Solid hydrogen storage reactor and hydrogen storage / desorption method thereof

Abstract

The invention relates to the technical field of hydrogen storage, and discloses a solid hydrogen storage reactor and a hydrogen storage / desorption method thereof. The solid hydrogen storage reactor comprises a heat-conducting fluid substrate (1) and a hydrogen storage material substrate (2) which are sequentially stacked, wherein the hydrogen storage material substrate (2) is filled with a solid hydrogen storage composite material; wherein a first flow channel is engraved on the heat-conducting fluid substrate (1) and is used for allowing heat-conducting fluid to pass through; a second flow channel is engraved on the hydrogen storage material substrate (2) and used for hydrogen to pass through, and the first flow channel is not communicated with the second flow channel. The solid hydrogen storage reactor has the characteristic of high heat transfer efficiency, and is beneficial to improving the hydrogen absorption rate.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen storage, and in particular to a solid hydrogen storage reactor and a hydrogen storage / dehydrogenation method thereof. Background Art

[0002] With the increasing global demand for energy and CO 2 With serious emissions and worsening environmental pollution, people are paying more and more attention to the development of clean and renewable energy. As a secondary energy source, hydrogen energy has the characteristics of wide sources, clean and carbon-free, flexible and efficient, and a wide range of application scenarios. It can be widely used in energy, transportation, industry, construction and other fields. It is an ideal interconnected medium to promote the clean and efficient use of traditional fossil energy and support the large-scale development of renewable energy. It will gradually become an important direction of the global energy technology revolution.

[0003] Hydrogen can be stored and transported. Improving the efficiency of hydrogen storage and transportation and reducing the cost of hydrogen storage and transportation are the development focuses of hydrogen storage and transportation technology. At present, hydrogen storage mainly includes three types of methods: gaseous hydrogen storage, liquid hydrogen storage, and solid hydrogen storage. High-pressure gaseous hydrogen storage is the main method of hydrogen storage at this stage, with the advantages of fast hydrogen filling and discharging speed and simple container structure. However, high-pressure gaseous hydrogen storage has disadvantages such as low volume density and low safety. At the same time, existing high-pressure equipment and high-pressure storage tank technology mostly rely on imports. Liquid hydrogen storage refers to the low-temperature liquefaction of hydrogen and storage in a low-temperature insulated liquid storage tank, which has the advantage of high hydrogen storage density. However, the high cost of liquid hydrogen equipment, high energy consumption in the liquefaction process, and evaporation loss during use are problems that need to be solved urgently. Solid hydrogen storage refers to the storage of hydrogen through chemical adsorption or physical adsorption using metal hydrides, nanomaterials, etc. as carriers. Solid hydrogen storage has the advantages of high hydrogen storage density, low hydrogen storage pressure, high hydrogen release purity, and good safety. It is an important direction for the development of hydrogen storage in the future.

[0004] Hydrogen storage alloy materials refer to a type of material that stores hydrogen in the form of metal hydrides. Hydrogen storage alloys have the advantages of good reversibility of hydrogen absorption and desorption, high hydrogen storage density per unit volume, high hydrogen desorption purity, and high safety. Metal hydrides are formed by a reversible reaction between metal alloys and hydrogen at specific temperatures and pressures. The absorption of hydrogen is an exothermic reaction, while the desorption of hydrogen is an endothermic process. The former only occurs when the supply pressure is greater than the equilibrium pressure, and the latter only occurs when the pressure is lower than the equilibrium pressure. However, existing solid hydrogen storage reactors have poor heat transfer performance, resulting in poor control of the hydrogen absorption and desorption rates of the hydrogen storage system and low reversible hydrogen storage density.

[0005] In summary, designing a reaction system with high heat transfer efficiency and safe and easy loading is crucial to improving the performance of metal hydride hydrogen storage systems. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems of poor heat transfer performance of solid hydrogen storage reactors in the prior art, which leads to poor control of hydrogen absorption and desorption rates of the hydrogen storage system and low reversible hydrogen storage density, and to provide a solid hydrogen storage reactor and a hydrogen storage / desorption method thereof. The solid hydrogen storage reactor has the characteristics of high heat transfer efficiency and is conducive to improving the hydrogen absorption rate.

[0007] In order to achieve the above-mentioned object, the present invention provides a solid hydrogen storage reactor on one hand, comprising a heat transfer fluid substrate and a hydrogen storage material substrate filled with a solid hydrogen storage composite material stacked in sequence; Wherein, the heat transfer fluid substrate is engraved with a first flow channel for the passage of the heat transfer fluid; The hydrogen storage material substrate is engraved with a second flow channel for the passage of hydrogen, and the first flow channel and the second flow channel are not connected.

[0008] Preferably, the heat transfer fluid substrate has a first flow channel engraved on one side for the heat transfer fluid to pass through; the hydrogen storage material substrate has a second flow channel engraved on one side for the hydrogen to pass through, and the first flow channel and the second flow channel are not connected.

[0009] Preferably, the first flow channel and the second flow channel are each independently a serpentine flow channel or a parallel flow channel.

[0010] Preferably, the first flow channel and the second flow channel are serpentine flow channels and are arranged in parallel.

[0011] Preferably, the facets of the first flow channel and the second flow channel are independently square facets or triangular sawtooth facets, preferably triangular sawtooth facets.

[0012] Preferably, along the stacking direction of the heat transfer fluid substrate and the hydrogen storage material substrate in the solid hydrogen storage reactor, the first flow channel and the second flow channel are arranged in the same direction.

[0013] A second aspect of the present invention provides a hydrogen storage / dehydrogenation method of the solid hydrogen storage reactor according to the first aspect, the method comprising: During the hydrogen storage process, hydrogen is fed into the second flow channel of the hydrogen storage material substrate to undergo a hydrogen absorption reaction with the solid hydrogen storage composite material, and a heat transfer fluid is fed into the first flow channel of the heat transfer fluid substrate to absorb heat generated by the hydrogen absorption reaction; During the dehydrogenation process, the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction, and the heat transfer fluid is fed into the first flow channel of the heat transfer fluid substrate to provide heat for the desorption reaction of the hydrogen.

[0014] Through the above technical solution, the beneficial effects of the present invention include: The solid hydrogen storage reactor of the present invention comprises a hydrogen storage material substrate and a heat transfer fluid substrate engraved with flow channels, which is beneficial for the hydrogen to fully contact and react with the solid hydrogen storage composite material during the hydrogen storage process, while keeping the hydrogen absorption reaction temperature at a favorable position to improve the hydrogen absorption rate; it is beneficial for the introduced heat transfer fluid to promptly remove the heat released in the hydrogen storage material substrate reaction system to improve the heat exchange efficiency; it is beneficial for the heat transfer fluid to promptly provide heat for the desorption of hydrogen during the hydrogen release process to maintain a suitable hydrogen release rate.

