WO2014102084A2 - Apparatus and method for producing low-temperature compressed gas or liquefied gas - Google Patents

Apparatus and method for producing low-temperature compressed gas or liquefied gas Download PDF

Info

Publication number
WO2014102084A2
WO2014102084A2 PCT/EP2013/076745 EP2013076745W WO2014102084A2 WO 2014102084 A2 WO2014102084 A2 WO 2014102084A2 EP 2013076745 W EP2013076745 W EP 2013076745W WO 2014102084 A2 WO2014102084 A2 WO 2014102084A2
Authority
WO
WIPO (PCT)
Prior art keywords
heat exchanger
gas
low
heat transfer
transfer medium
Prior art date
Application number
PCT/EP2013/076745
Other languages
French (fr)
Other versions
WO2014102084A3 (en
WO2014102084A8 (en
Inventor
Kenji Hirose
Shinji Tomita
Original Assignee
L'air Liquide
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by L'air Liquide filed Critical L'air Liquide
Priority to EP13811874.0A priority Critical patent/EP2938951B1/en
Priority to ES13811874.0T priority patent/ES2634765T3/en
Priority to US14/655,261 priority patent/US10036589B2/en
Priority to CN201380073836.8A priority patent/CN105143799B/en
Publication of WO2014102084A2 publication Critical patent/WO2014102084A2/en
Publication of WO2014102084A3 publication Critical patent/WO2014102084A3/en
Publication of WO2014102084A8 publication Critical patent/WO2014102084A8/en

Links

Classifications

    • 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
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/0015—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
    • 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
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • 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
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/002—Argon
    • 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
    • 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
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop
    • F25J1/0222—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 intermediate heat exchange fluid between the cryogenic component and the fluid to be liquefied
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop
    • 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
    • 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
    • F25J1/0262—Details of the cold heat exchange system
    • F25J1/0264—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams
    • 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
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0281—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc. characterised by the type of prime driver, e.g. hot gas expander
    • 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
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0285—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings
    • 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
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0292—Refrigerant compression by cold or cryogenic suction of the refrigerant gas
    • 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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/03—Mixtures
    • F17C2221/032—Hydrocarbons
    • F17C2221/033—Methane, e.g. natural gas, CNG, LNG, GNL, GNC, PLNG
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0146—Two-phase
    • F17C2223/0153—Liquefied gas, e.g. LPG, GPL
    • F17C2223/0161—Liquefied gas, e.g. LPG, GPL cryogenic, e.g. LNG, GNL, PLNG
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/033—Small pressure, e.g. for liquefied gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/01—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the phase
    • F17C2225/0107—Single phase
    • F17C2225/0123—Single phase gaseous, e.g. CNG, GNC
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/03—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the pressure level
    • F17C2225/035—High pressure, i.e. between 10 and 80 bars
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0302—Heat exchange with the fluid by heating
    • F17C2227/0309—Heat exchange with the fluid by heating using another fluid
    • F17C2227/0316—Water heating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0302—Heat exchange with the fluid by heating
    • F17C2227/0309—Heat exchange with the fluid by heating using another fluid
    • F17C2227/0323—Heat exchange with the fluid by heating using another fluid in a closed loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0367—Localisation of heat exchange
    • F17C2227/0388—Localisation of heat exchange separate
    • F17C2227/0393—Localisation of heat exchange separate using a vaporiser
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2265/00—Effects achieved by gas storage or gas handling
    • F17C2265/05—Regasification
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0134—Applications for fluid transport or storage placed above the ground
    • F17C2270/0136—Terminals
    • 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
    • F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]

