WO2013175905A1 - Dispositif de production d'hydrogène liquide - Google Patents

Dispositif de production d'hydrogène liquide Download PDF

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Publication number
WO2013175905A1
WO2013175905A1 PCT/JP2013/061414 JP2013061414W WO2013175905A1 WO 2013175905 A1 WO2013175905 A1 WO 2013175905A1 JP 2013061414 W JP2013061414 W JP 2013061414W WO 2013175905 A1 WO2013175905 A1 WO 2013175905A1
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Prior art keywords
hydrogen
liquid hydrogen
boil
gas
circulating
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PCT/JP2013/061414
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English (en)
Japanese (ja)
Inventor
和英 袴田
山下　誠二
俊博 小宮
祥二 神谷
憲二郎 新道
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川崎重工業株式会社
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Priority to AU2013264211A priority Critical patent/AU2013264211B2/en
Priority to RU2014125729/06A priority patent/RU2573423C1/ru
Priority to US14/376,504 priority patent/US20150068246A1/en
Publication of WO2013175905A1 publication Critical patent/WO2013175905A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/02—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point using Joule-Thompson effect; using vortex effect
    • 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/06—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point using expanders
    • 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"
    • F25J1/004—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 flash gas recovery
    • 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
    • F25J1/0201—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 only internal refrigeration means, i.e. without external refrigeration
    • F25J1/0202—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 only internal refrigeration means, i.e. without external refrigeration in a quasi-closed internal 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
    • F25J1/0243—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
    • 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
    • F25J1/0244—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
    • 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
    • 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
    • F25J1/0277—Offshore use, e.g. during shipping
    • F25J1/0278—Unit being stationary, e.g. on floating barge or fixed platform
    • 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B40/00—Subcoolers, desuperheaters or superheaters
    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/60—Details about pipelines, i.e. network, for feed or product distribution
    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/62—Details of storing a fluid in a tank
    • 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

Definitions

  • the present invention relates to a liquid hydrogen production apparatus equipped with a boil-off gas treatment mechanism that re-liquefies and reuses boil-off gas generated in a liquid hydrogen storage tank such as a liquid hydrogen transport ship.
  • Hydrogen has been widely used as a raw material and a reducing agent in technical fields such as the chemical industry, petroleum refining industry, and steel industry.
  • the use of hydrogen as a fuel or energy source is expected in various technical fields due to the global policy for reducing carbon dioxide emissions and the continuous rise in fossil fuels such as crude oil.
  • various uses as fuel for internal combustion engines for automobiles and turbines for generators have been proposed.
  • Hydrogen is produced by steam reforming of hydrocarbons, electrolysis of water, etc., but can also be produced by a hydrogen production system that produces hydrogen using low-grade coal such as lignite as the main raw material.
  • the hydrogen production system is usually installed in the vicinity of the production area of low-grade coal.
  • demand areas for hydrogen are mainly populated areas such as urban areas and away from low-grade coal production areas, so it is necessary to transport the hydrogen produced by the hydrogen production system to these demand areas. .
  • the hydrogen produced by the hydrogen production system is usually cooled and liquefied by a hydrogen liquefaction facility and stored in a liquid hydrogen storage tank, and then liquid hydrogen is appropriately used. It is made to transport to a demand place in the form (for example, refer patent document 1).
  • a liquid hydrogen transport ship including a liquid hydrogen storage tank for storing cryogenic liquid hydrogen while keeping it cold is used.
  • liquid hydrogen storage tank at the port near the location of the hydrogen liquefier or the liquid hydrogen storage tank (hereinafter referred to as “loading port”).
  • Liquid hydrogen storage tank of the liquid hydrogen transport ship is filled with liquid hydrogen.
  • the liquid hydrogen storage tank of the liquid hydrogen transport ship is located near the unloading port. Liquid hydrogen is supplied to the liquid hydrogen storage tank.
  • the liquid hydrogen transport ship returns to the loading port from the loading port, leaving an appropriate amount (for example, several vol% of the volume of the liquid hydrogen storage vessel) of the liquid hydrogen for cold storage in the liquid hydrogen storage vessel.
  • liquid hydrogen is filled again from the liquid hydrogen storage tank to the liquid hydrogen storage tank of the liquid hydrogen transport ship.
  • the temperature inside the liquid hydrogen storage tank of the liquid hydrogen transport ship rises due to heat input from outside the storage tank during berthing.
  • the temperature of the upper part of the liquid hydrogen storage tank is higher than the saturation temperature of liquid hydrogen. Therefore, when the liquid hydrogen storage tank is filled with liquid hydrogen, the liquid hydrogen is vaporized due to the difference between the temperature in the liquid hydrogen storage tank and the temperature of the liquid hydrogen to be filled, and a large amount of boil-off gas is generated.