[0015] The solid hydrogen storage reactor of the present invention loads the solid hydrogen storage mixed material into the flow channel of the hydrogen storage material substrate, which is convenient for loading.

[0016] The solid hydrogen storage reactor of the present invention can adjust the reactor capacity by adjusting the number and area of ​​the substrates according to different application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a schematic structural diagram of the solid hydrogen storage reactor of the present invention; Figure 2 It is a structural schematic diagram of a cross section of a heat transfer fluid substrate or a hydrogen storage material substrate in the solid hydrogen storage reactor of the present invention; Figure 3 is a schematic diagram of the first and second flow channel types of the present invention ( Figure 3 In the middle, a is a parallel flow channel. Figure 3 b is a serpentine flow channel); Figure 4 Schematic diagram of the facets of the flow channel in the heat transfer fluid substrate or the hydrogen storage material substrate in the solid hydrogen storage reactor of the present invention ( Figure 4 a in the middle is a square facet. Figure 4 The middle b is a wavy facet. Figure 4 c in the middle is a triangular sawtooth facet); Figure 5 Schematic diagram of the connection between the heat transfer fluid substrates or hydrogen storage material substrates in the solid hydrogen storage reactor of the present invention ( Figure 5 In the figure, a is a parallel connection; Figure 5 b is a series connection); Figure 6-7 They are respectively a graph showing a relationship between the amount of hydrogen absorbed and the time of hydrogen absorbed, and a graph showing a relationship between the average temperature of the hydrogen storage bed and the time of hydrogen absorbed in Example 1 of the present invention; Figure 8-9 They are respectively a graph showing the relationship between the amount of hydrogen absorbed and the time of hydrogen absorbed, and a graph showing the relationship between the average temperature of the hydrogen storage bed and the time of hydrogen absorbed of Example 2 of the present invention; Figure 10-11 They are respectively a graph showing a relationship between the amount of hydrogen absorbed and the time of hydrogen absorbed, and a graph showing a relationship between the average temperature of the hydrogen storage bed and the time of hydrogen absorbed of Example 3 of the present invention; Figure 12-13They are respectively a graph showing a relationship between the amount of hydrogen absorbed and the time of hydrogen absorbed, and a graph showing a relationship between the average temperature of the hydrogen storage bed and the time of hydrogen absorbed of Example 4 of the present invention; Fig.14 is a schematic structural diagram of a solid hydrogen storage reactor of Comparative Example 1; Figure 15-16 They are respectively a graph showing the relationship between the amount of hydrogen absorbed and the time of hydrogen absorbed in comparative example 1 of the present invention and a graph showing the relationship between the average temperature of the inner tank and the time of hydrogen absorbed; Figure 17-18 They are respectively a graph showing the relationship between the amount of hydrogen absorbed and the time of hydrogen absorbed in comparative example 2 of the present invention and a graph showing the relationship between the average temperature of the hydrogen storage bed and the time of hydrogen absorbed.

[0018] Description of Reference Numerals DETAILED DESCRIPTION The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0019] In one aspect, the present invention provides a solid hydrogen storage reactor, which comprises a heat transfer fluid substrate 1 and a hydrogen storage material substrate 2 filled with a solid hydrogen storage composite material stacked in sequence; Wherein, the heat transfer fluid substrate 1 is engraved with a first flow channel for the passage of the heat transfer fluid; The hydrogen storage material substrate 2 is engraved with a second flow channel for the passage of hydrogen, and the first flow channel and the second flow channel are not connected.

[0020] The heat-conducting fluid substrate 1 and the hydrogen storage material substrate 2 filled with a solid hydrogen storage composite material described in the present invention can be stacked in sequence in the order of heat-conducting fluid substrate 1 and hydrogen storage material substrate 2 in a group of two substrates, or can be stacked in the order of heat-conducting fluid substrate 1, hydrogen storage material substrate 2, and heat-conducting fluid substrate 1 in a group of three substrates.

[0021] The present invention has no particular limitation on the number of stacked heat transfer fluid substrates 1 and hydrogen storage material substrates 2, which can be appropriately selected according to the application. Preferably, the number of stacked heat transfer fluid substrates 1 and hydrogen storage material substrates 2 is independently 2-100.

[0022] Preferably, the heat transfer fluid substrate 1 has a first flow channel engraved on one side for the heat transfer fluid to pass through; the hydrogen storage material substrate 2 has a second flow channel engraved on one side for the hydrogen to pass through, and the first flow channel and the second flow channel are not connected.

[0023] The first flow channel and the second flow channel of the present invention are applicable to various flow channel types. In order to improve heat exchange efficiency, preferably, the first flow channel and the second flow channel are independently serpentine flow channels or parallel flow channels.

[0024] The serpentine flow channel of the present invention refers to a single curved flow channel, such as Figure 3 As shown in a.

[0025] The parallel flow channel of the present invention refers to a flow channel composed of multiple groups of parallel channels, such as Figure 3 As shown in b.

[0026] Preferably, the ratio of the unidirectional length to the depth of the serpentine flow channel is 5-100: 1. This preferred implementation is more conducive to improving the heat exchange efficiency.

[0027] In the present invention, the one-way length refers to the longest straight-line distance of the serpentine flow channel flowing in the same direction.

[0028] Preferably, the ratio of the length to the depth of a single group of the parallel flow channels is 5-100: 1. This preferred implementation is more conducive to improving the heat exchange efficiency.

[0029] In the present invention, the single group length refers to the longest straight-line distance of parallel flow channels flowing in the same direction.

[0030] According to the present invention, preferably, the first flow channel and the second flow channel have the same shape and are arranged in parallel.

[0031] The parallel arrangement described in the present invention means that the flow direction of the heat transfer fluid in the first flow channel is the same as the flow direction of the hydrogen in the second flow channel.

[0032] Further preferably, the first flow channel and the second flow channel are serpentine flow channels and are arranged in parallel. With this preferred embodiment, the heat transfer efficiency can be further improved, and the hydrogen absorption and desorption speed can be increased.

[0033] According to the present invention, preferably, along the stacking direction of the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 in the solid hydrogen storage reactor, the first flow channel and the second flow channel are arranged in the same direction.

[0034] In the present invention, along the stacking direction of the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 in the solid hydrogen storage reactor, the first flow channel and the second flow channel are arranged in the same direction, which means: When the solid hydrogen storage reactor is placed horizontally (the sealing end plates mentioned below are on the left and right sides, such as Figure 1 As shown), the setting position of the first flow channel on the heat transfer fluid substrate 1 and the setting position of the second flow channel on the hydrogen storage material substrate 2 can be both on the left side or on the right side.

[0035] When the solid hydrogen storage reactor is placed vertically (the sealing end plates mentioned below are on the upper and lower sides), the setting position of the first flow channel on the heat transfer fluid substrate 1 and the setting position of the second flow channel on the hydrogen storage material substrate 2 can be both on the upper side or on the lower side.

