CN114777412A - Hydrogen liquefying plant with thermal siphon type hydrogen subcooler - Google Patents

Hydrogen liquefying plant with thermal siphon type hydrogen subcooler Download PDF

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Publication number
CN114777412A
CN114777412A CN202210339493.6A CN202210339493A CN114777412A CN 114777412 A CN114777412 A CN 114777412A CN 202210339493 A CN202210339493 A CN 202210339493A CN 114777412 A CN114777412 A CN 114777412A
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hydrogen
heat exchanger
gas
liquid
subcooler
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CN202210339493.6A
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CN114777412B (en
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周刚
李静
龚领会
刘立强
李正宇
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Technical Institute of Physics and Chemistry of CAS
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Technical Institute of Physics and Chemistry of CAS
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    • 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
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
    • F25J1/0037—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work of a return stream
    • 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
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0045—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by vaporising a liquid return stream
    • 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
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    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/005—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
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    • 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
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    • 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
    • F25J1/0224—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 in combination with an internal quasi-closed 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
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    • 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
    • F25J1/0249—Controlling refrigerant inventory, i.e. composition or quantity
    • F25J1/025—Details related to the refrigerant production or treatment, e.g. make-up supply from feed gas itself
    • 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
    • F25J5/00—Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants
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    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
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    • 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
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/02—Separating impurities in general from the feed stream
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    • 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
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    • F25J2245/90—Processes or apparatus involving steps for recycling of process streams the recycled stream being boil-off gas from storage
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    • 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
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/02—Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
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    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F25J2270/06—Internal refrigeration with work-producing gas expansion loop with multiple gas expansion loops
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    • 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
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    • F25J2270/14—External refrigeration with work-producing gas expansion loop
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    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

The invention relates to the technical field of hydrogen liquefaction, in particular to a hydrogen liquefaction device with a thermosyphon type hydrogen subcooler. The invention adopts a thermosiphon hydrogen subcooler, gas-liquid two-phase hydrogen input by a raw material gas path is subcooled into subcooled liquid hydrogen, and the normal-para-hydrogen is converted at the same time, and the generated product hydrogen with qualified para-hydrogen content enters a liquid hydrogen storage tank to form a liquid hydrogen product; the invention adopts the thermosyphon hydrogen subcooler, fully utilizes the latent heat and sensible heat of the liquid hydrogen, and has high liquefaction efficiency, good safety and low energy consumption.

Description

Hydrogen liquefying plant with thermal siphon type hydrogen subcooler
Technical Field
The invention relates to the technical field of hydrogen liquefaction, in particular to a hydrogen liquefying device with a thermosyphon type hydrogen subcooler.
Background
With the development of industry and the improvement of living standard of people, the demand of energy sources is increasing day by day. Because the reserves of fossil energy such as coal, petroleum and the like are limited and pollute the environment, efficient and clean secondary energy needs to be developed, and renewable green energy needs to be searched. The hydrogen is the most common element in the nature, has rich resources and various sources, and has the advantages of high combustion heat value, cleanness, environmental protection, storage, renewability and the like as a secondary energy source. The hydrogen energy can simultaneously meet the requirements of resources, environment and sustainable development, and the unique advantages enable the hydrogen energy to have wide application in the fields of energy and chemical industry.
Hydrogen energy is concerned worldwide and becomes a research hotspot field in recent years; the utilization of hydrogen energy needs to solve a series of problems of preparation, storage, transportation, application and the like, and the storage and transportation of hydrogen energy are the key points of hydrogen energy application. The raw material gas of hydrogen is compressed and then cooled to below minus 250 ℃ to become liquid hydrogen. The density of liquid hydrogen under normal pressure is 845 times that of gaseous hydrogen, and the mass density and the volume density of the liquid hydrogen are higher. Liquid hydrogen has great advantages and economy in aspects of long-distance transportation, storage and the like due to the advantage of high volume energy density, and plays an important role in hydrogen energy utilization; therefore, hydrogen gasification becomes an important option for hydrogen applications.
Hydrogen is usually an equilibrium mixture of orthohydrogen and parahydrogen, and the equilibrium concentration of hydrogen varies significantly with temperature; when the temperature is lowered, orthohydrogen having a high energy ground state is spontaneously converted to parahydrogen of a lower energy state until it cannot be converted to equilibrium hydrogen at the temperature; at room temperature in thermal equilibrium, hydrogen consists of approximately 75% normal hydrogen and 25% para-hydrogen, referred to as normal hydrogen; the normal-to-secondary conversion of gaseous hydrogen can only take place in the presence of a catalyst, while liquid hydrogen can spontaneously undergo normal-to-secondary conversion without a catalyst, but at a slower rate; the positive-secondary conversion of hydrogen is an exothermic reaction, and in order to avoid vaporization of liquid hydrogen products caused by conversion heat and reduce energy consumption of reliquefaction during the storage of liquid hydrogen, the content of parahydrogen in the products should exceed 95% for a large-scale hydrogen liquefaction device.
