Solid hydrogen storage reactor and hydrogen storage / desorption method of solid hydrogen storage reactor

Abstract

The invention relates to the technical field of hydrogen storage, and discloses a solid hydrogen storage reactor and a hydrogen storage / desorption method of the solid hydrogen storage reactor. The solid hydrogen storage reactor comprises a reactor jacket, a reactor inner pipe filled with a hydrogen storage material and a gas pipe arranged in the reactor inner pipe, wherein the outer side of the gas pipe is arranged to be of an inner spiral structure, and a spiral gas flow channel is formed by the outer side of the gas pipe and the inner side of the reactor inner pipe and used for circulation of hydrogen; wherein an outer spiral structure is arranged on the inner side of the reactor jacket; the outer side of the reactor inner pipe is of an inner spiral structure, and the inner side of the reactor outer sleeve and the outer side of the reactor inner pipe form a spiral heat-conducting fluid runner used for circulation of heat-conducting fluid. The solid hydrogen storage reactor has a high heat exchange 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 of the solid hydrogen storage reactor. Background Art

[0002] As a clean and efficient secondary energy source, the safe storage of hydrogen energy is the most critical link in its application process. Among them, alloy hydrogen storage has the advantages of high hydrogen storage density, low hydrogen storage pressure, controllable hydrogen absorption and desorption, high hydrogen purity, and system safety. It is an important direction for the development of hydrogen storage technology. Hydrogen storage alloys generate a lot of heat when absorbing hydrogen, and need to absorb a lot of heat from the outside when releasing hydrogen, and the temperature seriously affects the absorption / desorption rate of hydrogen storage alloys. Due to the drastic lattice expansion / contraction of hydrogen storage alloys during the absorption / desorption process, the hydrogen storage alloys are pulverized. After pulverization, the heat transfer performance of the hydrogen storage alloys is extremely poor, and its effective thermal conductivity is only about 1W / (m·K), which affects the heat transfer performance of the solid hydrogen storage reactor. In order to improve the heat transfer problem of solid hydrogen storage reactors, CN105289440A and CN114508695A respectively disclose a hydrogen storage reactor and system coupled with a finned spiral coil heat exchanger and an internal heat anti-expansion metal hydrogen storage device, in which a spiral coil heat exchange channel and a straight tube for passing a heat exchange fluid are arranged in the reaction bed, and a plurality of fins are arranged in parallel on the outer surface of the heat exchange channel to enhance the heat transfer effect between the heat exchange fluid and the metal hydride. However, since the spiral coil heat exchange channel is located inside the reactor, the heat exchange channel is easily broken and damaged by thermal stress during the hydrogen absorption and dehydrogenation reaction.

[0003] CN111195808A uses a heat exchange method in which a plurality of copper-water heat pipes and fins of relatively small diameter are fixed between the reaction beds. The structure is simple and the space utilization rate is high. However, since the heat exchangers are mostly tube bundles of relatively small diameter, the heat exchange efficiency is average.

[0004] CN108131563A and CN113277467A respectively set spiral structural parts inside the metal hydride hydrogen storage tank and set activated carbon partitions outside to improve the thermal conductivity of the hydrogen storage alloy powder bed, greatly alleviate the alloy powder deposition and cycle compression effects, and improve safety and reliability. However, this metal hydride hydrogen storage tank does not have a heat exchange fluid involved in heat exchange coupling, and the heat exchange efficiency is relatively general.

[0005] CN103883874A discloses a hydrogen storage tank with an external heat exchange structure, which is composed of a tank body filled with metal hydride material and a shell provided with a heat exchange structure. The heat exchange structure can be set to a direct current shape, a baffle shape, a single spiral shape and a multi-spiral shape according to the heat exchange requirements to ensure uniform heat exchange, but this external heat exchange structure has a large resistance to heat transfer oil and a general heat exchange efficiency.

[0006] CN214500868U microchannels the heat exchange plate to increase the heat exchange area, which has a good heat exchange effect. However, due to the complex processing of the microchannel, the thermal stress generated during the hydrogenation and dehydrogenation process is easy to damage the microchannel heat exchange plate.

[0007] How to improve the structure of the solid hydrogen storage reactor and further enhance the heat transfer efficiency inside the reactor has become a problem that needs to be solved urgently. Summary of the invention

[0008] The purpose of the present invention is to overcome the problem that the heat transfer of the solid hydrogen storage reactor in the prior art needs to be further improved, and to provide a solid hydrogen storage reactor and a hydrogen storage / dehydrogenation method of the solid hydrogen storage reactor. The solid hydrogen storage reactor has a high heat exchange rate.

[0009] In order to achieve the above object, the present invention provides a solid hydrogen storage reactor, which comprises: a reactor jacket, a reactor inner tube filled with hydrogen storage material, and an air pipe disposed inside the reactor inner tube;

[0010] The outer side of the gas pipe is configured as an inner spiral structure, and the outer side of the gas pipe and the inner side of the reactor inner tube form a spiral gas flow channel for the circulation of hydrogen;

[0011] The inner side of the reactor jacket is configured as an outer spiral structure; the outer side of the reactor inner tube is configured as an inner spiral structure; the inner side of the reactor jacket and the outer side of the reactor inner tube form a spiral heat transfer fluid flow channel for the circulation of the heat transfer fluid.