[0036] The present invention has no particular limitation on the facets of the flow channel, which may be square facets, such as Figure 4 As shown in a, it can also be a wavy facet, such as Figure 4 As shown in b, it can also be a triangular sawtooth facet, such as Figure 4 Preferably, the facets of the first flow channel and the second flow channel are independently square facets or triangular sawtooth facets, preferably triangular sawtooth facets. With this preferred embodiment, the heat transfer area can be increased, thereby improving the heat transfer efficiency and making the hydrogen absorption and desorption speed faster.

[0037] Preferably, in the triangular sawtooth facet, the triangular sawtooth is an isosceles triangle.

[0038] Further preferably, in the triangular sawtooth facet, the angle of the triangular sawtooth vertex is 50-120°, preferably 60-90°. With this preferred embodiment, the heat transfer area can be further increased, thereby improving the heat transfer efficiency and making the hydrogen absorption and desorption speed faster.

[0039] In the present invention, the facets of the first flow channel and the second flow channel refer to the cross-sections of the solid parts of the substrate.

[0040] When the facets of the first flow channel are triangular sawtooth facets, the one-way width of the first flow channel is the distance between the highest points of the triangular sawtooth.

[0041] When the facets of the second flow channel are triangular sawtooth facets, the single group width of the second flow channel is the distance between the highest points of the triangular sawtooth.

[0042] According to the present invention, preferably, the ratio of the depth of the first flow channel to the thickness of the heat transfer fluid substrate 1 is 0.4-0.9: 1, preferably 0.7-0.9: 1. With this preferred embodiment, both high heat transfer efficiency and high volume utilization can be taken into account.

[0043] According to the present invention, preferably, the volume of the first flow channel accounts for 40-90%, preferably 40-70%, of the volume of the heat transfer fluid substrate 1. With this preferred embodiment, high heat transfer efficiency and high volume utilization can be achieved.

[0044] According to the present invention, preferably, the ratio of the depth of the second flow channel to the thickness of the hydrogen storage material substrate 2 is 0.4-0.9: 1, preferably 0.7-0.9: 1. With this preferred embodiment, both high heat transfer efficiency and high volume utilization can be taken into account.

[0045] According to the present invention, preferably, the volume of the second flow channel accounts for 40-90%, preferably 40-70%, of the volume of the hydrogen storage material substrate 2. With this preferred embodiment, both high heat transfer efficiency and high volume utilization can be taken into account.

[0046] According to the present invention, preferably, the solid hydrogen storage composite material is filled in the second flow channel of the hydrogen storage material substrate 2. This preferred embodiment is conducive to sufficient contact between hydrogen and the solid hydrogen storage composite material.

[0047] According to the present invention, preferably, the filling volume of the solid hydrogen storage composite material accounts for 40-90% of the volume of the second flow channel, preferably 50-70%. With this preferred embodiment, the hydrogen transmission speed can be guaranteed, while increasing the contact between the solid hydrogen storage composite materials and improving the heat transfer efficiency.

[0048] The present invention has a wide range of selection for the type of the solid hydrogen storage composite material, which can be various conventional solid hydrogen storage composite materials in the art. Preferably, the solid hydrogen storage composite material includes a hydrogen storage material and a thermal conductive material. By adopting this preferred embodiment, the heat transfer coefficient of the hydrogen storage material bed can be effectively improved, while reducing the stress change caused by the expansion and contraction of the hydrogen storage material during the hydrogen absorption and desorption process.

[0049] The present invention has no particular limitation on the amount of the hydrogen storage material and the heat conductive material, which can be selected conventionally in the art. Preferably, the mass ratio of the hydrogen storage material to the heat conductive material is 1:0.01-0.2.

[0050] The present invention has a wide range of choices for the types of hydrogen storage materials, which can be conventionally selected in the art. Preferably, the hydrogen storage material is selected from at least one of titanium-based, zirconium-based, vanadium-based and rare earth-based hydrogen storage alloys.

[0051] Preferably, the rare earth hydrogen storage alloy is a lanthanum and / or cerium hydrogen storage alloy. 5 Hydrogen storage materials (lanthanide hydrogen storage alloys) are used as examples.

[0052] The present invention has a wide range of choices for the thermally conductive material, which can be a conventional choice in the art. Preferably, the thermally conductive material is selected from at least one of expanded graphite, thermally conductive fiber, graphite sheet, carbon nanotube, aluminum powder, copper powder, titanium powder, foamed aluminum, foamed nickel and foamed copper.

[0053] The above hydrogen storage materials and thermal conductive materials are both commercially available.

[0054] The present invention has a wide range of choices for the type of the heat transfer fluid, which can be a conventional choice in the art. Preferably, the heat transfer fluid is water, ethylene glycol or heat transfer oil.

[0055] The present invention has no particular limitation on the thickness of the heat transfer fluid substrate and the hydrogen storage material substrate, and can be appropriately selected according to the application. Preferably, the thickness of the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 is independently 5-100 mm.

[0056] The present invention has no particular limitation on the volume of the heat transfer fluid substrate and the hydrogen storage material substrate, and they can be appropriately selected according to the application.

[0057] The present invention has no particular limitation on the longitudinal cross-sectional shapes of the heat transfer fluid substrate and the hydrogen storage material substrate, which can be regular or irregular. Preferably, the longitudinal cross-sectional shapes of the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are independently square or circular.

[0058] Preferably, the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 have the same longitudinal cross-sectional shape.

[0059] The present invention has no particular limitation on the materials of the heat transfer fluid substrate and the hydrogen storage material substrate, which can be conventionally selected in the art. Preferably, the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are independently made of aluminum, aluminum alloy, copper, copper alloy, carbon steel or stainless steel.

[0060] According to the present invention, preferably, the heat transfer fluid substrate 1 is provided with a heat transfer fluid inlet and a heat transfer fluid outlet, and each heat transfer fluid substrate 1 is connected through a fluid pipeline 4. This preferred embodiment facilitates the inflow and outflow of the heat transfer fluid.

[0061] There are two main forms of communication between the heat transfer fluid substrates 1 through the fluid pipeline 4: 1) When the heat transfer fluid substrates 1 are connected in parallel through the fluid pipelines 4, as Figure 5 As shown in a, the inlets of the heat-conducting fluid substrates 1 are connected in parallel via the fluid pipeline 4 , and the outlets of the heat-conducting fluid substrates 1 are connected in parallel via the fluid pipeline 4 .

[0062] 2) When the heat transfer fluid substrates 1 are connected in series through the fluid pipelines 4, as Figure 5 As shown in b, the inlet and outlet of each heat transfer fluid substrate 1 are connected in series via a fluid pipeline 4 .

[0063] According to the present invention, preferably, the hydrogen storage material substrate 2 is provided with a gas inlet and a gas outlet, and each hydrogen storage material substrate 2 is connected through a gas pipeline 5. This preferred embodiment facilitates the inflow and outflow of hydrogen.