However, the liquid hydrogen conversion efficiency is low and the energy consumption is high in the prior art; therefore, the prior art has defects and needs to be further developed.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a hydrogen liquefying apparatus having a thermosyphon-type hydrogen subcooler, so as to solve the problems of low liquefying efficiency and high energy consumption in the prior art.
The purpose of the invention is realized by the following technical scheme:
the invention provides a hydrogen liquefying device with a thermosyphon hydrogen subcooler, which comprises: the system comprises a gas management module, a refrigeration module and a liquid hydrogen storage tank connected with the refrigeration module, wherein the gas management module is used for regulating and controlling the gas pressure output by the gas management module to the refrigeration module; the refrigeration module comprises a first heat exchanger and a thermosiphon hydrogen subcooler, the thermosiphon hydrogen subcooler comprises a hydrogen liquid separator, an eighth heat exchanger and a fourth normal-secondary hydrogen converter arranged in the eighth heat exchanger, and the gas management module is connected with the first heat exchanger;
the first heat exchanger and the liquid hydrogen storage tank are sequentially connected to form a first gas path, the first heat exchanger, the eighth heat exchanger and the liquid hydrogen storage tank are sequentially connected to form a second gas path, and hydrogen is input from the high-pressure side of the first heat exchanger and led to the second gas path; the upper end of the hydrogen-liquid separator is connected with the first gas circuit, the lower end of the hydrogen-liquid separator is connected with one side of the eighth heat exchanger, and the other side of the eighth heat exchanger is connected with the upper end of the hydrogen-liquid separator;
the backflow end of the hydrogen-liquid separator is connected with the gas management module through the first heat exchanger to form a third gas path, and the liquid hydrogen storage tank is connected with the gas management module through the first heat exchanger to form a fourth gas path.
Further, the hydrogen liquefying device also comprises a liquid nitrogen precooling device, a second heat exchanger connected with the first heat exchanger, a ninth heat exchanger connected with the second heat exchanger and a cooling unit connected with the ninth heat exchanger;
a first ortho-para-hydrogen converter is arranged in the ninth heat exchanger, the first ortho-para-hydrogen converter is connected with a cooling unit, and the cooling unit is connected with a fourth ortho-para-hydrogen converter;
and the liquid nitrogen precooling device is respectively connected with the first heat exchanger, the second heat exchanger and the ninth heat exchanger and is used for precooling the first heat exchanger, the second heat exchanger and the ninth heat exchanger.
Furthermore, the hydrogen liquefying device also comprises a first low-temperature adsorber and a second low-temperature adsorber which are connected in parallel, one end of the first low-temperature adsorber and one end of the second low-temperature adsorber which are connected in parallel are connected with the second heat exchanger, and the other end of the first low-temperature adsorber and the other end of the second low-temperature adsorber are connected with the first orthoparahydrogen converter.
Furthermore, the cooling unit comprises a third heat exchanger, a fourth heat exchanger, a fifth heat exchanger, a sixth heat exchanger and a seventh heat exchanger, the output ends of the third heat exchanger, the fourth heat exchanger, the fifth heat exchanger, the sixth heat exchanger and the seventh heat exchanger are sequentially connected and connected to the first gas path and the second gas path, and the return ends of the third heat exchanger, the fourth heat exchanger, the fifth heat exchanger, the sixth heat exchanger and the seventh heat exchanger are connected to the third gas path;
the third heat exchanger is connected with the first normal-parahydrogen converter, and the seventh heat exchanger is connected with the liquid hydrogen storage tank.
Furthermore, the hydrogen liquefying device also comprises a third low-temperature adsorber arranged on the first gas circuit, one end of the third low-temperature adsorber is connected with the second heat exchanger, and the other end of the third low-temperature adsorber is connected with the third heat exchanger.
Further, the hydrogen liquefying device also comprises a second ortho-para hydrogen converter and a third ortho-para hydrogen converter which are connected with the second gas path;
one end of the second ortho-para hydrogen converter is connected with the low pressure side of the fourth heat exchanger, and the other end of the second ortho-para hydrogen converter is connected with the high pressure side of the fourth heat exchanger; one end of the third ortho-para hydrogen converter is connected with the low pressure side of the sixth heat exchanger, and the other end of the third ortho-para hydrogen converter is connected with the high pressure side of the sixth heat exchanger.