  • the berthing period of the liquid hydrogen transport ship is relatively short, such as one to several days, it is necessary to process a large amount of boil-off gas in a short period.
  • boil-off gas generated in large quantities is mixed with raw material hydrogen supplied from the hydrogen production system to the hydrogen liquefier, reliquefied by the hydrogen liquefier, and reused.
  • the boil-off gas is very low in temperature, there is a problem in that when used as a raw material for a hydrogen liquefaction device, a problem occurs in the hydrogen liquefaction device designed on the assumption that raw material hydrogen is supplied at room temperature. .
  • the boil-off gas is heated to room temperature and mixed with the raw material hydrogen, such a problem can be avoided.
  • the present invention has been made in order to solve the above-described conventional problems, and the boil-off gas generated in the liquid hydrogen storage tank of a transportation means such as a liquid hydrogen transport ship that transports liquid hydrogen is wasted in its cold energy. Therefore, it is an object to be solved to provide means that enables effective reutilization without re-liquefaction and reuse as liquid hydrogen.
  • the liquid hydrogen production apparatus made to solve the above problems includes a refrigeration cycle section using circulating hydrogen as a refrigerant, and a liquid hydrogen generation section that generates liquid hydrogen from hydrogen gas.
  • This liquid hydrogen production apparatus includes a boil-off gas introduction unit that introduces boil-off gas generated in the liquid hydrogen storage tank into a predetermined introduction location of the refrigeration cycle unit, and surplus due to the boil-off gas introduced from the boil-off gas introduction unit A circulating hydrogen discharge unit that discharges the circulating hydrogen from a predetermined discharge point of the refrigeration cycle unit to the liquid hydrogen generation unit.
  • the refrigeration cycle unit is provided between a compressor that compresses circulating hydrogen, an expander that expands circulating hydrogen, and the compressor and the expander, and upstream of the compressor. And one or more sets of heat exchanging units including a low temperature side heat exchanging unit and a high temperature side heat exchanging unit on the downstream side of the compressor.
  • the liquid hydrogen generation unit is provided with a raw material hydrogen passage for circulating the hydrogen gas supplied from the raw material hydrogen supply source, an expansion valve provided downstream of the raw material hydrogen passage, and expands the hydrogen gas to generate liquid hydrogen, It has one or more hydrogen gas cooling units that cool the hydrogen gas by exchanging heat with the one or more heat exchange units of the refrigeration cycle unit.
  • the predetermined introduction location of the refrigeration cycle section is located downstream from the expander and upstream from the compressor, and the predetermined discharge location of the refrigeration cycle section is the first low temperature side heat exchange located upstream from the compressor. And the first high temperature side heat exchanger located downstream of the compressor.
  • a plurality of predetermined introduction points of the refrigeration cycle unit are provided according to a difference between the temperature of circulating hydrogen in the refrigeration cycle unit and the temperature of boil-off gas generated in the liquid hydrogen storage tank. Is preferred. Moreover, it is preferable that the predetermined discharge
  • the expander is preferably an expansion turbine.
  • the expansion valve is preferably a Joule Thomson valve.
  • examples of the liquid hydrogen storage tank include a liquid hydrogen storage tank of a liquid hydrogen transport ship.
  • a very low temperature boil-off gas discharged from a liquid hydrogen storage tank of a liquid hydrogen transport ship is introduced into a portion where the circulating hydrogen in the hydrogen circulation passage of the refrigeration cycle section flows at a very low temperature.
  • the circulating hydrogen that becomes excessive due to the introduction of the boil-off gas is discharged from the portion where the circulating hydrogen in the hydrogen circulation passage flows at about room temperature to the portion where the source hydrogen in the raw material hydrogen passage flows at about room temperature.
  • the difference between the temperature of the circulating hydrogen and the temperature of the raw material hydrogen is relatively small, there is no problem in the liquid hydrogen production apparatus because the excess circulating hydrogen is discharged into the raw material hydrogen passage. Further, since excess circulating hydrogen is discharged, the amount of circulating hydrogen in the refrigeration cycle unit is maintained at an appropriate value.
  • the surplus circulating hydrogen discharged to the raw material hydrogen passage is liquefied again in the liquid hydrogen generating section to become liquid hydrogen.
  • a very low temperature boil-off gas is introduced into the liquid hydrogen production apparatus, while an amount of liquid hydrogen corresponding to the boil-off gas introduction amount is generated.
  • a very low temperature boil-off gas is introduced into the liquid hydrogen production apparatus without causing any trouble in each part of the liquid hydrogen production apparatus, and the liquid hydrogen corresponding to the amount of boil-off gas introduced is reduced. Can be generated. That is, the very low temperature boil-off gas generated in the liquid hydrogen storage tank is effectively reutilized without wasting its cold energy and is reused as liquid hydrogen.
  • FIG. 1 is a schematic diagram showing a system configuration of a liquid hydrogen production apparatus according to the present invention.
