EP1469265A1 - Process for nitrogen liquefaction by recovering the cold derived from liquid methane gasification - Google Patents

Process for nitrogen liquefaction by recovering the cold derived from liquid methane gasification Download PDF

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Publication number
EP1469265A1
EP1469265A1 EP04007031A EP04007031A EP1469265A1 EP 1469265 A1 EP1469265 A1 EP 1469265A1 EP 04007031 A EP04007031 A EP 04007031A EP 04007031 A EP04007031 A EP 04007031A EP 1469265 A1 EP1469265 A1 EP 1469265A1
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Prior art keywords
nitrogen
cryogenic fluid
liquid
heat exchanger
cryogenic
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EP04007031A
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German (de)
French (fr)
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EP1469265B1 (en
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Emanuele Bigi
Alessandro Bigi
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SIAD MACCHINE IMPIANTI SpA
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SIAD MACCHINE IMPIANTI SpA
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02Processes 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
    • F25J1/0203Processes 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 a single-component refrigerant [SCR] fluid in a closed vapor compression cycle
    • F25J1/0204Processes 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 a single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a single flow SCR cycle
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012Primary atmospheric gases, e.g. air
    • F25J1/0015Nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003Processes 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
    • F25J1/0047Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/005Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/006Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/007Primary atmospheric gases, mixtures thereof
    • F25J1/0072Nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02Processes 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
    • F25J1/0221Processes 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
    • F25J1/0222Processes 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J1/02Processes 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
    • F25J1/0228Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0234Integration with a cryogenic air separation unit
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J1/02Processes 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
    • F25J1/0243Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0262Details of the cold heat exchange system
    • F25J1/0264Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams
    • F25J1/0265Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer
    • F25J1/0268Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer using a dedicated refrigeration means
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J1/02Processes 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
    • F25J1/0243Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0292Refrigerant compression by cold or cryogenic suction of the refrigerant gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02Processes 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
    • F25J1/0243Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0296Removal of the heat of compression, e.g. within an inter- or afterstage-cooler against an ambient heat sink
    • F25J1/0297Removal of the heat of compression, e.g. within an inter- or afterstage-cooler against an ambient heat sink using an externally chilled fluid, e.g. chilled water
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04006Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04048Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams
    • F25J3/0406Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams of nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04248Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04254Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using the cold stored in external cryogenic fluids
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04248Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04333Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/04351Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/62Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
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    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/08Cold compressor, i.e. suction of the gas at cryogenic temperature and generally without afterstage-cooler
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J2230/30Compression of the feed stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/42Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being nitrogen