[0012] 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:

[0013] During the hydrogen storage process, hydrogen is fed into the spiral gas flow channel between the inner side of the reactor inner tube and the outer side of the gas pipe to react with the hydrogen storage material to absorb hydrogen, and a heat transfer fluid is fed into the spiral heat transfer fluid flow channel between the outer side of the reactor inner tube and the inner side of the reactor jacket to absorb heat generated by the hydrogen absorption reaction.

[0014] During the dehydrogenation process, the hydrogen storage material adsorbing hydrogen undergoes a desorption reaction, and the heat transfer fluid is fed into the heat transfer fluid flow channel to provide heat for the desorption reaction of the hydrogen.

[0015] Through the above technical solution, the beneficial effects of the present invention include:

[0016] The solid hydrogen storage reactor provided by the present invention has a simple structure and low cost. By arranging an inner spiral structure and an outer spiral structure on the inner tube of the reactor and the outer jacket of the reactor respectively, a double-helical heat-conducting fluid flow channel is formed, the heat exchange rate is improved, the heat exchange area of ​​the solid hydrogen storage reactor is effectively increased, and the heat exchange effect is improved; by arranging an inner spiral structure on the outside of the gas pipe to form a single spiral gas flow channel with the inner side of the inner tube of the reactor, it is beneficial to increase the hydrogen absorption and desorption rate, and at the same time, hydrogen can pass quickly, effectively preventing the hydrogen storage alloy powder from clogging the hydrogen channel. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is an overall structural diagram of the solid hydrogen storage reactor of the present invention;

[0018] Figure 2 is a structural diagram of the inner tube of the solid hydrogen storage reactor of the present invention;

[0019] Figure 3 is a structural diagram of the outer jacket of the solid hydrogen storage reactor of the present invention;

[0020] Figure 4 It is an overall structural diagram of the gas pipe of the solid hydrogen storage reactor of the present invention;

[0021] Figure 5 is a partial structural diagram of the trachea of ​​the present invention;

[0022] Figure 6 is a mass hydrogen storage density-time curve diagram of Example 1 of the present invention;

[0023] Figure 7 is a temperature-time curve diagram of Example 1 of the present invention;

[0024] Figure 8 is a mass hydrogen storage density-time curve diagram of Example 2 of the present invention;

[0025] Fig. 9 is a temperature-time curve diagram of Example 2 of the present invention;

[0026] Fig.10 is a mass hydrogen storage density-time curve diagram of Comparative Example 1 of the present invention;

[0027] Fig.11 It is a temperature-time curve diagram of Comparative Example 1 of the present invention;

[0028] Fig.12 is a mass hydrogen storage density-time curve diagram of Comparative Example 2 of the present invention;

[0029] Fig.13 It is a temperature-time curve diagram of Comparative Example 2 of the present invention.

[0030] Description of Reference Numerals

[0031] 1. Gas outlet; 2. Reactor jacket; 3. Reactor inner tube;

[0032] 4. Heat transfer fluid inlet; 5. Heat transfer fluid outlet; 6. Hydrogen inlet;

[0033] 7. Hydrogen outlet; 8. Air pipe; 9. Partition. DETAILED DESCRIPTION

[0034] 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.

[0035] In one aspect, the present invention provides a solid hydrogen storage reactor, the solid hydrogen storage reactor comprising: a reactor jacket 2, a reactor inner tube 3 filled with hydrogen storage material, and an air pipe 8 disposed inside the reactor inner tube 3;

[0036] The outer side of the gas pipe 8 is set to an inner spiral structure, and the outer side of the gas pipe 8 and the inner side of the reactor inner tube 3 form a spiral gas flow channel for the circulation of hydrogen;

[0037] The inner side of the reactor jacket 2 is configured as an outer spiral structure; the outer side of the reactor inner tube 3 is configured as an inner spiral structure; the inner side of the reactor jacket 2 and the outer side of the reactor inner tube 3 form a spiral heat transfer fluid flow channel for the circulation of the heat transfer fluid.

[0038] The present invention has no particular limitation on the specific location of the air pipe 8, as long as it is placed inside the reactor inner tube 3. Preferably, the air pipe 8 is placed at the center of the reactor inner tube 3.

[0039] According to the present invention, preferably, in the outer spiral structure of the reactor jacket 2, the depth of the threaded flange is 1-6 mm, preferably 2-5 mm.

[0040] By setting the depth of the threaded flange within the above range, the heat exchange area and flow distance can be increased, and the heat transfer fluid flows in a spiral structure, thereby significantly enhancing the heat exchange effect.

[0041] In the present invention, the threaded flange refers to a portion protruding from the inner side of the reactor jacket.

[0042] In the present invention, the thread profile can be a regular shape or an irregular shape, for example, an equilateral triangle, a trapezoid, a rectangle, a pentagon, a hexagon or other polygon, etc. Preferably, in the outer spiral structure of the reactor jacket 2, the thread profile is an equilateral triangle. By adopting this preferred embodiment, the heat conduction area is effectively increased while reducing stress concentration.

[0043] According to the present invention, preferably, in the external helical structure of the reactor jacket 2 , the axial distance between corresponding points on two adjacent thread profiles is 5-20% of the length of the reactor jacket 2 .

[0044] According to the present invention, preferably, in the external helical structure of the reactor jacket 2, the thread lead angle is 10-45°, preferably 20-30°.

