CN114704765A - Hydrogen liquefaction and boil-off gas recondensation system based on cryocooler - Google Patents

Hydrogen liquefaction and boil-off gas recondensation system based on cryocooler Download PDF

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Publication number
CN114704765A
CN114704765A CN202210337034.4A CN202210337034A CN114704765A CN 114704765 A CN114704765 A CN 114704765A CN 202210337034 A CN202210337034 A CN 202210337034A CN 114704765 A CN114704765 A CN 114704765A
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hydrogen
module
stop valve
liquefaction
liquid
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CN202210337034.4A
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CN114704765B (en
Inventor
王凯
史超越
宛传聪
邱利民
植晓琴
周黎旸
施国有
任占胜
李顶付
张明
赵云波
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Zhejiang University ZJU
Juhua Group Corp
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Zhejiang University ZJU
Juhua Group Corp
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C5/00—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
    • F17C5/02—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with liquefied gases
    • F17C5/04—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with liquefied gases requiring the use of refrigeration, e.g. filling with helium or hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • F17C13/04—Arrangement or mounting of valves
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/007—Primary atmospheric gases, mixtures thereof
    • F25J1/0072—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0225—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using other external refrigeration means not provided before, e.g. heat driven absorption chillers
    • F25J1/0227—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using other external refrigeration means not provided before, e.g. heat driven absorption chillers within a refrigeration cascade
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0244—Operation; Control and regulation; Instrumentation
    • F25J1/0245—Different modes, i.e. 'runs', of operation; Process control
    • F25J1/0247—Different modes, i.e. 'runs', of operation; Process control start-up of the process
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0275—Construction and layout of liquefaction equipments, e.g. valves, machines adapted for special use of the liquefaction unit, e.g. portable or transportable devices
    • F25J1/0276—Laboratory or other miniature devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/90—Boil-off gas from storage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/90—Processes or apparatus involving steps for recycling of process streams the recycled stream being boil-off gas from storage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/908—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by regenerative chillers, i.e. oscillating or dynamic systems, e.g. Stirling refrigerator, thermoelectric ("Peltier") or magnetic refrigeration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/908—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by regenerative chillers, i.e. oscillating or dynamic systems, e.g. Stirling refrigerator, thermoelectric ("Peltier") or magnetic refrigeration
    • F25J2270/91—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by regenerative chillers, i.e. oscillating or dynamic systems, e.g. Stirling refrigerator, thermoelectric ("Peltier") or magnetic refrigeration using pulse tube refrigeration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Clinical Laboratory Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

The invention discloses a hydrogen liquefying and evaporated gas re-condensing system based on a cryogenic refrigerator, which comprises a hydrogen cylinder, a pre-cooling module, a liquefying module and a liquid hydrogen storage tank, wherein the hydrogen cylinder is connected with the pre-cooling module; a liquid inlet pipe is arranged at the lower part of the liquid hydrogen storage tank, an exhaust pipe is arranged at the upper part of the liquid hydrogen storage tank, a second stop valve is arranged at a filling port of the liquid inlet pipe, and a fourth stop valve is arranged at an exhaust port of the exhaust pipe; the hydrogen cylinder is connected with the precooling module and the liquefying module in sequence through pipelines and then is connected with the liquid inlet pipe, and the exhaust pipe is connected with the input end of the liquefying module through a pipeline with a third stop valve; and a pipeline connecting the precooling module and the liquefying module is provided with a stop valve No. five, and a pipeline connecting the liquefying module and the liquid inlet pipe is provided with a stop valve No. one. By utilizing the invention, the hydrogen evaporated gas can be re-condensed in the liquid hydrogen storage process, and the zero evaporation storage of the liquid hydrogen is realized.

Description

Hydrogen liquefaction and boil-off gas recondensation system based on cryocooler
Technical Field
The invention relates to the technical field of liquid hydrogen production and storage, in particular to a hydrogen liquefaction and evaporated gas recondensing system based on a cryogenic refrigerator.
Background
As the most promising next-generation energy carrier, hydrogen has the characteristics of high calorific value, zero pollution and the like, and is widely applied to a plurality of fields of spaceflight, automobiles, semiconductors and the like. With the increasing market demand for hydrogen, higher requirements are placed on the safe and efficient storage of hydrogen.
