Mobile hydrogen liquefaction, storage and transfer integrated device

Abstract

The present invention discloses a movable hydrogen liquefaction, storage and transfer integrated device, relates to the field of hydrogen energy storage technology, and is intended to solve the problem that current equipment cannot achieve lossless storage of liquid hydrogen, cannot achieve lossless precooling, and cannot be portable and ready for use. A movable hydrogen liquefaction, storage and transfer integrated device comprises an external process pipeline, the external process pipeline comprises an air intake pipeline and a circulation loop, the air intake pipeline is connected with a liquid nitrogen precooling module, the liquid nitrogen precooling module is connected with a liquid hydrogen production tank, the liquid hydrogen production tank comprises a storage area and a refrigeration area, and the storage area is connected with a liquid hydrogen storage tank via a pipeline. The device of the present invention can carry out lossless storage of liquid hydrogen, can achieve rapid precooling, reduce the waste of hydrogen, and achieve the ready-to-use of liquid hydrogen.

Description

Technical Field

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

[0002] Currently, large-scale hydrogen liquefaction facilities primarily utilize two methods: direct hydrogen expansion refrigeration based on the Claude cycle, and liquefying hydrogen using a helium expansion refrigeration cycle. Both methods rely on turbine expanders, which are the primary source of cooling energy for the system to reach the 20K temperature range. Turbine expansion refrigeration systems are 50%-70% more efficient than traditional JT throttling systems, and their mature technology makes them the mainstream choice for large-scale hydrogen liquefaction systems. Currently, most small-scale hydrogen liquefaction systems are based on GM refrigerators or liquid nitrogen combined with GM refrigerators. Existing technologies do not address the issues of lossless hydrogen storage, liquid hydrogen transfer, portability, or pre-cooling of the device.

[0003] The Chinese patent with publication number CN118669712A specifically relates to a zero-emission liquid hydrogen production and storage system and method. Although it involves the production and storage of liquid hydrogen, it does not involve how to reduce the loss of liquid hydrogen reserves and cannot solve the above-mentioned problems. Summary of the Invention

[0004] The present invention solves the problems that current equipment cannot achieve lossless storage of liquid hydrogen, lossless pre-cooling, and mobility for immediate use. It proposes a movable integrated hydrogen liquefaction, storage, and transfer device that can achieve lossless storage of liquid hydrogen, rapid pre-cooling, reduce hydrogen waste, and enable immediate use of liquid hydrogen.

[0005] In order to achieve the above-mentioned objectives, the present invention adopts the following technical solution: a movable integrated hydrogen liquefaction, storage and transfer device, including an external process pipeline, the external process pipeline including an air inlet pipeline and a circulation loop, the air inlet pipeline is connected to a liquid nitrogen pre-cooling module, the liquid nitrogen pre-cooling module is connected to a liquid hydrogen production tank, the liquid hydrogen production tank includes a storage area and a refrigeration area, and the storage area is connected to a liquid hydrogen storage tank through a pipeline.

[0006] The device of this technical solution mainly includes external process pipelines, liquid nitrogen pre-cooling modules, liquid hydrogen production tanks and liquid hydrogen storage tanks, which complete the processes of gas replacement, system pre-cooling, hydrogen liquefaction and liquid hydrogen transfer in sequence, thereby realizing lossless pre-cooling and lossless storage. The liquid hydrogen storage tank is movable, which can be separated from the entire system and has its own mobile device to realize external liquid hydrogen filling. It can realize liquid hydrogen filling of equipment that cannot be close to the small hydrogen liquefaction device, further realizing the hydrogen supply function for small and micro liquid hydrogen usage scenarios.

[0007] The present invention is further configured as follows: the refrigeration area includes several refrigeration modules connected end to end, the refrigeration module includes a low-temperature refrigerator and a heat exchanger, the cold head of the low-temperature refrigerator is connected to one end of the heat exchanger, and the other end of the heat exchanger is connected to the normal-para-hydrogen converter.

[0008] In the refrigeration area of the present technical solution, multiple refrigeration modules are connected end to end. One of the refrigeration modules is mainly composed of a low-temperature refrigerator and a heat exchanger, and the last heat exchanger is connected to the heat exchanger arranged in the storage area.

[0009] The present invention is further configured as follows: the storage area includes an open heat exchanger and a fifth normal-para hydrogen converter connected to the open heat exchanger, the open heat exchanger is exposed in the storage area, and the open heat exchanger is connected to a fifth low-temperature refrigerator.

[0010] In this technical solution, the open heat exchanger is welded to the cold head of the fifth cryogenic refrigerator and placed in the storage area, thereby realizing lossless storage of the liquid hydrogen production tank while liquefying the gaseous hydrogen in the gas phase space.

[0011] The present invention is further configured as follows: the liquid hydrogen storage tank includes a mobile liquid hydrogen storage and filling tank, one end of the mobile liquid hydrogen storage and filling tank is connected to a liquid hydrogen transfer hose, and the other end of the mobile liquid hydrogen storage and filling tank is connected to a liquid hydrogen vacuum socket pipe.

[0012] In this technical solution, the mobile liquid hydrogen storage and filling tanks are connected to the liquid hydrogen production tanks through liquid hydrogen vacuum socket pipes and liquid hydrogen transfer hoses, respectively, which can be quickly disassembled and installed.

[0013] The present invention is further configured as follows: the liquid nitrogen pre-cooling module includes a liquid nitrogen pre-cooling storage tank, a first normal-para hydrogen converter is provided in the liquid nitrogen pre-cooling storage tank, one end of the first normal-para hydrogen converter is connected to the air intake pipeline, and the other end of the first normal-para hydrogen converter is connected to the liquid hydrogen production tank.