Definitions

  • This invention relates to a process for recovering the cold deriving from liquid methane gasification.
  • methane tankers specialized for this purpose have to be used.
  • methane tankers the methane is contained in suitable tanks under high thermal insulation (using the Dewar flask principle).
  • this methane On reaching land, this methane has to be transported or used in gaseous form, and must therefore be vaporized and heated. To express this concept in other words, it could be said that in order to undergo vaporization and heating, it must transfer its "cold” to another fluid, which hence itself becomes cold during said heat transfer.
  • thermodynamic refrigeration cycles it is known that to cool a gas to a temperature less than the temperature of the environment in which it is present requires considerable energy consumption related to the application of usual thermodynamic refrigeration cycles.
  • this energy consumption is imposed by the need to compress the gas to be liquefied so that it becomes hot, and then to extract from it the heat associated with the temperature increase deriving from this compression more efficiently as it is effected at a higher temperature level.
  • Subsequent expansion of the compressed and cooled gas in a turbine further reduces its temperature to cryogenic values, with resultant liquefaction of the gas.
  • liquid methane transported by methane tankers contains a "negative energy" or cold, which it would be extremely advantageous to recover.
  • one of the usual methods of heating liquid methane is to pass the liquid methane through a heat exchanger through which water circulates in counter-current to heat said methane from a temperature of -150°C to a temperature of +15°C.
  • this gasification method alters the ecosystem as it causes artificial intermittent cooling of the sea.
  • the known art uses the said cold mainly during cooling by suitable heat exchangers.
  • An object of the present invention is to define a process for using the cold deriving from liquid methane gasification which is more advantageous than those currently used.
  • Nitrogen assuming that to be the cryogenic fluid compressed by a first of said compressor units, is liquefied in a heat exchanger by further nitrogen circulating in closed cycle which is continuously compressed by a second compressor unit and then expanded in a cryogenic turbine to achieve final cooling to a temperature of -190°C.
  • the nitrogen cooled by the turbine in this manner is used to cool all the nitrogen compressed by the first compressor unit until a temperature of -180°C is attained, at which the nitrogen liquefies.
  • the liquid nitrogen produced in this manner is then used in the air fractionation plant to produce liquid oxygen, nitrogen and argon, and for all other possible uses of liquid nitrogen.
  • a liquid methane inlet line 1 leads to a pump 2.
  • the pump 2 (indicatively of centrifugal type) feeds the liquid methane to a heat exchanger 4, which subtracts heat from a line 5 through which nitrogen passes in counter-current.
  • This nitrogen originates from another heat exchanger 6 in which a water line 7 had previously raised its temperature from about -98°C to about -34°C.
  • Said nitrogen is maintained at a relatively high pressure to increase the temperature difference between the methane and nitrogen in order, other conditions being equal, to achieve greater absorption of the cold provided by the liquid methane.
  • the nitrogen cooled in this manner by heat transfer with liquid methane leaves the heat exchanger 4 through a line 8, which branches into two lines 9 and 10 to enable the cold of the nitrogen to be used to cool the nitrogen circulating within specific circuits 16, 20 of the apparatus in which said nitrogen is liquefied.
  • the line 9 conveys the cold withdrawn from the methane to the interstage coolers (heat exchangers) 11, 12, 13 located respectively at the outlet of three stages 16, 15, 14 of a conventional compressor unit for the nitrogen in the circuit 18, which is of closed type.
  • the nitrogen of the closed circuit 18, cooled in this manner has a pressure of about 10 bar and a temperature of about -141°C.
  • the nitrogen cooled in this manner in the closed circuit 18, passes through a heat exchanger 16 to absorb heat from the nitrogen compressed in an open circuit 20.
  • the nitrogen of the open circuit 20 undergoes the following cooling sequence: cooling implemented by an intake heat exchanger 27, cooling implemented by a plurality of interstage heat exchangers (28, 29, 30, 31) and further cooling implemented by a final heat exchanger 32 upstream of said heat exchanger 19 located in the final part of said open circuit 20.
  • Said heat exchangers 27, 28, 29, 30, 31 32 subtract heat from the nitrogen of the open circuit 20 by transferring to it the cold present in the nitrogen passing through the line 10, itself cooled by the cold subtracted from the liquid methane in the heat exchanger 4.
  • the nitrogen of the two lines 9 and 10 flows into a common line 33, through which the nitrogen is fed to a compressor 34 which circulates it at a pressure of about 70 bar along the paths already described and in the directions indicated by the arrows.
  • the nitrogen enters the open circuit 20 in the gaseous state through the line 21 and leaves in the liquid state through a line 3, by optimum use of the cold deriving from the vaporization of the liquid methane.
  • liquid nitrogen produced in this manner can itself be used in the usual air fractionation plants to produce liquid oxygen, nitrogen and argon, and in addition for all the usual possible uses of liquid nitrogen.
  • the process for recovering cold from liquid methane by liquid nitrogen production cycles in the aforedescribed manner results in substantial energy savings.

Abstract

This process for nitrogen liquefaction by recovering the cold derived from liquid methane gasification has the characteristic of cooling with the liquid methane (1) a cryogenic fluid (5), preferably nitrogen, and then using said cryogenic fluid as coolant fluid (9,10) in two nitrogen compressor units of the nitrogen liquefier, both for the interstage coolers (11,12,13,27,28,29,30,31,32) and for the intake coolers (27) and for the final delivery coolers (19,32) of one of the nitrogen compressor unit.
The use of nitrogen cooled by the methane enables liquid nitrogen to be produced (3) in a liquefier consisting of the two said compressor units and a cryogenic turbine (17), with a very low specific energy consumption.