At present, the storage modes of hydrogen mainly include high-pressure gaseous hydrogen storage, metal hydride hydrogen storage, low-temperature liquid hydrogen storage and the like. The high-pressure gaseous hydrogen storage is used for compressing hydrogen to a high-pressure state and storing the hydrogen in a steel gas cylinder, and the pressure of the hydrogen can reach 70-90 MPa. The high-pressure gaseous hydrogen storage technology is mature, the cost is low, but the unit hydrogen storage density is low, the large-scale transportation and utilization of hydrogen are not facilitated, and potential safety hazards exist due to high storage pressure. The metal hydride stores hydrogen, hydrogen atoms or molecules are tightly combined with other elements by a physical adsorption or chemical adsorption method, and the hydrogen is desorbed and separated out when the hydrogen is used. Compared with high-pressure gaseous hydrogen storage, the metal hydride hydrogen storage is safer, the hydrogen storage density is higher, but the technology is immature, the reaction kinetics in the dehydrogenation process is slow, the reversibility is low, the dehydrogenation temperature is high, and the method is still in a laboratory stage. The low-temperature liquid hydrogen storage is characterized in that hydrogen is liquefied and then stored in a liquid hydrogen container, the density of the liquid hydrogen is hundreds of times of that of normal-pressure hydrogen, the high-density storage of the hydrogen can be realized, the low-temperature liquid hydrogen storage is generally low in pressure and higher in safety, and the low-temperature liquid hydrogen storage is a hydrogen storage mode with great prospect in the future.
Although the safety of the low-temperature liquid hydrogen storage mode is high, liquid hydrogen is continuously evaporated along with the inevitable heat leakage of the liquid hydrogen container, and when the pressure of an air pillow in the container is higher than the working pressure, the hydrogen is discharged through the safety valve. Because of the characteristics of flammability, explosiveness and easy diffusion of hydrogen, the liquid hydrogen container always has potential safety hazard, which is not beneficial to the storage and use of hydrogen.
Hydrogen has two spin isomers of orthohydrogen and parahydrogen, with normal hydrogen at room temperature consisting of 75% orthohydrogen and 25% parahydrogen, and hydrogen at boiling point consisting of 0.21% orthohydrogen and 99.79% parahydrogen. The equilibrium fraction of the two forms of hydrogen is a function of temperature, and the rotational energy of orthohydrogen and parahydrogen is also temperature dependent. Thus, when the hydrogen gas liquefies as the temperature is reduced, ortho-hydrogen spontaneously converts to para-hydrogen and releases heat, but the spontaneous conversion rate is extremely slow, which can affect the storage of liquid hydrogen. In order to obtain equilibrium hydrogen at a normal boiling point, an ortho-para-hydrogen catalyst is required to be added in the liquefaction process, and ortho-hydrogen is converted into para-hydrogen with an equilibrium concentration in the hydrogen cooling liquefaction process, so that the evaporation loss of liquid hydrogen is reduced.
Meanwhile, the conventional liquid hydrogen production generally adopts a large hydrogen liquefying device, and the device has large scale and high operation cost, and is not suitable for small and medium-sized occasions, such as laboratories and the like. The production and storage of a small amount of liquid hydrogen at the laboratory level can meet the requirements of development and test of liquid hydrogen related equipment and liquid hydrogen heat and mass transfer test, can also provide a required liquid hydrogen environment for low-temperature material tests or low-temperature physical tests and the like, and has important significance for research and test of laboratories.
Disclosure of Invention
The invention provides a hydrogen liquefying and evaporated gas recondensing system based on a cryogenic refrigerator, which can realize small-scale production of liquid hydrogen, simultaneously carry out catalytic conversion on the hydrogen in the liquefying process to obtain the liquid hydrogen with balanced concentration, can recondense the evaporated gas of the hydrogen in the storing process of the liquid hydrogen to realize zero evaporation storage of the liquid hydrogen, has the functions of research and test, and can be used for small and medium-sized occasions such as laboratories and the like to be flexibly used.
