually composed of multiple hydrogen storage tanks arranged in parallel, each hydrogen storage tank can have a separate and unchanging number, and the pressure sensor, flow sensor, air inlet valve and air outlet valve corresponding to each hydrogen storage tank can be independently grouped and controlled, the purified hydrogen storage method of the present application can open the air outlet valves corresponding to several hydrogen storage tanks to release hydrogen according to the flow demand of the user end; and when the remaining hydrogen storage capacity of a certain hydrogen storage tank is close to the capacity corresponding to the hydrogen supply pressure, the air outlet valve corresponding to the hydrogen storage tank is closed, and the air outlet valve corresponding to another hydrogen storage tank is opened. It can be understood that the remaining hydrogen storage capacity mentioned in the present application refers to the hydrogen storage capacity of the pressure-regulated hydrogen storage tank group when it is not in a hydrogen absorption saturation state (i.e., the real-time hydrogen storage capacity of the pressure-regulated hydrogen storage tank group).

[0079] In addition, to facilitate classification control, this application will mark hydrogen storage tanks that are unable to continue to discharge hydrogen under the hydrogen supply pressure as empty tanks, hydrogen storage tanks that can still continue to discharge hydrogen under the hydrogen supply pressure and have been used (i.e., can discharge hydrogen under the hydrogen supply pressure and are not saturated with hydrogen) as partially used tanks, and hydrogen storage tanks that are saturated with hydrogen under the hydrogen supply pressure as full tanks. It is understandable that the empty tanks mentioned in this application only refer to hydrogen storage tanks that are unable to continue to discharge hydrogen under the hydrogen supply pressure, and do not mean that the hydrogen storage material in the hydrogen storage tank is completely discharged; the full tanks mentioned in this application refer to hydrogen storage tanks that are filled with hydrogen with the air inlet valve opened and without flow restriction until the hydrogen pressure no longer changes within ten minutes, and the hydrogen storage tank is considered to be saturated with hydrogen.

[0080] According to the above-mentioned embodiment of the present application, in the purified hydrogen storage method of the present application, the status of all hydrogen storage tanks in the hydrogen storage tank group is detected in real time, and an insufficient capacity alarm is issued when more than 80% of the hydrogen storage tanks are empty, so as to remind timely hydrogen replenishment / charging.

[0081] Preferably, the priority of hydrogen filling of empty tanks is higher than that of hydrogen filling of partially used tanks; that is, after the filling is completed at the user end, this application gives priority to filling the empty tanks with hydrogen, and then filling the partially used tanks with hydrogen, so as to store more hydrogen as soon as possible and prepare for the next filling.

[0082] The technical features of the above embodiments can be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0083] The above embodiments merely illustrate several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A purified hydrogen storage device, characterized in that: include: Hydrogen transmission pipeline; A purified hydrogen storage unit, comprising a hydrogen purification tank group filled with a first metal hydride hydrogen storage material and a hydrogen storage tank group filled with a second metal hydride hydrogen storage material, wherein the hydrogen purification tank group and the hydrogen storage tank group are sequentially installed in series on the hydrogen transmission pipeline along the hydrogen transmission direction; as well as a circulating liquid bath unit, the circulating liquid bath unit comprising a first liquid bath chamber accommodating the hydrogen purification tank group, a second liquid bath chamber accommodating the hydrogen storage tank group, and a circulating liquid infusion tank having a circulating liquid infusion pipeline; the second liquid bath chamber and the first liquid bath chamber are sequentially installed in series along the liquid infusion direction on the circulating liquid infusion pipeline, for circulating liquid to the second liquid bath chamber and the first liquid bath chamber through the circulating liquid infusion tank, so that the hydrogen storage tank group and the hydrogen purification tank group absorb and release hydrogen respectively under the liquid bath; The circulating infusion tank includes a liquid storage tank body and a one-way liquid valve installed in the circulating infusion pipeline. The one-way liquid valve is located in the pipeline between the second liquid-transfer chamber and the first liquid-transfer chamber, and is used to allow liquid to flow from the second liquid-transfer chamber to the first liquid-transfer chamber and prevent liquid from flowing from the first liquid-transfer chamber to the second liquid-transfer chamber.

2. The purified hydrogen storage device according to claim 1, characterized in that: The first metal hydride hydrogen storage material is a Ti-based Laves phase hydrogen storage material with a platform pressure between 1 MPa and 3 MPa at room temperature; the second metal hydride hydrogen storage material is a Ti-based Laves phase hydrogen storage material or a rare earth AB5 type hydrogen storage material with a platform pressure between 2 MPa and 6 MPa at room temperature.