[0014] In this technical solution, the first para-hydrogen converter is installed inside the liquid nitrogen pre-cooling tank and immersed in liquid nitrogen. After the hydrogen flows into the liquid nitrogen pre-cooling tank, it exchanges heat with the liquid nitrogen and completes the catalytic conversion of para-hydrogen in the liquid nitrogen temperature zone. The hydrogen after heat exchange flows out.

[0015] The present invention is further configured as follows: the air inlet pipeline includes a raw hydrogen unloading hose, the raw hydrogen unloading hose is connected to a pressure reducing valve, the other end of the pressure reducing valve is connected to a flow regulating valve, the other end of the flow regulating valve is connected to a hydrogen flow meter, and the other end of the hydrogen flow meter is connected to a liquid nitrogen pre-cooling module.

[0016] In this technical solution, a first stop valve and a second stop valve are further provided between the raw hydrogen gas unloading hose and the pressure reducing valve, and the first stop valve is connected to the purge nitrogen gas source.

[0017] The present invention is further configured as follows: the circulation loop includes a low-temperature hydrogen circulation fan connected to the liquid hydrogen storage tank, and the other end of the low-temperature hydrogen circulation fan is connected to the liquid hydrogen production tank.

[0018] In this technical solution, the circulation loop also includes several stop valves and a vacuum pump.

[0019] The present invention is further configured such that: the mobile liquid hydrogen storage and filling tank is further connected to a first safety valve and a ninth stop valve respectively, and the first safety valve and the ninth stop valve are both connected to a first flame arrester.

[0020] The present invention is further configured as follows: the liquid hydrogen vacuum bell-and-spigot pipe includes a liquid hydrogen vacuum bell-and-spigot pipe male head and a liquid hydrogen vacuum bell-and-spigot pipe female head, and the liquid hydrogen vacuum bell-and-spigot pipe female head and the liquid hydrogen vacuum bell-and-spigot pipe male head are embedded and connected and fixed with a fixing piece.

[0021] In this technical solution, the male and female ends of the vacuum bell-and-spigot pipe can be connected by bolts or snaps, which can achieve quick disassembly and installation.

[0022] The present invention is further configured as follows: one end of the liquid hydrogen transfer hose 30 is connected to the pipeline where the eighth shut-off valve 31 is located through a flange, and the other end of the liquid hydrogen transfer hose 30 is connected to the pipeline where the seventh shut-off valve 29 is located through a flange.

[0023] In this technical solution, the liquid hydrogen transfer hose is connected to the flange of the inlet pipe of the eighth shut-off valve through a flange, which can be quickly disassembled and installed.

[0024] The technical solution of the present invention can bring the following beneficial effects:

[0025] The present invention relates to a mobile hydrogen liquefaction, storage and transfer integrated device, which can store liquid hydrogen without loss, achieve rapid pre-cooling, reduce hydrogen waste, and realize on-demand use of liquid hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a schematic diagram of the principle of the mobile hydrogen liquefaction, storage and transfer integrated device of the present application.

[0027] Figure 2 This is a schematic diagram of the liquid hydrogen production tank of the mobile hydrogen liquefaction, storage and transfer integrated device of the present application.

[0028] Figure 3 It is a partial cross-sectional view of the liquid hydrogen production tank of the movable hydrogen liquefaction, storage and transfer integrated device of the present application.

[0029] Figure 4 This is a schematic diagram of the interior of the liquid hydrogen production tank of the mobile hydrogen liquefaction, storage and transfer integrated device of the present application.

[0030] Figure 5 This is a schematic diagram of the liquid hydrogen vacuum bell-and-spigot pipe after installation of the movable hydrogen liquefaction, storage and transfer integrated device of the present application.

[0031] Figure 6 This is a schematic diagram of the present invention's mobile hydrogen liquefaction, storage and transfer integrated device before installation.

[0032] Figure 7 This is a schematic diagram of the connection of the liquid hydrogen transfer hose of the mobile hydrogen liquefaction, storage and transfer integrated device of the present application.

[0033] Figure 8 It is a schematic diagram of the mobile liquid hydrogen storage and filling tank of the mobile hydrogen liquefaction, storage and transfer integrated device of the present application. Description of the drawings:

[0035] 1. Raw hydrogen gas unloading hose 2, first stop valve 3, second stop valve 4, pressure reducing valve 5, flow regulating valve 6, hydrogen flowmeter 7, liquid nitrogen pre-cooling storage tank 8, first normal-para hydrogen converter 9, third stop valve 10, first heat exchanger 11, second normal-para hydrogen converter 12, second heat exchanger 13, third normal-para hydrogen converter 14, third heat exchanger 15, fourth normal-para hydrogen converter 16, fourth heat exchanger 17, open heat exchanger 18, fifth normal-para hydrogen converter 19, first cryogenic refrigerator 20, second cryogenic refrigerator 21, third cryogenic refrigerator 22, fourth cryogenic refrigerator 23, fifth cryogenic refrigerator 24, fourth stop valve 25, fifth stop valve 26, liquid hydrogen vacuum socket Pipe 27, sixth stop valve 28, mobile liquid hydrogen storage and filling tank 29, seventh stop valve 30, liquid hydrogen transfer hose 31, eighth stop valve 32, ninth stop valve 33, first safety valve 34, first flame arrester 35, tenth stop valve 36, eleventh stop valve 37, twelfth stop valve 38, low-temperature hydrogen circulation fan 39, thirteenth stop valve 40, second safety valve 41, fourteenth stop valve 42, fifteenth stop valve 43, third safety valve 44, second flame arrester 45, vacuum pump 46, storage area 47, refrigeration area 48, liquid hydrogen production tank 49, liquid hydrogen production tank partition 26-1, liquid hydrogen vacuum bell-and-spigot pipe female end 26-2, liquid hydrogen vacuum bell-and-spigot pipe male end. DETAILED DESCRIPTION