  • a liquid hydrogen production apparatus HS includes a refrigeration cycle section R that uses circulating hydrogen (hereinafter referred to as “circulated hydrogen”) and hydrogen gas (hereinafter referred to as “raw material hydrogen”). ”) Is cooled by the refrigeration cycle section R and then adiabatically expanded to generate liquid hydrogen, and a liquid hydrogen generation section P is provided.
  • circulated hydrogen circulating hydrogen
  • raw material hydrogen hydrogen gas
  • the refrigeration cycle section R includes an annular hydrogen circulation passage 1 for circulating and circulating the circulating hydrogen.
  • the circulating hydrogen circulates clockwise in the positional relationship in FIG.
  • upstream and downstream in the direction of the circulating hydrogen flow are simply referred to as “upstream” and “downstream”, respectively.
  • the hydrogen circulation passage 1 is provided with a compressor 2, a circulating hydrogen cooler 3 positioned downstream of the compressor 2, and an expansion turbine 4 positioned downstream of the circulating hydrogen cooler 3.
  • the compressor 2 is a compressor driven by, for example, an electric motor, adiabatically compresses circulating hydrogen at normal temperature (for example, 0.1 MPaA) and normal temperature (for example, 300 K), and thereby high pressure (for example, 2 MPaA) and high temperature (for example, 780 K).
  • the circulating hydrogen cooler 3 is, for example, a heat exchanger that uses low-temperature cooling water as a refrigerant, and cools high-pressure, high-temperature circulating hydrogen so as to reach a normal temperature while maintaining the pressure.
  • this high-pressure, normal-temperature circulating hydrogen is kept at a very low temperature (for example, 40K) while maintaining the pressure by a first heat exchanger E1 and a second heat exchanger E2 described later. ).
  • the expansion turbine 4 is a turbine that takes out pressure energy or kinetic energy of high-pressure gas by converting it into mechanical energy, and is driven by high-pressure and extremely low-temperature circulating hydrogen, while reducing the pressure and temperature of the circulating hydrogen.
  • at least a part of the circulating hydrogen is liquefied and brought to a state of extremely low temperature (for example, 20 K) at normal pressure.
  • an expander such as a Joule-Thomson valve that adiabatically expands the circulating hydrogen may be used.
  • the hydrogen circulation passage 1 is provided with first and second low temperature side heat exchange sections 5 and 6 at a site downstream of the expansion turbine 4 and upstream of the compressor 2, while being downstream of the circulation hydrogen cooler 3 and the expansion turbine.
  • First and second high temperature side heat exchanging units 7 and 8 are provided in a portion upstream of the fourth side.
  • the 1st low temperature side heat exchange part 5 and the 1st high temperature side heat exchange part 7 are arrange
  • the 2nd low temperature side heat exchange part 6 and the 2nd high temperature side heat exchange part 8 are arrange
  • the 1st low temperature side heat exchange part 5 and the 1st high temperature side heat exchange part 7 are the components of the 1st heat exchanger E1 demonstrated later, the 2nd low temperature side heat exchange part 6 and the 2nd high temperature side heat
  • the exchange unit 8 is a component of the second heat exchanger E2 described later.
  • the liquid hydrogen generation part P includes a raw material hydrogen passage 11 through which raw material hydrogen at normal temperature is circulated at a high pressure (for example, 2 MPaA) supplied from the raw material hydrogen supply source 10.
  • a Joule-Thomson valve 12 is connected to the downstream end of the source hydrogen passage 11 with respect to the direction of source hydrogen flow (toward the right in the positional relationship shown in FIG. 1).
  • the raw material hydrogen passage 11 is provided with a first raw material hydrogen cooling section 13 and a second raw material hydrogen cooling section 14 in order from the upstream in the flow direction of the raw material hydrogen.
  • the first raw material hydrogen cooling unit 13 and the second raw material hydrogen cooling unit 14 cool the raw material hydrogen at high pressure and room temperature to a very low temperature (for example, 40 K) while maintaining the pressure substantially.
  • the Joule-Thomson valve 12 reduces the pressure and temperature by adiabatically expanding high-pressure and very low-temperature raw material hydrogen, and liquefies at least a part of the raw material hydrogen to generate liquid hydrogen.
  • the raw material hydrogen may be liquefied using an expansion valve other than the Joule-Thomson valve.
  • the 1st raw material hydrogen cooling part 13 is a component of the 1st heat exchanger E1 explained later
  • the 2nd raw material hydrogen cooling part 14 is a component of the 2nd heat exchanger E2 explained later.