[0064] There are two main forms of communication between the hydrogen storage material substrates 2 through the gas pipeline 5: 1) When the hydrogen storage material substrates 2 are connected in parallel through the gas pipeline 5, as Figure 5 As shown in a, the inlets of the hydrogen storage material substrates 2 are connected in parallel via the gas pipeline 5 , and the outlets of the hydrogen storage material substrates 2 are connected in parallel via the gas pipeline 5 .

[0065] 2) When the hydrogen storage material substrates 2 are connected in series through the gas pipeline 5, as Figure 5 As shown in b, the inlet and outlet of each hydrogen storage material substrate 2 are connected in series via a gas pipeline 5 .

[0066] According to the present invention, preferably, the solid hydrogen storage reactor further comprises filters 6 arranged at the gas inlet and outlet to prevent the outflow of the solid hydrogen storage composite material powder.

[0067] The present invention has no particular limitation on the type of the filter 6 , which can be a conventional choice in the art, and the present invention does not make any requirement therefor.

[0068] The present invention has no particular limitation on the accuracy of the filter 6, and the filter 6 can be designed according to the particle size of the solid hydrogen storage composite material.

[0069] According to the present invention, preferably, the solid hydrogen storage reactor further comprises a sealing end plate 3 for sealing the solid hydrogen storage reactor.

[0070] In the present invention, the thickness, volume, material and longitudinal cross-sectional shape of the sealing end plate 3 are selected to be the same as those of the above-mentioned heat transfer fluid substrate 1 and hydrogen storage material substrate 2 .

[0071] Preferably, the sealing end plates 3 are placed at both ends of the solid hydrogen storage reactor, and the solid hydrogen storage reactor is sealed by bolts 7 .

[0072] Preferably, bolt openings 8 are provided on the heat transfer fluid substrate 1 , the hydrogen storage material substrate 2 , and the end sealing plate 3 .

[0073] Preferably, the bolt 7 passes through a bolt opening 8 .

[0074] According to a particularly preferred embodiment of the present invention, a solid hydrogen storage reactor comprises a heat transfer fluid substrate 1 and a hydrogen storage material substrate 2 filled with a solid hydrogen storage composite material stacked in sequence; The heat transfer fluid substrate 1 has a first flow channel engraved on one side for the heat transfer fluid to pass through; the hydrogen storage material substrate 2 has a second flow channel engraved on one side for the hydrogen to pass through, and the first flow channel and the second flow channel are not connected; The first flow channel and the second flow channel are serpentine flow channels and are arranged in parallel; The facets of the first flow channel and the second flow channel are triangular sawtooth facets; The triangular sawtooth is an isosceles triangle; In the triangular sawtooth facet, the angle of the triangular sawtooth vertex is 60-90°; Along the stacking direction of the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 in the solid hydrogen storage reactor, the first flow channel and the second flow channel are arranged in the same direction; The ratio of the depth of the first flow channel to the thickness of the heat transfer fluid substrate 1 is 0.4-0.9:1; The volume of the first flow channel accounts for 40-90% of the volume of the heat transfer fluid substrate 1; The ratio of the depth of the second flow channel to the thickness of the hydrogen storage material substrate 2 is 0.4-0.9:1; The volume of the second flow channel accounts for 40-90% of the volume of the hydrogen storage material substrate 2 .

[0075] The solid hydrogen storage reactor of the above-mentioned preferred embodiment of the present invention is further beneficial to the full contact and reaction between hydrogen and the solid hydrogen storage composite material during the hydrogen storage process, and is beneficial to the heat transfer fluid introduced to remove the heat released in the hydrogen storage material substrate reaction system in time, thereby improving the heat exchange efficiency, while keeping the hydrogen absorption reaction temperature at a favorable position, thereby increasing the hydrogen absorption rate; it is further beneficial for the heat transfer fluid to provide heat for the desorption of hydrogen in time during the hydrogen release process to maintain a suitable hydrogen release rate.

[0076] The second aspect of the present invention provides a hydrogen storage / dehydrogenation method of the solid hydrogen storage reactor according to the first aspect, the method comprising: During the hydrogen storage process, hydrogen is fed into the second flow channel of the hydrogen storage material substrate to undergo a hydrogen absorption reaction with the solid hydrogen storage composite material, and a heat transfer fluid is fed into the first flow channel of the heat transfer fluid substrate to absorb heat generated by the hydrogen absorption reaction; During the dehydrogenation process, the solid hydrogen storage composite material adsorbing hydrogen undergoes a desorption reaction. A heat transfer fluid is fed into the first flow channel of the heat transfer fluid substrate to provide heat for the desorption reaction of hydrogen.

[0077] According to the present invention, preferably, in the hydrogen storage process, the conditions of the hydrogen absorption reaction include: a temperature of 10-200° C. and a pressure of 0.1-100 MPa.

[0078] The present invention has no particular limitation on the flow rate of the heat transfer fluid during the hydrogen storage process, and it can be appropriately selected according to the hydrogen absorption rate, and the present invention does not impose any limitation thereon.

[0079] According to the present invention, preferably, in the hydrogen release process, the conditions of the desorption reaction (hydrogen release reaction) include: a temperature of 30-300° C. and a pressure of 0.1-100 MPa.

[0080] The present invention has no particular limitation on the flow rate of the heat transfer fluid during the dehydrogenation process, and can be appropriately selected according to the dehydrogenation rate, which is not limited in the present invention.

[0081] According to the present invention, preferably, during the dehydrogenation process, the temperature of the heat transfer fluid is 50-300°C.

[0082] The present invention has a wide range of choices for the type of the heat transfer fluid, which can be a conventional choice in the art. Preferably, the heat transfer fluid is water, ethylene glycol or heat transfer oil.

[0083] In the present invention, unless otherwise specified, the terms "first" and "second" do not indicate a sequence of precedence or a limitation on each material or step, but are merely used to distinguish that they are not the same material or step.

[0084] The present invention will be described in detail below through examples.

[0085] The reactor was numerically simulated using COMSO software. The mass, energy and momentum balance equations were constructed. The specific equations are as follows: Mass conservation equation for hydrogen storage materials: The mass conservation equation for gases is: in, m is the mass change, ε is the porosity of the hydrogen storage material in the inner tank 1, ρ s is the density of hydrogen storage material, t is the reaction time, u g is the velocity field of hydrogen, ρ g is the gas density.

[0086] The velocity field for hydrogen is calculated using Darcy's law: in, K is the permeability, μ g is the viscosity coefficient of hydrogen, P g is the hydrogen pressure.