A hydrogen liquefaction and evaporated gas re-condensation system based on a cryogenic refrigerator comprises a hydrogen cylinder, a pre-cooling module, a liquefaction module and a liquid hydrogen storage tank; a liquid inlet pipe is arranged at the lower part of the liquid hydrogen storage tank, an exhaust pipe is arranged at the upper part of the liquid hydrogen storage tank, a second stop valve is arranged at a filling port of the liquid inlet pipe, and a fourth stop valve is arranged at an exhaust port of the exhaust pipe;
the hydrogen cylinder is connected with the precooling module and the liquefying module in sequence through pipelines and then is connected with the liquid inlet pipe, and the exhaust pipe is connected with the input end of the liquefying module through a pipeline with a third stop valve; and a pipeline connecting the precooling module and the liquefying module is provided with a stop valve No. five, and a pipeline connecting the liquefying module and the liquid inlet pipe is provided with a stop valve No. one.
In the technical scheme, hydrogen in the hydrogen cylinder is precooled by a liquid nitrogen bath and is refrigerated by a low-temperature refrigerator of the liquefaction module, so that the liquefaction of the hydrogen is realized; and refrigerating the liquid hydrogen evaporated gas in the liquid hydrogen storage tank by using a low-temperature refrigerator to re-condense the evaporated gas, thereby realizing zero evaporation storage of the liquid hydrogen.
Further, the liquefaction module comprises a cryogenic refrigerator, an outer cylinder and a heat exchanger; the outer cylinder is connected with the low-temperature refrigerator, and a cold head of the low-temperature refrigerator is extended into the outer cylinder; the heat exchanger is connected with a cold head of the low-temperature refrigerator, and fins are arranged at the top of the heat exchanger. Wherein, the low temperature refrigerator can be a GM refrigerator or a pulse tube refrigerator.
In order to improve the liquefaction efficiency, the fins are preferably column ribs made of oxygen-free copper, so that the contact surface area of the heat exchanger is increased.
In order to increase the heat exchange area of the pre-cooling module, the pre-cooling module is preferably a shell-and-tube heat exchanger, the shell side of the pre-cooling module is a liquid nitrogen bath, the tube side of the pre-cooling module is hydrogen, and the gas pipeline is spirally coiled in the heat exchanger.
And the pipelines between the hydrogen cylinder and the pre-cooling module adopt a normal-temperature hydrogen pipeline, and the pipelines between the pre-cooling module and the liquefaction module, between the liquefaction module and the liquid inlet pipe and between the exhaust pipe and the liquefaction module are high-vacuum heat-insulating pipes. The liquid inlet pipe and the exhaust pipe are high vacuum heat insulation pipes.
In order to reduce the heat leakage of the system, the first stop valve, the second stop valve, the third stop valve, the fourth stop valve and the fifth stop valve are all low-temperature jacket vacuum stop valves, a vacuum jacket is arranged outside the stop valves, and the valve rods are made of non-metal materials.
In order to reduce heat leakage of the system, the liquid hydrogen storage tank is preferably a double-layer vacuum heat insulation storage tank, an interlayer of the storage tank is wrapped with multiple layers of heat insulation materials and is pumped to high vacuum, and a supporting structure is arranged between the inner layer tank body and the outer layer tank body and is made of non-metal materials.
Preferably, the hydrogen pipeline in the pre-cooling module and the heat exchanger in the liquefaction module are both filled with an ortho-para hydrogen catalyst. The ortho-para hydrogen catalyst is a hydrated iron oxide catalyst.
Compared with the prior art, the invention has the beneficial effects that:
the hydrogen liquefaction and evaporated gas recondensation system based on the cryogenic refrigerator realizes the conversion of the normal hydrogen and the secondary hydrogen of the hydrogen and small-scale liquefaction by utilizing liquid nitrogen precooling and the refrigeration of the cryogenic refrigerator, can utilize the cold energy of the cryogenic refrigerator to recondense the evaporated gas of the liquid hydrogen in the liquid hydrogen storage tank in the process of storing the liquid hydrogen, realizes the zero evaporation storage of the liquid hydrogen, and can be used for the research and test of small and medium-sized occasions at the laboratory level.
Drawings
FIG. 1 is a schematic diagram of the overall configuration of a cryocooler-based hydrogen liquefaction and boil-off gas recondensing system according to the present invention;
FIG. 2 is a schematic structural diagram of a pre-cooling module according to the present invention;
FIG. 3 is a heat exchanger block diagram of a liquefaction module of the present invention;
FIG. 4 is a schematic flow diagram of the liquefaction process of the cryocooler-based hydrogen liquefaction and boil-off gas recondensation system of the present invention;
fig. 5 is a schematic diagram of the recondensing flow of the cryocooler-based hydrogen liquefaction and boil-off gas recondensing system of the present invention.