Definitions

  • the present invention relates to an apparatus and a method for cooling and compressing a fluid to produce a low-temperature compressed fluid using the cold of a liquefied natural gas (hereafter also referred to as "LNG”), and is particularly useful as a technique for liquefying nitrogen gas that is produced by an air separation apparatus or the like.
  • LNG liquefied natural gas
  • Natural gas is stored as a liquefied natural gas (LNG) for facility in transportation and storage, or the like, and is used mainly for thermal power generation or for city gas after being vaporized. Then, a technique of effectively utilizing the cold of LNG is developed.
  • LNG liquefied natural gas
  • a process is used such that nitrogen gas is compressed by a compressor up to a pressure such that the nitrogen gas can be liquefied by heat exchange with the LNG, and subsequently the nitrogen gas is subjected to the heat exchange with the LNG in a heat exchanger to vaporize the LNG by raising the temperature and to liquefy the nitrogen gas.
  • the amount of LNG supplied to the gas liquefying process may generally fluctuate due to the fluctuation in the demand for thermal power generation, city gas, or the like, and the amount of cold that can be used may also fluctuate. Therefore, there is a demand for an apparatus or a method by which the cold of LNG can be efficiently used so that the amount of production of the liquefied fluid or the like may not be affected even when the supplied LNG decreases in amount.
  • the temperature at which a gas having a normal pressure starts being liquefied is about -80°C for LNG, while the temperature is about -120°C for nitrogen.
  • the LNG that is subject to heat exchange with this nitrogen is still in a liquid state having a large latent heat, so that, in view of this process alone, the cold of the LNG is not sufficiently used.
  • An object of the present invention is to provide an apparatus and a method for cooling and compressing a fluid to produce a low-temperature compressed fluid that can efficiently use the cold of LNG and can reduce the energy that is needed in producing the low-temperature compressed fluid.
  • the present inventors and others have made eager studies in order to solve the aforementioned problems and, as a result, have found that the aforementioned object can be achieved by an apparatus and a method for producing a low-temperature compressed fluid described below, thereby completing the present invention.
  • An apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention using a Rankine cycle system comprises; a first compression device for adiabatically compressing a heat transfer med ium ; a first heat exchanger for constant-pressure heating the adiabatically compressed heat transfer medium; an expansion device for adiabatically expanding the heated heat transfer medium; a second heat exchanger for constant-pressure cooling the adiabatically expanded heat transfer medium; a first flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and at least one second compression device that is coupled to the expansion device; wherein, at the second heat exchanger, a low-temperature liquefied natural gas and the heat transfer medium undergo heat transfer, wherein, at the first heat exchanger, a fed material gas and the heat transfer medium undergo heat transfer to produce a low- temperature fluid from the material gas, and wherein, the low-temperature fluid is thereafter compressed at the second compression device to produce a low-temperature compressed fluid.
  • a method for cooling and compressing a fluid to produce a low-temperature compressed fluid comprises a Rankine cycle system in which a heat transfer medium that has been adiabatically compressed by first compression device is heated in a first heat exchanger at a constant pressure, thereafter adiabatically expanded by expansion device, and further cooled in a second heat exchanger at a constant pressure, wherein a liquefied natural gas in a low-temperature liquefied state is guided into the second heat exchanger to transfer the cold thereof to the heat transfer medium, and a material gas that has been fed is guided into the first heat exchanger to be cooled by the heat transfer medium and thereafter guided into at least one second compression device that is coupled to the expansion device, so as to be extracted as a low-temperature compressed fluid.
  • the cold of LNG can be efficiently used in preparing a low- temperature compressed fluid, and reduction of needed energy can be ach ieved.
  • the heat transfer is efficiently carried out by heat exchange with a compressed fluid, and the cold needed in preparing a low-temperature gas is extremely small as compared with the cold needed in preparing a low-temperature fluid under conventional conditions of normal pressure using the cold of LNG.
  • a Rankine cycle system (hereafter also referred to as "RC") that can effectively use the heat exchange with a compressed fluid is applied in preparing a low-temperature fluid, whereby the cold of LNG can be used much more efficiently, and the energy needed in transferring the cold can be reduced to a great extent by efficiently transferring the cold of high-pressure LNG via the heat transfer medium of the RC and transferring the cold energy from the adiabatically compressed heat transfer medium to a fed material gas at normal pressure.
  • RC Rankine cycle system
  • An apparatus using the above-described apparatus further comprises; a second flow passageway for guiding the low-temperature compressed fluid from the second compression device to at least one of the first heat exchanger and the second heat exchanger to form a liquefied component, an adjustment valve for adjusting a pressure of the low-temperature compressed fluid from at least one of the first heat exchanger and the second heat exchanger, and a gas-liquid separator into which the low-temperature compressed fluid is guided via the adjustment valve, performing gas-liquid separation so as to permit the liquefied component to be extracted therefrom.
  • a method according to the present invention uses the above-described method, wherein the low-temperature compressed fluid from the second compression device is cooled in the first heat exchanger or the second heat exchanger and subjected to pressure adjustment by an adjustment valve, and a liquefied component is subjected to gas-liquid separation in a gas-liquid separator and is extracted as a low-temperature liquefied component from the gas-liquid separator.
  • the temperature of the LNG is around -155°C while the boiling point of nitrogen under ambient air pressure is -196°C, so that this difference in temperature levels must be compensated between these.
  • the present invention realizes such a function with use of a Rankine cycle system.
  • the heat transfer medium used in the Rankine cycle system is cooled to about -150 to -155°C by using the cold of LNG to ensure the cold to be transferred to nitrogen gas or the like.
  • the cold is transferred through the first heat exchanger to the nitrogen gas or the like in a normal pressure or in a low-pressurized condition, and further the cold is transferred through the second heat exchanger to the nitrogen gas or the like compressed to a high pressure, whereby a liquefied nitrogen gas can be efficiently prepared.
  • a critical pressure or above for example, 5 to 6 MPa
  • the cold of the LNG can be used more efficiently, and the energy needed in transferring the cold can be reduced to a great extent.
  • the present invention relates also to the apparatus for producing a liquefied fluid described above, wherein the apparatus further comprises: a third heat exchanger disposed in a third flow passageway for guiding the heat transfer medium from the first heat exchanger to the expansion device, wherein the heat transfer medium, the liquefied natural gas from the second heat exchanger, and the low-temperature compressed fluid from the second compression device undergo heat exchange at the third heat exchanger.
  • the cold of the LNG can be used further more efficiently, and preparation of a liquefied fluid having a high energy efficiency can be carried out.
  • cooling water is introduced in the third heat exchanger to perform heat exchange by cold energy having a large heat capacity, transfer of preparatory or auxiliary hot heat to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid can be carried out even to transient fluctuation or the like at the time of starting or at the time of stopping, thereby ensuring a stable use of the cold of LNG and a stable energy efficiency.
  • the present invention relates also to the apparatus for producing a liquefied fluid described above, wherein first pressure-raising device, a first branching flow passageway, second pressure-raising device, and a second branching flow passageway are disposed in a fourth flow passageway through which the material gas is guided to the first heat exchanger; a fourth heat exchanger and a third branching flow passageway are disposed in a fifth flow passageway through which the liquefied component from the gas-liquid separator is guided; which has a sixth flow passageway through which a gas component from the gas-liquid separator is guided to the first branching flow passageway via the first heat exchanger or the second heat exchanger, and a seven flow passageway through which the liquefied component that has been branched at the third branching flow passageway is guided to the second branching flow passageway via the fourth heat exchanger and the first heat exchanger or the second heat exchanger, where the liquefied component from the gas-liquid separator is extracted therefrom via the fourth heat exchanger.
  • the present invention has made it possible to supply a liquefied fluid in a stable condition and with a good energy efficiency by providing compressors in plural stages as material gas feeding device and returning the liquefied fluid in a stable condition immediately before being extracted to mix the liquefied fluid with the material gas thereof.
  • the present invention relates also to the apparatus for producing a liquefied fluid described above, wherein the Rankine cycle system is comprised with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities, where the material gas from the first heat exchanger is guided into the first heat exchanger after being compressed by second compression device that is coupled to the expansion device involved in one Rankine cycle system using a heat transfer medium having a low boiling point or a small heat capacity, and thereafter the material gas from the first heat exchanger is guided into the first heat exchanger after being compressed by second compression device that is coupled to the expansion device involved in another Rankine cycle system using a heat transfer medium having a high boiling point or a large heat capacity.
  • an apparatus for producing a liquefied fluid is used in line in semiconductor production equipment or the like, so that a continuous supply of gas is demanded, and also the amount of supply, the pressure of supply, and the like thereof may largely fluctuate. Also, as described before, there are cases in which the stable supply of LNG is not necessarily ensured.
  • the present invention has made it possible to supply a liquefied fluid in a stable condition and with a good energy efficiency by constructing with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities for the heat transfer medium that carries out the transfer of the cold of LNG and adjusting the control elements that can be easily controlled, such as the flow rate and the pressure of the heat transfer medium, in each Rankine cycle system with regard to the fluctuating elements in these cases.
  • Fig. 1 is a schematic view illustrating a basic exemplary structure of an apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention
  • Fig. 2 is a schematic view exemplifying one mode of the first exemplary structure of an apparatus for producing a liquefied fluid according to the present invention
  • Fig. 3 is a schematic view exemplifying another mode of the first exemplary structure of an apparatus for producing a liquefied fluid according to the present invention
  • Fig. 4 is a schematic view illustrating the second exemplary structure of an apparatus for producing a liquefied fluid according to the present invention
  • Fig. 5 is a schematic view illustrating the third exemplary structure of an apparatus for producing a liquefied fluid according to the present invention
  • Fig. 6 is a schematic view illustrating the fourth exemplary structure of an apparatus for producing a liquefied fluid according to the present invention.
  • Fig. 7 is a schematic view illustrating an exemplary structure of a gas liquefying process according to a conventional art.
  • An apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention (hereafter referred to as "present apparatus") using a Rankine cycle system (RC) comprises; a first compression device for adiabatically compressing a heat transfer medium, a first heat exchanger for constant- pressure heating the adiabatically compressed heat transfer medium; an expansion device for adiabatically expanding the heated heat transfer medium; a second heat exchanger for constant-pressure cooling the adiabatically expanded heat transfer medium; a (first) flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and at least one second compression device that is coupled to the expansion device; wherein, at the second heat exchanger, a low-temperature liquefied natural gas (LNG) and the heat transfer medium undergo heat transfer, wherein, at the first heat exchanger, a fed material gas and the heat transfer medium undergo heat transfer to produce a low-temperature fluid from the material gas, and wherein, the low-temperature fluid is thereafter compressed at the
  • the basic structure of the present apparatus will be schematically exemplified in Fig. 1 .
  • the present apparatus has a Rankine cycle system (RC) in which a heat transfer medium circulates.
  • the heat transfer medium forms a circulation system in which, sequentially, the heat transfer medium is adiabatically compressed by a compression pump 1 which serves as a first compression device, constant-pressure cooled by a material gas in a first heat exchanger 2, adiabatically expanded by a turbine 3 which serves as an expansion device, constant-pressure cooled by the cold of LNG in a second heat exchanger 4, and sucked again by the compression pump 1 .
  • a compression pump 1 which serves as a first compression device