[0036] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific implementation method described herein is only an optimal embodiment of the present invention, which is only used to explain the present invention and does not limit the scope of protection of the present invention. All other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0037] Hydrogen has played an increasingly important role in the construction of low-carbon energy systems in recent years due to its clean, efficient, high energy density, and easy energy conversion. The currently widely used room-temperature, high-pressure storage and transportation methods, due to their low transportation efficiency, high transportation costs, and long refueling and refilling times, can no longer meet the needs of large-scale market applications of hydrogen energy in the future. Low-temperature storage and transportation technology, however, offers advantages such as high transportation efficiency, high safety, good hydrogen purity retention, low long-distance transportation costs, and short refueling and refilling times. It is expected to become a core supporting technology for the storage and transportation links of the hydrogen energy industry chain, and will have a decisive impact on the industrialization of hydrogen energy. Liquid hydrogen is a liquid obtained by cooling hydrogen gas to a temperature of -253°C, so hydrogen liquefaction equipment is required to liquefy gaseous hydrogen into liquid hydrogen.

[0038] Currently, large-scale hydrogen liquefaction plants primarily utilize two methods: direct hydrogen expansion refrigeration based on the Claude cycle, and liquefying hydrogen using a helium expansion refrigeration cycle. Both rely on a turbine expander, which is the primary source of cooling energy required to reach the 20K temperature range. Turbine expansion refrigeration systems offer high efficiency, 50%-70% higher than traditional JT throttling systems. With mature technology, they are the mainstream choice for large-scale hydrogen liquefaction systems.

[0039] Most of the current small-scale hydrogen liquefaction systems are based on GM refrigerators or liquid nitrogen + GM refrigerators, and the existing technology does not mention the issues of lossless hydrogen storage, liquid hydrogen transfer, portability, and device pre-cooling.

[0040] The existing technology mainly has the following shortcomings:

[0041] 1. Currently, large-scale hydrogen liquefaction devices are all turbine expansion refrigeration systems. Due to their large size and expensive initial investment, they are generally installed as fixed facilities in hydrogen liquefaction plants. Their operation requires strict guarantee conditions. Systems that require liquid hydrogen can only obtain liquid hydrogen at hydrogen liquefaction plants and cannot be used as mobile facilities to provide liquid hydrogen services for the distributed liquid hydrogen market. In addition, large-scale hydrogen liquefaction systems have high startup costs. For scenarios where small amounts of liquid hydrogen are required, using large-scale hydrogen liquefaction systems to supply hydrogen is not economical.

[0042] 2Cannot be stored without loss

[0043] The existing liquid hydrogen storage system does not have the corresponding refrigeration equipment to maintain a low-temperature environment, which will cause a large amount of boil-off gas to be discharged outside the system through the safety relief system, resulting in the loss of liquid hydrogen reserves;

[0044] 3. Unable to achieve lossless pre-cooling or rapid pre-cooling

[0045] Small hydrogen liquefaction devices generally do not have pre-cooling medium circulation devices, and cannot achieve lossless or rapid pre-cooling of the device. Small hydrogen liquefaction devices rely solely on static pre-cooling of the refrigerator. The medium in the system is not disturbed by distance, the heat transfer rate is slow, and the pre-cooling time is long. When liquid hydrogen is slowly added to the pre-cooling system, due to the huge temperature difference during pre-cooling, a large amount of evaporated liquid hydrogen is discharged from the safety relief device, resulting in a large amount of hydrogen waste.

[0046] Example 1

[0047] This embodiment proposes a mobile hydrogen liquefaction, storage and transfer integrated device, refer to Figures 1 to 8 It mainly includes external process pipelines, liquid nitrogen pre-cooling modules, liquid hydrogen production tanks 48 and liquid hydrogen storage tanks. Among them, the external process pipelines mainly include air intake pipelines and circulation loops. Specifically, the air intake pipeline is connected to the liquid nitrogen pre-cooling module; the liquid nitrogen pre-cooling module is connected to the liquid hydrogen production tank 48. The liquid hydrogen production tank 48 includes a storage area 46 and a refrigeration area 47. The storage area 46 is connected to the liquid hydrogen storage tank through a pipeline.

[0048] In this technical solution, the above-mentioned device can complete the processes of gas replacement, system pre-cooling, hydrogen liquefaction and liquid hydrogen transfer in sequence, thereby realizing lossless pre-cooling and lossless storage. The liquid hydrogen storage tank is movable, which can be separated from the entire system and has its own mobile device to realize external liquid hydrogen filling. It can realize the filling of liquid hydrogen to equipment that cannot be close to the small hydrogen liquefaction device, and further realize the hydrogen supply function for small and micro liquid hydrogen usage scenarios.

[0049] refer to Figure 1 、 Figure 3 and Figure 4 As for the refrigeration area 47, it mainly includes several refrigeration modules connected end to end. The refrigeration module includes a low-temperature refrigerator and a heat exchanger. The cold head of the low-temperature refrigerator is connected to one end of the heat exchanger, and the other end of the heat exchanger is connected to the normal-para-hydrogen converter.

[0050] refer to Figure 3 A liquid hydrogen production tank partition 49 is provided between the storage area 46 and the refrigeration area 47. The storage area 46 and the refrigeration area 47 are separated by the liquid hydrogen production tank partition 49. For the arrangement and connection relationship of other components, please refer to Figure 4 See the following description for details.

[0051] In this embodiment, the cryogenic refrigerator includes a first cryogenic refrigerator 19, a second cryogenic refrigerator 20, a third cryogenic refrigerator 21, and a fourth cryogenic refrigerator 22, and the heat exchanger mainly includes a first heat exchanger 10, a second heat exchanger 12, a third heat exchanger 14, and a fourth heat exchanger 16, and the normal para-hydrogen converter includes a second normal para-hydrogen converter 11, a third normal para-hydrogen converter 13, and a fourth normal para-hydrogen converter 15.