In the figure: the system comprises a hydrogen cylinder 1, a precooling module 2, a liquefying module 3, a liquid hydrogen storage tank 4, a cryogenic refrigerator 5, an outer cylinder 6, a heat exchanger 7, an exhaust pipe 8, a liquid inlet pipe 9, a stop valve 10, a stop valve 11, a stop valve 12, a stop valve III, a stop valve 13, a stop valve IV, a stop valve 14, a stop valve V, a filling port 15, an exhaust port 16, a liquid nitrogen bath 17, a normal-secondary hydrogen catalyst 18 and a fin 19.
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples, which are intended to facilitate the understanding of the invention without limiting it in any way.
As shown in fig. 1, a hydrogen liquefying and boil-off gas recondensing system based on a cryogenic refrigerator includes a hydrogen cylinder 1, a precooling module 2, a liquefying module 3 and a liquid hydrogen storage tank 4. The lower part of liquid hydrogen storage tank 4 is equipped with feed liquor pipe 9, and upper portion has blast pipe 8, and the fill mouth 15 department of feed liquor pipe 9 is equipped with No. two stop valves 11, and 16 departments of the gas vent of blast pipe 8 are equipped with No. four stop valves 13.
The hydrogen cylinder 1 is connected with the precooling module 2 and the liquefying module 3 in sequence through pipelines and then is connected with the liquid inlet pipe 9, and the exhaust pipe 8 is connected with the input end of the liquefying module 3 through a pipeline with a third stop valve 12; a fifth stop valve 14 is arranged on a pipeline connecting the precooling module 2 and the liquefaction module 3, and a first stop valve 10 is arranged on a pipeline connecting the liquefaction module 3 and the liquid inlet pipe 9.
As shown in fig. 1 and 3, the liquefaction module 3 includes a cryocooler 5, an outer cylinder 6, and a heat exchanger 7; the outer cylinder 6 is connected with the low-temperature refrigerator 5, and the cold head of the low-temperature refrigerator 5 is extended into the outer cylinder 6; the heat exchanger 7 is connected with a cold head of the low-temperature refrigerator 5, and the inner top of the heat exchanger 7 is provided with fins 19.
As shown in fig. 2, the hydrogen gas line in pre-cooling module 2 is filled with an n-para-hydrogen catalyst 18, and when hydrogen gas passes through the hydrogen gas line, the hydrogen gas exchanges heat with liquid nitrogen bath 17 and is catalytically converted by n-para-hydrogen catalyst 18. As shown in fig. 3, the heat exchanger 7 within the liquefaction module 3 is also filled with an ortho-para hydrogen catalyst 18. The ortho-para hydrogen catalyst 18 is a hydrated iron oxide catalyst.
As shown in fig. 4, the liquefaction process of the present invention is as follows:
in the liquefaction process, the second stop valve 11 and the fourth stop valve 13 are opened, and the first stop valve 10, the third stop valve 12, and the fifth stop valve 14 are closed. Liquid nitrogen is filled into the liquid hydrogen storage tank 4 from the filling port 15 through the liquid inlet pipe 9, the wall temperature of the liquid hydrogen storage tank is cooled to the liquid nitrogen temperature, and evaporated nitrogen is exhausted from the exhaust port 16 through the exhaust pipe 8.
And then, opening a first stop valve 10, a fourth stop valve 13 and a fifth stop valve 14, and closing a second stop valve 11 and a third stop valve 12, wherein the liquid nitrogen bath 17 is not added into the precooling module 2, and the cryocooler 5 in the liquefaction module 3 does not work. The normal temperature hydrogen from the hydrogen cylinder 1 passes through the precooling module 2 and the liquefying module 3 and then enters the liquid hydrogen storage tank 4 through the liquid inlet pipe 9, and the cold nitrogen gas remained in the storage tank after the liquid nitrogen is precooled is discharged from the exhaust port 16 through the exhaust pipe 8 until no nitrogen gas remains in the liquid hydrogen storage tank 4.