  • a turbine 3 which serves as an expansion device
  • the "heat transfer medium” may be selected from among various substances such as hydrocarbon, liquefied ammonia, liquefied chlorine, and water.
  • the heat transfer media may include not only liquids but also gases, so that a gas having a large heat capacity, such as carbon dioxide, may be applied.
  • a gas having a large heat capacity such as carbon dioxide
  • the optimum boiling point or heat capacity can be designed by using a mixture of a plurality of compounds.
  • the cold energy of LNG can be thermally transferred in a plurality of temperature bands by using, for example, a mixture of "methane + ethane + propane” in one RC and using a mixture of "ethane + propane + butane” in another RC.
  • the LNG of a predetermined flow rate is supplied to the second heat exchanger 4, whereby a predetermined amount of cold is ensured.
  • a material gas of a desired flow rate is supplied to the first heat exchanger 2 by a feed pump 5, whereby a predetermined amount of cold is transferred to the material gas to cool the material gas to a desired temperature.
  • the material gas is guided into the compressor 6 which is second compression device so as to be compressed to a desired pressure and is extracted as a desired low-temperature compressed fluid.
  • the low-temperature compressed fluid is produced in such a condition that, in the present apparatus in which a Rankine cycle system (RC) is formed, a liquefied natural gas in a low-temperature liquefied state is guided into the second heat exchanger 4 to transfer the cold thereof to the heat transfer medium, and the material gas that is fed by the feed pump 5 is guided into the first heat exchanger 2 to be cooled by the heat transfer medium and thereafter guided into at least one second compression device (compressor) 6 that is coupled to the expansion device (turbine) 3, so as to be extracted as a low-temperature compressed fluid.
  • RC Rankine cycle system
  • the heat transfer medium of the RC is used as the heat transfer medium of the RC; LNG of about 6 MPa is guided into the second heat exchanger 4; and nitrogen gas is fed as a material gas.
  • the heat transfer medium guided at about 0.05 MPa into the second heat exchanger 4 is guided out after being cooled to about -1 15°C, adiabatically compressed to about 1 .8 MPa by the compression pump 1 , guided into the first heat exchanger 2, guided out after being heated by heat exchange with the material gas, adiabatically expanded by the turbine 3, and guided at about -45°C and under about 0.05 MPa into the second heat exchanger 4.
  • the nitrogen gas guided at about 2.1 MPa into the first heat exchanger 2 is guided out after being cooled to about -90°C, compressed to about 5 MPa by the compressor 6 coupled to the turbine 3, and extracted as a low-temperature compressed nitrogen gas having a temperature of about -90°C and a pressure of about 5 MPa.
  • a case in which a low-temperature compressed nitrogen gas was prepared using the present apparatus was compared with a case in which a low-temperature compressed nitrogen gas was prepared using a conventional method, so as to verify the energy efficiency thereof. As will be described below, an improvement of about 50% or more could be achieved by using the present apparatus.
  • a nitrogen gas of 677 Nm 3 /h could be pressurized from 20 bar to 37 bar.
  • the entrance temperature of the compressor was 40°C
  • the exit temperature thereof was 1 1 1 °C.
  • the amount of LNG needed to obtain a similar low-temperature compressed nitrogen gas that is, to pressurize a nitrogen gas of 677 Nm 3 /h from 20 bar to 37 bar, was 0.485 ton/h.
  • FIG. 2 A basic exemplary structure (first exemplary structure) of an apparatus (hereafter referred to as "present liquefaction apparatus") for producing a liquefied fluid using the present apparatus will be schematically shown in Fig. 2.
  • present liquefaction apparatus for producing a liquefied fluid using the present apparatus
  • the present liquefaction apparatus has a Rankine cycle system (RC) similar to that of the present apparatus and comprises a (second) flow passageway through which the low-temperature compressed fluid from the second compression device 6 to at least one of the first heat exchanger 2 and the second heat exchanger 4 (the second heat exchanger 4 in the first exemplary structure), an adjustment valve 7 for adjusting the pressure of the low-temperature compressed fluid containing a liquefied component from the first heat exchanger 2 or the second heat exchanger 4 (from the second heat exchanger 4 in the first exemplary structure), and a gas-liquid separator 8 into which the low-temperature compressed fluid is guided via the adjustment valve 7 so as to perform gas-liquid separation of the liquefied component, whereby the low-temperature liquefied component from the gas-liquid separator 8 is extracted.
  • RC Rankine cycle system
  • the difficulty of heat transfer due to the difference between the temperature of the supplied LNG and the boiling point of the material gas can be eliminated by effectively using the RC.
  • the cold can be efficiently used for liquefying the low- temperature gas.
  • the liquefied fluid can be prepared stably and efficiently.
  • the low-temperature compressed fluid from the second compression device 6 is cooled in the second heat exchanger 4 and is subjected to pressure adjustment by the adjustment valve 7, and the liquefied component is subjected to gas-liquid separation in the gas-liquid separator 8 and extracted as a low-temperature liquefied component from the gas-liquid separator 8.
  • the material gas is, for example, ethane or propane having a comparatively higher boiling point than nitrogen or oxygen
  • the low-temperature compressed fluid can be liquefied by being guided into the first heat exchanger 2, as is exemplified in Fig. 3.
  • the temperature difference from the cold of the LNG is small, and the cold of the LNG sufficient for liquefaction can be transferred via the heat transfer medium when the source material is guided out from the first heat exchanger 2 and again guided into the first heat exchanger 2 in a compressed state.
  • the pressure of the LNG > “the pressure of the material gas” (for example, about 50 bar)
  • the LNG may leak to the material gas side, so that the risk thereof can be evaded with such a structure.
  • This low-temperature compressed nitrogen gas is further guided into the second heat exchanger 4 to be cooled to about -153°C and then is expanded via the adjustment valve 7 to be cooled to about -179°C, whereafter the liquefied nitrogen gas mainly containing a liquefied component is guided into the gas-liquid separator 8.
  • the liquefied component that has been subjected to gas-liquid separation in the gas-liquid separator 8 is extracted as a liquefied nitrogen gas of about -179°C and about 0.05 MPa.
  • LNG was supplied at 1 ton/h, and an energy of 0.28 kWh/Nm 3 was needed in preparing a liquefied nitrogen gas of about 0.05 MPa.
  • the present liquefaction apparatus has a Rankine cycle system (RC), an adjustment valve 7, and a gas- liquid separator 8, wherein a third heat exchanger 9 is disposed in a (third) flow passageway through which the heat transfer medium from the first heat exchanger 2 is guided to the expansion device (turbine) 3, where the heat transfer medium, the liquefied natural gas from the second heat exchanger 4, and the low-temperature compressed fluid from the second compression device (compressor) 6 undergo heat exchange in the third heat exchanger 9.
  • RC Rankine cycle system
  • an adjustment valve 7 a gas- liquid separator 8
  • a third heat exchanger 9 is disposed in a (third) flow passageway through which the heat transfer medium from the first heat exchanger 2 is guided to the expansion device (turbine) 3, where the heat transfer medium, the liquefied natural gas from the second heat exchanger 4, and the low-temperature compressed fluid from the second compression device (compressor) 6 undergo heat exchange in the third heat exchanger 9.
  • the cold of the LNG can be used further more efficiently, and preparation of a liquefied fluid having a high energy efficiency can be carried out.
  • a structure in which the low-temperature compressed fluid can be liquefied by being guided into the first heat exchanger 2 can be applied.
  • the cold of the LNG can be used further more efficiently by using the residual cold of the LNG for cooling the heat transfer medium that has been heated in the first heat exchanger 2 and the low-temperature compressed fluid that has been compressed to have an increased heat quantity.
  • a structure in which cooling water is introduced in the third heat exchanger 9 will be exemplified here. Heat exchange with cold energy having a large heat capacity can be carried out, and quick transfer of hot heat can be achieved to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid.
  • the third exemplary structure of the present liquefaction apparatus will be schematically shown in Fig. 5.
  • the present liquefaction apparatus according to the third exemplary structure is characterized in that first pressure-raising device (feed pump) 5, a first branching flow passageway S1 , second pressure-raising device 10, and a second branching flow passageway S2 are disposed in a (fourth) flow passageway L5 through which the material gas is guided to the first heat exchanger 2; a fourth heat exchanger 1 1 and a third branching flow passageway S3 are disposed in a (fifth) flow passageway L8 through which the liquefied component from the gas-liquid separator 8 is guided; the apparatus has a (sixth) flow passageway L1 1 through which a gas component from the gas-liquid separator 8 is guided to the first branching flow passageway S1 via the second heat exchanger 4, and has a (seven) flow passageway L12 through which the liquefied component that has been branched at the third branching
  • Supply of a liquefied fluid being stable and having a good energy efficiency has been enabled by disposing compressors in a plurality of stages as the material gas feeding device and by returning the liquefied fluid in a stable condition immediately before being extracted and mixing it with the material gas.
  • a structure will be exemplified in which a second adjustment valve 12 is disposed in the third branching flow passageway S3, and part of the liquefied fluid from the fourth heat exchanger 1 1 is again guided into the fourth heat exchanger 1 1 via the second adjustment valve 12.
  • a liquefied fluid having a further lower temperature is prepared by adiabatically expanding the low-temperature liquefied fluid with the second adjustment valve 12 and can be allowed to function as the cold in the fourth heat exchanger 1 1 .
  • the present liquefaction apparatus is characterized in that the apparatus using a plurality of Rankine cycle systems comprising a plurality of heat transfer media having different boiling points or heat capacities, wherein the material gas from the first heat exchanger 2 is guided into the first heat exchanger 2 after being compressed by second compression device 6a that is coupled to the expansion device 3a involved in one Rankine cycle system RCa using a heat transfer medium having a low boiling point or a small heat capacity, and thereafter the material gas from the first heat exchanger 2 is guided into the first heat exchanger 2 after being compressed by second compression device 6b that is coupled to the expansion device 3b involved in another Rankine cycle system RCb using a heat transfer medium having a high boiling point or a large heat capacity.
  • Supply of a liquefied fluid being stable and having a good energy efficiency has been enabled by constructing with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities with respect to the heat transfer media that are involved in transferring the cold of the LNG and by adjusting the control elements that can be easily controlled, such as the flow rate and the pressure of the heat transfer media in each Rankine cycle system, with respect to the fluctuating elements such as the supply amount and the supply pressure of the liquefied fluid.
  • the plurality of heat transfer media having different boiling points or heat capacities as referred to herein include not only a case in which the substances themselves are different and a case in which the substances constituting the mixtures or compounds are different but also a case in which the composition of the mixture of a plurality of substances is different.
  • two Rankine cycle systems having different characteristics can be constructed by forming one heat transfer medium with a mixture of 20% of methane, 40% of ethane, and 40% of propane and forming the other heat transfer medium with a mixture of 2% of methane, 49% of ethane, and 49% of propane.
  • a heat transfer function of a further wider range can be formed.
  • the temperature band in which the cold of the LNG can be used because of the relationship between the temperature of the cold of the LNG and the boiling point of the material gas or the temperature of the compressed gas (fluid) as described above, so that the cold of the LNG can be used in a plurality of temperature bands by arranging one Rankine cycle system RCa and another Rankine cycle system RCb in series as in the fourth exemplary structure.
  • the cold energy of the LNG can be thermally transferred in a plurality of temperature bands by using a mixture of "methane + ethane + propane” in one Rankine cycle system RCa and using a mixture of "ethane + propane + butane” in another Rankine cycle system RCb.
  • the cold energy of the LNG can be efficiently used by arranging one Rankine cycle system RCa and another Rankine cycle system RCb in series as in the fourth exemplary structure and by using the cold energy of the LNG, for example, in a range of -150 to -100°C in the one Rankine cycle system RCa and using the cold energy of the LNG, for example, in a range of -150 to -100°C in the other Rankine cycle system RCb. Also, when this is used as an energy for compressing the nitrogen gas, the energy (consumed electric power) needed per liquefied nitrogen production amount can be greatly reduced.
  • each exemplary structure has been described on the basis of each descriptive view; however, the present apparatus or the present liquefaction apparatus is not limited to these but is constructed with a wider concept including a combination of the constituent elements thereof or a combination with other related known constituent elements.