Furthermore, the hydrogen liquefaction device also comprises a first hydrogen turbo-expander unit and a second hydrogen turbo-expander unit, one end of the first hydrogen turbo-expander unit is connected to a first air path between the third heat exchanger and the fourth heat exchanger, and the other end of the first hydrogen turbo-expander unit is connected to the high-pressure side of the fifth heat exchanger;
one end of the second hydrogen turbo expander unit is connected to the low-pressure side of the fifth heat exchanger, and the other end of the second hydrogen turbo expander unit is connected to the low-pressure side of the sixth heat exchanger and sequentially connected with the fifth heat exchanger, the fourth heat exchanger, the third heat exchanger, the first heat exchanger and the gas management module.
Furthermore, an eighth throttling valve is arranged between the upper end of the hydrogen-liquid separator and the first gas circuit, a ninth throttling valve is arranged on the first gas circuit and is positioned between the eighth throttling valve and the liquid hydrogen storage tank, and a tenth throttling valve is arranged on the second gas circuit and is positioned between the cooling unit and the eighth heat exchanger.
Furthermore, the gas management module comprises a medium-pressure hydrogen compressor unit and a high-pressure hydrogen compressor unit which are connected in series, wherein one end of the medium-pressure hydrogen compressor unit, which is far away from the high-pressure hydrogen compressor unit, is connected with the reflux end of the first heat exchanger, and one end of the high-pressure hydrogen compressor unit, which is far away from the medium-pressure hydrogen compressor unit, is connected with the input end of the first heat exchanger;
the medium-pressure hydrogen compressor unit and the high-pressure hydrogen compressor unit are connected through a first heat exchanger and a third heat exchanger.
Further, the hydrogen liquefaction device still includes gaseous buffer tank, and gaseous buffer tank one end is connected with first heat exchanger, and the other end passes through the thirteenth governing valve and is connected with the second gas circuit.
The invention provides a hydrogen liquefying device with a thermosiphon hydrogen subcooler, which adopts the thermosiphon hydrogen subcooler, wherein gas-liquid two-phase hydrogen input by a raw material gas circuit (a second gas circuit) is subcooled into subcooled liquid hydrogen, and meanwhile, normal-secondary hydrogen is converted, and the generated product hydrogen with qualified secondary hydrogen content enters a liquid hydrogen storage tank to form a liquid hydrogen product; the invention adopts the thermosyphon hydrogen subcooler, fully utilizes the latent heat and sensible heat of the liquid hydrogen, and has high liquefaction efficiency, good safety and low energy consumption.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and do not constitute a limitation of the invention. In the drawings:
fig. 1 is a structural view of a hydrogen liquefying apparatus having a thermosyphon hydrogen subcooler of the present invention.
Wherein the reference numbers are: the heat exchanger comprises HEX1, HEX2, a second heat exchanger, HEX3, a third heat exchanger, HEX4, a fourth heat exchanger, HEX5, a fifth heat exchanger, HEX6, a sixth heat exchanger, HEX7, a seventh heat exchanger, HEX-OP4, an eighth heat exchanger and HEX-OP1, a ninth heat exchanger;
OP 1-first ortho-para-hydrogen converter, OP 2-second ortho-para-hydrogen converter, OP 3-third ortho-para-hydrogen converter, OP 4-fourth ortho-para-hydrogen converter, a 1-first low temperature adsorber, a 2-second low temperature adsorber, A3-third low temperature adsorber;
the Cold Box, the D4200 liquid hydrogen storage Tank, the D4100 hydrogen gas liquid separator, the D3100 nitrogen gas liquid separator and the Buffer Tank;
CV 04-load valve, CV 03-unload valve, CV 02-low pressure bypass valve, CV 01-medium pressure bypass valve, CV 08-eighth throttle valve, CV 09-ninth throttle valve, CV 10-tenth throttle valve, CV 12-twelfth regulating valve, CV 13-thirteenth regulating valve.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The hydrogen liquefying device has different process requirements in a starting precooling stage and a stable operation stage; several issues need to be considered: 1. the external liquid hydrogen storage tank has large heat capacity, and the external liquid hydrogen storage tank has large capacity and large heat capacity for 5TPD (5 tons/day) and 10TPD (10 tons/day) hydrogen liquefying devices, and the problem of precooling of the liquid hydrogen storage tank in a start-up precooling stage needs to be considered; 2. in the stable operation stage, the product hydrogen with qualified parahydrogen content is required to enter the liquid hydrogen storage tank, the higher the liquid phase fraction in the product hydrogen is, the better the liquid phase fraction is, and the full liquid phase is preferred, so that the return gas pipeline of the liquid hydrogen storage tank can be reduced, and the pressure of a safety valve of a tank body of the liquid hydrogen storage tank can be reduced; 3. after the hydrogen liquefaction device enters a stable operation stage, the circulation gas circuit performs closed refrigeration circulation, and the hydrogen raw material gas in the raw material gas circuit is completely liquefied and converted into product hydrogen with qualified secondary hydrogen content through the normal secondary hydrogen and enters the liquid hydrogen storage tank.