And finally, opening a first stop valve 10, a third stop valve 12 and a fifth stop valve 14, closing a second stop valve 11 and a fourth stop valve 13, adding a liquid nitrogen bath 17 into the precooling module 2, and operating the cryogenic refrigerator 5 in the liquefaction module 3. Normal-temperature hydrogen from the hydrogen cylinder 1 enters the pre-cooling module 2 through a pipeline, exchanges heat with a liquid nitrogen bath 17 in the pre-cooling module 2 and is catalytically converted through an n-sec-hydrogen catalyst 18 to obtain 77K low-temperature hydrogen in an equilibrium state. The low-temperature hydrogen enters the heat exchanger 7 in the liquefaction module 3 through a pipeline, the heat exchanger 7 is connected with a cold head of the cryogenic refrigerator 5, cold energy of the cold head is transferred to the fins 19 at the top of the heat exchanger 7 through solid heat conduction, the low-temperature hydrogen is cooled to 20K through surface heat exchange with the fins 19 and catalytic conversion through an ortho-para hydrogen catalyst 18 in the heat exchanger 7, the low-temperature hydrogen is liquefied into liquid hydrogen, and the liquid hydrogen enters the liquid hydrogen storage tank 4 through the liquid inlet pipe 9. Before the inner wall surface of the liquid hydrogen storage tank 4 is not cooled to the liquid hydrogen temperature, the liquid hydrogen is evaporated due to heat exchange after entering the liquid hydrogen storage tank 4, the evaporated hydrogen returns to the heat exchanger 7 in the liquefaction module 3 through the exhaust pipe 8 again, is liquefied into liquid hydrogen again and enters the liquid hydrogen storage tank 4, and after the inner wall surface of the liquid hydrogen storage tank 4 is cooled to the liquid hydrogen temperature, the liquid hydrogen is accumulated and stored in the liquid hydrogen storage tank 4.
As shown in fig. 5, in the recondensing flow, the first stop valve 10 and the third stop valve 12 are opened, and the second stop valve 11, the fourth stop valve 13, and the fifth stop valve 14 are closed. In the liquid hydrogen storage process, because of the inevitable heat leakage of liquid hydrogen storage tank 4, liquid hydrogen in liquid hydrogen storage tank 4 constantly evaporates, reaches in the exhaust pressure back liquid hydrogen evaporation gas through 8 discharges of blast pipe and get into the heat exchanger 7 in the liquefaction module 3, through with fin 19 heat transfer, is liquefied into liquid hydrogen again, gets back to liquid hydrogen storage tank 4 again through feed liquor pipe 9, realizes the zero evaporation of liquid hydrogen and stores.
The embodiments described above are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions and equivalents made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims (8)

1. A hydrogen liquefying and evaporated gas recondensing system based on a cryogenic refrigerator is characterized by comprising a hydrogen cylinder (1), a precooling module (2), a liquefying module (3) and a liquid hydrogen storage tank (4); a liquid inlet pipe (9) is arranged at the lower part of the liquid hydrogen storage tank (4), an exhaust pipe (8) is arranged at the upper part of the liquid hydrogen storage tank, a second stop valve (11) is arranged at a filling port (15) of the liquid inlet pipe (9), and a fourth stop valve (13) is arranged at an exhaust port (16) of the exhaust pipe (8);
the hydrogen cylinder (1) is sequentially connected with the precooling module (2) and the liquefying module (3) through pipelines and then is connected with the liquid inlet pipe (9), and the exhaust pipe (8) is connected with the input end of the liquefying module (3) through a pipeline with a third stop valve (12); a fifth stop valve (14) is arranged on a pipeline connecting the pre-cooling module (2) and the liquefaction module (3), and a first stop valve (10) is arranged on a pipeline connecting the liquefaction module (3) and the liquid inlet pipe (9).
2. A cryocooler-based hydrogen liquefaction and boil-off gas recondensing system according to claim 1, wherein the liquefaction module (3) comprises a cryocooler (5), an outer cylinder (6) and a heat exchanger (7); the outer cylinder (6) is connected with the low-temperature refrigerator (5), and a cold head of the low-temperature refrigerator (5) is extended into the outer cylinder (6); the heat exchanger (7) is connected with a cold head of the low-temperature refrigerator (5), and fins (19) are arranged at the top of the heat exchanger (7).
3. The cryocooler-based hydrogen liquefaction and boil-off gas recondensing system according to claim 1, wherein a normal-temperature hydrogen pipeline is adopted as a pipeline between the hydrogen cylinder (1) and the pre-cooling module (2), and pipelines between the pre-cooling module (2) and the liquefaction module (3), between the liquefaction module (3) and the liquid inlet pipe (9), and between the exhaust pipe (8) and the liquefaction module (3) are high-vacuum heat-insulating pipes.