Landscapes

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

Abstract

An apparatus and a method for cooling and compressing a fluid to produce a low- temperature compressed fluid that can efficiently use the cold of LNG and can reduce the energy needed, the apparatus using a Rankine cycle system comprising; a first compression device(1), a first heat exchanger (2), an expansion device(3), a second heat exchanger (4), and a first flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and at least one second compression device(6) that is coupled to the expansion device, wherein, at the second heat exchanger, a low-temperature liquefied natural gas and the heat transfer medium undergo heat transfer, wherein, at the first heat exchanger, a fed material gas and the heat transfer medium undergo heat transfer to produce a low-temperature fluid from the material gas, and wherein, the low-temperature fluid is thereafter compressed at the second compression device to produce a low-temperature compressed fluid.

Description

APPARATUS AND METHOD FOR PRODUCING LOW-TEMPERATURE COMPRESSED GAS OR LIQUEFIED GAS The present invention relates to an apparatus and a method for cooling and compressing a fluid to produce a low-temperature compressed fluid using the cold of a liquefied natural gas (hereafter also referred to as "LNG"), and is particularly useful as a technique for liquefying nitrogen gas that is produced by an air separation apparatus or the like.
Natural gas (NG) is stored as a liquefied natural gas (LNG) for facility in transportation and storage, or the like, and is used mainly for thermal power generation or for city gas after being vaporized. Then, a technique of effectively utilizing the cold of LNG is developed. Generally, as equipment for liquefying nitrogen gas or the like by using the cold of LNG, a process is used such that nitrogen gas is compressed by a compressor up to a pressure such that the nitrogen gas can be liquefied by heat exchange with the LNG, and subsequently the nitrogen gas is subjected to the heat exchange with the LNG in a heat exchanger to vaporize the LNG by raising the temperature and to liquefy the nitrogen gas.
Also, with respect to the electric power for driving the compressor, the tarif at night is set to be lower than the tarif for daytime, so that a gas liquefying process for efficiently liquefying a gas while taking the fluctuation of the supply amount of the above LNG and the difference in the electric power tarif into consideration is proposed. For example, referring to Fig. 7, there is known a method of liquefying a gas by using the cold of liquefied natural gas by a liquefaction process provided with at least one gas compressor 101 , at least one gas expansion turbine 103, and a heat exchanger 102 for performing heat exchange between the gas and the liquefied natural gas, in which the aforesaid expansion turbine 103 is stopped or operated in a decreased amount when the supplied liquefied natural gas increases in amount, while the aforesaid expansion turbine 103 is started or operated in an increased amount when the supplied liquefied natural gas decreases in amount (See, for example, JP-A-05-45050).
However, with an apparatus for producing a low-temperature liquefied fluid or the like such as described above, various problems such as the following occurred in some cases.
(i) The amount of LNG supplied to the gas liquefying process may generally fluctuate due to the fluctuation in the demand for thermal power generation, city gas, or the like, and the amount of cold that can be used may also fluctuate. Therefore, there is a demand for an apparatus or a method by which the cold of LNG can be efficiently used so that the amount of production of the liquefied fluid or the like may not be affected even when the supplied LNG decreases in amount.
(ii) In order to pressurize a gas having a normal temperature and a normal pressure in a process for producing a compressed gas, addition of a large amount of energy and the cold for restraining the gas temperature rise accompanying the compression will be needed. In producing a compressed gas for general use that is consumed in a large amount, such as a nitrogen gas, there is a big problem for an efficient use of the cold and a comprehensive reduction of energy.
(iii) With respect to the temperature at which a gas having a normal pressure starts being liquefied, the temperature is about -80°C for LNG, while the temperature is about -120°C for nitrogen. For example, in a process for liquefying nitrogen gas at a normal pressure using LNG as the cold, in a state in which the liquefaction of nitrogen has started, the LNG that is subject to heat exchange with this nitrogen is still in a liquid state having a large latent heat, so that, in view of this process alone, the cold of the LNG is not sufficiently used. Also, it is not necessarily easy to use the cold of the residual LNG for other purposes, so that there is a big problem for an efficient use of energy including the cold of LNG in such a liquefaction process. An object of the present invention is to provide an apparatus and a method for cooling and compressing a fluid to produce a low-temperature compressed fluid that can efficiently use the cold of LNG and can reduce the energy that is needed in producing the low-temperature compressed fluid.
The present inventors and others have made eager studies in order to solve the aforementioned problems and, as a result, have found that the aforementioned object can be achieved by an apparatus and a method for producing a low-temperature compressed fluid described below, thereby completing the present invention.
An apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention using a Rankine cycle system comprises; a first compression device for adiabatically compressing a heat transfer med ium ; a first heat exchanger for constant-pressure heating the adiabatically compressed heat transfer medium; an expansion device for adiabatically expanding the heated heat transfer medium; a second heat exchanger for constant-pressure cooling the adiabatically expanded heat transfer medium; a first flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and at least one second compression device that is coupled to the expansion device; wherein, at the second heat exchanger, a low-temperature liquefied natural gas and the heat transfer medium undergo heat transfer, wherein, at the first heat exchanger, a fed material gas and the heat transfer medium undergo heat transfer to produce a low- temperature fluid from the material gas, and wherein, the low-temperature fluid is thereafter compressed at the second compression device to produce a low-temperature compressed fluid.
Also, a method for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention comprises a Rankine cycle system in which a heat transfer medium that has been adiabatically compressed by first compression device is heated in a first heat exchanger at a constant pressure, thereafter adiabatically expanded by expansion device, and further cooled in a second heat exchanger at a constant pressure, wherein a liquefied natural gas in a low-temperature liquefied state is guided into the second heat exchanger to transfer the cold thereof to the heat transfer medium, and a material gas that has been fed is guided into the first heat exchanger to be cooled by the heat transfer medium and thereafter guided into at least one second compression device that is coupled to the expansion device, so as to be extracted as a low-temperature compressed fluid.
With such a structure, the cold of LNG can be efficiently used in preparing a low- temperature compressed fluid, and reduction of needed energy can be ach ieved. Specifically, in the process of verifying the present invention, it has been found out that the heat transfer is efficiently carried out by heat exchange with a compressed fluid, and the cold needed in preparing a low-temperature gas is extremely small as compared with the cold needed in preparing a low-temperature fluid under conventional conditions of normal pressure using the cold of LNG. Based on such a knowledge, in the present invention, a Rankine cycle system (hereafter also referred to as "RC") that can effectively use the heat exchange with a compressed fluid is applied in preparing a low-temperature fluid, whereby the cold of LNG can be used much more efficiently, and the energy needed in transferring the cold can be reduced to a great extent by efficiently transferring the cold of high-pressure LNG via the heat transfer medium of the RC and transferring the cold energy from the adiabatically compressed heat transfer medium to a fed material gas at normal pressure.
An apparatus according to the present invention using the above-described apparatus further comprises; a second flow passageway for guiding the low-temperature compressed fluid from the second compression device to at least one of the first heat exchanger and the second heat exchanger to form a liquefied component, an adjustment valve for adjusting a pressure of the low-temperature compressed fluid from at least one of the first heat exchanger and the second heat exchanger, and a gas-liquid separator into which the low-temperature compressed fluid is guided via the adjustment valve, performing gas-liquid separation so as to permit the liquefied component to be extracted therefrom.
Also, a method according to the present invention uses the above-described method, wherein the low-temperature compressed fluid from the second compression device is cooled in the first heat exchanger or the second heat exchanger and subjected to pressure adjustment by an adjustment valve, and a liquefied component is subjected to gas-liquid separation in a gas-liquid separator and is extracted as a low-temperature liquefied component from the gas-liquid separator.
When the cold of LNG is used in preparing a liquefied fluid such as nitrogen gas, the temperature of the LNG is around -155°C while the boiling point of nitrogen under ambient air pressure is -196°C, so that this difference in temperature levels must be compensated between these. The present invention realizes such a function with use of a Rankine cycle system. The heat transfer medium used in the Rankine cycle system is cooled to about -150 to -155°C by using the cold of LNG to ensure the cold to be transferred to nitrogen gas or the like. After the pressure is raised typically to a critical pressure or above (for example, 5 to 6 MPa), the cold is transferred through the first heat exchanger to the nitrogen gas or the like in a normal pressure or in a low-pressurized condition, and further the cold is transferred through the second heat exchanger to the nitrogen gas or the like compressed to a high pressure, whereby a liquefied nitrogen gas can be efficiently prepared. In preparing a liquefied fluid, the cold of the LNG can be used more efficiently, and the energy needed in transferring the cold can be reduced to a great extent.
The present invention relates also to the apparatus for producing a liquefied fluid described above, wherein the apparatus further comprises: a third heat exchanger disposed in a third flow passageway for guiding the heat transfer medium from the first heat exchanger to the expansion device, wherein the heat transfer medium, the liquefied natural gas from the second heat exchanger, and the low-temperature compressed fluid from the second compression device undergo heat exchange at the third heat exchanger.
With such a structure, the cold of the LNG can be used further more efficiently, and preparation of a liquefied fluid having a high energy efficiency can be carried out. In particular, when cooling water is introduced in the third heat exchanger to perform heat exchange by cold energy having a large heat capacity, transfer of preparatory or auxiliary hot heat to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid can be carried out even to transient fluctuation or the like at the time of starting or at the time of stopping, thereby ensuring a stable use of the cold of LNG and a stable energy efficiency.
The present invention relates also to the apparatus for producing a liquefied fluid described above, wherein first pressure-raising device, a first branching flow passageway, second pressure-raising device, and a second branching flow passageway are disposed in a fourth flow passageway through which the material gas is guided to the first heat exchanger; a fourth heat exchanger and a third branching flow passageway are disposed in a fifth flow passageway through which the liquefied component from the gas-liquid separator is guided; which has a sixth flow passageway through which a gas component from the gas-liquid separator is guided to the first branching flow passageway via the first heat exchanger or the second heat exchanger, and a seven flow passageway through which the liquefied component that has been branched at the third branching flow passageway is guided to the second branching flow passageway via the fourth heat exchanger and the first heat exchanger or the second heat exchanger, where the liquefied component from the gas-liquid separator is extracted therefrom via the fourth heat exchanger.