Description

  • This invention relates to a process for recovering the cold deriving from liquid methane gasification.
  • As methane has to be obtained from many regions of the world, it is not always possible to use usual methane pipelines, and instead methane tankers specialized for this purpose have to be used.
  • To be able to transport the maximum quantity of methane, these tankers are designed to transport it in liquid form in order to reduce its volume. However to remain in the liquid state, the methane has to be maintained at cryogenic temperature, the value of which depends on the storage pressure (for example -154°C at 2 bar absolute).
  • In methane tankers the methane is contained in suitable tanks under high thermal insulation (using the Dewar flask principle).
  • On reaching land, this methane has to be transported or used in gaseous form, and must therefore be vaporized and heated. To express this concept in other words, it could be said that in order to undergo vaporization and heating, it must transfer its "cold" to another fluid, which hence itself becomes cold during said heat transfer.
  • In this respect, it is known that to cool a gas to a temperature less than the temperature of the environment in which it is present requires considerable energy consumption related to the application of usual thermodynamic refrigeration cycles.
  • Substantially, this energy consumption is imposed by the need to compress the gas to be liquefied so that it becomes hot, and then to extract from it the heat associated with the temperature increase deriving from this compression more efficiently as it is effected at a higher temperature level. Subsequent expansion of the compressed and cooled gas in a turbine further reduces its temperature to cryogenic values, with resultant liquefaction of the gas.
  • Hence on this basis, liquid methane transported by methane tankers contains a "negative energy" or cold, which it would be extremely advantageous to recover.
  • In this respect, one of the usual methods of heating liquid methane is to pass the liquid methane through a heat exchanger through which water circulates in counter-current to heat said methane from a temperature of -150°C to a temperature of +15°C.
  • Besides not providing any energy recovery, this gasification method alters the ecosystem as it causes artificial intermittent cooling of the sea.
  • This is because the water used to heat the methane is withdrawn from the sea, cooled and then returned to the sea at a temperature lower than that at which it was withdrawn.
  • Because of the progressive importance assumed by methane traffic, current research is aimed at recovering the cold possessed by liquid methane in liquid air production cycles (Linde machine, Claude machine).
  • These cycles consist of repeated compression, cooling and expansion until the air becomes liquid at a temperature of -195°C.
  • More specifically, the known art uses the said cold mainly during cooling by suitable heat exchangers.
  • However this known art does not provide a technical basis suitable for using the said cold offered by liquid methane in a manner able to reduce the energy consumption relating to the cooling and liquefaction of technical gases normally used in industry (nitrogen, oxygen, argon).
  • To illustrate these concepts with numerical examples, expressive of current industrial reality, 13,000 kWh are required to liquefy 25,000 Normal (atmospheric pressure, 0°C) cubic metres of nitrogen.
  • If the cold yielded by liquid methane during its gasification or expansion to ambient temperature is used with current techniques, this energy consumption is reduced to only 8,400 kWh, hence saving 4,600 kWh.
  • This is evidently a considerable saving, but which could be better utilized if a method could be found for using the said cold to liquefy industrial gases in a more direct manner within the liquefaction process.
  • An object of the present invention is to define a process for using the cold deriving from liquid methane gasification which is more advantageous than those currently used.
  • This and other objects which will be more apparent hereinafter will be seen to have been attained on reading the ensuing description of a process for recovering the cold deriving from liquid methane gasification characterised by cooling with the liquid methane a cryogenic fluid, preferably nitrogen, then using said cryogenic fluid as the cooling fluid in two nitrogen compressor units of a liquefier, both for the interstage coolers and for the intake and final delivery coolers.