  • the liquid hydrogen production apparatus HS includes a first low temperature side heat exchange unit 5, a first high temperature side heat exchange unit 7, and a first raw material hydrogen cooling unit 13 across the refrigeration cycle unit R and the liquid hydrogen generation unit P. And a second heat exchanger E2 having the second low temperature side heat exchange unit 6, the second high temperature side heat exchange unit 8 and the second raw material hydrogen cooling unit 14 as constituent elements. It has been. Both the first heat exchanger E1 and the second heat exchanger E2 are configured to circulate hydrogen in the hydrogen circulation passage 1 by circulating hydrogen flowing in a portion downstream of the expansion turbine 4 and upstream of the compressor 2 in the hydrogen circulation passage 1. The circulating hydrogen flowing through the portion downstream from the cooler 3 and upstream from the expansion turbine 4 is cooled, and the raw hydrogen flowing through the raw hydrogen passage 11 is cooled.
  • heat exchangers E1 and E2 are provided across the refrigeration cycle section R and the liquid hydrogen generation section P.
  • the number of such heat exchangers installed is two. It is not limited to the group, and three or more (for example, three, four, five,...) Heat exchangers may be provided. That is, the number of installed heat exchangers is preferably set according to the heat transfer area and other heat exchange characteristics of each heat exchanger.
  • thermodynamic state of the circulating hydrogen and the raw hydrogen flowing in the refrigeration cycle section R or the liquid hydrogen generation section P changes will be described.
  • the circulating hydrogen at an ordinary pressure (for example, 0.1 MPaA) and an extremely low temperature (for example, 20K) at least a part of which has flowed out of the expansion turbine 4 passes through the second low temperature side heat exchange section 6 when the second hydrogen is circulated.
  • the circulating hydrogen flowing in the high temperature side heat exchange section 8 is cooled and the raw hydrogen flowing in the second raw hydrogen cooler 14 is cooled.
  • the temperature of the normal pressure circulating hydrogen flowing out from the second low temperature side heat exchanger 6 rises to a slightly higher temperature (for example, 80K).
  • the liquefied circulating hydrogen is vaporized when flowing through the second low temperature side heat exchange section 6.
  • the circulating hydrogen flowing out from the second heat exchanger E2 flows through the first high temperature side heat exchange unit 7 when flowing through the first low temperature side heat exchange unit 5.
  • the circulating hydrogen being cooled is cooled, and the raw hydrogen flowing in the first raw hydrogen cooler 13 is cooled.
  • the temperature of the normal pressure circulating hydrogen flowing out from the first heat exchanger E1 rises to room temperature (for example, 300K).
  • the circulating hydrogen at normal temperature and normal temperature flows into the compressor 2, is adiabatically compressed by the compressor 2, and becomes a high temperature (for example, 780 K) at a high pressure (for example, 2 MPaA).
  • the high-pressure, high-temperature gas circulating hydrogen that has flowed out of the compressor 2 is first cooled by the circulating hydrogen cooler 3 to be at a normal temperature (for example, 300 K).
  • This high-pressure, normal-temperature circulating hydrogen is cooled by circulating hydrogen flowing in the first low-temperature side heat exchange unit 5 when flowing through the first high-temperature side heat exchange unit 7, and has a very low temperature (for example, 80 K). It becomes a state.
  • the high-pressure and very low-temperature circulating hydrogen that has flowed out of the first high-temperature side heat exchange unit 7 (first heat exchanger E1) flows through the second high-temperature side heat exchange unit 8 when flowing through the second high-temperature side heat exchange unit 8.
  • 6 is cooled by the circulating hydrogen flowing in the interior of the fuel cell 6 and is in a low temperature (for example, 40K) state.
  • the high-pressure circulating hydrogen that has become extremely low temperature flows into the expansion turbine 4 and is expanded by the expansion turbine 4, and is at an extremely low temperature (for example, 0.1 MPaA) at least partially liquefied. For example, the state becomes 20K).
  • the raw hydrogen supplied at high pressure (for example, 2 MPaA) and normal temperature (for example, 300 K) supplied from the raw hydrogen supply source 10 flows through the first low temperature side heat exchange unit 5 when flowing through the first raw material hydrogen cooling unit 13. It is cooled by the circulating hydrogen that is present, and is in a very low temperature (for example, 80K) state.
  • the high-pressure and very low-temperature raw material hydrogen that has flowed out of the first raw material hydrogen cooling unit 13 (first heat exchanger E1) flows into the second low-temperature side heat exchange unit 6 when flowing through the second raw material hydrogen cooling unit 14. It is cooled by the circulating hydrogen flowing through it, and becomes a low temperature (for example, 40K) state.
  • the high-pressure raw material hydrogen that has become extremely low temperature is expanded by Joule-Thompson expansion when passing through the Joule-Thomson valve 12, and is at an extremely low temperature (for example, 0.1 MPaA) at least partially liquefied.
  • the state becomes 20K
  • the liquefied raw material hydrogen is liquid hydrogen which is a product of the liquid hydrogen production apparatus HS, and is stored in the liquid hydrogen storage tank 15.