In order to solve the problems, the invention provides a hydrogen liquefying device with a thermosyphon type hydrogen subcooler, in the starting precooling stage of the hydrogen liquefying device, circulating hydrogen is throttled to obtain two-phase hydrogen containing liquid hydrogen, the two-phase hydrogen enters a liquid hydrogen storage tank, and the liquid hydrogen storage tank is precooled and cooled; after the liquid hydrogen storage tank is cooled to a proper temperature, such as 50K, the hydrogen liquefying device enters a stable production stage; the method adopts the thermosiphon hydrogen subcooler, and in the stable production stage, gas-liquid two-phase hydrogen generated by the raw material gas circuit is subcooled into subcooled liquid hydrogen, and meanwhile, the orthohydrogen is converted, and the generated product hydrogen with qualified parahydrogen content enters the liquid hydrogen storage tank to form a liquid hydrogen product; the method comprehensively considers different process requirements of a pre-cooling stage and a stable production stage when the hydrogen liquefier is started, adopts the thermosiphon hydrogen subcooler, and fully utilizes the latent heat and the sensible heat of the liquid hydrogen; the circulating gas circuit and the raw material gas circuit are not communicated at the stable operation stage, so that the purity of the liquid hydrogen product is prevented from being influenced; in the stable operation stage, the return gas of the liquid hydrogen storage tank does not enter the circulating gas circuit any more, so that excessive gas in the circulating gas circuit is avoided, the overall regulation and control complexity of the hydrogen liquefier is increased, and the heat balance of the circulating gas circuit and the raw material gas circuit in the hydrogen liquefier is favorably maintained; the hydrogen liquefying device has high liquefying efficiency, good safety and low energy consumption.
As shown in fig. 1, a hydrogen liquefying apparatus having a thermosyphon hydrogen subcooler according to an embodiment of the present invention includes: the system comprises a medium-pressure hydrogen compressor unit CL, a high-pressure hydrogen compressor unit CH, a hydrogen buffer tank, a Cold Box Cold Box, a liquid nitrogen precooling device, a first hydrogen turboexpander unit, a second hydrogen turboexpander unit, a raw material gas circuit low-temperature adsorber group, a circulating gas circuit low-temperature adsorber, a heat exchanger group, a normal-secondary hydrogen converter group, a thermosiphon hydrogen subcooler, a normal-temperature regulating valve, a low-temperature regulating valve, a throttling valve and a liquid hydrogen storage tank D4200.
The system comprises a liquid nitrogen precooling device, a first hydrogen turbo-expander unit, a second hydrogen turbo-expander unit, a raw material gas path low-temperature adsorber group, a circulating gas path low-temperature adsorber, a heat exchanger group, an orthohydrogen converter group, a thermosiphon hydrogen subcooler, a low-temperature regulating valve and a throttle valve which are all arranged in a cold box; wherein the group of orthonormal para-hydrogen converters comprises a first orthonormal para-hydrogen converter OP1, a second orthonormal para-hydrogen converter OP2, a third orthonormal para-hydrogen converter OP3 and a fourth orthonormal para-hydrogen converter OP 4; the low-temperature adsorber group comprises a first low-temperature adsorber a1 and a second low-temperature adsorber a 2.
The medium-pressure hydrogen compressor unit and the high-pressure hydrogen compressor unit are both oil-free piston compressors, and form a hydrogen compressor station; the hydrogen Buffer Tank, the loading valve CV04, the unloading valve CV03, the low-pressure bypass valve CV02 and the medium-pressure bypass valve CV01 form a gas management module of the hydrogen liquefier; the gas management module is used for adjusting and controlling the inlet and outlet pressures of the medium-pressure hydrogen compressor unit and the high-pressure hydrogen compressor unit.
The liquid nitrogen precooling device comprises a liquid nitrogen inlet pipeline, a liquid nitrogen inlet pipeline regulating valve CV06, a nitrogen-liquid separator D3100, a liquid nitrogen pipeline, a nitrogen-liquid separator outlet pipeline, a gas-nitrogen exhaust pipeline, a gas-nitrogen return pipeline and the like; the liquid nitrogen precooling device is used for precooling the first heat exchanger, the second heat exchanger and the ninth heat exchanger HEX-OP 1; the liquid nitrogen precooling device adopts a thermosiphon liquid nitrogen heat exchanger, fully utilizes the latent heat and sensible heat of the liquid nitrogen and has high precooling efficiency.