[0045] In the present invention, the definition of thread lead angle is well known to those skilled in the art.

[0046] The present invention has no particular limitation on the number of turns of the thread in the external spiral structure of the reactor jacket 2 , and the number of turns can be appropriately adjusted according to the height of the reactor jacket 2 .

[0047] According to the present invention, preferably, in the inner spiral structure of the reactor inner tube 3, the depth of the thread groove is 50-70% of the thickness of the reactor inner tube 3 wall, preferably 60-70%.

[0048] By setting the depth of the thread groove within the above range, the heat exchange area and flow distance can be increased, and the heat transfer fluid flows in a spiral structure, and the heat exchange effect is significantly enhanced.

[0049] In the present invention, the thread groove refers to: a portion that is recessed on the outer side of the reactor inner tube.

[0050] In the present invention, the wall thickness of the reactor inner tube 3 refers to the wall thickness measured at any point on the outer wall of the reactor inner tube 3 where no spiral structure is provided.

[0051] In the present invention, in the internal spiral structure of the reactor inner tube 3, the thread profile can be a regular shape or an irregular shape, for example, an equilateral triangle, a trapezoid, a rectangle, a pentagon, a hexagon or other polygon, etc. Preferably, in the internal spiral structure of the reactor inner tube 3, the thread profile is an equilateral triangle. By adopting this preferred embodiment, the heat conduction area is effectively increased while reducing stress concentration.

[0052] According to the present invention, preferably, in the internal spiral structure of the reactor inner tube 3 , the axial distance between corresponding points on two adjacent thread profiles is 5-10% of the length of the reactor inner tube 3 .

[0053] According to the present invention, preferably, in the internal spiral structure of the reactor inner tube 3, the thread lead angle is 10-45°, preferably 20-30°.

[0054] The present invention has no particular limitation on the number of turns of the thread in the inner spiral structure of the reactor inner tube 3 , and it can be appropriately adjusted according to the height of the reactor inner tube 3 .

[0055] According to the present invention, preferably, the wall thickness of the reactor inner tube 3 is 10-15 mm.

[0056] For better heat exchange, preferably, one of the starting points of the inner spiral structure of the reactor inner tube 3 is on the same horizontal line as one of the starting points of the outer spiral structure of the reactor outer jacket 2; the depth of the thread groove in the inner spiral structure of the reactor inner tube 3 is equal to the depth of the thread flange in the outer spiral structure of the reactor outer jacket 2; the thread profile in the inner spiral structure of the reactor inner tube 3 is equal to the thread profile in the outer spiral structure of the reactor outer jacket 2; the axial distance between corresponding points on two adjacent thread profiles in the inner spiral structure of the reactor inner tube 3 is equal to the axial distance between corresponding points on two adjacent thread profiles in the outer spiral structure of the reactor outer jacket 2; the thread lead angle in the inner spiral structure of the reactor inner tube 3 is equal to the thread lead angle in the outer spiral structure of the reactor outer jacket 2.

[0057] According to the present invention, preferably, in the internal spiral structure of the air pipe 8 , the depth of the thread groove is 20-40% of the diameter of the air pipe 8 .

[0058] According to the present invention, preferably, in the inner spiral structure of the air pipe 8, the width of the thread groove is 1-6 mm.

[0059] In the present invention, in the internal spiral structure of the air pipe 8, the thread profile can be a regular shape or an irregular shape, for example, it can be an equilateral triangle, a trapezoid, a rectangle, or a polygon such as a pentagon or a hexagon, etc. Preferably, in the internal spiral structure of the air pipe 8, the thread profile is a rectangle. This preferred embodiment is used to shorten the hydrogen absorption and desorption time, increase the hydrogen absorption and desorption rate, and reduce the stress effect.

[0060] According to the present invention, preferably, in the internal spiral structure of the air pipe 8 , the axial distance between corresponding points on two adjacent thread profiles is 5-10% of the length of the air pipe 8 .

[0061] According to the present invention, preferably, in the internal spiral structure of the air pipe 8, the thread lead angle is 10-30°, preferably 20-30°.

[0062] According to the present invention, preferably, the diameter of the gas pipe 8 is 20-50% of the inner diameter of the reactor inner tube 3 .

[0063] In the present invention, the diameter of the air pipe refers to the diameter of the cross section of any point on the air pipe 8 where no spiral portion is provided.

[0064] The present invention has no particular limitation on the number of turns of the thread in the inner spiral structure of the air pipe 8 , and it can be appropriately adjusted according to the height of the air pipe 8 .

[0065] According to the present invention, preferably, the solid hydrogen storage reactor further comprises a hydrogen inlet 6 and a hydrogen outlet 7 arranged at both ends of the reactor inner tube 3 for the entry and exit of hydrogen.

[0066] The solid hydrogen storage reactor of the present invention can be placed horizontally (with the hydrogen inlet and the hydrogen outlet on the left and right sides) or vertically (with the hydrogen inlet and the hydrogen outlet on the upper and lower sides).

[0067] When the solid hydrogen storage reactor is placed vertically, in order to improve heat exchange efficiency, preferably, hydrogen enters from the bottom and exits from the top. That is, the hydrogen inlet 6 is located at the lower end of the reactor inner tube 3, and the hydrogen outlet 7 is located at the upper end of the reactor inner tube 3.

[0068] According to the present invention, preferably, a gas outlet hole 1 is further provided on the gas pipe 8 near the hydrogen inlet 6, so as to allow hydrogen to flow into the spiral gas flow channel from the gas outlet hole.

[0069] In order to ensure that hydrogen passes through the gas flow channel, preferably, the gas outlet 1 is located on the spiral structure inside the gas pipe 8, such as Figure 5 As shown ( Figure 5 Schematic diagram of the structure of the part below the partition plate 9 on the air pipe 8).

[0070] The present invention has no particular limitation on the number of the air outlet holes 1 , which may be one or more, as long as they are located on the spiral structure inside the air pipe 8 and below the partition plate 9 described below.

[0071] In order to enable hydrogen to pass from the gas outlet into the spiral gas flow channel, the present invention preferably sets the portion from the hydrogen inlet 6 to the gas outlet 1 in the gas pipe 8 as a hollow structure, and the remaining portion as a solid structure.

[0072] According to the present invention, preferably, a partition plate 9 is further provided on the gas pipe 8 to prevent the hydrogen storage material from blocking the gas outlet.

[0073] In order to better prevent the hydrogen storage material from clogging the gas outlet holes, preferably, the partition plate 9 is in seamless contact with the reactor inner tube 3 .

[0074] The present invention has no particular limitation on the location of the partition, and the partition can play a barrier role as long as it is located between the hydrogen storage material and the gas outlet 1 .

[0075] In order to allow hydrogen to better contact and react with the hydrogen storage material, preferably, the hydrogen storage material is placed in the reactor inner tube 3 in the form of pressed tablets.

[0076] Preferably, the hydrogen storage material pellets are passed through the gas pipe 8 .

[0077] The present invention has no particular limitation on the type of the hydrogen storage material, which can be a conventional choice in the art.

[0078] The present invention has no particular limitation on the size, number of hydrogen storage material tablets, and distance between adjacent hydrogen storage material tablets, and they can be appropriately selected according to different application scenarios and actual hydrogen storage requirements.

[0079] According to the present invention, preferably, the solid hydrogen storage reactor further comprises a heat transfer fluid inlet 4 and a heat transfer fluid outlet 5 arranged on the reactor jacket 2 for the entry and exit of the heat transfer fluid.

[0080] In the present invention, the heat transfer fluid inlet 4 and the heat transfer fluid outlet 5 can be on the same side of the reactor jacket 2 or on different sides of the reactor jacket 2. Preferably, the heat transfer fluid inlet 4 and the heat transfer fluid outlet 5 are located on different sides of the reactor jacket 2.

[0081] In the present invention, the heat transfer fluid inlet 4 is located on the left side of the reactor jacket 2, and the heat transfer fluid outlet 5 is located on the right side of the reactor jacket 2; or, the heat transfer fluid inlet 4 is located on the right side of the reactor jacket 2, and the heat transfer fluid outlet 5 is located on the left side of the reactor jacket 2.

[0082] When the solid hydrogen storage reactor is placed vertically, in order to improve the heat exchange efficiency, preferably, the heat transfer fluid enters from the bottom and exits from the top. The heat transfer fluid inlet 4 is located at the bottom of the reactor jacket 2, and the heat transfer fluid outlet 5 is located at the top of the reactor jacket 2.

[0083] The present invention has a wide range of choices for the type of 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.

[0084] According to the present invention, preferably, the inner diameter of the reactor jacket 2 is 10-30 mm larger than the outer diameter of the reactor inner tube 3. With this preferred embodiment, while ensuring an appropriate amount of heat transfer fluid, the threads between the jacket and the inner tube can form a spiral flow channel, facilitating the spiral flow of the heat transfer fluid and increasing the heat exchange effect.

[0085] In the present invention, the inner diameter of the reactor jacket 2 refers to the diameter of the cross section of any point on the inner wall of the reactor jacket 2 where the spiral portion is arranged.

[0086] The outer diameter of the reactor inner tube 3 refers to the diameter of the cross section at any point on the outer wall of the reactor inner tube 3 where no spiral portion is provided.

[0087] According to the present invention, preferably, the height of the reactor jacket 2 is 50-200 mm shorter than the height of the reactor inner tube 3. This preferred embodiment prevents the hydrogen storage material from accumulating and expanding at the hydrogen inlet and outlet.

[0088] In the present invention, the height difference between the two ends of the reactor jacket 2 and the two ends corresponding to the reactor inner tube 3 can be the same or different. Preferably, the height difference between the two ends of the reactor jacket 2 and the two ends corresponding to the reactor inner tube 3 is the same.

[0089] It can be understood that when the height of the reactor jacket 2 is 100 mm shorter than the height of the reactor inner tube 3, the lower end of the reactor jacket is 50 mm shorter than the lower end of the reactor inner tube, and the upper end of the reactor jacket is 50 mm shorter than the upper end of the reactor inner tube.

[0090] The present invention has no particular limitation on the size of the reactor inner tube 3, which can be appropriately selected according to the hydrogen storage capacity.

[0091] According to the present invention, preferably, both ends of the reactor inner tube 3 are independently configured as spiral structures for sealing the pipe joints. This is a conventional configuration in the art and will not be described in detail in the present invention.

[0092] The present invention has no particular limitation on the specific connection method between the reactor jacket 2 and the reactor inner tube 3, as long as the above conditions can be met. Preferably, the reactor jacket 2 is sleeved outside the reactor inner tube 3.

[0093] Preferably, two ends of the reactor jacket 2 are abutted by nuts at two ends of the reactor inner tube 3 .

[0094] In the present invention, the reactor gas pipe 8 and the reactor inner tube 3 can be connected according to conventional methods in the art. Preferably, the reactor gas pipe 8 and the reactor inner tube 3 are connected by threads.

[0095] According to a particularly preferred embodiment of the present invention, a solid hydrogen storage reactor comprises: a reactor jacket 2, a reactor inner tube 3 filled with hydrogen storage material, and an air pipe 8 disposed inside the reactor inner tube 3;

[0096] The outer side of the gas pipe 8 is set to an inner spiral structure, and the outer side of the gas pipe 8 and the inner side of the reactor inner tube 3 form a spiral gas flow channel for the circulation of hydrogen;

[0097] The inner side of the reactor jacket 2 is configured as an outer spiral structure; the outer side of the reactor inner tube 3 is configured as an inner spiral structure, and the inner side of the reactor jacket 2 and the outer side of the reactor inner tube 3 form a spiral heat transfer fluid flow channel for the circulation of the heat transfer fluid;

[0098] In the external spiral structure of the reactor jacket 2, the thread profile is an equilateral triangle;

[0099] In the outer spiral structure of the reactor jacket 2, the thread lead angle is 20-30°;

[0100] In the internal spiral structure of the reactor inner tube 3, the thread profile is an equilateral triangle;

[0101] In the internal spiral structure of the reactor inner tube 3, the thread lead angle is 20-30°.

[0102] The adoption of the above preferred implementation manner is more conducive to improving the heat exchange effect.

[0103] 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:

[0104] During the hydrogen storage process, hydrogen is fed into the spiral gas flow channel between the inner side of the reactor inner tube and the outer side of the gas pipe to react with the hydrogen storage material to absorb hydrogen, and a heat transfer fluid is fed into the spiral heat transfer fluid flow channel in the cavity between the outer side of the reactor inner tube and the inner side of the reactor jacket to absorb heat generated by the hydrogen absorption reaction.

[0105] During the dehydrogenation process, the hydrogen storage material adsorbing hydrogen undergoes a desorption reaction, and the heat transfer fluid is fed into the heat transfer fluid flow channel to provide heat for the desorption reaction of the hydrogen.

[0106] The pressures mentioned in the following hydrogen absorption reaction and desorption reaction of the present invention are all gauge pressures.

[0107] According to the present invention, preferably, in the hydrogen storage process, the conditions of the hydrogen absorption reaction include: a temperature of 10-60° C. and a pressure of 1-5 MPa.

[0108] The present invention has no particular limitation on the flow rate of the heat transfer fluid in the hydrogen storage process, and can be appropriately selected according to the hydrogen absorption rate (determined by the reaction conditions), and the present invention does not impose any limitation thereon.

[0109] According to the present invention, preferably, in the process of dehydrogenation, the conditions of the desorption reaction include: a temperature of 60-200° C. and a pressure of 0-0.5 MPa.

[0110] According to the present invention, preferably, during the dehydrogenation process, the temperature of the heat transfer fluid is 60-300°C.

[0111] 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 (determined by the reaction conditions), and the present invention does not impose any limitation thereon.

[0112] 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.

[0113] The present invention will be described in detail below through examples.

[0114] Example 1

[0115] A solid hydrogen storage reactor, such as Figure 1-4 As shown, the structure is as follows:

[0116] The hydrogen storage reactor includes a reactor jacket 2, a reactor inner tube 3 filled with hydrogen storage material, an air pipe 8 placed at the center of the reactor inner tube 3, a hydrogen inlet 6 and a hydrogen outlet 7 arranged at both ends of the reactor inner tube 3, and a heat transfer fluid inlet 4 and a heat transfer fluid outlet 5 arranged on the reactor jacket 2 and located on different sides.

[0117] The outer side of the reactor inner tube 3 is set as an inner spiral structure, and the inner side of the reactor jacket 2 is set as an outer spiral structure. The inner side of the reactor jacket 2 and the outer side of the reactor inner tube 3 form a spiral heat transfer fluid flow channel. One of the starting points of the inner spiral structure of the reactor inner tube 3 is on the same horizontal line as one of the starting points of the outer spiral structure of the reactor jacket 2. In the inner spiral structure of the reactor inner tube 3, the thread groove depth is 6mm, the thread tooth profile is an equilateral triangle, the axial distance between the corresponding points on the two adjacent thread tooth profiles is 15mm, and the thread lead angle is 20°; the inner side of the reactor jacket 2 is set as an outer spiral structure, the thread flange depth is 6mm, the thread tooth profile is an equilateral triangle, the axial distance between the corresponding points on the two adjacent thread tooth profiles is 15mm, and the thread lead angle is 20°.

[0118] The outer side of the air pipe 8 is set to an internal spiral structure, the thread groove depth is 1.6mm, the thread width is 1.6mm, the thread tooth profile is rectangular, the axial distance between corresponding points on two adjacent thread tooth profiles is 5% of the height of the air pipe 3, and the thread lead angle is 20°; the outer side of the air pipe 8 and the inner side of the reactor inner tube 3 form a spiral gas flow channel.

[0119] The gas pipe 8 is provided with a gas outlet 1 at the starting point of the internal thread structure near the hydrogen inlet. The portion from the hydrogen inlet 6 to the gas outlet 1 in the gas pipe 8 is a hollow structure, and the remaining portion is a solid structure. 2 The alloy pressed sheet stack passes through the air pipe 8 and is placed in the middle of the air pipe 8, and there is no gap between the alloy pressed sheet and the inner wall of the reactor inner tube 3. 2 A partition plate 9 is also arranged between the alloy pressed sheet and the gas outlet 1. The partition plate 9 is in seamless contact with the inner wall of the reactor. The distance between the gas outlet and the partition plate 9 is 5 mm.

[0120] The reactor inner tube 3 has an outer diameter of 60 mm, a wall thickness of 10 mm, and a length of 300 mm. The reactor outer jacket 2 has an inner diameter of 80 mm and an outer diameter of 100 mm. The two ends of the reactor outer jacket 2 are 50 mm shorter than the corresponding two ends of the reactor inner tube. The diameter of the air pipe 8 is 8 mm and the length is 300 mm.

[0121] The reactor jacket 2 is sleeved on the outside of the reactor inner tube 3; the two ends of the reactor jacket 2 are butted by nuts at the two ends of the reactor inner tube 3. The reactor gas pipe 8 is connected to the reactor inner tube 3 by threads. The two ends of the reactor inner tube 3 are independently set as spiral structures for pipe joint sealing.

[0122] During the hydrogen storage process, hydrogen is fed into the gas pipe 8 from the hydrogen inlet 6 at the lower end of the reactor inner tube, and the gas flow channel from the gas outlet 1 to the outside of the gas pipe 8 and the inside of the reactor inner tube undergoes hydrogen absorption reaction with the hydrogen storage material. The hydrogen absorption temperature is 20°C and the hydrogen absorption pressure is 3MPa. Deionized water is fed into the heat transfer fluid flow channel between the outside of the reactor inner tube and the inside of the reactor jacket from the heat transfer fluid inlet at the bottom of the reactor jacket to absorb the heat generated by the hydrogen absorption reaction.

[0123] During the dehydrogenation process, the hydrogen storage material adsorbed with hydrogen undergoes a desorption reaction at an initial temperature of 60°C and a constant outlet pressure of 0.1MPa, and deionized water at 65°C is continuously introduced into the heat transfer fluid flow channel at a flow rate of 1.2L / min to provide the heat required for desorption. In the above process, the temperature compensation speed is fast, and the heat required for desorption can be quickly maintained, which is conducive to the dehydrogenation process.

[0124] During hydrogen storage, Figure 6 As shown, it can be seen that the maximum hydrogen absorption rate is reached at about 1000 s, and the maximum mass hydrogen storage density can reach 1.55%, which shows that the solid hydrogen storage reaction of the present invention has a good hydrogen storage effect.

[0125] During hydrogen storage, Figure 7 As shown, it can be seen that the temperature of the inner tube of the reactor rises rapidly within 500 seconds to reach 55°C, and then drops to room temperature in about 2000 seconds under the control of the oil bath temperature, achieving rapid cooling, indicating that the solid hydrogen storage reactor of the present invention has good heat exchange effect.

[0126] Example 2

[0127] A solid hydrogen storage reactor, such as Figure 1-4 As shown, the structure is as follows:

[0128] The hydrogen storage reactor includes a reactor jacket 2, a reactor inner tube 3 filled with hydrogen storage material, an air pipe 8 placed at the center of the reactor inner tube 3, a hydrogen inlet 6 and a hydrogen outlet 7 arranged at both ends of the reactor inner tube 3, and a heat transfer fluid inlet 4 and a heat transfer fluid outlet 5 arranged on the reactor jacket 2 and located on different sides.

[0129] The outer side of the reactor inner tube 3 is set as an inner spiral structure, and the inner side of the reactor jacket 2 is set as an outer spiral structure. The inner side of the reactor jacket 2 and the outer side of the reactor inner tube 3 form a spiral heat transfer fluid flow channel. One of the starting points of the inner spiral structure of the reactor inner tube 3 is on the same horizontal line as one of the starting points of the outer spiral structure of the reactor jacket 2. The outer side of the reactor inner tube 3 is set as an inner spiral structure, the thread groove depth is 10.5mm, the thread tooth profile is an equilateral triangle, the axial distance between the corresponding points on the two adjacent thread tooth profiles is 20mm, and the thread lead angle is 30°; the inner side of the reactor jacket 2 is set as an outer spiral structure, the thread flange depth is 10.5mm, the thread tooth profile is an equilateral triangle, the axial distance between the corresponding points on the two adjacent thread tooth profiles is 20mm, and the thread lead angle is 30°.

[0130] The outer side of the air pipe 8 is set to an internal spiral structure, the thread groove depth is 6 mm, the thread width is 6 mm, the thread tooth profile is rectangular, the axial distance between corresponding points on two adjacent thread tooth profiles is 10% of the height of the air pipe 3, and the thread lead angle is 30°; the outer side of the air pipe 8 and the inner side of the reactor inner tube 3 form a spiral gas flow channel.

[0131] The gas pipe 8 is provided with a gas outlet 1 at the starting point of the internal thread structure near the hydrogen inlet. The portion from the hydrogen inlet 6 to the gas outlet 1 in the gas pipe 8 is a hollow structure, and the remaining portion is a solid structure. 2 The alloy pressed sheet stack passes through the air pipe 8 and is placed in the middle of the air pipe 8, and there is no gap between the alloy pressed sheet and the inner wall of the reactor inner tube 3. 2 A partition plate 9 is also arranged between the alloy pressed sheet and the gas outlet 1. The partition plate 9 is in seamless contact with the inner wall of the reactor. The distance between the gas outlet and the partition plate 9 is 5 mm.

[0132] The reactor inner tube 3 has an outer diameter of 60 mm, a wall thickness of 15 mm, and a length of 300 mm. The reactor outer jacket 2 has an inner diameter of 80 mm and an outer diameter of 110 mm. The two ends of the reactor outer jacket 2 are 50 mm shorter than the corresponding two ends of the reactor inner tube. The diameter of the air pipe 8 is 15 mm and the length is 300 mm.

[0133] The reactor jacket 2 is sleeved on the outside of the reactor inner tube 3; the two ends of the reactor jacket 2 are butted by nuts at the two ends of the reactor inner tube 3. The reactor gas pipe 8 is connected to the reactor inner tube 3 by threads. The two ends of the reactor inner tube 3 are independently set as spiral structures for pipe joint sealing.

[0134] During the hydrogen storage process, hydrogen is fed into the reactor gas pipe 8 from the hydrogen inlet 6 at the lower end of the reactor inner tube, and the gas flow channel from the gas outlet 1 to the outside of the gas pipe 8 and the inside of the reactor inner tube undergoes hydrogen absorption reaction with the hydrogen storage material. The hydrogen absorption temperature is 14°C and the hydrogen absorption pressure is 3MPa. Deionized water is fed into the heat transfer fluid flow channel between the outside of the reactor inner tube and the inside of the reactor jacket from the heat transfer fluid inlet at the lower part of the reactor jacket to absorb the heat generated by the hydrogen absorption reaction.

[0135] During the dehydrogenation process, the hydrogen storage material adsorbed with hydrogen undergoes a desorption reaction at an initial temperature of 60°C and a constant outlet pressure of 0.1MPa, and deionized water at 65°C is continuously introduced into the heat transfer fluid flow channel at a flow rate of 1.2L / min to provide the heat required for desorption. In the above process, the temperature compensation speed is fast, and the heat required for desorption can be quickly maintained, which is conducive to the dehydrogenation process.

[0136] During hydrogen storage, Figure 8 As shown, it can be seen that the maximum hydrogen absorption rate is reached at about 1000 s, and the maximum mass hydrogen storage density can reach 1.8%, which shows that the solid hydrogen storage reaction of the present invention has a good hydrogen storage effect.

[0137] During hydrogen storage, Fig. 9 As shown, it can be seen that the temperature of the inner tube of the reactor rises rapidly within 500 seconds to reach 55°C, and then drops to room temperature in about 2000 seconds under the control of the oil bath temperature, achieving rapid cooling, indicating that the solid hydrogen storage reactor of the present invention has good heat exchange effect.

[0138] Comparative Example 1

[0139] A solid hydrogen storage reactor with a direct-current heat exchange structure is used, that is, the method of Example 1 is followed, except that the inner side of the reactor jacket 2 is not configured as an outer spiral structure; the outer side of the reactor inner tube 3 is not configured as an inner spiral structure.

[0140] During hydrogen storage, Fig.10 As shown, it can be seen that the hydrogen absorption rate of the solid hydrogen storage reactor of Comparative Example 1 slows down, reaching the maximum hydrogen absorption rate at around 1750s, and the maximum mass hydrogen release density also decreases to 1.3%.

[0141] During hydrogen storage, Fig.11As shown, it can be seen that the solid hydrogen storage reactor of Comparative Example 1 has an insignificant heat transfer effect. After absorbing hydrogen, the temperature in the reactor rises rapidly, and then drops slowly, dropping to the oil bath setting temperature at around 3000s. The oil bath temperature is not well transferred to the reactor inner tube. The heat exchange effect is poor.

[0142] During the hydrogen desorption process, due to poor heat transfer and slow temperature compensation, the temperature inside the reactor is low, which hinders the hydrogen desorption process.

[0143] Comparative Example 2

[0144] The method of Example 1 is followed, except that the inner side of the reactor jacket 2 is configured as an inner spiral structure; the outer side of the reactor inner tube 3 is configured as an outer spiral structure. The inner spiral structure of the inner side of the reactor jacket 2 is the same as the inner spiral structure of the outer side of the reactor inner tube in Example 1; the outer spiral structure of the outer side of the reactor inner tube 3 is the same as the outer spiral structure of the inner side of the reactor jacket in Example 1.

[0145] During hydrogen storage, Fig.12 As shown in the figure, it can be seen that the hydrogen absorption rate slows down due to the low heat transfer efficiency. The maximum hydrogen absorption rate is reached at around 2500s, and the maximum mass hydrogen storage density is 1.35% at 5500s.

[0146] During hydrogen storage, Fig.13 As shown in the figure, it can be seen that the temperature drops to the oil bath setting temperature at around 2500s, and the temperature rises for a short period of time during the cooling process. This shows that the heat transfer effect is still not good.

[0147] During the hydrogen desorption process, due to poor heat transfer and slow temperature compensation, the temperature inside the reactor is low, which hinders the hydrogen desorption process.

[0148] 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 reactor outer shell (2), a reactor inner tube (3) filled with hydrogen storage material, and an air pipe (8) disposed inside the reactor inner tube (3); The outer side of the gas pipe (8) is configured as an inner spiral structure, and the outer side of the gas pipe (8) and the inner side of the reactor inner tube (3) form a spiral gas flow channel for the circulation of hydrogen; The inner side of the reactor jacket (2) is configured as an outer spiral structure; the outer side of the reactor inner tube (3) is configured as an inner spiral structure; the inner side of the reactor jacket (2) and the outer side of the reactor inner tube (3) form a spiral heat transfer fluid flow channel for the circulation of the heat transfer fluid.

2. The solid hydrogen storage reactor according to claim 1, wherein: In the external spiral structure of the reactor jacket (2), the depth of the threaded flange is 1-6 mm, preferably 2-5 mm; Preferably, in the external spiral structure of the reactor jacket (2), the thread profile is an equilateral triangle; Preferably, in the external spiral structure of the reactor jacket (2), the axial distance between corresponding points on two adjacent thread profiles is 5-20% of the length of the reactor jacket (2); Preferably, in the external helical structure of the reactor jacket (2), the thread lead angle is 10-45°, preferably 20-30°.

3. The solid hydrogen storage reactor according to claim 1, wherein: In the internal spiral structure of the reactor inner tube (3), the depth of the thread groove is 50-70% of the thickness of the reactor inner tube (3), preferably 60-70%; Preferably, in the internal spiral structure of the reactor inner tube (3), the thread profile is an equilateral triangle; Preferably, in the internal spiral structure of the reactor inner tube (3), the axial distance between corresponding points on two adjacent thread profiles is 5-10% of the length of the reactor inner tube (3); Preferably, in the internal spiral structure of the reactor inner tube (3), the thread lead angle is 10-45°, preferably 20-30°; Preferably, the wall thickness of the reactor inner tube (3) is 10-15 mm.

4. The solid hydrogen storage reactor according to any one of claims 1 to 3, wherein: In the internal spiral structure of the trachea (8), the depth of the thread groove is 20-40% of the diameter of the trachea (8); Preferably, in the internal spiral structure of the trachea (8), the thread groove width is 1-6 mm; Preferably, in the internal spiral structure of the air pipe (8), the thread profile is rectangular; Preferably, in the internal spiral structure of the trachea (8), the axial distance between corresponding points on two adjacent thread profiles is 5-10% of the length of the trachea (8); Preferably, in the internal spiral structure of the air pipe (8), the thread lead angle is 10-30°; Preferably, the diameter of the gas pipe (8) is 20-50% of the inner diameter of the reactor inner tube (3).

5. The solid hydrogen storage reactor according to any one of claims 1 to 4, wherein: The solid hydrogen storage reactor further comprises a hydrogen inlet (6) and a hydrogen outlet (7) arranged at both ends of the reactor inner tube (3) for the entry and exit of hydrogen; Preferably, the gas pipe (8) is also provided with a gas outlet hole (1) near the hydrogen inlet (6), so that the hydrogen can flow into the spiral gas flow channel from the gas outlet hole (1); Preferably, the air outlet (1) is located on the spiral structure inside the air pipe (8); Preferably, a partition plate (9) is also provided on the gas pipe (8) to prevent the hydrogen storage material from blocking the gas outlet hole; Preferably, the hydrogen storage material is placed in the reactor inner tube (3) in the form of a compressed tablet; Preferably, the hydrogen storage material pellets are passed through the gas tube (8).

6. The solid hydrogen storage reactor according to any one of claims 1 to 5, wherein: The solid hydrogen storage reactor further comprises a heat transfer fluid inlet (4) and a heat transfer fluid outlet (5) arranged on the reactor jacket (2) for the heat transfer fluid to enter and exit.

7. The solid hydrogen storage reactor according to any one of claims 1 to 6, wherein: The inner diameter of the reactor jacket (2) is 10-30 mm larger than the outer diameter of the reactor inner tube (3); Preferably, the length of the reactor jacket (2) is 50-200 mm shorter than the length of the reactor inner tube (3).

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 spiral gas flow channel between the inner side of the reactor inner tube and the outer side of the gas pipe to react with the hydrogen storage material to absorb hydrogen, and a heat transfer fluid is fed into the spiral heat transfer fluid flow channel between the outer side of the reactor inner tube and the inner side of the reactor jacket to absorb heat generated by the hydrogen absorption reaction. During the dehydrogenation process, the hydrogen storage material adsorbing hydrogen undergoes a desorption reaction, and the heat transfer fluid is fed into the heat transfer fluid flow channel to provide heat for the desorption reaction of the hydrogen.

9. The method according to claim 8, wherein: During the hydrogen storage process, the conditions for the hydrogen absorption reaction include: a temperature of 10-60° C. and a pressure of 1-5 MPa.

10. The method according to claim 8, wherein: During the hydrogen release process, the conditions of the desorption reaction include: a temperature of 60-200° C. and a pressure of 0-0.5 MPa; Preferably, during the dehydrogenation process, the temperature of the heat transfer fluid is 60-300° C.; preferably, the heat transfer fluid is water, ethylene glycol or heat transfer oil.

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