[0052] Among them, one end of the first heat exchanger 10 is connected to the liquid nitrogen pre-cooling module, the first heat exchanger 10 is connected to the cold head of the first cryogenic refrigerator 19, the other end of the first heat exchanger 10 is connected to the second normal para-hydrogen converter 11, the other end of the second normal para-hydrogen converter 11 is connected to the second heat exchanger 12, the second heat exchanger 12 is connected to the second cryogenic refrigerator 20, the other end of the second heat exchanger 12 is connected to the third normal para-hydrogen converter 13, the other end of the third normal para-hydrogen converter 13 is connected to the third heat exchanger 14, the third heat exchanger 14 is connected to the cold head of the third cryogenic refrigerator 21, the other end of the third heat exchanger 14 is connected to the fourth normal para-hydrogen converter 15, the other end of the fourth normal para-hydrogen converter 15 is connected to the fourth heat exchanger 16, the fourth heat exchanger 16 is connected to the cold head of the fourth cryogenic refrigerator 22, and the other end of the fourth heat exchanger 16 is connected to the fifth normal para-hydrogen converter 18.

[0053] In the refrigeration area of the present technical solution, multiple refrigeration modules are connected end to end. One of the refrigeration modules is mainly composed of a low-temperature refrigerator and a heat exchanger, and the last heat exchanger is connected to the heat exchanger arranged in the storage area.

[0054] refer to Figure 1 and Figure 2 The storage area 46 includes an open heat exchanger 17 and a fifth normal-parahydrogen converter 18. The fifth normal-parahydrogen converter 18 is connected to the open heat exchanger 17. The open heat exchanger 17 is exposed in the storage area 46. The open heat exchanger 17 is connected to the fifth low-temperature refrigerator 23.

[0055] More specifically, one end of the fifth normal-para-hydrogen converter 18 is connected to the fourth heat exchanger 16 in the refrigeration area 47, and the other end of the sixth normal-para-hydrogen converter 18 is connected to the open heat exchanger 17. The open heat exchanger 17 and the sixth normal-para-hydrogen converter 18 are both arranged in the storage area 46, and the open heat exchanger 17 is also connected to the fifth low-temperature refrigerator 23.

[0056] In this technical solution, the open heat exchanger 17 is welded to the cold head of the fifth cryogenic refrigerator 23, and the open heat exchanger 17 is placed in the storage area 46, so as to realize the lossless storage of the liquid hydrogen production tank 48 while liquefying the gaseous hydrogen in the gas phase space.

[0057] refer to Figure 1 and Figure 5The liquid hydrogen storage tank includes a mobile liquid hydrogen storage and filling tank 28, one end of the mobile liquid hydrogen storage and filling tank 28 is connected to a liquid hydrogen transfer hose 30, and the other end of the mobile liquid hydrogen storage and filling tank 28 is connected to a liquid hydrogen vacuum socket pipe 26.

[0058] In this technical solution, the mobile liquid hydrogen storage and filling tank 28 is connected to the liquid hydrogen production tank 48 through the liquid hydrogen vacuum socket pipe 26 and the liquid hydrogen transfer hose 30, respectively, which can be quickly disassembled and installed.

[0059] The liquid hydrogen vacuum bell-and-spigot pipe 26 mainly includes a liquid hydrogen vacuum bell-and-spigot pipe male head 26-2 and a liquid hydrogen vacuum bell-and-spigot pipe female head 26-1 fixed to each other. The liquid hydrogen vacuum bell-and-spigot pipe female head 26-1 and the liquid hydrogen vacuum bell-and-spigot pipe male head 26-2 are embedded and connected and fixed with fixing parts.

[0060] refer to Figure 6 Before installation, the female end 26-1 of the liquid hydrogen vacuum bell-and-spigot pipe and the male end 26-2 of the liquid hydrogen vacuum bell-and-spigot pipe are separated from each other, and the male end and the female end correspond to each other, and a corresponding flow pipe is provided inside the male end 26-2 of the liquid hydrogen vacuum bell-and-spigot pipe.

[0061] refer to Figure 5 After installation and fixation, the liquid hydrogen vacuum bell-and-spigot pipe female head 26-1 and the liquid hydrogen vacuum bell-and-spigot pipe male head 26-2 cooperate with each other to fix. After the liquid hydrogen vacuum bell-and-spigot pipe female head 26-1 and the liquid hydrogen vacuum bell-and-spigot pipe male head 26-2 are completed, bolts or snaps can be used for fixed connection to achieve quick disassembly and installation.

[0062] refer to Figure 7 The liquid hydrogen transfer hose 30 is connected at both ends to the pipeline containing the eighth shut-off valve 31 and the pipeline containing the seventh shut-off valve 29, respectively. Specifically, one end of the liquid hydrogen transfer hose 30 is connected to the pipeline containing the eighth shut-off valve 31 via a flange, and the other end of the liquid hydrogen transfer hose 30 is also connected to the pipeline containing the seventh shut-off valve 29 via a flange. The flanged connection of the liquid hydrogen transfer hose 30 to the flange of the inlet pipeline of the eighth shut-off valve 31 allows for quick disassembly and installation.

[0063] When the transfer is completed, the liquid hydrogen transfer hose 30 can be disconnected from the pipeline connected to the eighth shut-off valve 31, the male and female ends of the liquid hydrogen vacuum socket pipe 26 are disconnected, and the mobile liquid hydrogen storage and filling tank 28 can be disconnected from the entire device, so that it can be freely moved to external hydrogen-using equipment, and connected to the hydrogen-using equipment through the liquid hydrogen transfer hose 30, and the residual pressure inside the mobile liquid hydrogen storage and filling tank 28 or its own booster pipeline is used to increase the pressure for transfer.