The first hydrogen turboexpander set consists of two hydrogen turbines E11 and E12 which are connected in series; the second hydrogen turbo-expander set consists of two hydrogen turbines E21 and E22 connected in series; the first low-temperature adsorber A1 and the second low-temperature adsorber A2 of the raw material gas circuit (first gas circuit) are connected in parallel and switched to use, one works, and the other can be regenerated at the same time; the circulation circuit low-temperature adsorber (third low-temperature adsorber) A3 can be manually regenerated on line, and the heat exchanger group comprises a first heat exchanger HEX1, a second heat exchanger HEX2, a liquid nitrogen normal-secondary hydrogen conversion heat exchanger (ninth heat exchanger) HEX-OP1, a third heat exchanger HEX3, a fourth heat exchanger HEX4, a fifth heat exchanger HEX5, a sixth heat exchanger HEX6, a seventh heat exchanger HEX7 and a liquid hydrogen normal-secondary hydrogen conversion heat exchanger (eighth heat exchanger) HEX-OP 4.
The first heat exchanger HEX1 and the liquid hydrogen storage tank D4200 are sequentially connected to form a first gas path, the first heat exchanger HEX1, the eighth heat exchanger HEX-OP4 and the liquid hydrogen storage tank D4200 are sequentially connected to form a second gas path, and hydrogen input from the high-pressure side of the first heat exchanger HEX1 is led to the second gas path; the upper end of the hydrogen liquid separator D4100 is connected with the first gas circuit, the lower end of the hydrogen liquid separator D4100 is connected with one side of the eighth heat exchanger HEX-OP4, and the other side of the eighth heat exchanger HEX-OP4 is connected with the upper end of the hydrogen liquid separator D4100; the return end of the hydrogen gas-liquid separator D4100 is connected with the gas management module through the first heat exchanger HEX1 and forms a third gas path, and the liquid hydrogen storage tank D4200 is connected with the gas management module through the first heat exchanger HEX1 and forms a fourth gas path.
The heat exchanger comprises an output end and a return end, wherein the output end is a gas path at one end of the direction of the gas flowing to the liquid hydrogen storage tank, namely a first gas path and a second gas path; the backflow end is a gas path for gas to flow back to one end of the first heat exchanger, namely a third gas path and a fourth gas path; the heat exchanger has a high pressure side and a low pressure side, with the direction of fig. 1 as the reference, and the right side of the heat exchanger is the low pressure side.
The throttle valves comprise an eighth throttle valve CV08, a ninth throttle valve CV09 and a tenth throttle valve CV10, and a twelfth throttle valve CV12 is a rapid cooling pipeline valve in the starting debugging stage; the first ortho-para hydrogen converter OP1 is a liquid nitrogen temperature grade ortho-para hydrogen converter embedded in HEX-OP1, and is converted isothermally; the second ortho-para-hydrogen converter OP2 and the third ortho-para-hydrogen converter OP3 are adiabatic reforming, and the fourth ortho-para-hydrogen converter OP4 is a liquid hydrogen temperature-level ortho-para-hydrogen converter embedded in the eighth heat exchanger HEX-OP4, isothermal reforming.
The hydrogen gas-liquid separator D4100, the liquid hydrogen normal-para hydrogen conversion heat exchanger HEX-OP4, the liquid injection pipeline 7, the liquid hydrogen pipeline 1, the gas return pipeline 2 and the gas return pipeline 3 form a thermosiphon loop; the liquid level of the hydrogen-liquid separator D4100 is higher than the top of the liquid hydrogen normal-para hydrogen conversion heat exchanger HEX-OP4, so that the channel of the heat exchanger HEX-OP4 is completely soaked in the liquid hydrogen.
In a start-up precooling stage, hydrogen in a circulating gas path enters the ninth throttle valve CV09 through the pipeline 6 to generate gas-liquid two-phase fluid, wherein liquid hydrogen is used for precooling the liquid hydrogen storage tank D4200, gas-phase hydrogen returns through the pipeline 10 and returns to the low-pressure inlet side of the first heat exchanger HEX1 through the twelfth throttle valve CV12, and the temperature is rapidly reduced; after the liquid hydrogen storage tank D4200 is cooled to a proper temperature, for example, 50K, the ninth throttle valve CV09 is slowly closed, the eighth throttle valve CV08 is slowly opened, liquid accumulation starts when the liquid level of D4100 reaches a certain height, the tenth throttle valve CV10 starts throttling, and the hydrogen liquefaction device enters a stable production stage.
The circulating gas-liquid hydrogen used for the pre-cooling liquid hydrogen storage tank D4200 is unqualified in para-hydrogen content, and the part of liquid hydrogen is discarded; during the process of circulating the gas-liquid hydrogen precooling liquid hydrogen storage Tank D4200, hydrogen in the gas Buffer Tank Buffer Tank can be reduced, and at the moment, the gas is supplemented to the hydrogen Buffer Tank Buffer Tank from the feed gas path through a thirteenth regulating valve CV 13.