[0087] For the hydrogen absorption reaction process, the reaction rate equation is as follows: For the hydrogen release reaction process, the reaction rate equation is as follows: in, C a and C d are the pre-exponential factors of hydrogen absorption and desorption reactions, E a and E d are the activation energies of hydrogen absorption and desorption reactions, respectively. R g is the gas constant, T is the reaction temperature, P eq is the equilibrium pressure of the chemical reaction, ρ ss is the density of the hydrogen storage material after hydrogen absorption is complete, ρ 0 is the initial density of the hydrogen storage material.

[0088] The equilibrium pressure of a chemical reaction can be given by the Van't Hoff equation: The energy balance equation for the hydrogen absorption and desorption reaction in the inner tank 1 is as follows: in, M g is the molar mass of hydrogen; The heat capacity of the hydrogen storage bed is: The effective thermal conductivity of the hydrogen storage bed is: in, C p,g and C p,s are the heat capacities of hydrogen and hydrogen storage materials, respectively, e and λ g are the thermal conductivities of hydrogen and hydrogen storage materials, respectively.

[0089] For the heat transfer fluid, the mass balance equation is: in, ρ f is the density of the heat transfer fluid, u f is the velocity field of the heat transfer fluid.

[0090] For a heat transfer fluid, the momentum balance equation is as follows: The heat transfer equation inside the fluid is as follows: in: in, C p,f is the heat capacity of the heat transfer fluid, λ f is the effective thermal conductivity of the heat transfer fluid, P f is the heat transfer fluid pressure.

[0091] For solid materials such as tank walls and partitions, the heat transfer equation is as follows: in, is the heat capacity of the solid (tank wall or partition), is the effective thermal conductivity of the solid (tank wall or partition).

[0092] The heat transfer equation between the inner tank, outer tank and partition is: in, q is the heat flux, h is the heat transfer coefficient between the two, T 1 and T 2 Refers to the respective temperatures of the contact surfaces of two adjacent phases where heat transfer occurs (for example, when calculating the heat transfer between the inner tank and the partition, T 1 and T 2 Refers to the contact surface temperature of the inner tank and the partition respectively).

[0093] Example 1 like Figure 1 As shown, the solid hydrogen storage reactor includes a heat-conducting fluid substrate 1, a hydrogen storage material substrate 2, a sealing end plate 3, a fluid pipeline 4, a gas pipeline 5, a filter 6 and a bolt 7. The heat-conducting fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3 are all rectangular structures made of 304 stainless steel with a length of 70 mm, a width of 44 mm and a thickness of 13.5 mm. The heat-conducting fluid substrate 1 and the hydrogen storage material substrate 2 are stacked as a group, and the number of stacking groups is 10. Two sealing end plates 3 are stacked at both ends of the reactor and sealed by bolts 7. Bolt ports 8 are distributed on the heat-conducting fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3, and the bolts 7 pass through the bolt ports 8.

[0094] like Figure 2 and Figure 3As shown, the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are respectively engraved with a serpentine liquid flow channel (first flow channel) and a serpentine gas flow channel (second flow channel) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located at both ends of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in a, the flow channel facet is a square facet.

[0095] The ratio of the unidirectional length to the depth of the first flow channel of the heat transfer fluid substrate 1 is 5:1, the ratio of the first flow channel depth to the substrate thickness is 0.88:1, and the ratio of the first flow channel volume to the substrate volume is 0.53:1. The first flow channel is filled with heat transfer fluid deionized water.

[0096] The ratio of the unidirectional length to the depth of the first flow channel of the hydrogen storage material substrate 2 is 5:1, the ratio of the first flow channel depth to the substrate thickness is 0.8:1, and the ratio of the second flow channel volume to the substrate volume is 0.53:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 2. The solid hydrogen storage composite material is composed of LaNi 5 The hydrogen storage material is mixed with expanded graphite, and the mass ratio of the two is 1:0.03. The filling volume of the solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel.

[0097] Each heat transfer fluid substrate 1 has a heat transfer fluid inlet and outlet, which are connected in parallel through a fluid pipeline 4. Each hydrogen storage material substrate 2 has a gas inlet and outlet, which are connected in parallel through a gas pipeline 5. There are filters 6 at the gas inlet and outlet, and the filter 6 is a 316 stainless steel sintered porous material with a filtration accuracy of 0.5 μm.

[0098] When the reactor is in use, during the hydrogen storage process, the hydrogen inlet pressure is maintained at 0.8 MPa and passed into the second flow channel of the hydrogen storage material substrate to undergo a hydrogen absorption reaction with the solid hydrogen storage composite material at an initial temperature of 20°C. In each heat transfer fluid substrate 1, a heat transfer fluid (deionized water) at 20°C is fed into its first flow channel at a flow rate of 1.2 L / min to absorb the heat generated by the hydrogen absorption reaction.

[0099] During the dehydrogenation process, the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction at an initial temperature of 343K and a constant outlet pressure of 0.1MPa, and 343K deionized water is continuously introduced into the first flow channel of the heat transfer fluid substrate 1 at a flow rate of 1.2L / min to provide the heat required for desorption. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, which can ensure that the heat transfer fluid provides sufficient energy required for desorption of the hydrogen storage material, thereby increasing the dehydrogenation rate.

[0100] Comsol simulation was used to calculate the changes of various parameters in the reactor over time.

[0101] like Figure 6 The curve of hydrogen absorption amount changing with time shows that 204 s after the start of the hydrogen absorption reaction, the hydrogen absorption amount of the hydrogen storage device reaches 90% of the maximum hydrogen absorption amount. Compared with comparative example 1, the hydrogen absorption time is reduced by 69%, and compared with comparative example 2 with no flow channel structure, the hydrogen absorption time is reduced by 29%, and the hydrogen absorption efficiency is significantly improved.

[0102] like Figure 7 The curve showing the change of the average temperature of the hydrogen storage bed with time shows that the total time that the average temperature of the hydrogen storage bed exceeds 323.15K (50°C) is 207 s, which is 68% shorter than that of comparative example 1 and 37% shorter than that of comparative example 2 with no flow channel structure, and the heat exchange efficiency is significantly improved.

[0103] Example 2 like Figure 1 As shown, the solid hydrogen storage reactor includes a heat-conducting fluid substrate 1, a hydrogen storage material substrate 2, a sealing end plate 3, a fluid pipeline 4, a gas pipeline 5, a filter 6 and a bolt 7. The heat-conducting fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3 are all rectangular structures made of 304 stainless steel with a length of 210 mm, a width of 44 mm and a thickness of 12 mm. The heat-conducting fluid substrate 1 and the hydrogen storage material substrate 2 are stacked as a group, and the number of stacking groups is 5. Two sealing end plates 3 are stacked at both ends of the reactor and sealed by bolts 7. Bolt ports 8 are distributed on the heat-conducting fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3, and the bolts 7 pass through the bolt ports 8.

[0104] like Figure 2 and Figure 3 As shown, the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are respectively engraved with a serpentine liquid flow channel (first flow channel) and a serpentine gas flow channel (second flow channel) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located on both sides of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in a, the flow channel facet is a square facet.