[0064] refer to Figure 1The liquid nitrogen pre-cooling module includes a liquid nitrogen pre-cooling storage tank 7, in which a first normal-para-hydrogen converter 8 is arranged. One end of the first normal-para-hydrogen converter 8 is connected to the air intake pipeline, and the other end of the first normal-para-hydrogen converter 8 is connected to the liquid hydrogen production storage tank 48.

[0065] In this technical solution, the first normal-para hydrogen converter 8 is installed inside the liquid nitrogen pre-cooling storage tank 7 and immersed in liquid nitrogen. After the hydrogen flows into the liquid nitrogen pre-cooling storage tank 7, it exchanges heat with the liquid nitrogen and completes the catalytic conversion of normal-para hydrogen in the liquid nitrogen temperature zone. The hydrogen after heat exchange flows out.

[0066] refer to Figure 1 The air inlet pipeline includes a raw hydrogen unloading hose 1, the raw hydrogen unloading hose 1 is connected to the pressure reducing valve 4, the other end of the pressure reducing valve 4 is connected to the flow regulating valve 5, the other end of the flow regulating valve 5 is connected to the hydrogen flow meter 6, and the other end of the hydrogen flow meter 6 is connected to the liquid nitrogen pre-cooling module.

[0067] In this embodiment, a first stop valve 2 and a second stop valve 3 are provided between the raw hydrogen gas discharge hose 1 and the pressure reducing valve 4. The first stop valve 2 is connected to the purge nitrogen gas source. The first stop valve 2 and the second stop valve 3 are respectively connected to the raw hydrogen gas discharge hose 1.

[0068] The circulation loop includes a low-temperature hydrogen circulation fan 38 connected to the liquid hydrogen storage tank, and the other end of the low-temperature hydrogen circulation fan 38 is connected to the liquid hydrogen production tank 48.

[0069] In this embodiment, the circulation loop further includes several stop valves and a vacuum pump, including an eighth stop valve 31, a tenth stop valve 35, an eleventh stop valve 36, a twelfth stop valve 37, a thirteenth stop valve 39, a second safety valve 40, a fourteenth stop valve 41, and a vacuum pump 45.

[0070] One end of the eighth stop valve 31 is connected to the liquid hydrogen transfer hose 30, the other end of the eighth stop valve 31 is connected to the low-temperature hydrogen circulation fan 38, the other end of the low-temperature hydrogen circulation fan 38 is connected to the twelfth stop valve 37, the other end of the twelfth stop valve 37 is respectively connected to the liquid nitrogen pre-cooling module and the third stop valve 9, and the other end of the third stop valve 9 is connected to the first heat exchanger 10.

[0071] One end of the tenth stop valve 35 is connected to the fourth stop valve 24 . One end of the eleventh stop valve 36 is connected to the storage area 46 , and the other end of the eleventh stop valve 36 is connected to the fifth stop valve 25 . The other end of the fifth stop valve 25 is connected to the liquid hydrogen vacuum bell pipe 26 .

[0072] One end of the thirteenth stop valve 39 is connected to the low-temperature hydrogen circulation fan 38 , and the other end of the thirteenth stop valve 39 is connected to the second flame arrester 44 . One end of the second safety valve 40 is connected to the low-temperature hydrogen circulation fan 38 , and the other end of the second safety valve 40 is connected to the second flame arrester 44 .

[0073] One end of the vacuum pump 45 is connected to the fourteenth stop valve 41 , the other end of the fourteenth stop valve 41 is connected to the eleventh stop valve 36 , and the other end of the vacuum pump 45 is connected to the second flame arrester 44 .

[0074] In addition, the storage area 46 is also connected to the third safety valve 43 , and the third safety valve 43 is also connected to the second flame arrester 44 and the fifteenth stop valve 42 .

[0075] The mobile liquid hydrogen storage and refueling tank 28 is further connected to a first safety valve 33 and a ninth stop valve 32 , respectively. Both the first safety valve 33 and the ninth stop valve 32 are connected to a first flame arrester 34 .

[0076] For more detailed connection relationships, please refer to Figure 1 , I will not go into details here.

[0077] The implementation steps of the above device are described here:

[0078] Before being put into use, the air in the device needs to be replaced with inert gas nitrogen. After the device is filled with nitrogen, the nitrogen needs to be replaced with hydrogen. After the replacement is completed, the device can enter the pre-cooling stage. When the device is pre-cooled, the hydrogen liquefaction process can start. The storage area 46 is the initial storage area for the produced liquid hydrogen. When liquid hydrogen needs to be transferred to the outside, the liquid hydrogen in the storage area 46 can be transferred to the mobile liquid hydrogen storage and filling tank 28. The mobile liquid hydrogen storage and filling tank 28 can be quickly disassembled from the entire device to further transfer liquid hydrogen to the outside. The detailed process is described below.

[0079] Step 1: Gas Replacement

[0080] The purge nitrogen gas source is connected to the first stop valve 2, and the raw hydrogen gas unloading hose 1 is connected to the hydrogen gas source. The present invention is provided with a pressure reducing valve 4 at the gas inlet, and the pressure before the valve is 1-35MPa. It has good compatibility with the gas source pressures of the raw gas and the purge gas. When the air in the device is replaced by nitrogen, the entire device is evacuated by a vacuum pump 45. After reaching a certain vacuum degree, for example, a negative pressure of 0.1MPa, high-purity nitrogen gas is then flushed into the device through the first stop valve 2 to restore the system pressure to 0.1Mpa. The above steps are repeated until the oxygen content in the sample gas taken out of the device is ≤0.5%, and the nitrogen replacement is completed. The nitrogen in the device is then replaced by hydrogen, and the system is evacuated by a vacuum pump 45. After reaching a certain vacuum degree, for example, a negative pressure of 0.1MPa, the system is filled with hydrogen through the raw hydrogen gas unloading hose 1 to restore the system pressure to 0.1Mpa. The above steps are repeated until the nitrogen content in the hydrogen in the system is ≤100ppm, and the hydrogen replacement is completed.