4. The cryocooler-based hydrogen liquefaction and boil-off gas recondensing system of claim 1, wherein the inlet (9) and outlet (8) conduits are high vacuum insulated conduits.
5. The cryocooler-based hydrogen liquefaction and boil-off gas recondensing system of claim 1, wherein the pre-cooling module (2) is a shell and tube heat exchanger.
6. The cryocooler-based hydrogen liquefaction and boil-off gas recondensing system according to claim 1, wherein the first stop valve (10), the second stop valve (11), the third stop valve (12), the fourth stop valve (13) and the fifth stop valve (14) are all low-temperature jacket vacuum stop valves.
7. The cryocooler-based hydrogen liquefaction and boil-off gas recondensing system of claim 1, wherein the hydrogen line in the pre-cooling module (2) and the heat exchanger (7) in the liquefaction module (3) are both filled with an ortho-para hydrogen catalyst.
8. The cryocooler-based hydrogen liquefaction and boil-off gas recondensing system of claim 7, wherein the ortho-para hydrogen catalyst is a hydrated iron oxide catalyst.
CN202210337034.4A 2022-03-31 2022-03-31 Hydrogen liquefaction and boil-off gas recondensation system based on cryocooler Active CN114704765B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116222147A (en) * 2022-12-28 2023-06-06 华中科技大学 Experimental grade liquid hydrogen condensation preparation device
CN116464904A (en) * 2023-06-12 2023-07-21 浙江大学 Vehicle-mounted liquid hydrogen heat-insulating storage container and liquid hydrogen filling method thereof
EP4335815A1 (en) * 2022-08-25 2024-03-13 Purem GmbH Hydrogen storage arrangement

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003002601A (en) * 2001-06-15 2003-01-08 Air Liquide Japan Ltd Method and apparatus for manufacturing hydrogen gas
CN101004240A (en) * 2006-12-25 2007-07-25 浙江大学 Lossless system for storing liquid hydrogen based on low temperature refrigerator
CN103836333A (en) * 2012-11-27 2014-06-04 北京航天试验技术研究所 Thermal-isolation conversion refrigerating device for parahydrogen
CN107014151A (en) * 2017-06-01 2017-08-04 成都深冷液化设备股份有限公司 A kind of device and method of liquefaction of hydrogen
CN109028755A (en) * 2018-05-28 2018-12-18 张家港富瑞氢能装备有限公司 A kind of n- parahydrogen conversion process when producing liquid hydrogen
CN114001273A (en) * 2021-11-30 2022-02-01 中船动力研究院有限公司 Hydrogen liquefaction and hydrogen storage system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003002601A (en) * 2001-06-15 2003-01-08 Air Liquide Japan Ltd Method and apparatus for manufacturing hydrogen gas
CN101004240A (en) * 2006-12-25 2007-07-25 浙江大学 Lossless system for storing liquid hydrogen based on low temperature refrigerator
CN103836333A (en) * 2012-11-27 2014-06-04 北京航天试验技术研究所 Thermal-isolation conversion refrigerating device for parahydrogen
CN107014151A (en) * 2017-06-01 2017-08-04 成都深冷液化设备股份有限公司 A kind of device and method of liquefaction of hydrogen
CN109028755A (en) * 2018-05-28 2018-12-18 张家港富瑞氢能装备有限公司 A kind of n- parahydrogen conversion process when producing liquid hydrogen
CN114001273A (en) * 2021-11-30 2022-02-01 中船动力研究院有限公司 Hydrogen liquefaction and hydrogen storage system

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4335815A1 (en) * 2022-08-25 2024-03-13 Purem GmbH Hydrogen storage arrangement
CN116222147A (en) * 2022-12-28 2023-06-06 华中科技大学 Experimental grade liquid hydrogen condensation preparation device
CN116222147B (en) * 2022-12-28 2024-04-19 华中科技大学 Experimental grade liquid hydrogen condensation preparation device
CN116464904A (en) * 2023-06-12 2023-07-21 浙江大学 Vehicle-mounted liquid hydrogen heat-insulating storage container and liquid hydrogen filling method thereof

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