[0105] The ratio of the unidirectional length to the depth of the first flow channel on the heat transfer fluid substrate 1 is 20:1, the ratio of the first flow channel depth to the substrate thickness is 0.88:1, and the ratio of the flow channel volume to the substrate volume is 0.54:1. The first flow channel is filled with heat transfer fluid deionized water.

[0106] The ratio of the unidirectional length to the depth of the first flow channel of the hydrogen storage material substrate 2 is 20:1, the ratio of the first flow channel depth to the substrate thickness is 0.88:1, and the ratio of the flow channel volume to the substrate volume is 0.54:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 2. The solid hydrogen storage composite material is composed of LaNi 5The hydrogen storage material is mixed with expanded graphite, and the mass ratio of the two is 1:0.03. The filling volume of the solid hydrogen storage composite material accounts for 60% of the volume of the second flow channel.

[0107] Each heat transfer fluid substrate 1 has a heat transfer fluid inlet and outlet, which are connected in parallel through a fluid pipeline 4. Each hydrogen storage material substrate 2 has a gas inlet and outlet, which are connected in parallel through a gas pipeline 5. There are filters 6 at the gas inlet and outlet, and the filter 6 is a 316 stainless steel sintered porous material with a filtration accuracy of 0.5 μm.

[0108] When the reactor is in use, during the hydrogen storage process, the hydrogen inlet pressure is maintained at 0.8 MPa and is passed into the second flow channel of the hydrogen storage material substrate to undergo a hydrogen absorption reaction with the solid hydrogen storage composite material at an initial temperature of 20° C. In each heat transfer fluid substrate 1, a heat transfer fluid (deionized water) at 20° C. is fed into its first flow channel at a flow rate of 3 L / min to absorb the heat generated by the hydrogen absorption reaction.

[0109] During the dehydrogenation process, the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction at an initial temperature of 343K and a constant outlet pressure of 0.1MPa, and deionized water at 343K is continuously introduced at a flow rate of 3 L / min to provide the heat required for desorption. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, which can ensure that the heat transfer fluid provides sufficient energy required for desorption of the hydrogen storage material, thereby increasing the dehydrogenation rate.

[0110] Comsol simulation was used to calculate the changes of various parameters in the reactor over time.

[0111] like Figure 8 The curve of hydrogen absorption amount changing with time shows that 277 s after the start of the hydrogen absorption reaction, the hydrogen absorption amount of the hydrogen storage device reaches 90% of the maximum hydrogen absorption amount. Compared with comparative example 1, the hydrogen absorption time is reduced by 58%, and compared with comparative example 2 without flow channel, the hydrogen absorption time is reduced by 4%.

[0112] like Fig. 9 The curve showing the change of the average temperature of the hydrogen storage bed with time shows that the total time when the average temperature of the hydrogen storage bed exceeds 323.15K is 283s, which is 56% less than that of comparative example 1 and 13% less than that of comparative example 2 without flow channel.

[0113] Example 3 like Figure 1As shown, the solid hydrogen storage reactor includes a heat transfer fluid substrate 1, a hydrogen storage material substrate 2, a sealing end plate 3, a fluid pipeline 4, a gas pipeline 5, a filter 6 and a bolt 7. The heat transfer fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3 are all 304 stainless steel rectangular substrate materials with a length of 60 mm, a width of 40 mm and a thickness of 9 mm. The heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are stacked as a group, and the number of stacking groups is 25. Two sealing end plates 3 are stacked at both ends of the reactor and sealed by bolts 7. Bolt ports 8 are distributed on the heat transfer fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3, and the bolts 7 pass through the bolt ports 8.

[0114] like Figure 2 and Figure 3 As shown, the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are respectively engraved with a serpentine liquid flow channel (first flow channel) and a serpentine gas flow channel (second flow channel) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located on both sides of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in c, the flow channel facet is a triangular sawtooth facet, the triangular sawtooth is an isosceles triangle, and the vertex angle is 90°.

[0115] The ratio of the unidirectional length to the depth of the first flow channel on the heat transfer fluid substrate 1 is 7.3:1, the ratio of the first flow channel depth to the substrate thickness is 0.75:1, and the ratio of the flow channel volume to the substrate volume is 0.49:1. The first flow channel is filled with heat transfer fluid deionized water.

[0116] The ratio of the unidirectional length to the depth of the first flow channel of the hydrogen storage material substrate 2 is 7.3:1, the ratio of the first flow channel depth to the substrate thickness is 0.75:1, and the ratio of the flow channel volume to the substrate volume is 0.49:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 2. The solid hydrogen storage composite material is composed of LaNi 5 The hydrogen storage material is mixed with expanded graphite, and the mass ratio of the two is 1:0.05. The solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel.

[0117] Each heat transfer fluid substrate 1 has a heat transfer fluid inlet and outlet, which are connected in parallel through a fluid pipeline 4. Each hydrogen storage material substrate 2 has a gas inlet and outlet, which are connected in parallel through a gas pipeline 5. There are filters 6 at the gas inlet and outlet, and the filter 6 is a 316 stainless steel sintered porous material with a filtration accuracy of 0.5 μm.

[0118] When the reactor is in use, during the hydrogen storage process, the hydrogen inlet pressure is maintained at 0.8 MPa and is passed into the second flow channel of the hydrogen storage material substrate to perform a hydrogen absorption reaction with the solid hydrogen storage composite material at an initial temperature of 20°C. In each heat transfer fluid substrate 1, a heat transfer fluid (deionized water) at 20°C is fed into its first flow channel at a flow rate of 3.7L / min to absorb the heat generated by the hydrogen absorption reaction.

[0119] During the dehydrogenation process, the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction at an initial temperature of 343K and a constant outlet pressure of 0.1MPa, and 343K deionized water is continuously introduced at a flow rate of 3.7L / min to provide the heat required for desorption. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, which can ensure that the heat transfer fluid provides sufficient energy required for desorption of the hydrogen storage material, thereby increasing the dehydrogenation rate.

[0120] Comsol simulation was used to calculate the changes of various parameters in the reactor over time.

[0121] like Fig.10 The curve of hydrogen absorption over time shows that 111 seconds after the start of the hydrogen absorption reaction, the hydrogen absorption of the hydrogen storage device reaches 90% of the maximum hydrogen absorption. Compared with comparative example 1, the hydrogen absorption time is reduced by 83%, and compared with comparative example 2 without a flow channel, the hydrogen absorption time is reduced by 61%.

[0122] like Fig.11 The curve of the average temperature of the hydrogen storage bed changing with time shows that the total time for the average temperature of the hydrogen storage bed to exceed 323.15 K is 78 seconds. Compared with the comparative example 1, the over-temperature time is reduced by 88%, and compared with the comparative example 2 without flow channel, the over-temperature time is reduced by 76%.