  • the liquid hydrogen stored in the liquid hydrogen storage tank 15 is appropriately filled in the liquid hydrogen storage tank of the liquid hydrogen transport ship 16 anchored at a port (loading port) near the location of the liquid hydrogen production apparatus HS.
  • Table 1 summarizes the thermodynamic state of the circulating hydrogen or raw material hydrogen in each part in the refrigeration cycle section R or the liquid hydrogen generation section P shown by a to k in FIG.
  • G means gas
  • L means liquid.
  • Table 1 Thermodynamic state of circulating hydrogen or raw hydrogen
  • the liquid hydrogen production apparatus HS according to the present invention is further generated in a liquid hydrogen storage tank (not shown) of the liquid hydrogen transport ship 16 anchored at a port (loading port) near the location of the liquid hydrogen production apparatus HS.
  • a boil-off gas processing mechanism is provided for re-liquefying the boil-off gas to generate liquid hydrogen.
  • the boil-off gas processing mechanism of the liquid hydrogen production apparatus HS according to the present invention introduces the boil-off gas while introducing the low-temperature boil-off gas into the portion where the circulating hydrogen in the hydrogen circulation passage of the refrigeration cycle section flows at a low temperature.
  • the excess circulating hydrogen is discharged from the portion where the circulating hydrogen in the hydrogen circulation passage of the refrigeration cycle section flows at room temperature, and is supplied to the portion where the source hydrogen in the raw hydrogen passage of the liquid hydrogen generation section flows at room temperature.
  • the boil-off gas is re-liquefied and mixed as liquid hydrogen.
  • the boil-off gas treatment mechanism includes a boil-off gas introduction part C and a circulating hydrogen discharge part D.
  • the boil-off gas introduction section C introduces a very low temperature boil-off gas generated in the liquid hydrogen storage tank of the liquid hydrogen transport ship 16 into the hydrogen circulation passage 1 at a site downstream from the expansion turbine 4 and upstream from the compressor 2.
  • the boil-off gas introduction part C is configured so that the boil-off gas introduction site into the hydrogen circulation passage 1 is minimized so that the difference between the circulating hydrogen temperature and the boil-off gas temperature at the boil-off gas introduction site is minimized. Switching according to the temperature of the boil-off gas.
  • the circulating hydrogen discharge unit D discharges the normal temperature circulating hydrogen in the hydrogen circulation passage 1 to the raw material hydrogen passage 11 upstream from the first raw hydrogen cooling unit 13 with respect to the flow direction of the raw hydrogen, and converts it into normal temperature raw hydrogen. Mix. That is, the circulating hydrogen discharge unit D removes excess circulating hydrogen generated by the introduction of the boil-off gas from the hydrogen circulation passage 1 between the first low temperature side heat exchange unit 5 and the compressor 2 or the circulating hydrogen cooler 3 and the first. It discharges from the hydrogen circulation passage 1 to the high temperature side heat exchange section 7 to the raw material hydrogen passage 11. In the embodiment shown in FIG. 1, excess circulating hydrogen is discharged from the hydrogen circulation passage 1 between the circulation hydrogen cooler 3 and the first high temperature side heat exchange unit 7 to the raw material hydrogen passage 11. .
  • the boil-off gas introduction part C has a boil-off gas introduction passage 17 that pipes a very low-temperature boil-off gas generated in the liquid hydrogen storage tank of the liquid hydrogen transport ship 16 to the liquid hydrogen production apparatus HS at a normal pressure (for example, 0.1 MPaA). Have.
  • a normal pressure for example, 0.1 MPaA
  • the periphery of the boil-off gas introduction passage 17 is insulated.
  • a first boil-off gas supply passage 19 and a second boil-off gas supply passage 20 are connected to the downstream end of the boil-off gas introduction passage 17 with respect to the flow direction of the boil-off gas via a switching valve 18.
  • the switching valve 18 selectively connects the boil-off gas introduction passage 17 to the first boil-off gas supply passage 19 or the second boil-off gas supply passage 20 or closes the boil-off gas introduction passage 17.
  • the downstream end of the first boil-off gas supply passage 19 is connected to the hydrogen circulation passage 1 between the first low-temperature side heat exchange unit 5 and the second low-temperature side heat exchange unit 6,
  • the downstream end of the two boil-off gas supply passage 20 is connected to the hydrogen circulation passage 1 between the second low temperature side heat exchange unit 6 and the expansion turbine 4. Therefore, the boil-off gas introduction unit C switches the passage connection mode of the switching valve 18 to convert the boil-off gas in the boil-off gas introduction passage 17 into the first low temperature side heat exchange unit 5 and the second low temperature side heat exchange unit 6.
  • the hydrogen circulation passage 1 between the second low temperature side heat exchange section 6 and the expansion turbine 4 can be alternatively supplied.