[0081] Step 2: System precooling

[0082] After the gas replacement is completed, the refrigerator is turned on, including the first low-temperature refrigerator 19, the second low-temperature refrigerator 20, the third low-temperature refrigerator 21, the fourth low-temperature refrigerator 22, the fifth low-temperature refrigerator 23, and the low-temperature hydrogen circulation fan 38. During the pre-cooling process, the hydrogen density in the pipeline will increase and the pressure will drop. It is necessary to adjust the second stop valve 3 and the flow regulating valve 5 to add a certain amount of hydrogen to the device to maintain the gauge pressure in the device at about 0.1 MPa. The present invention can achieve pre-cooling of different devices. When it is necessary to pre-cool the storage area 46 and the refrigeration area 47, the third stop valve 9-first heat exchanger 10-second normal-para-hydrogen converter 11-second heat exchanger 12-third normal-para-hydrogen converter 13-third exchange The cooling unit 10 is pre-cooled by a circuit consisting of the heat exchanger 14-the fourth normal-para-hydrogen converter 15-the fourth heat exchanger 16-the fifth normal-para-hydrogen converter 18-the storage area 46-the fourth stop valve 24-the tenth stop valve 35-the low-temperature hydrogen circulation fan 38-the twelfth stop valve 37-the third stop valve 9, or pre-cooled by a circuit consisting of the third stop valve 9-the first heat exchanger 10-the second normal-para-hydrogen converter 11-the second heat exchanger 12-the third normal-para-hydrogen converter 13-the third heat exchanger 14-the fourth normal-para-hydrogen converter 15-the fourth heat exchanger 16-the fifth normal-para-hydrogen converter 18-the storage area 46-the eleventh stop valve 36-the tenth stop valve 35-the low-temperature hydrogen circulation fan 38-the twelfth stop valve 37-the third stop valve 9. When the cooling unit 10 is pre-cooled, the cooling unit 10 is pre-cooled by a circuit consisting of the third stop valve 9-the first heat exchanger 10-the second normal-para-hydrogen converter 11-the second heat exchanger 12-the third normal-para-hydrogen converter 13-the third heat exchanger 14-the fourth normal-para-hydrogen converter 15-the fourth heat exchanger 16-the fifth normal-para-hydrogen converter 18-the storage area 46-the eleventh stop valve 36-the tenth stop valve 35-the low-temperature hydrogen circulation fan 38-the twelfth stop valve 37-the third stop valve 9. When pre-cooling the storage area 46, the refrigeration area 47, the mobile liquid hydrogen storage and filling tank 28 and its accessories, pre-cooling can be performed through a loop consisting of the third stop valve 9-the first heat exchanger 10-the second normal-para-hydrogen converter 11-the second heat exchanger 12-the third normal-para-hydrogen converter 13-the third heat exchanger 14-the fourth normal-para-hydrogen converter 15-the fourth heat exchanger 16-the fifth normal-para-hydrogen converter 18-the storage area 46-the fourth stop valve 24-the fifth stop valve 25-the liquid hydrogen vacuum bell pipe 26-the sixth stop valve 27-the mobile liquid hydrogen storage and filling tank 28-the seventh stop valve 29-the liquid hydrogen transfer hose 30-the eighth stop valve 31-the low-temperature hydrogen circulation fan 38-the twelfth stop valve 37-the third stop valve 9 , or pre-cooling is performed through a loop consisting of the third stop valve 9 - the first heat exchanger 10 - the second normal-para-hydrogen converter 11 - the second heat exchanger 12 - the third normal-para-hydrogen converter 13 - the third heat exchanger 14 - the fourth normal-para-hydrogen converter 15 - the fourth heat exchanger 16 - the fifth normal-para-hydrogen converter 18 - the storage area 46 - the eleventh stop valve 36 - the fifth stop valve 25 - the liquid hydrogen vacuum bell pipe 26 - the sixth stop valve 27 - the mobile liquid hydrogen storage and filling tank 28 - the seventh stop valve 29 - the liquid hydrogen transfer hose 30 - the eighth stop valve 31 - the low-temperature hydrogen circulation fan 38 - the twelfth stop valve 37 - the third stop valve 9. When there is liquid hydrogen in the storage area 46 and the mobile liquid hydrogen storage and filling tank 28 and its accessories need to be pre-cooled separately,Precooling can be achieved through a circuit consisting of the third shut-off valve 9 - first heat exchanger 10 - second normal-para-hydrogen converter 11 - second heat exchanger 12 - third normal-para-hydrogen converter 13 - third heat exchanger 14 - fourth normal-para-hydrogen converter 15 - fourth heat exchanger 16 - fifth normal-para-hydrogen converter 18 - storage area 46 - eleventh shut-off valve 36 - fifth shut-off valve 25 - liquid hydrogen vacuum bell pipe 26 - sixth shut-off valve 27 - mobile liquid hydrogen storage and filling tank 28 - seventh shut-off valve 29 - liquid hydrogen transfer hose 30 - eighth shut-off valve 31 - low-temperature hydrogen circulation fan 38 - twelfth shut-off valve 37 - third shut-off valve 9.