It is known in the art that, by compressing the material gas in multiple stages, the material gas can be efficiently fed, and the heat exchange efficiency in the heat exchanger into which such a material gas is introduced will be improved. The present invention has made it possible to supply a liquefied fluid in a stable condition and with a good energy efficiency by providing compressors in plural stages as material gas feeding device and returning the liquefied fluid in a stable condition immediately before being extracted to mix the liquefied fluid with the material gas thereof.
The present invention relates also to the apparatus for producing a liquefied fluid described above, wherein the Rankine cycle system is comprised with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities, where the material gas from the first heat exchanger is guided into the first heat exchanger after being compressed by second compression device that is coupled to the expansion device involved in one Rankine cycle system using a heat transfer medium having a low boiling point or a small heat capacity, and thereafter the material gas from the first heat exchanger is guided into the first heat exchanger after being compressed by second compression device that is coupled to the expansion device involved in another Rankine cycle system using a heat transfer medium having a high boiling point or a large heat capacity.
In many cases, an apparatus for producing a liquefied fluid is used in line in semiconductor production equipment or the like, so that a continuous supply of gas is demanded, and also the amount of supply, the pressure of supply, and the like thereof may largely fluctuate. Also, as described before, there are cases in which the stable supply of LNG is not necessarily ensured. The present invention has made it possible to supply a liquefied fluid in a stable condition and with a good energy efficiency by constructing with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities for the heat transfer medium that carries out the transfer of the cold of LNG and adjusting the control elements that can be easily controlled, such as the flow rate and the pressure of the heat transfer medium, in each Rankine cycle system with regard to the fluctuating elements in these cases. BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic view illustrating a basic exemplary structure of an apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention;
Fig. 2 is a schematic view exemplifying one mode of the first exemplary structure of an apparatus for producing a liquefied fluid according to the present invention;
Fig. 3 is a schematic view exemplifying another mode of the first exemplary structure of an apparatus for producing a liquefied fluid according to the present invention;
Fig. 4 is a schematic view illustrating the second exemplary structure of an apparatus for producing a liquefied fluid according to the present invention;
Fig. 5 is a schematic view illustrating the third exemplary structure of an apparatus for producing a liquefied fluid according to the present invention;
Fig. 6 is a schematic view illustrating the fourth exemplary structure of an apparatus for producing a liquefied fluid according to the present invention; and
Fig. 7 is a schematic view illustrating an exemplary structure of a gas liquefying process according to a conventional art.
An apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention (hereafter referred to as "present apparatus") using a Rankine cycle system (RC) comprises; a first compression device for adiabatically compressing a heat transfer medium, a first heat exchanger for constant- pressure heating the adiabatically compressed heat transfer medium; an expansion device for adiabatically expanding the heated heat transfer medium; a second heat exchanger for constant-pressure cooling the adiabatically expanded heat transfer medium; a (first) flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and at least one second compression device that is coupled to the expansion device; wherein, at the second heat exchanger, a low-temperature liquefied natural gas (LNG) and the heat transfer medium undergo heat transfer, wherein, at the first heat exchanger, a fed material gas and the heat transfer medium undergo heat transfer to produce a low-temperature fluid from the material gas, and wherein, the low-temperature fluid is thereafter compressed at the second compression device to produce a low-temperature compressed fluid. Hereafter, the embodiments of the present invention will be described with reference to the attached drawings. Here, in the present embodiments, cases in which nitrogen gas is the gas to be liquefied may be exemplified; however, the present invention can be applied similarly to liquefaction of other gases, for example, air, argon, and the like. Also, conditions such as the temperature, the pressure, and the flow rate of each section can be suitably changed in accordance with other conditions such as the type of the gas and the flow rate.
The basic structure of the present apparatus will be schematically exemplified in Fig. 1 . The present apparatus has a Rankine cycle system (RC) in which a heat transfer medium circulates. The heat transfer medium forms a circulation system in which, sequentially, the heat transfer medium is adiabatically compressed by a compression pump 1 which serves as a first compression device, constant-pressure cooled by a material gas in a first heat exchanger 2, adiabatically expanded by a turbine 3 which serves as an expansion device, constant-pressure cooled by the cold of LNG in a second heat exchanger 4, and sucked again by the compression pump 1 . By such a structure, the cold of LNG can be stably and efficiently transferred to the material gas. Here, the "heat transfer medium" may be selected from among various substances such as hydrocarbon, liquefied ammonia, liquefied chlorine, and water. Also, at a normal temperature and under a normal pressure, the heat transfer media may include not only liquids but also gases, so that a gas having a large heat capacity, such as carbon dioxide, may be applied. Besides the case in which methane, ethane, propane, butane, or the like is used singly as the hydrocarbon, the optimum boiling point or heat capacity can be designed by using a mixture of a plurality of compounds. In particular, when a plurality of RCs are used as will be described later, the cold energy of LNG can be thermally transferred in a plurality of temperature bands by using, for example, a mixture of "methane + ethane + propane" in one RC and using a mixture of "ethane + propane + butane" in another RC.
The LNG of a predetermined flow rate is supplied to the second heat exchanger 4, whereby a predetermined amount of cold is ensured. By controlling the supply flow rate of the LNG, the cold that is transferred to the material gas can be easily adjusted. A material gas of a desired flow rate is supplied to the first heat exchanger 2 by a feed pump 5, whereby a predetermined amount of cold is transferred to the material gas to cool the material gas to a desired temperature. Further, the material gas is guided into the compressor 6 which is second compression device so as to be compressed to a desired pressure and is extracted as a desired low-temperature compressed fluid. By such a structure, a desired low-temperature compressed fluid can be produced in a stable condition. Also, the energy efficiency can be improved to a great extent as compared with a conventional apparatus in which the cold of LNG and the material gas are subjected to direct heat exchange.
As described above, the low-temperature compressed fluid is produced in such a condition that, in the present apparatus in which a Rankine cycle system (RC) is formed, a liquefied natural gas in a low-temperature liquefied state is guided into the second heat exchanger 4 to transfer the cold thereof to the heat transfer medium, and the material gas that is fed by the feed pump 5 is guided into the first heat exchanger 2 to be cooled by the heat transfer medium and thereafter guided into at least one second compression device (compressor) 6 that is coupled to the expansion device (turbine) 3, so as to be extracted as a low-temperature compressed fluid.
Specifically, an example will be assumed in which a mixture obtained by blending ethane and propane in an equal molar ratio as a major component, for example, is used as the heat transfer medium of the RC; LNG of about 6 MPa is guided into the second heat exchanger 4; and nitrogen gas is fed as a material gas. In the example, the heat transfer medium guided at about 0.05 MPa into the second heat exchanger 4 is guided out after being cooled to about -1 15°C, adiabatically compressed to about 1 .8 MPa by the compression pump 1 , guided into the first heat exchanger 2, guided out after being heated by heat exchange with the material gas, adiabatically expanded by the turbine 3, and guided at about -45°C and under about 0.05 MPa into the second heat exchanger 4. The nitrogen gas guided at about 2.1 MPa into the first heat exchanger 2 is guided out after being cooled to about -90°C, compressed to about 5 MPa by the compressor 6 coupled to the turbine 3, and extracted as a low-temperature compressed nitrogen gas having a temperature of about -90°C and a pressure of about 5 MPa.
A case in which a low-temperature compressed nitrogen gas was prepared using the present apparatus was compared with a case in which a low-temperature compressed nitrogen gas was prepared using a conventional method, so as to verify the energy efficiency thereof. As will be described below, an improvement of about 50% or more could be achieved by using the present apparatus.
(i) A case in which a low-temperature compressed nitrogen gas was prepared using a conventional method
Assuming that LNG was supplied at 1 ton/h and a compressor was operated at an electric power of 15.7 kWh, a nitrogen gas of 677 Nm3/h, for example, could be pressurized from 20 bar to 37 bar. During this time, the entrance temperature of the compressor was 40°C, and the exit temperature thereof was 1 1 1 °C.
(ii) A case in which a low-temperature compressed nitrogen gas was prepared using the present method
The amount of LNG needed to obtain a similar low-temperature compressed nitrogen gas, that is, to pressurize a nitrogen gas of 677 Nm3/h from 20 bar to 37 bar, was 0.485 ton/h.
(iii) When the two cases were compared, it had been found out that the electric power could be reduced by about 8 kWh, that is, by about 52%, from the following formula 1 .
(1 - 0.485) x 0.515 = 8.09 [kWh]
8.09 / 15.7 = 0.52 ... (formula 1 )
Apparatus for producing a liquefied fluid using the present apparatus
A basic exemplary structure (first exemplary structure) of an apparatus (hereafter referred to as "present liquefaction apparatus") for producing a liquefied fluid using the present apparatus will be schematically shown in Fig. 2. Hereafter, elements common to those of the present apparatus will be denoted with common nominations and reference symbols, and a description thereof may be omitted. The present liquefaction apparatus has a Rankine cycle system (RC) similar to that of the present apparatus and comprises a (second) flow passageway through which the low-temperature compressed fluid from the second compression device 6 to at least one of the first heat exchanger 2 and the second heat exchanger 4 (the second heat exchanger 4 in the first exemplary structure), an adjustment valve 7 for adjusting the pressure of the low-temperature compressed fluid containing a liquefied component from the first heat exchanger 2 or the second heat exchanger 4 (from the second heat exchanger 4 in the first exemplary structure), and a gas-liquid separator 8 into which the low-temperature compressed fluid is guided via the adjustment valve 7 so as to perform gas-liquid separation of the liquefied component, whereby the low-temperature liquefied component from the gas-liquid separator 8 is extracted. In addition to the functions in the above-described present apparatus, the difficulty of heat transfer due to the difference between the temperature of the supplied LNG and the boiling point of the material gas can be eliminated by effectively using the RC. In other words, by transferring the cold of the LNG further to the compressed low-temperature gas, the cold can be efficiently used for liquefying the low- temperature gas. By such a structure, the liquefied fluid can be prepared stably and efficiently.