  • a blower 21 (or a compressor) having a very low compression ratio for sending the boil-off gas to the downstream side in order from the upstream side in the boil-off gas introduction passage 17.
  • a first flow rate sensor 22 for detecting the flow rate of the boil-off gas flowing in the boil-off gas introduction passage 17 and a temperature sensor 23 for detecting the temperature of the boil-off gas.
  • the detection value of the first flow sensor 22 and the detection value of the temperature sensor 23 are input to the controller 24 described later.
  • the boil-off gas generated in the liquid hydrogen storage tank of the liquid hydrogen transport ship 16 is normal pressure, and the circulating hydrogen in the hydrogen circulation passage 1 is normal pressure at the portion where the boil-off gas is supplied, so the compression ratio is very low.
  • the boil-off gas can be easily supplied to the hydrogen circulation passage 1 by the blower 21. At this time, since the boil-off gas is hardly compressed, the temperature of the boil-off gas hardly changes. If the pressure of the boil-off gas is higher than the pressure of circulating hydrogen at the site where the boil-off gas is introduced, the blower 21 may be omitted.
  • the circulating hydrogen discharge unit D is connected to the first raw material hydrogen with respect to the hydrogen circulation passage 1 between the circulating hydrogen cooler 3 and the first high temperature side heat exchange unit 7 and the flow direction of the raw material hydrogen via the on-off valve 25.
  • a circulation hydrogen discharge passage 26 connecting the raw material hydrogen passage 11 upstream of the cooling unit 13 is provided.
  • the on-off valve 25 connects the hydrogen circulation passage 1 between the circulation hydrogen cooler 3 and the first high temperature side heat exchange unit 7 to the circulation hydrogen discharge passage 26, or between the hydrogen circulation passage 1 and the circulation hydrogen discharge passage 26. Disconnect the connection.
  • the circulating hydrogen discharge passage 26 includes a compressor 27 that sends the discharged hydrogen to the downstream side in order from the upstream side in the flow direction of the circulating hydrogen discharged from the hydrogen circulation passage 1, and the inside of the circulating hydrogen discharge passage 26.
  • a flow rate control valve 28 for controlling the flow rate of the circulating hydrogen flowing through the circulating hydrogen discharge passage 26 and a second flow rate sensor 29 for detecting the flow rate of the circulating hydrogen flowing through the circulating hydrogen discharge passage 26 are provided.
  • the detection value of the second flow sensor 29 is input to the controller 24.
  • the circulating hydrogen in the hydrogen circulation passage 1 between the circulating hydrogen cooler 3 and the first high temperature side heat exchange unit 7 and the raw hydrogen in the raw hydrogen passage 11 upstream from the first raw hydrogen cooling unit 13 are: Although both are high pressures, the pressures are almost equal to each other. Therefore, the circulating hydrogen can be easily discharged into the raw hydrogen passage 11 by the compressor 27 having a very low compression ratio. At this time, since the circulating hydrogen is hardly compressed, the temperature of the circulating hydrogen hardly changes. In addition, when the pressure of the circulating hydrogen in this part is higher than the pressure of raw material hydrogen, the compressor 27 may be omitted.
  • the controller 24 is a comprehensive control device for a boil-off gas processing mechanism equipped with a computer, and the boil-off gas flow rate detected by the first flow sensor 22, the boil-off gas temperature detected by the temperature sensor 23, The control valve 18, the blower 21, the on-off valve 25, the compressor 27, and the flow control valve 28 are controlled using the flow rate of circulating hydrogen detected by the two flow sensor 29 as control information.
  • the control method of the boil-off gas processing mechanism by the controller 24 will be specifically described.
  • the liquid hydrogen transport ship 16 leaves an appropriate amount (for example, several vol% of the volume of the liquid hydrogen storage tank of the transport ship) in the liquid hydrogen storage tank, and keeps it in the loading port near the liquid hydrogen storage tank 15.
  • liquid hydrogen is filled from the liquid hydrogen storage tank 15 into the liquid hydrogen storage tank (hereinafter referred to as “transport ship storage tank”) of the liquid hydrogen transport ship 16.
  • transport ship storage tank the liquid hydrogen storage tank
  • the berthing period of the liquid hydrogen transport ship 16 is normally considered to be one day to several days.
  • the temperature of the transport ship storage tank particularly the temperature of the upper part of the transport ship storage tank, is higher than the saturation temperature of liquid hydrogen due to heat input from outside the storage tank during navigation or anchorage.
  • the temperature of the blow-off gas generated in the transport ship storage tank is 50 to 80 K at the start of liquid hydrogen filling.
  • the temperature of the blow-off gas becomes 20 to 50K, and the liquefaction of hydrogen The temperature is close to the temperature.
  • the blower 21 is activated by the controller 24, and the very low temperature (for example, 20 to 80K) boil-off gas generated in the storage tank of the transport vessel passes through the boil-off gas introduction passage 17 while maintaining the temperature. It is introduced into the hydrogen production apparatus HS.
  • the controller 24 causes the boil-off gas introduction passage 17 to be connected to the switching valve 18. Control is performed so as to be connected to the first boil-off gas supply passage 19.
  • the controller 24 causes the switch valve 18 and the boil-off gas introduction passage 17 to The two boil-off gas supply passages 20 are controlled to be connected.
  • the controller 24 stops the blower 21 and controls the switching valve 18 so that the boil-off gas introduction passage 17 is closed.
  • the boil-off gas when the temperature of the boil-off gas is relatively high, for example, when the temperature is 50 K or more and 80 K or less, the boil-off gas is hydrogen between the first low temperature side heat exchange unit 5 and the second low temperature side heat exchange unit 6. It is mixed with, for example, 80 K of circulating hydrogen in the circulation passage 1.
  • the temperature of the boil-off gas when the temperature of the boil-off gas is relatively low, for example, 20 K or more and less than 50 K, the boil-off gas is contained in the hydrogen circulation passage 1 between the second low-temperature side heat exchange unit 6 and the expansion turbine 4. For example, mixed with 20K of circulating hydrogen.
  • the boil-off gas introduction site into the hydrogen circulation passage 1 is switched according to the boil-off gas temperature so that the difference between the circulating hydrogen temperature and the boil-off gas temperature at the boil-off gas introduction site is minimized. For this reason, the temperature distribution of the circulating hydrogen in the hydrogen circulation passage 1 is not particularly affected. As described above, since the boil-off gas is introduced into the hydrogen circulation passage 1 at a very low temperature similar to that generated in the transport ship storage tank, the cooling heat of the boil-off gas is not wasted.
  • the boil-off gas When the boil-off gas is introduced into the hydrogen circulation passage 1 at a very low temperature similar to that generated in the transport ship storage tank, the boil-off gas is heated to room temperature (300 K) and introduced into the raw material hydrogen passage 11.
  • the energy efficiency of the liquid hydrogen production apparatus HS can be greatly improved.
  • the flow rate and temperature of the boil-off gas are 0.53 kg / s and 20 K, respectively, the heat capacity of hydrogen is 14.4 kJ / (kg ⁇ K). Therefore, as shown by the following formula, approximately 2.
  • the energy of 1 MW can be reduced.
  • the boil-off gas supply passages are correspondingly increased and the boil-off gas introduction passage 17 is selectively connected to any one of these boil-off gas supply passages.
  • a controller 24 that controls the switching valve so that the difference between the circulating hydrogen temperature and the boil-off gas temperature at the boil-off gas introduction site is minimized by the controller 24 according to the boil-off gas temperature. That's fine.
  • the number of heat exchangers is N (N ⁇ 3), that is, when N low-temperature side heat exchange units are provided, the hydrogen circulation passage 11 between the low-temperature side heat exchange units, A total of N boil-off gas supply passages are connected to the hydrogen circulation passage 11 between the most upstream low temperature side heat exchange section and the expansion turbine 4, and a switching valve is provided that can selectively select these. Just do it.
  • the number of heat exchangers is N (N ⁇ 3)
  • the number of boil-off gas supply passages may be less than N as long as the number is 2 or more.
  • the controller 24 activates the compressor 27 and sets the on-off valve 25 between the circulation hydrogen cooler 3 and the first high temperature side heat exchange unit 7.
  • the hydrogen circulation passage 1 and the circulation hydrogen discharge passage 26 are controlled to be connected.
  • the controller 24 controls the flow rate control valve 28 so that the flow rate of circulating hydrogen detected by the second flow rate sensor 29 matches the flow rate of boil-off gas detected by the first flow rate sensor 22.
  • the valve opening degree of the flow control valve 28 is changed.
  • an amount of circulating hydrogen equal to the amount of boil-off gas introduced into the hydrogen circulation passage 1 is discharged from the hydrogen circulation passage 1 to the source hydrogen passage 11 and mixed with the source hydrogen. Accordingly, the amount of circulating hydrogen in the hydrogen circulation passage 1 is maintained at an appropriate value.
  • the controller 24 stops the compressor 27, while the on-off valve 25 is connected to the hydrogen circulation passage 1 and the circulation hydrogen discharge passage 26. Control the connection to be cut off.
  • the circulating hydrogen discharged from the hydrogen circulation passage 1 to the raw hydrogen passage 11 through the circulating hydrogen discharge passage 26 is normal temperature, the temperature of the raw hydrogen flowing in the raw hydrogen passage 11 is not lowered. . Therefore, such mixing of the circulating hydrogen with the raw material hydrogen passage 11 does not cause any trouble in the liquid hydrogen generator P or the liquid hydrogen production apparatus HS designed on the assumption that normal temperature raw material hydrogen is supplied.