3. The purified hydrogen storage device according to claim 1, characterized in that: The first metal hydride hydrogen storage material is Ti 0.95 Zr 0.05 Mn 0.9 Cr 0.9 V 0.2 alloy; the second metal hydride hydrogen storage material is Ti 0.85 Zr 0.17 Cr 0.9 Mn 0.2 Fe 0.8 V 0.1 alloy.

4. The purified hydrogen storage device according to any one of claims 1 to 3, characterized in that: The hydrogen purification tank group includes at least one purification tank body installed in the hydrogen transmission pipeline, and the first metal hydride hydrogen storage material is filled in the form of tablets or powder.

5. The purified hydrogen storage device according to claim 4, characterized in that: The hydrogen storage tank group includes a plurality of hydrogen storage tank bodies and a plurality of porous tube bodies installed in the hydrogen storage tank bodies in a one-to-one correspondence; the plurality of hydrogen storage tank bodies are installed side by side in the hydrogen transmission pipeline, the porous tube bodies extend from the air inlet of the hydrogen storage tank body toward the air outlet of the hydrogen storage tank body, and the second metal hydride hydrogen storage material is filled between the hydrogen storage tank body and the porous tube bodies.

6. The purified hydrogen storage device according to claim 5, characterized in that: The hydrogen transmission pipeline includes a series main pipe, a parallel branch pipe, an air inlet valve, an air outlet valve and a one-way gas valve; one end of each parallel branch pipe is connected to the air inlet or air outlet of the hydrogen storage tank body, and the other end of each parallel branch pipe is connected to the series main pipe; the air inlet valve is installed on the parallel branch pipe connected to the air inlet of the hydrogen storage tank body, and the air outlet valve is installed on the parallel branch pipe connected to the air outlet of the hydrogen storage tank body; the purification tank body and the one-way gas valve are respectively installed on the series main pipe, and the one-way gas valve is located in the pipeline between the hydrogen purification tank group and the hydrogen storage tank group.

7. The purified hydrogen storage device according to claim 6, characterized in that: The pressure at the left inflection point of the PCT curve of the second metal hydride hydrogen storage material at room temperature is higher than the filling pressure of the hydrogenation load; and the gas outlet valve is a pressure reducing valve.

8. The purified hydrogen storage device according to claim 6, characterized in that: The purified hydrogen storage device further includes a control unit, which includes a controller controllably connected to the purified hydrogen storage unit and the circulating liquid bath unit, a flow sensor installed on the parallel branch pipe, a pressure sensor installed on the hydrogen storage tank body, and temperature sensors installed on the purified tank body and the hydrogen storage tank body respectively; the controller is communicatively connected to the flow sensor, the pressure sensor, and the temperature sensor, and is used to control the purified hydrogen storage unit and the circulating liquid bath unit to perform corresponding operations based on information collected via the flow sensor, the pressure sensor, and the temperature sensor.

9. The purified hydrogen storage device according to claim 8, characterized in that: The circulating infusion tank further includes a thermostat installed in the liquid storage tank body, which is used to adjust the temperature of the liquid in the liquid storage tank body; the controller includes a hydrogen transmission controller and a liquid bath controller, the hydrogen transmission controller is communicatively connected to the flow sensor and the pressure sensor, and the hydrogen transmission controller is controllably connected to the air inlet valve and the air outlet valve, which is used to independently control the opening and closing of the air inlet valve and the air outlet valve in groups; the liquid bath controller is communicatively connected to the temperature sensor, and the liquid bath controller is controllably connected to the circulating infusion tank, which is used to control the circulating infusion tank to circulate liquid of a predetermined temperature to the first liquid bath chamber and the second liquid bath chamber.

10. A method for purifying hydrogen storage, characterized in that: The purified hydrogen storage device according to any one of claims 1 to 9 comprises the following steps: Controlling the circulating infusion tank to circulate liquid with a predetermined temperature to a second liquid-transfer chamber and a first liquid-transfer chamber which are sequentially installed in series in the circulating infusion pipeline along the infusion direction; When the hydrogenation load requires hydrogen filling, controlling the hydrogen storage tank group filled with the second metal hydride hydrogen storage material to release hydrogen under the liquid bath provided by the second liquid bath; as well as When the hydrogenation load is completed, the hydrogen purification tank group filled with the first metal hydride hydrogen storage material is controlled to release hydrogen under the liquid bath provided by the first liquid bath chamber, and the hydrogen storage tank group is controlled to absorb the hydrogen released through the hydrogen purification tank under the liquid bath provided by the second liquid bath chamber.

11. The method for purifying and storing hydrogen according to claim 10, characterized in that: The purified hydrogen storage method further comprises the steps of: While the hydrogen storage tank group releases hydrogen, the hydrogen purification tank group is controlled to absorb hydrogen from the hydrogen transmission pipeline under the liquid bath provided by the first liquid transition chamber.

Images