  • Nitrogen, assuming that to be the cryogenic fluid compressed by a first of said compressor units, is liquefied in a heat exchanger by further nitrogen circulating in closed cycle which is continuously compressed by a second compressor unit and then expanded in a cryogenic turbine to achieve final cooling to a temperature of -190°C. The nitrogen cooled by the turbine in this manner is used to cool all the nitrogen compressed by the first compressor unit until a temperature of -180°C is attained, at which the nitrogen liquefies. The liquid nitrogen produced in this manner is then used in the air fractionation plant to produce liquid oxygen, nitrogen and argon, and for all other possible uses of liquid nitrogen.
  • The invention is illustrated by way of non-limiting example in the accompanying drawing, which shows a general scheme of a plant for implementing the process.
  • With reference to said drawing, a liquid methane inlet line 1 leads to a pump 2. The pump 2 (indicatively of centrifugal type) feeds the liquid methane to a heat exchanger 4, which subtracts heat from a line 5 through which nitrogen passes in counter-current.
  • This nitrogen originates from another heat exchanger 6 in which a water line 7 had previously raised its temperature from about -98°C to about -34°C.
  • Said nitrogen is maintained at a relatively high pressure to increase the temperature difference between the methane and nitrogen in order, other conditions being equal, to achieve greater absorption of the cold provided by the liquid methane.
  • The nitrogen cooled in this manner by heat transfer with liquid methane leaves the heat exchanger 4 through a line 8, which branches into two lines 9 and 10 to enable the cold of the nitrogen to be used to cool the nitrogen circulating within specific circuits 16, 20 of the apparatus in which said nitrogen is liquefied.
  • More precisely, the line 9 conveys the cold withdrawn from the methane to the interstage coolers (heat exchangers) 11, 12, 13 located respectively at the outlet of three stages 16, 15, 14 of a conventional compressor unit for the nitrogen in the circuit 18, which is of closed type.
  • At the outlet of the interstage cooler 11 the nitrogen of the closed circuit 18, cooled in this manner, has a pressure of about 10 bar and a temperature of about -141°C.
  • In this state it is expanded through a conventional cryogenic turbine 17 by which its temperature falls to -190°C and its pressure to 1.4 bar.
  • The nitrogen, cooled in this manner in the closed circuit 18, passes through a heat exchanger 16 to absorb heat from the nitrogen compressed in an open circuit 20.
  • This open circuit 20 comprises an inlet line 21, into which gaseous nitrogen is fed at a pressure of 1.15 bar absolute and a temperature of +15°C. This nitrogen undergoes successive compressions by a compressor unit composed of a first stage 22, a second stage 23, a third stage 24, a fourth stage 25 and a fifth stage 26.
  • The nitrogen of the open circuit 20 undergoes the following cooling sequence: cooling implemented by an intake heat exchanger 27, cooling implemented by a plurality of interstage heat exchangers (28, 29, 30, 31) and further cooling implemented by a final heat exchanger 32 upstream of said heat exchanger 19 located in the final part of said open circuit 20.
  • Said heat exchangers 27, 28, 29, 30, 31 32, subtract heat from the nitrogen of the open circuit 20 by transferring to it the cold present in the nitrogen passing through the line 10, itself cooled by the cold subtracted from the liquid methane in the heat exchanger 4.
  • After collecting heat through the respective heat exchangers 11, 12, 13, 27, 28, 29, 30, 31, 32, the nitrogen of the two lines 9 and 10 flows into a common line 33, through which the nitrogen is fed to a compressor 34 which circulates it at a pressure of about 70 bar along the paths already described and in the directions indicated by the arrows.
  • As a result of this, the nitrogen enters the open circuit 20 in the gaseous state through the line 21 and leaves in the liquid state through a line 3, by optimum use of the cold deriving from the vaporization of the liquid methane.
  • The liquid nitrogen produced in this manner can itself be used in the usual air fractionation plants to produce liquid oxygen, nitrogen and argon, and in addition for all the usual possible uses of liquid nitrogen.
  • Advantageously, the process for recovering cold from liquid methane by liquid nitrogen production cycles in the aforedescribed manner results in substantial energy savings.
  • With reference to the already stated real numerical values referring to a volume of 25,000 Normal cubic metres of nitrogen, the energy consumption using this process decreases to only 3,700 kWh, so drastically reducing the current energy requirement using the common liquefaction methods (for nitrogen liquefaction).

Claims (4)

  1. A process for recovering the cold deriving from liquid methane gasification, characterised by cooling with the liquid methane (1) a cryogenic fluid (5), preferably nitrogen, and then using said cryogenic fluid as coolant fluid in two compressor units (14-15-16, 22-23-24-25-26) for said nitrogen cryogenic fluid, both for the interstage coolers (11, 12, 13, 27, 28, 29, 30, 31, 32) and for the intake and final delivery coolers (27, 32), the cryogenic fluid (3) compressed by a first of said compressor units (22-23-24-25-26) being liquefied in a heat exchanger (19) by the action of another cryogenic fluid circulating in closed circuit, which is continuously compressed by a second of said compressor units (14-15-16) and then expanded through a cryogenic turbine (17) to achieve cooling to a temperature lower than the liquefaction temperature of the cryogenic fluid.
  2. A process as claimed in claim 1, wherein the cryogenic fluid is nitrogen which by cooling through the cryogenic turbine (17) is brought to a temperature of -190°C so as to obtain liquefaction of the nitrogen on reaching -180°C through said heat exchanger (19), the liquid nitrogen leaving through a controlled line (3) of said open circuit.
  3. A process as claimed in claim 2, wherein the nitrogen is used in an air fractionation plant for the production of liquid oxygen, nitrogen and argon or for other possible uses of liquid nitrogen.
  4. An apparatus for implementing the process, characterised in that the cryogenic fluid (preferably nitrogen) circulating within a first closed circuit (33) is cooled by liquid methane via heat exchanger means (4), said cooled cryogenic fluid being used to cool within a second closed circuit (18) another separate cryogenic fluid, said second closed circuit comprising compressor means (14, 15, 16), expander means (17) and heat exchanger means (19), and to cool and liquefy in an open circuit (20) a further separate cryogenic fluid, said open circuit comprising compressor means (22-26) and heat exchanger means (32), said further cryogenic fluid circulating through said heat exchanger means (19) of said second closed circuit (18) before leaving said open circuit (20).
EP04007031A 2003-04-08 2004-03-24 Process for nitrogen liquefaction by recovering the cold derived from liquid methane gasification Expired - Lifetime EP1469265B1 (en)

Priority Applications (1)

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SI200430051T SI1469265T1 (en) 2003-04-08 2004-03-24 Process for nitrogen liquefaction by recovering the cold derived from liquid methane gasification

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ITBG20030027 2003-04-08
IT000027A ITBG20030027A1 (en) 2003-04-08 2003-04-08 RECOVERY PROCEDURE FOR REFRIGERATORS ARISING FROM THE GASIFICATION OF LIQUID METHANE.

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AT (1) ATE328258T1 (en)
DE (1) DE602004001004T2 (en)
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IT (1) ITBG20030027A1 (en)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008023000A2 (en) 2006-08-23 2008-02-28 Shell Internationale Research Maatschappij B.V. Method and apparatus for the vaporization of a liquid hydrocarbon stream
WO2014155108A3 (en) * 2013-03-27 2015-08-06 Highview Enterprises Limited Method and apparatus in a cryogenic liquefaction process
US9459042B2 (en) 2007-12-21 2016-10-04 Shell Oil Company Method of producing a gasified hydrocarbon stream; method of liquefying a gaseous hydrocarbon stream; and a cyclic process

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007005494A1 (en) * 2007-01-30 2008-07-31 Dge Dr.-Ing. Günther Engineering Gmbh Producing liquid methane from a gas containing methane and carbon dioxide comprises scrubbing the gas to remove carbon dioxide and using the liquefied carbon dioxide to liquefy the methane
CN103775239B (en) * 2013-01-17 2017-01-04 摩尔动力(北京)技术股份有限公司 Nearly constant temperature pressure low-temperature receiver heat engine

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183677A (en) * 1960-06-16 1965-05-18 Conch Int Methane Ltd Liquefaction of nitrogen in regasification of liquid methane
FR1453071A (en) * 1964-12-16 1966-04-15 Conch Int Methane Ltd Gas liquefaction process
GB1120712A (en) * 1964-07-01 1968-07-24 John Edward Arregger Improvements in or relating to the separation of gas mixtures by low temperature distillation
GB1376678A (en) * 1971-03-30 1974-12-11 Snam Progetti Process for liquefying permanent gases
DE2434238A1 (en) * 1974-07-16 1976-01-29 Linde Ag System to store and retrieve stored energy - has gas type auxiliary energy storage medium which is liquefied when energy requirements are low
US4054433A (en) * 1975-02-06 1977-10-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Incorporated cascade cooling cycle for liquefying a gas by regasifying liquefied natural gas
JPH02171580A (en) * 1988-12-23 1990-07-03 Kobe Steel Ltd Air separating device
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
EP1055894A1 (en) * 1999-05-26 2000-11-29 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Air separation method and air separation plant

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183677A (en) * 1960-06-16 1965-05-18 Conch Int Methane Ltd Liquefaction of nitrogen in regasification of liquid methane
GB1120712A (en) * 1964-07-01 1968-07-24 John Edward Arregger Improvements in or relating to the separation of gas mixtures by low temperature distillation
FR1453071A (en) * 1964-12-16 1966-04-15 Conch Int Methane Ltd Gas liquefaction process
GB1376678A (en) * 1971-03-30 1974-12-11 Snam Progetti Process for liquefying permanent gases
DE2434238A1 (en) * 1974-07-16 1976-01-29 Linde Ag System to store and retrieve stored energy - has gas type auxiliary energy storage medium which is liquefied when energy requirements are low
US4054433A (en) * 1975-02-06 1977-10-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Incorporated cascade cooling cycle for liquefying a gas by regasifying liquefied natural gas
JPH02171580A (en) * 1988-12-23 1990-07-03 Kobe Steel Ltd Air separating device
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
EP1055894A1 (en) * 1999-05-26 2000-11-29 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Air separation method and air separation plant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 014, no. 432 (M - 1026) 17 September 1990 (1990-09-17) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008023000A2 (en) 2006-08-23 2008-02-28 Shell Internationale Research Maatschappij B.V. Method and apparatus for the vaporization of a liquid hydrocarbon stream
US9459042B2 (en) 2007-12-21 2016-10-04 Shell Oil Company Method of producing a gasified hydrocarbon stream; method of liquefying a gaseous hydrocarbon stream; and a cyclic process
WO2014155108A3 (en) * 2013-03-27 2015-08-06 Highview Enterprises Limited Method and apparatus in a cryogenic liquefaction process
CN105308404A (en) * 2013-03-27 2016-02-03 高维有限公司 Method and apparatus in a cryogenic liquefaction process
CN105308404B (en) * 2013-03-27 2018-02-23 高维有限公司 Method and apparatus in low-temperature liquefaction technique
US11408675B2 (en) 2013-03-27 2022-08-09 Highview Enterprises Limited Method and apparatus in a cryogenic liquefaction process

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EP1469265B1 (en) 2006-05-31
ITBG20030027A1 (en) 2004-10-09
DE602004001004D1 (en) 2006-07-06
ES2264059T3 (en) 2006-12-16
PT1469265E (en) 2006-09-29
ATE328258T1 (en) 2006-06-15
SI1469265T1 (en) 2006-10-31
DE602004001004T2 (en) 2006-12-14

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