The hydrogen gas liquid separator D4100 is a hydrogen gas subcooler, subcooled liquid hydrogen in a liquid hydrogen pipeline 1 at the bottom of the hydrogen gas liquid separator D4100 is used for cooling gas-liquid two-phase fluid from a raw material gas circuit, and the subcooled liquid hydrogen becomes saturated hydrogen and enters the hydrogen gas liquid separator D4100 through a pipeline 2; the saturated hydrogen in the hydrogen-liquid separator D4100 is returned to the inlet of the low-pressure side of the seventh heat exchanger HEX7 through the pipeline 3.
The raw material hydrogen is throttled by a tenth throttle valve CV10 to become a gas-liquid two-phase fluid, passes through an eighth heat exchanger HEX-OP4, is subcooled by subcooled liquid hydrogen from a liquid hydrogen pipeline 1 at the bottom of a hydrogen liquid separator D4100 to become subcooled liquid hydrogen, and simultaneously passes through a fourth normal-to-secondary hydrogen converter OP4 to perform isothermal normal-to-secondary hydrogen conversion, so that the product hydrogen with qualified secondary hydrogen content enters a liquid hydrogen storage tank D4200.
The working process of the hydrogen liquefying device is as follows:
a circulating hydrogen path:
(1) and high-pressure hydrogen discharged by the piston high-pressure hydrogen compressor unit CH enters a cold box.
(2) The high-pressure hydrogen entering the Cold Box Cold Box is cooled to a certain temperature by the return Cold hydrogen and LN for precooling through the first heat exchanger HEX1 and the second heat exchanger HEX2, then enters the third heat exchanger HEX3 to be cooled to be lower in temperature, and then is divided into two streams, most of the two streams enter two sets of turbines in series (a first hydrogen turbo expander set and a second hydrogen turbo expander set), the expansion loop with the intermediate temperature reduction carries out adiabatic expansion refrigeration, the hydrogen changed into low-temperature medium-pressure hydrogen returns to the inlet of the low-pressure side of the sixth heat exchanger HEX6, and sequentially passes through the fifth heat exchanger to the first heat exchanger (HEX 5-HEX 1) in a countercurrent mode, and then exits the Cold Box Cold Box after Cold energy recovery and returns to the gas suction end of the high-pressure hydrogen compressor set CH to be recycled.
(3) The other part of the split high-pressure hydrogen is continuously cooled by the refluxed low-temperature low-pressure hydrogen through a fourth heat exchanger to a seventh heat exchanger (HEX 4-HEX 7); in a starting precooling stage, circulating hydrogen is throttled by a ninth throttle valve CV09 to obtain two-phase hydrogen containing liquid hydrogen, the two-phase hydrogen enters a liquid hydrogen storage tank D4200, and precooling and cooling are carried out on the liquid hydrogen storage tank D4200; after the liquid hydrogen storage tank D4200 is cooled to a proper temperature, for example, 50K, the throttle valve CV09 is slowly closed, the eighth throttle valve CV08 is slowly opened, liquid accumulation of the hydrogen gas liquid separator D4100 is started, the tenth throttle valve CV10 starts throttling after the liquid level of the hydrogen gas liquid separator D4100 reaches a certain height, and the hydrogen liquefier enters a stable production stage; the circulating hydrogen is throttled by an eighth throttling valve CV08 to obtain two-phase hydrogen containing liquid hydrogen, and the two-phase hydrogen enters a hydrogen gas-liquid separator D4100; the hydrogen gas-liquid separator D4100 and the eighth heat exchanger HEX-OP4 form a thermosyphon loop, the density difference of hydrogen is fully utilized, the liquid hydrogen generated by the raw material gas circuit is cooled again to generate supercooled liquid hydrogen, meanwhile, the supercooled liquid hydrogen is subjected to OP conversion, and the generated product hydrogen with qualified parahydrogen content enters the liquid hydrogen storage tank D4200 to form a liquid hydrogen product; the liquid level height of the hydrogen gas-liquid separator D4100 must be higher than the top of the eighth heat exchanger HEX-OP4, so that the channel of the eighth heat exchanger HEX-OP4 is completely soaked in the liquid hydrogen.
(4) Saturated hydrogen steam generated in the hydrogen separator D4100 returns through the air return pipeline 3 and flows through the seventh heat exchanger HEX7 to cool the high-pressure hydrogen before throttling, and sequentially flows reversely through the sixth heat exchanger to the first heat exchangers (HEX 6-HEX 1), is discharged out of the cold box after cold energy is recovered, and then returns to the air suction end of the medium-pressure compressor CL, is compressed to medium-pressure through the medium-pressure compressor CL, and is mixed with the medium-pressure hydrogen of the turbine return air.
(5) In the starting precooling stage, return air in the liquid hydrogen storage tank D4200 is returned to the low-pressure side inlet of the HEX1 from the twelfth regulating valve CV12 for rapid cooling precooling.