In other words, the low-temperature compressed fluid from the second compression device 6 is cooled in the second heat exchanger 4 and is subjected to pressure adjustment by the adjustment valve 7, and the liquefied component is subjected to gas-liquid separation in the gas-liquid separator 8 and extracted as a low-temperature liquefied component from the gas-liquid separator 8. At this time, when the material gas is, for example, ethane or propane having a comparatively higher boiling point than nitrogen or oxygen, the low-temperature compressed fluid can be liquefied by being guided into the first heat exchanger 2, as is exemplified in Fig. 3. This is because the temperature difference from the cold of the LNG is small, and the cold of the LNG sufficient for liquefaction can be transferred via the heat transfer medium when the source material is guided out from the first heat exchanger 2 and again guided into the first heat exchanger 2 in a compressed state. Also, in the case of "the pressure of the LNG" > "the pressure of the material gas" (for example, about 50 bar), there is a possibility that the LNG may leak to the material gas side, so that the risk thereof can be evaded with such a structure.
Similarly as the specific example in the above-described present apparatus, a specific example will be assumed in which a mixture obtained by blending ethane and propane in an equal molar ratio as a major component, for example, is used as the heat transfer medium of the RC; LNG of about 6 MPa is guided into the second heat exchanger 4; and nitrogen gas is fed as a material gas. A material gas that has been guided at about 2.1 MPa into the first heat exchanger 2 becomes a low-temperature compressed nitrogen gas of about -90°C and about 5 MPa by passing through the compressor 6. This low-temperature compressed nitrogen gas is further guided into the second heat exchanger 4 to be cooled to about -153°C and then is expanded via the adjustment valve 7 to be cooled to about -179°C, whereafter the liquefied nitrogen gas mainly containing a liquefied component is guided into the gas-liquid separator 8. The liquefied component that has been subjected to gas-liquid separation in the gas-liquid separator 8 is extracted as a liquefied nitrogen gas of about -179°C and about 0.05 MPa.
Similarly as in the verification test in the above-described present apparatus, a case in which a liquefied nitrogen gas was prepared using the present liquefaction apparatus was compared with a case in which a liquefied nitrogen gas was prepared using a conventional method, so as to verify the energy efficiency thereof. As will be described below, an improvement of about 25% or more could be achieved by using the present apparatus.
(i) A case in which a liquefied nitrogen gas was prepared using a conventional method
LNG was supplied at 1 ton/h, and an energy of 0.28 kWh/Nm3 was needed in preparing a liquefied nitrogen gas of about 0.05 MPa.
(ii) A case in which a liquefied nitrogen gas was prepared using the present method
An energy of 0.21 kWh/Nm3 was sufficient in preparing a liquefied nitrogen gas of about 0.05 MPa under the conditions of the specific example in the above-described present liquefaction apparatus.
(iii) When the two cases are compared, it has been found out that the electric power could be reduced by about 25%, from the following formula 1 .
(0.28 - 0.21 ) / 0.28 = 0.25 ... (formula 1 )
Another exemplary structure (second exemplary structure) of the present liquefaction apparatus will be schematically shown in Fig. 4. Similarly as in the first exemplary structure, the present liquefaction apparatus according to the second exemplary structure has a Rankine cycle system (RC), an adjustment valve 7, and a gas- liquid separator 8, wherein a third heat exchanger 9 is disposed in a (third) flow passageway through which the heat transfer medium from the first heat exchanger 2 is guided to the expansion device (turbine) 3, where the heat transfer medium, the liquefied natural gas from the second heat exchanger 4, and the low-temperature compressed fluid from the second compression device (compressor) 6 undergo heat exchange in the third heat exchanger 9. In addition to the functions in the first exemplary structure, the cold of the LNG can be used further more efficiently, and preparation of a liquefied fluid having a high energy efficiency can be carried out. Here, similarly as in the first exemplary structure, a structure in which the low-temperature compressed fluid can be liquefied by being guided into the first heat exchanger 2 can be applied.
In other words, in the third heat exchanger 9, the cold of the LNG can be used further more efficiently by using the residual cold of the LNG for cooling the heat transfer medium that has been heated in the first heat exchanger 2 and the low-temperature compressed fluid that has been compressed to have an increased heat quantity. Also, a structure in which cooling water is introduced in the third heat exchanger 9 will be exemplified here. Heat exchange with cold energy having a large heat capacity can be carried out, and quick transfer of hot heat can be achieved to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid. Even to transient fluctuation or the like at the time of starting or at the time of stopping, preliminary or auxiliary transfer of hot energy can be achieved to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid, whereby stable use of the cold of the LNG and stable energy efficiency can be ensured.
The third exemplary structure of the present liquefaction apparatus will be schematically shown in Fig. 5. In addition to the second exemplary structure, the present liquefaction apparatus according to the third exemplary structure is characterized in that first pressure-raising device (feed pump) 5, a first branching flow passageway S1 , second pressure-raising device 10, and a second branching flow passageway S2 are disposed in a (fourth) flow passageway L5 through which the material gas is guided to the first heat exchanger 2; a fourth heat exchanger 1 1 and a third branching flow passageway S3 are disposed in a (fifth) flow passageway L8 through which the liquefied component from the gas-liquid separator 8 is guided; the apparatus has a (sixth) flow passageway L1 1 through which a gas component from the gas-liquid separator 8 is guided to the first branching flow passageway S1 via the second heat exchanger 4, and has a (seven) flow passageway L12 through which the liquefied component that has been branched at the third branching flow passageway S3 is guided to the second branching flow passageway S2 via the fourth heat exchanger 1 1 and the second heat exchanger 4, wherein the liquefied component from the gas-liquid separator 8 is extracted via the fourth heat exchanger 1 1 . Supply of a liquefied fluid being stable and having a good energy efficiency has been enabled by disposing compressors in a plurality of stages as the material gas feeding device and by returning the liquefied fluid in a stable condition immediately before being extracted and mixing it with the material gas.
In the third exemplary structure, a structure will be exemplified in which a second adjustment valve 12 is disposed in the third branching flow passageway S3, and part of the liquefied fluid from the fourth heat exchanger 1 1 is again guided into the fourth heat exchanger 1 1 via the second adjustment valve 12. Though having a low pressure, a liquefied fluid having a further lower temperature is prepared by adiabatically expanding the low-temperature liquefied fluid with the second adjustment valve 12 and can be allowed to function as the cold in the fourth heat exchanger 1 1 .
The temperature and the pressure of the gas or liquid in each flow passageway in the case in which liquefied nitrogen gas was prepared using the liquefaction apparatus according to the third exemplary structure were verified. The verification results are exemplified in Table 1 . [TABLE 1]
Figure imgf000018_0001
Figure imgf000018_0002
The fourth exemplary structure of the present l iquefaction apparatus will be schematically shown in Fig. 6. In addition to the third exemplary structure, the present liquefaction apparatus according to the fourth exemplary structure is characterized in that the apparatus using a plurality of Rankine cycle systems comprising a plurality of heat transfer media having different boiling points or heat capacities, wherein the material gas from the first heat exchanger 2 is guided into the first heat exchanger 2 after being compressed by second compression device 6a that is coupled to the expansion device 3a involved in one Rankine cycle system RCa using a heat transfer medium having a low boiling point or a small heat capacity, and thereafter the material gas from the first heat exchanger 2 is guided into the first heat exchanger 2 after being compressed by second compression device 6b that is coupled to the expansion device 3b involved in another Rankine cycle system RCb using a heat transfer medium having a high boiling point or a large heat capacity. Supply of a liquefied fluid being stable and having a good energy efficiency has been enabled by constructing with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities with respect to the heat transfer media that are involved in transferring the cold of the LNG and by adjusting the control elements that can be easily controlled, such as the flow rate and the pressure of the heat transfer media in each Rankine cycle system, with respect to the fluctuating elements such as the supply amount and the supply pressure of the liquefied fluid.
The plurality of heat transfer media having different boiling points or heat capacities as referred to herein include not only a case in which the substances themselves are different and a case in which the substances constituting the mixtures or compounds are different but also a case in which the composition of the mixture of a plurality of substances is different. For example, two Rankine cycle systems having different characteristics can be constructed by forming one heat transfer medium with a mixture of 20% of methane, 40% of ethane, and 40% of propane and forming the other heat transfer medium with a mixture of 2% of methane, 49% of ethane, and 49% of propane. By a combination thereof, transfer of the cold or the cold energy that matches with various fluctuating elements can be achieved, and efficient transfer of energy to the compression device coupled with the expansion device can be achieved.
Also, when heat transfer media having different components are used, a heat transfer function of a further wider range can be formed. In other words, there is a restriction on the temperature band in which the cold of the LNG can be used because of the relationship between the temperature of the cold of the LNG and the boiling point of the material gas or the temperature of the compressed gas (fluid) as described above, so that the cold of the LNG can be used in a plurality of temperature bands by arranging one Rankine cycle system RCa and another Rankine cycle system RCb in series as in the fourth exemplary structure. For example, the cold energy of the LNG can be thermally transferred in a plurality of temperature bands by using a mixture of "methane + ethane + propane" in one Rankine cycle system RCa and using a mixture of "ethane + propane + butane" in another Rankine cycle system RCb. The cold energy of the LNG can be efficiently used by arranging one Rankine cycle system RCa and another Rankine cycle system RCb in series as in the fourth exemplary structure and by using the cold energy of the LNG, for example, in a range of -150 to -100°C in the one Rankine cycle system RCa and using the cold energy of the LNG, for example, in a range of -150 to -100°C in the other Rankine cycle system RCb. Also, when this is used as an energy for compressing the nitrogen gas, the energy (consumed electric power) needed per liquefied nitrogen production amount can be greatly reduced.
As shown above, each exemplary structure has been described on the basis of each descriptive view; however, the present apparatus or the present liquefaction apparatus is not limited to these but is constructed with a wider concept including a combination of the constituent elements thereof or a combination with other related known constituent elements.