[0123] Example 4 like Figure 1 As shown, the solid hydrogen storage reactor includes a heat transfer fluid substrate 1, a hydrogen storage material substrate 2, a sealing end plate 3, a fluid pipeline 4, a gas pipeline 5, a filter 6 and a bolt 7. The heat transfer fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3 are all rectangular structures made of 304 stainless steel with a length of 110 mm, a width of 40 mm and a thickness of 12 mm. The heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are stacked as a group, and the number of stacking groups is 15. Two sealing end plates 3 are stacked at both ends of the reactor and sealed by bolts 7. Bolt ports 8 are distributed on the heat transfer fluid substrate 1, the hydrogen storage material substrate 2 and the sealing end plate 3, and the bolts 7 pass through the bolt ports 8.

[0124] like Figure 2 and Figure 3As shown, the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 are respectively engraved with parallel liquid flow channels (first flow channels) and parallel gas flow channels (second flow channels) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located on both sides of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in a, the flow channel facet is a square facet.

[0125] The ratio of the length to the depth of the first flow channel on the heat transfer fluid substrate 1 is 10:1, the ratio of the first flow channel depth to the substrate thickness is 0.88:1, and the ratio of the flow channel volume to the substrate volume is 0.45:1. The first flow channel is filled with heat transfer fluid deionized water.

[0126] The ratio of the length to the depth of the first flow channel of the hydrogen storage material substrate 2 is 10:1, the ratio of the depth of the first flow channel to the thickness of the substrate is 0.88:1, and the ratio of the volume of the flow channel to the volume of the substrate is 0.45:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 2. The solid hydrogen storage composite material is composed of LaNi 5 The hydrogen storage material is mixed with expanded graphite, and the mass ratio of the two is 1:0.03. The filling volume of the solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel.

[0127] Each heat transfer fluid substrate 1 has a heat transfer fluid inlet and outlet, which are connected in parallel through a fluid pipeline 4. Each hydrogen storage material substrate 2 has a gas inlet and outlet, which are connected in parallel through a gas pipeline 5. There are filters 6 at the gas inlet and outlet, and the filter 6 is a 316 stainless steel sintered porous material with a filtration accuracy of 0.5 μm.

[0128] When the reactor is in use, during the hydrogen storage process, the hydrogen inlet pressure is maintained at 0.8 MPa and is passed into the second flow channel of the hydrogen storage material substrate to perform a hydrogen absorption reaction with the solid hydrogen storage composite material at an initial temperature of 20°C. In each heat transfer fluid substrate 1, a heat transfer fluid (deionized water) at 20°C is fed into its first flow channel at a flow rate of 2.2L / min to absorb the heat generated by the hydrogen absorption reaction.

[0129] During the dehydrogenation process, the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction at an initial temperature of 343K and a constant outlet pressure of 0.1MPa, and deionized water at 343K is continuously introduced at a flow rate of 2.2L / min to provide the heat required for desorption. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, which can ensure that the heat transfer fluid provides sufficient energy required for desorption of the hydrogen storage material, thereby increasing the dehydrogenation rate.

[0130] Comsol simulation was used to calculate the changes of various parameters in the reactor over time.

[0131] like Fig.12 The curve of hydrogen absorption over time shows that 211 seconds after the start of the hydrogen absorption reaction, the hydrogen absorption of the hydrogen storage device reaches 90% of the maximum hydrogen absorption. Compared with comparative example 1, the hydrogen absorption time is reduced by 68%, and compared with comparative example 2 without a flow channel, the hydrogen absorption time is reduced by 27%.

[0132] like Fig.13 The curve showing the change of the average temperature of the hydrogen storage bed over time shows that the total time when the average temperature of the hydrogen storage bed exceeds 323.15 K is 215 seconds. Compared with the comparative example 1, the over-temperature time is reduced by 67%, and compared with the comparative example 2 without flow channel, the over-temperature time is reduced by 34%.

[0133] Comparative Example 1 Prior art hydrogen storage alloy reactor like Fig.14 As shown, the hydrogen storage alloy reactor includes an inner tank body, an outer tank body, a fluid pipeline and an air pipe. The outer tank body is sleeved on the outside of the inner tank body. Both the inner tank body and the outer tank body are made of 304 stainless steel. The height of the inner tank body is 312 mm, the inner diameter of the inner tank body is 30 mm, the height of the outer tank body is 312 mm, the inner diameter of the outer tank body is 50 mm, and the volume of the inner tank body is the same as the total volume of the second flow channel in Example 1. The air pipe is arranged on the top of the inner tank body and is connected to the inner tank body. The diameter of the air pipe is 6 mm. A filter is arranged inside the air pipe. The filter is made of sintered 316L stainless steel with an accuracy of 2 μm. Hydrogen is filtered by the filter and enters or is discharged from the inner tank body through the air pipe. The solid hydrogen storage composite material is placed in the inner tank body. The solid hydrogen storage composite material is composed of LaNi 5 The hydrogen storage material is mixed with expanded graphite, and the mass ratio of the two is 1:0.03. The solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel. The heat transfer fluid is introduced into the fluid pipeline of the outer tank, and the heat transfer fluid is deionized water.

[0134] During the hydrogen storage process, the hydrogen inlet pressure is maintained at 0.8MPa and passed into the inner tank body, where it undergoes a hydrogen absorption reaction with the solid hydrogen storage composite material in the inner tank body 1 under an initial temperature and pressure of 20°C; deionized water at a temperature of 20°C is passed into the fluid pipeline inlet of the outer tank body at a flow rate of 1.2L / min, absorbing the heat generated by the hydrogen absorption reaction and then flowing out through the fluid pipeline outlet.

[0135] During the dehydrogenation process, the hydrogen outlet pressure was maintained at 0.1 MPa. A heat transfer fluid (deionized water) at 70°C was delivered into the gas pipe at a flow rate of 1.2L / min to provide the heat required for the dehydrogenation reaction. Due to the uneven distribution of deionized water in the outer tank, the deionized water and the hydrogen storage material in some areas could not fully exchange heat, resulting in a local temperature drop in the hydrogen storage material and a low dehydrogenation rate.

[0136] like Fig.15The curve of hydrogen absorption amount changing with time shows that 654 s after the start of the hydrogen absorption reaction, the hydrogen absorption amount of the hydrogen storage device reaches 90% of the maximum hydrogen absorption amount.

[0137] like Fig.16 The curve showing the change of the average temperature of the inner tank body with time shows that the total time that the average temperature of the inner tank body exceeds 323.15K is 640 s.

[0138] Comparative Example 2 The method of Example 2 is followed, except that the heat transfer fluid substrate 1 and the hydrogen storage material substrate 2 of the solid hydrogen storage reactor are not provided with flow channels, but are provided with square grooves.

[0139] The heat transfer fluid substrate 1 is engraved with a square groove, and a liquid inlet and an outlet are provided at both ends of the groove. The ratio of the groove length to the depth is 20:1, the ratio of the groove depth to the substrate thickness is 0.85:1, and the ratio of the groove volume to the substrate volume is 0.54:1. Deionized water flows through the groove.

[0140] The hydrogen storage material substrate 2 is engraved with a square groove, and a liquid inlet and outlet are respectively provided at both ends of the groove. The ratio of the groove length to the depth is 20:1, the ratio of the groove depth to the substrate thickness is 0.85:1, the ratio of the groove volume to the substrate volume is 0.54:1, and the total volume of the groove is the same as the total volume of the second flow channel of the hydrogen storage material substrate 2 in Example 2. A solid hydrogen storage composite material is placed in the groove, and the solid hydrogen storage composite material is LaNi 5 The hydrogen storage material is mixed with expanded graphite, and the mass ratio of the two is 1:0.03. The solid hydrogen storage composite material occupies 50% of the volume of the groove.

[0141] When the reactor is used, during the hydrogen storage process, the hydrogen inlet pressure is maintained at 0.8 MPa and is passed into the groove of the hydrogen storage material substrate to absorb hydrogen with the solid hydrogen storage composite material at an initial temperature of 20°C. A heat transfer fluid (deionized water) at 20°C is fed into the groove of the heat transfer fluid substrate 1 at a flow rate of 3L / min to absorb the heat generated by the hydrogen absorption reaction. During the dehydrogenation process, the hydrogen outlet pressure is maintained at 0.1 MPa.

[0142] During the dehydrogenation process, the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction at an initial temperature of 343K and a constant outlet pressure of 0.1MPa, and 343K deionized water is continuously introduced into the groove of the heat transfer fluid substrate 1 at a flow rate of 3 L / min to provide the heat required for desorption. Since the deionized water is unevenly distributed in the groove structure, the deionized water and the hydrogen storage material in some areas cannot fully exchange heat, which causes the local temperature of the hydrogen storage material to decrease and the hydrogen desorption rate to be low.

[0143] Comsol simulation was used to calculate the changes of various parameters in the reactor over time.

[0144] like Fig.17 The curve of hydrogen absorption amount changing with time shows that 288 s after the start of the hydrogen absorption reaction, the hydrogen absorption amount of the hydrogen storage device reaches 90% of the maximum hydrogen absorption amount.

[0145] like Fig.18 The curve showing the change of the average temperature of the hydrogen storage bed with time shows that the total time that the average temperature of the hydrogen storage bed exceeds 323.15K is 327 s.

[0146] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A solid hydrogen storage reactor, characterized in that: The solid hydrogen storage reactor comprises a heat transfer fluid substrate (1) and a hydrogen storage material substrate (2) filled with a solid hydrogen storage composite material, which are stacked in sequence; Wherein, the heat-conducting fluid substrate (1) is engraved with a first flow channel for the passage of the heat-conducting fluid; The hydrogen storage material substrate (2) is engraved with a second flow channel for the passage of hydrogen, and the first flow channel and the second flow channel are not connected.

2. The solid hydrogen storage reactor according to claim 1, wherein: The first flow channel and the second flow channel are independently serpentine flow channels or parallel flow channels; Preferably, the ratio of the unidirectional length to the depth of the serpentine flow channel is 5-100:1; Preferably, the ratio of the length to the depth of a single group of the parallel flow channels is 5-100:

1.

3. The solid hydrogen storage reactor according to claim 2, wherein: The first flow channel and the second flow channel have the same shape and are arranged in parallel; Preferably, the first flow channel and the second flow channel are serpentine flow channels and are arranged in parallel; Preferably, along the stacking direction of the heat transfer fluid substrate (1) and the hydrogen storage material substrate (2) in the solid hydrogen storage reactor, the first flow channel and the second flow channel are arranged in the same direction.

4. The solid hydrogen storage reactor according to any one of claims 1 to 3, wherein: The facets of the first flow channel and the second flow channel are independently square facets or triangular sawtooth facets, preferably triangular sawtooth facets; Preferably, in the triangular sawtooth facet, the angle of the triangular sawtooth vertex is 50-120°, preferably 60-90°.

5. The solid hydrogen storage reactor according to any one of claims 1 to 4, wherein: The ratio of the depth of the first flow channel to the thickness of the heat transfer fluid substrate (1) is 0.4-0.9:1, preferably 0.7-0.9:1; Preferably, the volume of the first flow channel accounts for 40-90% of the volume of the heat transfer fluid substrate (1), preferably 40-70%; Preferably, the ratio of the depth of the second flow channel to the thickness of the hydrogen storage material substrate (2) is 0.5-0.9:1, preferably 0.7-0.9:1; Preferably, the volume of the second flow channel accounts for 40-90% of the volume of the hydrogen storage material substrate (2), preferably 40-70%; Preferably, the solid hydrogen storage composite material is filled in the second flow channel of the hydrogen storage material substrate (2).

6. The solid hydrogen storage reactor according to any one of claims 1 to 5, wherein: The heat-conducting fluid substrate (1) is provided with a heat-conducting fluid inlet and a heat-conducting fluid outlet, and each heat-conducting fluid substrate (1) is connected via a fluid pipeline (4); Preferably, the hydrogen storage material substrate (2) is provided with a gas inlet and a gas outlet, and the various hydrogen storage material substrates (2) are connected via a gas pipeline (5).

7. The solid hydrogen storage reactor according to claim 6, wherein: The solid hydrogen storage reactor further comprises filters (6) arranged at the gas inlet and the gas outlet, for preventing the outflow of the solid hydrogen storage composite material powder; Preferably, the solid hydrogen storage reactor further comprises a sealing end plate (3) for sealing the solid hydrogen storage reactor.

8. A method for storing / de-hydrogenating a solid hydrogen storage reactor according to any one of claims 1 to 7, the method comprising: During the hydrogen storage process, hydrogen is fed into the second flow channel of the hydrogen storage material substrate to undergo a hydrogen absorption reaction with the solid hydrogen storage composite material, and a heat transfer fluid is fed into the first flow channel of the heat transfer fluid substrate to absorb heat generated by the hydrogen absorption reaction; During the dehydrogenation process, the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction, and the heat transfer fluid is fed into the first flow channel of the heat transfer fluid substrate to provide heat for the desorption reaction of the hydrogen.

9. The method according to claim 8, wherein: In the hydrogen storage process, the conditions of the hydrogen absorption reaction include: temperature of 10-200° C. and pressure of 0.1-100 MPa.

10. The method according to claim 8, wherein: During the dehydrogenation process, the conditions of the desorption reaction include: a temperature of 30-300°C and a pressure of 0.1-100 MPa; Preferably, during the dehydrogenation process, the temperature of the heat transfer fluid is 50-300°C; Preferably, the heat transfer fluid is water, ethylene glycol or heat transfer oil.

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