(6) The circulating gas-liquid hydrogen used for the precooling liquid hydrogen storage tank D4200 is rejected because the content of the parahydrogen is unqualified; during the process of circulating the gas-liquid hydrogen precooling liquid hydrogen storage Tank D4200, hydrogen in the gas Buffer Tank Buffer Tank is reduced, and gas is supplied to the gas Buffer Tank Buffer Tank from a feed gas path through a thirteenth regulating valve CV 13.
The cooling and liquefying processes of the raw material gas are as follows:
(1) the raw material hydrogen (normal hydrogen) is cooled to a certain temperature by the return cold hydrogen and the LN for precooling through the first heat exchanger HEX1 and the second heat exchanger HEX2, then enters the first normal-secondary hydrogen converter OP1 soaked by liquid nitrogen for isothermal normal-secondary hydrogen conversion, and simultaneously the reaction heat is discharged through the liquid nitrogen.
(2) The hydrogen cooled by liquid nitrogen has an increased parahydrogen ratio, and then enters the third heat exchanger HEX3 and the fourth heat exchanger HEX4 to be further cooled by the cold hydrogen flowing back, and enters the second positive parahydrogen converter OP2, because no corresponding low-temperature liquid performs isothermal heat release, the positive parahydrogen conversion is adiabatic conversion, and the temperature of the low-temperature liquid is increased at the same time when the parahydrogen ratio is increased, so the hydrogen at the outlet of the second positive parahydrogen converter OP2 is reintroduced into the hot-end inlet of the fourth heat exchanger HEX4, and the reaction heat is taken away by the reflux gas in the fourth heat exchanger HEX 4.
(3) The low-temperature hydrogen from the fourth heat exchanger HEX4 enters the fifth heat exchanger HEX5 and the sixth heat exchanger HEX6, is further cooled by the cold hydrogen flowing back, enters the third positive-para-hydrogen converter OP3, undergoes positive-para-hydrogen adiabatic conversion in the third positive-para-hydrogen converter OP3, the hydrogen at the outlet of the third positive-para-hydrogen converter OP3 is reintroduced into the hot-end inlet of the sixth heat exchanger HEX6, and the reaction heat is taken away by the reflux gas in the sixth heat exchanger HEX 6.
(4) The low-temperature hydrogen coming out of the sixth heat exchanger HEX6 enters the seventh heat exchanger HEX7 to be further cooled by the return gas, at which point the temperature has reached the optimum temperature before throttling. Because the parahydrogen concentration of the throttled two-phase hydrogen is less than 95%, a fourth ortho-parahydrogen converter OP4 is added after a tenth throttle valve CV 10; the fourth ortho-para hydrogen converter OP4 was installed in the eighth heat exchanger HEX-OP4, soaked with liquid hydrogen, and the fourth ortho-para hydrogen converter OP4 was an isothermal type ortho-para hydrogen converter.
(5) After passing through the fourth ortho-para hydrogen converter OP4, the concentration of para-hydrogen exceeds 95%, and the para-hydrogen is completely cooled by the eighth heat exchanger HEX-OP4 to form liquid hydrogen with a certain supercooling degree, and the liquid hydrogen enters the liquid hydrogen storage tank D4200 to form a liquid hydrogen product.
(6) In the stable operation stage, the circulating gas circuit is not communicated with the raw material gas circuit, so that the purity of the liquid hydrogen product is prevented from being influenced; in the stable operation stage, the return gas of the liquid hydrogen storage tank D4200 does not enter the circulation gas circuit any more, so that excessive gas in the circulation gas circuit is avoided, the overall regulation and control complexity of the hydrogen liquefier is increased, and the heat balance of the circulation gas circuit and the raw material gas circuit in the hydrogen liquefier is kept.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. A hydrogen liquefying apparatus having a thermosyphon hydrogen subcooler, comprising: the liquid hydrogen storage tank is connected with the refrigeration module, and the gas management module is used for regulating and controlling the gas pressure output to the refrigeration module by the gas management module; the refrigeration module comprises a first heat exchanger and a thermosiphon hydrogen subcooler, the thermosiphon hydrogen subcooler comprises a hydrogen liquid separator, an eighth heat exchanger and a fourth normal-secondary hydrogen converter arranged in the eighth heat exchanger, and the gas management module is connected with the first heat exchanger;
the first heat exchanger and the liquid hydrogen storage tank are sequentially connected to form a first gas path, the first heat exchanger, the eighth heat exchanger and the liquid hydrogen storage tank are sequentially connected to form a second gas path, and hydrogen is input from the high-pressure side of the first heat exchanger and led to the second gas path; the upper end of the hydrogen liquid separator is connected with the first gas circuit, the lower end of the hydrogen liquid separator is connected with one side of the eighth heat exchanger, and the other side of the eighth heat exchanger is connected with the upper end of the hydrogen liquid separator;
the backflow end of the hydrogen gas-liquid separator is connected with the gas management module through the first heat exchanger to form a third gas path, and the liquid hydrogen storage tank is connected with the gas management module through the first heat exchanger to form a fourth gas path.