Claims

1 . An apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid,
the apparatus using a Rankine cycle system comprising:
a first compression device (1 ) for adiabatically compressing a heat transfer medium;
a first heat exchanger (2) for constant-pressure heating the adiabatically compressed heat transfer medium;
at least one expansion device (3,3a,3b) for adiabatically expanding the heated heat transfer medium;
a second heat exchanger (4) for constant-pressure cooling the adiabatically expanded heat transfer medium;
a first flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and
at least one second compression device (6,6a,6b) that is coupled to the expansion device or one of the expansion devices;
wherein, at the second heat exchanger, a low-temperature liquefied natural gas
(LNG) and the heat transfer medium undergo heat transfer,
wherein, at the first heat exchanger, a fed material gas (GN2) and the heat transfer medium undergo heat transfer to produce a low-temperature fluid (GPN2) from the material gas, and
wherein, the low-temperature fluid is thereafter compressed at the second compression device to produce a low-temperature compressed fluid.
2. The apparatus according to claim 1 ,
wherein the apparatus further comprises:
a second flow passageway for guiding the low-temperature compressed fluid from the second compression device (6, 6b) to at least one of the first heat exchanger (2) and the second heat exchanger (4) to form a liquefied component (LN2),
an adjustment valve (7) for adjusting a pressure of the low-temperature compressed fluid from at least one of the first heat exchanger and the second heat exchanger, and
a gas-liquid separator (8) into which the low-temperature compressed fluid is guided via the adjustment valve, performing gas-liquid separation so as to permit the liquefied component to be extracted therefrom.
3. The apparatus according to claim 1 or 2,
wherein the apparatus further comprises:
a third heat exchanger disposed in a third flow passageway for guiding the heat transfer medium from the first heat exchanger to the expansion device,
wherein the heat transfer medium, the liquefied natural gas from the second heat exchanger, and the low-temperature compressed fluid from the second compression device undergo heat exchange at the third heat exchanger.
4. The apparatus according to any one of claim 2,
wherein
a first pressure-raising device, a first branching flow passageway, second pressure-raising device, and a second branching flow passageway are disposed in a fourth flow passageway through which the material gas is guided to the first heat exchanger;
a fourth heat exchanger (1 1 ) and a third branching flow passageway are disposed in a fifth flow passageway through which the liquefied component from the gas-liquid separator (8) is guided;
which has a sixth flow passageway through which a gas component from the gas- liquid separator is guided to the first branching flow passageway via the first heat exchanger (2) or the second heat exchanger (4) , and a seven flow passageway through which the liquefied component that has been branched at the third branching flow passageway is guided to the second branching flow passageway via the fourth heat exchanger and the first heat exchanger or the second heat exchanger;
where the liquefied component (LN2) from the gas-liquid separator is extracted therefrom via the fourth heat exchanger.
5. The apparatus according to any one of claims 1 to 4, using a plurality of Rankine cycle systems comprising a plurality of heat transfer media having different boiling points or heat capacities,
where the material gas from the first heat exchanger (2) is guided into the first heat exchanger after being compressed by second compression device (6a) that is coupled to the expansion device (3a) forming part of one Rankine cycle system using a heat transfer medium having a low boiling point or a small heat capacity, and thereafter the material gas from the first heat exchanger is guided into the first heat exchanger after being compressed by a second compression device (6b) that is coupled to the expansion device (3b) forming part of another Rankine cycle system using a heat transfer medium having a high boiling point or a large heat capacity.
6. A method for cooling and compressing a fluid to produce a low-temperature compressed fluid,
which using a Rankine cycle system in which a heat transfer medium that has been adiabatically compressed by a first compression device is constant-pressure heated in a first heat exchanger (2) , thereafter adiabatically expanded by an expansion device (3), and further constant-pressure cooled in a second heat exchanger (4);
wherein a low-temperature liquefied natural gas (LNG) is guided into the second heat exchanger to transfer the cold thereof to the heat transfer medium, and a fed material gas is guided into the first heat exchanger to be cooled by the heat transfer medium and thereafter guided into at least one second compression device that is coupled to the expansion device, so as to be extracted as a low-temperature compressed fluid.
7. The method according claim 6,
wherein the low-temperature compressed fluid from the second compression device is cooled in the first heat exchanger or the second heat exchanger and subjected to pressure adjustment by an adjustment valve (7) and a liquefied component is subjected to gas-liquid separation in a gas-liquid separator (8) and is extracted as a low- temperature liquefied component (LN2) from the gas-liquid separator.
PCT/EP2013/076745 2012-12-28 2013-12-16 Apparatus and method for producing low-temperature compressed gas or liquefied gas WO2014102084A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP13811874.0A EP2938951B1 (en) 2012-12-28 2013-12-16 Apparatus and method for producing low-temperature compressed gas or liquefied gas
ES13811874.0T ES2634765T3 (en) 2012-12-28 2013-12-16 Apparatus and method for producing compressed gas at low temperature or liquefied gas
US14/655,261 US10036589B2 (en) 2012-12-28 2013-12-16 Apparatus and method for producing low-temperature compressed gas or liquefied gas
CN201380073836.8A CN105143799B (en) 2012-12-28 2013-12-16 For producing the apparatus and method of low temperature compression gas or liquefied gas