  • a very low temperature boil-off gas is introduced into the liquid hydrogen production apparatus HS without causing any trouble in its constituent elements.
  • Liquid hydrogen corresponding to the introduced amount can be generated.
  • the extremely low-temperature boil-off gas that is generated in large quantities in a short time in a transport ship storage tank can be effectively liquefied without wasting its cold energy and reused as liquid hydrogen. Can do.
  • surplus circulating hydrogen generated by the introduction of the boil-off gas into the hydrogen circulation passage 1 is circulated between the circulating hydrogen cooler 3 and the first high temperature side heat exchange unit 7.
  • the raw material hydrogen is discharged to the raw material hydrogen passage 11 upstream from the first raw material hydrogen cooler 13 in the flow direction of the raw material hydrogen.
  • the circulating hydrogen in the hydrogen circulation passage 1 between the first low-temperature side heat exchange section 5 and the compressor 2 is at room temperature, the first raw material with respect to this portion in the hydrogen circulation passage 1 and the flow direction of the raw material hydrogen.
  • a circulating hydrogen discharge passage that connects the raw material hydrogen passage 11 upstream from the hydrogen cooler 13 may be provided, and excess circulating hydrogen may be discharged to the raw hydrogen passage 11 through this circulating hydrogen discharge passage. .
  • the circulating hydrogen in the hydrogen circulation passage 1 between the first low temperature side heat exchange section 5 and the compressor 2 is at a normal pressure, while the raw hydrogen in the raw hydrogen passage 11 is at a high pressure.
  • the liquid hydrogen production apparatus is useful as an apparatus for producing liquid hydrogen from hydrogen produced using, for example, low-grade coal such as lignite as a main raw material.
  • low-grade coal such as lignite
  • it is suitable for re-liquefying and reusing the boil-off gas generated when the liquid hydrogen storage tank of the liquid hydrogen transport ship is filled with liquid hydrogen.
  • HS liquid hydrogen production device R refrigeration cycle section, P liquid hydrogen generation section, E1 first heat exchanger, E2 second heat exchanger, C boil-off gas introduction section, D circulating hydrogen discharge section, 1 hydrogen circulation passage, 2 compressor 3, 3 circulating hydrogen cooler, 4 expansion turbine, 5 first low temperature side heat exchange section, 6 second low temperature side heat exchange section, 7 first high temperature side heat exchange section, 8 second high temperature side heat exchange section, 10 raw material hydrogen Supply source, 11 raw hydrogen passage, 12 Joule Thomson valve, 13 first raw hydrogen cooling section, 14 second raw hydrogen cooling section, 15 liquid hydrogen storage tank, 16 liquid hydrogen transport ship, 17 boil-off gas introduction passage, 18 switching valve , 19 First boil-off gas supply passage, 20 Second boil-off gas supply passage, 21 Blower, 22 First flow sensor, 23 Temperature sensor, 24 Con Roller, 25 on-off valve, 26 circulating hydrogen discharge passage, 27 a compressor, 28 a flow control valve, 29 second flow rate sensor.

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  • Mechanical Engineering (AREA)
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  • General Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

Un dispositif de production d'hydrogène liquide (HS) est pourvu d'une unité à cycle frigorifique (R) dans laquelle l'hydrogène en circulation sert de frigorigène, et une unité de génération d'hydrogène liquide (P) pour générer de l'hydrogène liquide par refroidissement d'hydrogène comme matière première haute pression à l'aide de l'unité à cycle frigorifique (R) et par détente adiabatique de l'hydrogène comme matière première au moyen d'une valve de type Joule-Thomson (12). Un premier et un second échangeur de chaleur (E1, E2) sont disposés le long de l'unité à cycle frigorifique (R) et de l'unité de génération d'hydrogène liquide (P). Le dispositif de production d'hydrogène liquide (HS) est équipé d'un mécanisme de traitement du gaz d'évaporation pour générer de l'hydrogène liquide par reliquéfaction du gaz d'évaporation généré dans le réservoir de stockage d'hydrogène liquide sur un navire de transport d'hydrogène liquide (16). Le gaz d'évaporation est introduit dans une voie de circulation d'hydrogène (1) au niveau d'une section à laquelle l'hydrogène en circulation ayant une température extrêmement basse s'écoule, et l'excès d'hydrogène en circulation généré est déchargé vers une voie de circulation d'hydrogène comme matière première (11) depuis une section au niveau de laquelle l'hydrogène en circulation est à température ambiante.
PCT/JP2013/061414 2012-05-22 2013-04-17 Dispositif de production d'hydrogène liquide WO2013175905A1 (fr)

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RU2014125729/06A RU2573423C1 (ru) 2012-05-22 2013-04-17 Устройство для изготовления жидкого водорода
US14/376,504 US20150068246A1 (en) 2012-05-22 2013-04-17 Liquid hydrogen production device

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