[0083] Step 3: Hydrogen liquefaction process

[0084] The working pressure of the liquefaction process is 0.1MPa, and the hydrogen liquefaction capacity is 200L / d. When liquefaction begins, the raw hydrogen enters the device through the raw hydrogen unloading hose 1, passes through the second stop valve 3, the pressure reducing valve 4, the flow regulating valve 5, and the hydrogen flowmeter 6 in sequence, and enters the liquid nitrogen pre-cooling storage tank 7. The first positive para-hydrogen converter 8 is installed inside the liquid nitrogen pre-cooling storage tank 7 and immersed in liquid nitrogen. The hydrogen flows into the liquid nitrogen pre-cooling storage tank 7 through the pipeline, exchanges heat with the liquid nitrogen in the liquid nitrogen pre-cooling storage tank 7, and completes the positive para-hydrogen catalytic conversion in the liquid nitrogen temperature zone in the first positive para-hydrogen converter 8. The hydrogen after heat exchange flows out of the liquid nitrogen pre-cooling storage tank 7, flows into the liquid hydrogen production storage tank 48 through the third stop valve 9, and passes through the first heat exchanger 10, the second positive para-hydrogen converter 11, the second heat exchanger 12, the third positive para-hydrogen converter 13, the third heat exchanger 14, the fourth positive para-hydrogen converter 15, and the fourth heat exchanger in sequence through the hydrogen pipeline. Heat exchanger 16, the fifth normal-para hydrogen converter 18, and then flows into the storage area 46. The low-temperature hydrogen entering the storage area 46 finally obtains further cold energy under the action of the open heat exchanger 17 to complete liquefaction. The liquefied liquid hydrogen flows into the bottom of the storage area 46 by gravity. Among them, the first heat exchanger 10, the second heat exchanger 12, the third heat exchanger 14, and the fourth heat exchanger 16 are closed heat exchangers. The heat exchangers are connected to the cold heads of the first low-temperature refrigerator 19, the second low-temperature refrigerator 20, the third low-temperature refrigerator 21 and the fourth low-temperature refrigerator 22 to obtain cold energy. The hydrogen flows through the heat exchanger through the gas channel inside the heat exchanger to achieve heat exchange. The open heat exchanger 17 is a fin-type open heat exchanger, which is connected to the cold head of the fifth low-temperature refrigerator 23 to obtain cold energy and is exposed to the gas phase space of the storage area 46 to achieve heat exchange with the hydrogen in the gas phase space and achieve hydrogen liquefaction.

[0085] The first normal-para hydrogen converter 8 and the fifth normal-para hydrogen converter 18 are isothermal conversions, and the second normal-para hydrogen converter 11, the third normal-para hydrogen converter 13, and the fourth normal-para hydrogen converter 15 are adiabatic conversions. The normal-para hydrogen converters are filled with a normal-para hydrogen catalyst, which has the function of accelerating the conversion of normal hydrogen in the raw hydrogen into para hydrogen during the cooling process, so that the normal-para hydrogen reaches an equilibrium state as soon as possible, thereby preventing the liquid hydrogen from being vaporized due to the conversion heat of normal-para hydrogen.

[0086] Step 4: Liquid hydrogen injection

[0087] refer to Figure 1 、 Figure 3 、 Figure 4 and Figure 8 When the liquid hydrogen in the storage area 46 is stored to a certain level (the designed liquid storage volume in the storage area 46 is 1m³), and it needs to be transferred to the mobile liquid hydrogen storage and filling tank 28, ensure that the liquid hydrogen vacuum bell-and-socket pipe 26 is in a connected state, and use the pressure difference between the storage area 46 and the mobile liquid hydrogen storage and filling tank 28 to transfer liquid hydrogen to the mobile liquid hydrogen storage and filling tank 28. For example, the pressure difference can be obtained by injecting raw hydrogen into the storage area 46 to increase the pressure in the storage area 46. When the transfer is completed, the liquid hydrogen transfer hose 30 can be disconnected from the pipeline connected to the eighth shut-off valve 31, the male and female ends of the vacuum bell-and-socket pipe 26 are disconnected, and the mobile liquid hydrogen storage and filling tank 28 can be disconnected from the entire device, so that it can be freely moved to external hydrogen-using equipment, and connected to the hydrogen-using equipment through the liquid hydrogen transfer hose 30, and the residual pressure inside the mobile liquid hydrogen storage and filling tank 28 or its own booster pipeline is used to increase the pressure for transfer.

[0088] refer to Figure 8 Corresponding forklift slots and four pulleys are provided below the mobile liquid hydrogen storage and filling tank 28, so that the tank body can be moved with the help of a forklift or with the help of pulleys.

[0089] This embodiment uses multiple low-temperature refrigerators for closed heat exchange. The cold heads and heat exchangers of the low-temperature refrigerators are isolated by a separate vacuum cavity, resulting in low cooling loss and high cooling efficiency. Hydrogen flows through in a step-by-step cooling manner, ensuring that the cooling capacity of the refrigerator is maximized in the high-temperature zone. The combination of the cold box and the storage tank avoids cooling loss.

[0090] In this embodiment, a refrigerator heat exchanger is installed in the gas phase space of the storage area. When the liquid hydrogen in the storage area needs to be stored losslessly, the fifth low-temperature refrigerator is turned on to refrigerate the space in the storage area, so that the liquid hydrogen is in a zero-evaporation state, thereby realizing lossless storage of the liquid hydrogen.

[0091] In this embodiment, when there is no liquid nitrogen filling condition at the production site and there is no liquid nitrogen heat exchange in the first normal-para-hydrogen converter, the flow rate is adjusted accordingly by the flow control valve. Under another operating condition, this embodiment can achieve hydrogen liquefaction without liquid nitrogen.

[0092] In this embodiment, the air intake rate can be controlled by the opening of the flow control valve, and the pressure behind the pressure reducing valve can be used to control the liquefaction working pressure of the device, thereby changing the saturated pressure of hydrogen and the cooling capacity required for hydrogen liquefaction per unit mass, as well as the on-off adjustment and power adjustment of the low-temperature refrigerator, so as to achieve the adjustment of hydrogen liquefaction capacity.

[0093] In this embodiment, the liquid hydrogen production tank and the mobile liquid hydrogen storage tank are connected by a liquid hydrogen vacuum bell-and-spigot pipe, which results in less heat leakage during transfer than with a traditional vacuum hose connection.

[0094] In this embodiment, the design of the liquid hydrogen vacuum bell-and-spigot pipe and the liquid hydrogen transfer hose can separate the mobile liquid hydrogen storage and filling tank from the device and become an independent liquid hydrogen storage and transfer device.

[0095] In this embodiment, the mobile liquid hydrogen storage and filling tank is equipped with a mobile device, which can realize hydrogen filling for equipment that cannot be close to the small hydrogen liquefaction device.

[0096] In this embodiment, a low-temperature hydrogen circulation fan is provided to continuously circulate the low-temperature hydrogen in the hydrogen production and storage device, thereby reducing the temperature inside the device to a condition where liquid hydrogen can be produced and stored. There is no loss of hydrogen in this process, and the precooling speed is faster than that of a traditional static precooling system that relies solely on a refrigerator, and the hydrogen loss is smaller than that of a precooling system that slowly fills with liquid hydrogen.

[0097] In this embodiment, the mobile liquid hydrogen storage and filling tank is equipped with a self-pressurizing device, which can realize the transfer of liquid hydrogen to the outside.

[0098] Finally, it should be noted that the above embodiments are intended only to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions to the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention and are intended to be encompassed by the claims of the present invention.

Claims

1. A mobile hydrogen liquefaction, storage and transfer integrated device, characterized in that: The invention comprises an external process pipeline, which includes an air inlet pipeline and a circulation loop. The air inlet pipeline is connected to a liquid nitrogen pre-cooling module, which is connected to a liquid hydrogen production storage tank. The liquid hydrogen production storage tank includes a storage area and a refrigeration area. The storage area includes an open heat exchanger and a fifth normal-para-hydrogen converter connected to the open heat exchanger. The open heat exchanger is exposed to the storage area and is connected to a fifth low-temperature refrigerator. The air inlet pipeline includes a raw hydrogen gas unloading hose, which is connected to a pressure reducing valve, the other end of the pressure reducing valve is connected to a flow regulating valve, the other end of the flow regulating valve is connected to a hydrogen flow meter, and the other end of the hydrogen flow meter is connected to the liquid nitrogen pre-cooling module. The storage area is connected to the liquid hydrogen storage tank through a pipeline. The refrigeration area includes several refrigeration modules connected end to end. The refrigeration module includes a low-temperature refrigerator and a heat exchanger. The cold head of the low-temperature refrigerator is connected to one end of the heat exchanger, the other end of the heat exchanger is connected to the normal-para-hydrogen converter, and the last heat exchanger is connected to the fifth normal-para-hydrogen converter arranged in the storage area. The liquid hydrogen storage tank includes a mobile liquid hydrogen storage and filling tank. One end of the mobile liquid hydrogen storage and filling tank is connected to the circulation loop through a liquid hydrogen transfer hose; the other end of the mobile liquid hydrogen storage and filling tank is connected to the storage area through a liquid hydrogen vacuum socket pipe.

2. The portable hydrogen liquefaction, storage and transfer integrated device according to claim 1, characterized in that: The liquid nitrogen pre-cooling module comprises a liquid nitrogen pre-cooling storage tank (7), a first normal-para hydrogen converter (8) is arranged in the liquid nitrogen pre-cooling storage tank (7), one end of the first normal-para hydrogen converter (8) is connected to an air inlet pipeline, and the other end of the first normal-para hydrogen converter (8) is connected to a liquid hydrogen production storage tank (48).

3. The mobile hydrogen liquefaction, storage and transfer integrated device according to claim 1, characterized in that: The circulation loop comprises a low-temperature hydrogen circulation fan (38) connected to the liquid hydrogen storage tank, and the other end of the low-temperature hydrogen circulation fan (38) is connected to the liquid hydrogen production tank (48).

4. The mobile hydrogen liquefaction, storage and transfer integrated device according to claim 1, characterized in that: The mobile liquid hydrogen storage and filling tank (28) is further connected to a first safety valve (33) and a ninth stop valve (32), respectively. The first safety valve (33) and the ninth stop valve (32) are both connected to a first flame arrester (34).

5. The mobile hydrogen liquefaction, storage and transfer integrated device according to claim 1, characterized in that: The liquid hydrogen vacuum bell-and-spigot pipe (26) comprises a liquid hydrogen vacuum bell-and-spigot pipe male head (26-2) and a liquid hydrogen vacuum bell-and-spigot pipe female head (26-1), and the liquid hydrogen vacuum bell-and-spigot pipe female head (26-1) and the liquid hydrogen vacuum bell-and-spigot pipe male head (26-2) are embedded and connected and fixed using a fixing piece.

6. The portable integrated hydrogen liquefaction, storage and transfer device according to claim 3, characterized in that: One end of the liquid hydrogen transfer hose (30) is connected to the pipeline where the eighth stop valve (31) is located through a flange, and the other end of the liquid hydrogen transfer hose (30) is connected to the pipeline where the seventh stop valve (29) is located through a flange, and the other end of the eighth stop valve (31) is connected to the low-temperature hydrogen circulation fan (38).

7. The portable integrated hydrogen liquefaction, storage and transfer device according to claim 5, characterized in that: The liquid hydrogen vacuum bell-and-spigot pipe female end (26-1) and the liquid hydrogen vacuum bell-and-spigot pipe male end (26-2) are connected by bolts or snaps.

8. The portable integrated hydrogen liquefaction, storage and transfer device according to claim 1, characterized in that: A first stop valve and a second stop valve are further provided between the raw hydrogen gas unloading hose and the pressure reducing valve, and the first stop valve is connected to a purge nitrogen gas source.

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