2. The hydrogen gas liquefaction device with a thermosyphon hydrogen subcooler of claim 1, further comprising a liquid nitrogen precooling device, a second heat exchanger connected to the first heat exchanger, a ninth heat exchanger connected to the second heat exchanger, and a cooling unit connected to the ninth heat exchanger;
a first ortho-para hydrogen converter is arranged in the ninth heat exchanger, the first ortho-para hydrogen converter is connected with a cooling unit, and the cooling unit is connected with the fourth ortho-para hydrogen converter;
the liquid nitrogen precooling device is respectively connected with the first heat exchanger, the second heat exchanger and the ninth heat exchanger and is used for precooling the first heat exchanger, the second heat exchanger and the ninth heat exchanger.
3. The hydrogen liquefying apparatus having a thermosyphon hydrogen subcooler of claim 2, further comprising a first low-temperature adsorber and a second low-temperature adsorber connected in parallel to each other, wherein one end of the first low-temperature adsorber and the second low-temperature adsorber connected in parallel is connected to the second heat exchanger, and the other end is connected to the first normal-para hydrogen converter.
4. The hydrogen liquefying device with the thermosyphon hydrogen subcooler of claim 2, wherein the cooling unit comprises a third heat exchanger, a fourth heat exchanger, a fifth heat exchanger, a sixth heat exchanger and a seventh heat exchanger, output ends of the third heat exchanger, the fourth heat exchanger, the fifth heat exchanger, the sixth heat exchanger and the seventh heat exchanger are sequentially connected and connected to the first gas path and the second gas path, and return ends of the third heat exchanger, the fourth heat exchanger, the fifth heat exchanger, the sixth heat exchanger and the seventh heat exchanger are connected to the third gas path;
the third heat exchanger is connected with the first para-hydrogen converter, and the seventh heat exchanger is connected with the liquid hydrogen storage tank.
5. The hydrogen liquefaction device having a thermosyphon hydrogen subcooler of claim 4, further comprising a third cryogenic adsorber disposed on the first gas path, the third cryogenic adsorber having one end connected to the second heat exchanger and another end connected to the third heat exchanger.
6. The hydrogen liquefaction device having the thermosyphon hydrogen subcooler of claim 4, further comprising a second and a third ortho-para hydrogen converters connected to the second gas path;
one end of the second ortho-para hydrogen converter is connected with the low-pressure side of the fourth heat exchanger, and the other end of the second ortho-para hydrogen converter is connected with the high-pressure side of the fourth heat exchanger; one end of the third ortho-para hydrogen converter is connected with the low-pressure side of the sixth heat exchanger, and the other end of the third ortho-para hydrogen converter is connected with the high-pressure side of the sixth heat exchanger.
7. The hydrogen liquefying apparatus having a thermosyphon hydrogen subcooler of claim 4, further comprising a first hydrogen turboexpander unit and a second hydrogen turboexpander unit, wherein one end of the first hydrogen turboexpander unit is connected to the first gas path between the third heat exchanger and the fourth heat exchanger, and the other end of the first hydrogen turboexpander unit is connected to a high-pressure side of the fifth heat exchanger;
one end of the second hydrogen turbine expansion machine set is connected to the low-pressure side of the fifth heat exchanger, and the other end of the second hydrogen turbine expansion machine set is connected to the low-pressure side of the sixth heat exchanger and sequentially connected with the fifth heat exchanger, the fourth heat exchanger, the third heat exchanger, the first heat exchanger and the gas management module.
8. The hydrogen liquefying apparatus having a thermosyphon hydrogen subcooler of claim 2, wherein an eighth throttling valve is provided between an upper end of the hydrogen liquid separator and the first gas passage connection, a ninth throttling valve is provided on the first gas passage and is located between the eighth throttling valve and the liquid hydrogen storage tank, and a tenth throttling valve is provided on the second gas passage and is located between the cooling unit and the eighth heat exchanger.
9. The hydrogen liquefaction device with a thermosyphon hydrogen subcooler of claim 4, wherein the gas management module comprises an intermediate pressure hydrogen compressor train and a high pressure hydrogen compressor train in series, the end of the intermediate pressure hydrogen compressor train distal from the high pressure hydrogen compressor train being connected to the return end of the first heat exchanger, the end of the high pressure hydrogen compressor train distal from the intermediate pressure hydrogen compressor train being connected to the input end of the first heat exchanger;
the medium-pressure hydrogen compressor unit and the high-pressure hydrogen compressor unit are connected through the first heat exchanger and the third heat exchanger.
10. The hydrogen liquefying apparatus having a thermosyphon hydrogen subcooler of claim 7, further comprising a gas buffer tank connected at one end to the first heat exchanger and at the other end to the second gas path through a thirteenth regulating valve.
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