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012-288262 2012-12-28
JP2012288262 2012-12-28
JP2013-085114 2013-04-15
JP2013085114A JP6087196B2 (en) 2012-12-28 2013-04-15 Low temperature compressed gas or liquefied gas manufacturing apparatus and manufacturing method

Publications (3)

Publication Number Publication Date
WO2014102084A2 true WO2014102084A2 (en) 2014-07-03
WO2014102084A3 WO2014102084A3 (en) 2015-06-18
WO2014102084A8 WO2014102084A8 (en) 2015-08-06

Family

ID=49880726

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/076745 WO2014102084A2 (en) 2012-12-28 2013-12-16 Apparatus and method for producing low-temperature compressed gas or liquefied gas

Country Status (6)

Country Link
US (1) US10036589B2 (en)
EP (1) EP2938951B1 (en)
JP (1) JP6087196B2 (en)
CN (1) CN105143799B (en)
ES (1) ES2634765T3 (en)
WO (1) WO2014102084A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016147084A1 (en) * 2015-03-17 2016-09-22 Siad Macchine Impianti S.P.A. Plant for the liquefaction of nitrogen using the recovery of cold energy deriving from the evaporation of liquefied natural gas
WO2017071742A1 (en) * 2015-10-28 2017-05-04 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Apparatus and method for producing liquefied gas

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105953471B (en) * 2015-04-13 2020-05-22 李华玉 Second-class thermally-driven compression heat pump
FR3044747B1 (en) * 2015-12-07 2019-12-20 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude PROCESS FOR LIQUEFACTION OF NATURAL GAS AND NITROGEN
US20200370710A1 (en) * 2018-01-12 2020-11-26 Edward Peterson Thermal Cascade for Cryogenic Storage and Transport of Volatile Gases
TWI746977B (en) 2019-01-22 2021-11-21 法商液態空氣喬治斯克勞帝方法研究開發股份有限公司 Gas liquefaction method and gas liquefaction device
JP7379763B2 (en) 2019-07-25 2023-11-15 レール・リキード－ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Gas liquefaction method and gas liquefaction device
FR3099234B1 (en) 2019-07-26 2021-07-30 Air Liquide Refrigeration energy recovery process with production of electricity or liquefaction of a gas stream
CN110332763B (en) * 2019-08-06 2024-03-29 巴斯夫新材料有限公司 System and method for compressing gas using waste refrigeration assisted liquefaction cycle
JP7355979B2 (en) 2019-09-26 2023-10-04 レール・リキード－ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード gas liquefaction equipment
US11566841B2 (en) * 2019-11-27 2023-01-31 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Cryogenic liquefier by integration with power plant
CN110847987B (en) * 2019-12-24 2024-04-05 青岛中稷龙源能源科技有限公司 LNG cold energy power generation and comprehensive utilization system and method for mixed working medium
US11346602B2 (en) * 2020-05-05 2022-05-31 Praxair Technology, Inc. System and method for natural gas and nitrogen liquefaction with dual operating modes
US20220205714A1 (en) * 2020-12-28 2022-06-30 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method for efficient cold recovery in o2-h2 combustion turbine power generation system
CN113310281A (en) * 2021-06-15 2021-08-27 中国科学院理化技术研究所 Liquid air production device utilizing LNG cold energy

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0545050A (en) 1991-08-09 1993-02-23 Nippon Sanso Kk Method for liquefying permanent gas using cryogenic cold of liquefied natural gas

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE551602A (en) * 1955-10-10
NL134864C (en) * 1960-06-16
JPS5439343B2 (en) * 1971-09-21 1979-11-27
FR2187702B1 (en) * 1972-06-13 1976-11-12 Nuovo Pignone Spa
FR2300303A1 (en) * 1975-02-06 1976-09-03 Air Liquide CYCLE FR
JPS55146372A (en) * 1979-05-02 1980-11-14 Nippon Oxygen Co Ltd Method of liquefying air by liquefied natural gas
US4444015A (en) * 1981-01-27 1984-04-24 Chiyoda Chemical Engineering & Construction Co., Ltd. Method for recovering power according to a cascaded Rankine cycle by gasifying liquefied natural gas and utilizing the cold potential
US5137558A (en) * 1991-04-26 1992-08-11 Air Products And Chemicals, Inc. Liquefied natural gas refrigeration transfer to a cryogenics air separation unit using high presure nitrogen stream
WO2006030779A1 (en) * 2004-09-17 2006-03-23 The Doshisha Heat pump, heat pump system, and rankine cycle
ITMI20061149A1 (en) * 2006-06-14 2007-12-15 Eni Spa PROCEDURE AND PLANT FOR THE REGASIFICATION OF NATURAL LIQUEFIED GAS AND THE SUOM STORAGE
JP5471438B2 (en) * 2007-02-26 2014-04-16 旭硝子株式会社 Working medium for Rankine cycle system, heat pump cycle system or refrigeration cycle system
JP2011518269A (en) * 2008-02-18 2011-06-23 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Integration of air separator and steam reheat cycle

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0545050A (en) 1991-08-09 1993-02-23 Nippon Sanso Kk Method for liquefying permanent gas using cryogenic cold of liquefied natural gas

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016147084A1 (en) * 2015-03-17 2016-09-22 Siad Macchine Impianti S.P.A. Plant for the liquefaction of nitrogen using the recovery of cold energy deriving from the evaporation of liquefied natural gas
CN107429967A (en) * 2015-03-17 2017-12-01 西亚德汽车系统股份公司 Carry out the equipment of liquid nitrogen using the cold energy recovery obtained from the evaporation of liquefied natural gas
US10330381B2 (en) 2015-03-17 2019-06-25 Siad Macchine Impianti S.P.A. Plant for the liquefaction of nitrogen using the recovery of cold energy deriving from the evaporation of liquefied natural gas
CN107429967B (en) * 2015-03-17 2020-03-10 西亚德汽车系统股份公司 Plant for liquefying nitrogen using recovery of cold energy obtained from the evaporation of liquefied natural gas
WO2017071742A1 (en) * 2015-10-28 2017-05-04 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Apparatus and method for producing liquefied gas
CN108369057A (en) * 2015-10-28 2018-08-03 乔治洛德方法研究和开发液化空气有限公司 Device and method for producing liquid gas
US20180313603A1 (en) * 2015-10-28 2018-11-01 L'Air Liquide, Société Anonyme pour I'Etude et I'Exploitation des Procédés Georges Claude Apparatus and method for producing liquefied gas

Also Published As

Publication number Publication date
EP2938951B1 (en) 2017-06-21
JP2014142161A (en) 2014-08-07
CN105143799B (en) 2017-03-08
EP2938951A2 (en) 2015-11-04
ES2634765T3 (en) 2017-09-28
CN105143799A (en) 2015-12-09
WO2014102084A3 (en) 2015-06-18
JP6087196B2 (en) 2017-03-01
WO2014102084A8 (en) 2015-08-06
US20160109180A1 (en) 2016-04-21
US10036589B2 (en) 2018-07-31

Similar Documents

Publication Publication Date Title
EP2938951B1 (en) Apparatus and method for producing low-temperature compressed gas or liquefied gas
KR101677306B1 (en) Method for producing a stream of subcooled liquefied natural gas using a natural gas feedstream, and associated facility
US20180313603A1 (en) Apparatus and method for producing liquefied gas
JP5890748B2 (en) Liquid hydrogen production equipment
KR102200362B1 (en) A Treatment System of Liquefied Gas
CN101180509B (en) Process for sub-cooling an GNL stream obtained by cooling by means of a first refrigeration cycle, and associated installation
KR102265257B1 (en) liquefaction system of boil-off gas and ship having the same
JP6021430B2 (en) Reliquefaction method of boil-off gas generated from liquid hydrogen storage tank
JP2002510011A (en) Power production from compressed liquefied natural gas
KR102289476B1 (en) Hydrogen Liquefaction System and Method
AU2022256150A1 (en) Fluid cooling apparatus
JP7154385B2 (en) Management of make-up gas composition fluctuations for high pressure expander processes
EP3262359B1 (en) Apparatus for supplying liquid fuel gas
CN104913592A (en) Small natural gas liquefying technology
CN108027197B (en) Expansion storage method for liquefied natural gas flow of natural gas liquefaction equipment and related equipment
JP6290703B2 (en) Liquefied gas manufacturing apparatus and manufacturing method
JP7179155B2 (en) Primary loop start-up method for high pressure expander process
JP7198294B2 (en) System and method for recondensing boil-off gas from a liquefied natural gas tank
KR20230083406A (en) Hydrogen liquefaction system using LNG and mixed refrigerant
KR101616406B1 (en) Natural gas liquefaction apparatus
JP2019066063A (en) Natural gas production apparatus and natural gas production method
EA038638B1 (en) Method of natural gas supply

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201380073836.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13811874

Country of ref document: EP

Kind code of ref document: A2

REEP Request for entry into the european phase

Ref document number: 2013811874

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2013811874

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14655261

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE