US2500118A - Natural gas liquefaction - Google Patents

Natural gas liquefaction Download PDF

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US2500118A
US2500118A US611279A US61127945A US2500118A US 2500118 A US2500118 A US 2500118A US 611279 A US611279 A US 611279A US 61127945 A US61127945 A US 61127945A US 2500118 A US2500118 A US 2500118A
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nitrogen
condenser
methane
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Howell C Cooper
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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
    • 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
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0257Processes 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 characterised by the separated product stream separation of nitrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00Purification; Separation; Use of additives
    • 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
    • F25J1/0022Hydrocarbons, e.g. natural gas
    • 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
    • F25J1/0052Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • 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
    • F25J1/008Hydrocarbons
    • F25J1/0082Methane
    • 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
    • F25J1/008Hydrocarbons
    • F25J1/0085Ethane; Ethylene
    • 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
    • F25J1/0208Processes 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 in combination with an internal quasi-closed refrigeration loop, e.g. with deep flash recycle loop
    • 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
    • F25J1/0228Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235Heat exchange integration
    • F25J1/0237Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
    • 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
    • F25J1/0243Start-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
    • 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
    • F25J3/0204Processes 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 characterised by the feed stream
    • F25J3/0209Natural gas or substitute natural gas
    • 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
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0233Processes 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 characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • 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
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/02Processes or apparatus using separation by rectification in a single pressure main column system
    • 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
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/76Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration 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
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/04Recovery of liquid products
    • 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
    • F25J2270/00Refrigeration techniques used
    • F25J2270/12External refrigeration with liquid vaporising loop
    • 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
    • F25J2270/00Refrigeration techniques used
    • F25J2270/42Quasi-closed internal or closed external nitrogen refrigeration 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
    • F25J2270/00Refrigeration techniques used
    • F25J2270/60Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons
    • 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
    • F25J2270/00Refrigeration techniques used
    • F25J2270/90External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00Refrigeration
    • Y10S62/927Natural gas from nitrogen

Definitions

  • This invention relates to the liquefaction of natural gases for storage or transportation purposes, and more particularly to liquefaction of such gases containing nitrogen in substantial quantities, and constituting in fact a mixture of such nitrogen and the methane which is the principal combustible constituent.
  • the principal object of the invention is to rid the liquefaction apparatus of the nitrogen necessarily received by it, with a minimum loss .of methane; it having been the practice in the art heretofore to simply .vent the nitrogen under conditions entailing the loss of relatively greater amounts of methane.
  • the invention contemplates in this respect liquefaction of the entire methane and nitrogen contents of the natural gas at a lower pressure than would be necessary for liquefaction of the nitrogen only, so that a refrigerant such as methane is employable, utilizing its latent heat in the usual manner.
  • I is the incoming natural gas supply line, which leads to the product condenser 2 with pressure determined by the compressor 3 or equivalent pressure regulator.
  • the product condenser 2 is served with a refrigerant, which may be methane, liquefied in the methane condenser 4.
  • the methane circuit includes, commencing with the methane condenser 4, a methane heat exchanger 5, expansion valve 8, flash tank 1, expansion valve 8, product condenser 2, first storage compressort, intercooler l0, second stage compressor H with its intercooler l2 and third stage compressor l3 with its intercooler l4, methane precooler l5 and back to the methane condenser 4, it being understood that fiow in this methane circuit is in the direction of the order of the parts recited, by way of the suitable connections indicated in the drawing.
  • a bypass l6 by which gas from the flash tank I is passed through the heat exchanger 4 and returned to' the principal methane circuit ahead of the second stage compressor ll.
  • methane pressure will vary from 600 pounds, as it leaves its condenser 4 to 17 pounds as it leaves product condenser 2, as will be appreciated.
  • Liquefaction of the methane in its condenser 4 is accomplished by the employment of ethylene as a refrigerant, which ethylene is liquefied in the ethylene condenser 20.
  • the ethylene circuit is generally similar to the methane circuit, the ethylene. passing from its condenser 20 through expansion valve 2 I, flash tank 22, expansion valve 23, methane condenser 4, first stage compressor 24 with intercooler 25 and second stage compressor 26 with its aftercooler 21 and back to the ethylene condenser; a bypass 28 being provided from the flash tank 22, as before.
  • the ethylene in turn is liquefied in its condenser 20 by the employment of ammonia liquefled in the ammonia condenser 30 and employed in a substantially similar circuit including expansion valve 3
  • this ammonia circuit preferably includes a bypass around the ethylene condenser 20 and through the methane precooler l5, controlled by the expansion valve 38. It also includes the bypass 39 leading from the flash tank 32.
  • the ammonia leaves its condenser 30 at 100, enters the ethylene condenser 20 at 24, leaves the ethylene condenser at reenters the ammonia condenser 30 at varying in pressure from 250 pounds in its condenser to 17 pounds leaving the ethylene condenser.
  • the ammonia condenser is served by cooling water entering by line 40 and leaving by line 4
  • the temperature range available from the methane, for condensation of the natural gas mixture in the product condenser 2 is such that only a relatively low pressure of the natural gas such as175 pounds is necessary entering the condenser.
  • the natural gas mixture pressure may be adjusted dependent upon its nitrogen content so that only liquid, including liquefied nitrogen as well as liquefied methane will emerge from the bottom of the product condenser as through the line 50, where the temperature may be 240 and pressure 175 pounds.
  • is in the form of a tower having the bubble plates conventionally indicated and its operation depends upon a nitrogen liquefaction circuit whereby a liquid nitrogen spray is provided at the upper part of the tower by which gaseous methane is condensed and thereby rejected from a gaseous nitrogen outlet at the tower top.
  • the nitrogen liquefaction circuit includes the nitrogen condenser 60 wherein the nitrogen is liquefied, expansion valve 6
  • leads from the flash tank 62, by way of the precooler l0, and back into the circuit ahead of the interstage cooler 65.
  • the nitrogen condenser 60 is served by methane from the methane condenser 4 by a circuit which bypasses the product condenser 2 and includes the line 80, expansion valve 8
  • the nitrogen leaves its condenser 60 in liquid form at a --240, leaves the flash tank 62 at a -282, leaves the separator 4
  • the pressure within the nitrogen separator is 25 pounds, which is maintained substantially up to the first stage compressor 66, leaving the aftercooler 69 at 400 pounds.
  • the temperature of the nitrogen is at 310 which is below methane liquefying temperature so that any methane which emerges from the expansion valve 52 as a gas will be condensed and fall to the bottom of the separator where it will be at 260.
  • enters the described nitrogen circuit and its refrigerant capacity is largely conserved in the described heat exchangers 64, 65 and I0.
  • the nitrogen circuit a source of refrigerants, each servin is vented immediately ahead of its first compressor 66 under control of a valve 90 by which the nitrogen beyond that necessary for operation of the circuit, is disposed 01'.
  • the amount of nitrogen thus vented will be substantially the amount which enters the system by way of the supply line it being understood that a slight amount of nitrogen will remain in solution in the liquid methane leaving the nitrogen separator 5
  • the liquid methane is withdrawn subject to valve 9
  • the temperatures and pressures herein above recited are by way of example only and may vary somewhat according to various conditions, including. the capacity of the system.
  • the capacity is in the order of four million cubic feet of gas per day deliverable to storage, the entering gas comprising a mixture of about 91% methane and 9% nitrogen, by volume, at a temperature of
  • all of the incoming natural gas mixture is liquefied, under conditions very substantially less demanding than would be otherwise necessary for liquefaction of the nitrogen content alone; a common refrigerant source is employed for liquefaction of the mixture, and of the nitrogen necessary for separation; and purge of the nitrogen is had after recovery therefrom of most of its value as a refrigerant.
  • liquid methane from a natural gas mixture containing a substantial amount of nitrogen liquefying said mixture by heat exchange with a boiling refrigerant, separating nitrogen as a gas from the liquefied solution by reduction of pressure thereon in the presence of liquid nitrogen, employing previously separated and reliquefied nitrogen for the purpose, and venting the resultant gaseous nitrogen in excess of that required to be reliquefied for continuation of the separation process.
  • liquid methane from a natural gas mixture containing a substantial amount of nitrogen: liquefying said mixture by heat exchange with a boiling refrigerant, separating nitrogen as a gas from the liquefied solution by reduction of pressure thereon in the presence of liquid nitrogen, employing previously separated and reliquefied nitrogen for the purpose, and employing some of said refrigerant for said nitrogen reliquefaction.

Description

March 7, 1950 H. c. COOPER NATURAL GAS LIQUEF'ACTION Filed Aug. 18, 1945 INVENTOR. Ham/44 C. COOPER WQQ QQMQRTE Patented Mar. 7, 1950 UNITED STATES PATENT OFFICE 2,500,118 4 Y NATURAL GAS LIQUEFACTION Howell C. Cooper, Sewickley, Pa. Application August 18, 1945, Serial No. 611,279
2 Claims. (Cl. 62-1755) This invention relates to the liquefaction of natural gases for storage or transportation purposes, and more particularly to liquefaction of such gases containing nitrogen in substantial quantities, and constituting in fact a mixture of such nitrogen and the methane which is the principal combustible constituent.
The principal object of the invention is to rid the liquefaction apparatus of the nitrogen necessarily received by it, with a minimum loss .of methane; it having been the practice in the art heretofore to simply .vent the nitrogen under conditions entailing the loss of relatively greater amounts of methane.
Briefly, the invention contemplates in this respect liquefaction of the entire methane and nitrogen contents of the natural gas at a lower pressure than would be necessary for liquefaction of the nitrogen only, so that a refrigerant such as methane is employable, utilizing its latent heat in the usual manner.
Further objects of the invention are to conserve power in the process, as will appear.
Still further objects and advantages will be apparent from the following description taken in connection with the accompanying drawing conventionally and diagrammatically illustrating a circuit embodying the invention.
With reference now to the drawing, I is the incoming natural gas supply line, which leads to the product condenser 2 with pressure determined by the compressor 3 or equivalent pressure regulator.
The product condenser 2 is served with a refrigerant, which may be methane, liquefied in the methane condenser 4.
The methane circuit includes, commencing with the methane condenser 4, a methane heat exchanger 5, expansion valve 8, flash tank 1, expansion valve 8, product condenser 2, first storage compressort, intercooler l0, second stage compressor H with its intercooler l2 and third stage compressor l3 with its intercooler l4, methane precooler l5 and back to the methane condenser 4, it being understood that fiow in this methane circuit is in the direction of the order of the parts recited, by way of the suitable connections indicated in the drawing.
Also, in the methane circuit is a bypass l6 by which gas from the flash tank I is passed through the heat exchanger 4 and returned to' the principal methane circuit ahead of the second stage compressor ll.
from which it emerges at 126, partial expansion in the flash tank 'I from which the liquid emerges at 220, boiling within the product condenser 2 at a temperature of 252", taking up heat therein from which it emerges and enters the first stage compressor, as a gas, at 0, leaving the last cooler M at 100 and re-entering'its condenser 4 at a 8 wherein it is reconverted back from a gas to a liquid. The temperature in the bypasslii is --140.
Through this cycle the methane pressure will vary from 600 pounds, as it leaves its condenser 4 to 17 pounds as it leaves product condenser 2, as will be appreciated.
The temperatures recited are in degrees Fahrenheit and the pressures in pounds per square inch absolute, but it is to be understood that the This methane refrigerant circuit is generally a known one and its operation, briefly, includes liquefaction of the methane in its condenser 4 figures are recited above and hereinafter only by way of exemplification.
Liquefaction of the methane in its condenser 4 is accomplished by the employment of ethylene as a refrigerant, which ethylene is liquefied in the ethylene condenser 20. The ethylene circuit is generally similar to the methane circuit, the ethylene. passing from its condenser 20 through expansion valve 2 I, flash tank 22, expansion valve 23, methane condenser 4, first stage compressor 24 with intercooler 25 and second stage compressor 26 with its aftercooler 21 and back to the ethylene condenser; a bypass 28 being provided from the flash tank 22, as before.
The ethylene feeds its condenser at a -8, enters the methane condenser at a 145, leaves it at a 20 and re-enters its condenser 29 at a+ 100, its pressure running from 355 pounds in its condenser 20, to 17 pounds leaving the methane condenser.
The ethylene in turn is liquefied in its condenser 20 by the employment of ammonia liquefled in the ammonia condenser 30 and employed in a substantially similar circuit including expansion valve 3|, fiash tank 32, expansion valve 33, ethylene condenser 20, first stage compressor 34, intercooler 35, second stage compressor 36, aftercooler 31. However, this ammonia circuit preferably includes a bypass around the ethylene condenser 20 and through the methane precooler l5, controlled by the expansion valve 38. It also includes the bypass 39 leading from the flash tank 32.
The ammonia leaves its condenser 30 at 100, enters the ethylene condenser 20 at 24, leaves the ethylene condenser at reenters the ammonia condenser 30 at varying in pressure from 250 pounds in its condenser to 17 pounds leaving the ethylene condenser.
The ammonia condenser is served by cooling water entering by line 40 and leaving by line 4| and which may be served by a coolingtower not illustrated;
The system described will be recognized as what is known as of the cascade type whereinjs employed another in a lower temperature range or being served by another in a higher temperature range, or both. I
The temperature range available from the methane, for condensation of the natural gas mixture in the product condenser 2 is such that only a relatively low pressure of the natural gas such as175 pounds is necessary entering the condenser.
The methane temperature being fixed, the natural gas mixture pressure may be adjusted dependent upon its nitrogen content so that only liquid, including liquefied nitrogen as well as liquefied methane will emerge from the bottom of the product condenser as through the line 50, where the temperature may be 240 and pressure 175 pounds.
The nitrogen having been liquefied along with the methane, it is separated from the latter in a separator 5| which enters by way of an expansion valve 52.
The nitrogen separator 5| is in the form of a tower having the bubble plates conventionally indicated and its operation depends upon a nitrogen liquefaction circuit whereby a liquid nitrogen spray is provided at the upper part of the tower by which gaseous methane is condensed and thereby rejected from a gaseous nitrogen outlet at the tower top.
The nitrogen liquefaction circuit includes the nitrogen condenser 60 wherein the nitrogen is liquefied, expansion valve 6|, flash tank 62, expansion valve 63, separator 5|, nitrogen precooler 64, interstage cooler 65, compressor 66, intercooler 61, interstage cooler 65, second stage compressor 68, aftercooler 69, precoolers l and 64 and back to the nitrogen condenser 60. A bypass connection 1| leads from the flash tank 62, by way of the precooler l0, and back into the circuit ahead of the interstage cooler 65.
The nitrogen condenser 60 is served by methane from the methane condenser 4 by a circuit which bypasses the product condenser 2 and includes the line 80, expansion valve 8|, nitrogen condenser 60, line 82 and product condenser 2.
In the nitrogen liquefaction circuit the nitrogen leaves its condenser 60 in liquid form at a --240, leaves the flash tank 62 at a -282, leaves the separator 4| at a 310, the precooler 64 at a 70, the interstage cooler 65 at +70, the first stage compressor at +320", the interstage cooler 55 at 50, the second stage compressor 68 at +155", the aftercooler 69 at +100, the precooler 70 at -58 and reenters the condenser 60 at 239. The pressure within the nitrogen separator is 25 pounds, which is maintained substantially up to the first stage compressor 66, leaving the aftercooler 69 at 400 pounds.
Within the separator 5| the temperature of the nitrogen is at 310 which is below methane liquefying temperature so that any methane which emerges from the expansion valve 52 as a gas will be condensed and fall to the bottom of the separator where it will be at 260.
Nitrogen gasified in the separator 5| enters the described nitrogen circuit and its refrigerant capacity is largely conserved in the described heat exchangers 64, 65 and I0. The nitrogen circuit a source of refrigerants, each servin is vented immediately ahead of its first compressor 66 under control of a valve 90 by which the nitrogen beyond that necessary for operation of the circuit, is disposed 01'. Once the system is in operation, the amount of nitrogen thus vented will be substantially the amount which enters the system by way of the supply line it being understood that a slight amount of nitrogen will remain in solution in the liquid methane leaving the nitrogen separator 5|.
From the separator-the liquid methane is withdrawn subject to valve 9| to a storage tank 92 from which in turn it may be withdrawn as desired-through line 93, the storage tank being provided with the usual vent or relief 94 to take care of evaporation losses.
In summary, attention is again called to the fact that the temperatures and pressures herein above recited are by way of example only and may vary somewhat according to various conditions, including. the capacity of the system. In the example shown, the capacity is in the order of four million cubic feet of gas per day deliverable to storage, the entering gas comprising a mixture of about 91% methane and 9% nitrogen, by volume, at a temperature of It may also again be observed that all of the incoming natural gas mixture is liquefied, under conditions very substantially less demanding than would be otherwise necessary for liquefaction of the nitrogen content alone; a common refrigerant source is employed for liquefaction of the mixture, and of the nitrogen necessary for separation; and purge of the nitrogen is had after recovery therefrom of most of its value as a refrigerant.
I claim:
1. In the production of liquid methane from a natural gas mixture containing a substantial amount of nitrogen: liquefying said mixture by heat exchange with a boiling refrigerant, separating nitrogen as a gas from the liquefied solution by reduction of pressure thereon in the presence of liquid nitrogen, employing previously separated and reliquefied nitrogen for the purpose, and venting the resultant gaseous nitrogen in excess of that required to be reliquefied for continuation of the separation process.
2. In the production of liquid methane from a natural gas mixture containing a substantial amount of nitrogen: liquefying said mixture by heat exchange with a boiling refrigerant, separating nitrogen as a gas from the liquefied solution by reduction of pressure thereon in the presence of liquid nitrogen, employing previously separated and reliquefied nitrogen for the purpose, and employing some of said refrigerant for said nitrogen reliquefaction.
HOWELL C. COOPER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS

Claims (1)

1. IN THE PRODUCTION OF LIQUID METHANE FROM A NATURAL GAS MIXTURE CONTAINING A SUBSTANTIAL AMOUNT OF NITROGEN: LIQUEFYING SAID MIXTURE BY HEAT EXCHANGE WITH A BOILING REFRIGERANT, SEPARATING NITROGEN AS A GAS FROM THE LIQUEFIED SOLUTION BY REDUCTION OF PRESSURE THEREON IN THE PRESENCE OF LIQUID NITROGEN, EMPLOYING PREVIOUSLY SEPARATED AND RELIQUEFIED NITROGEN FOR THE PURPOSE, AND VENTING THE RESULTANT GASEOUS NITROGEN IN EX-
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US2595284A (en) * 1948-12-31 1952-05-06 Us Interior Method and apparatus for treatment of gaseous hydrocarbon mixtures
US2663169A (en) * 1949-08-04 1953-12-22 Lee S Twomey Manipulation of nitrogen-contaminated natural gases
US2677945A (en) * 1948-01-21 1954-05-11 Chemical Foundation Inc Transportation of natural gas
US2685181A (en) * 1952-04-30 1954-08-03 Emily C Schlitt Separation of the constituents of gaseous mixtures
US2690060A (en) * 1949-08-22 1954-09-28 Phillips Petroleum Co Fractional distillation
US2696088A (en) * 1949-08-04 1954-12-07 Lee S Twomey Manipulation of nitrogen-contaminated natural gases
US2716332A (en) * 1950-04-20 1955-08-30 Koppers Co Inc Systems for separating nitrogen from natural gas
US2823523A (en) * 1956-03-26 1958-02-18 Inst Gas Technology Separation of nitrogen from methane
US3205669A (en) * 1960-08-15 1965-09-14 Phillips Petroleum Co Recovery of natural gas liquids, helium concentrate, and pure nitrogen
US3224207A (en) * 1962-02-12 1965-12-21 Conch Int Methane Ltd Liquefaction of gases
US3257813A (en) * 1960-08-03 1966-06-28 Conch Int Methane Ltd Liquefaction of gases
DE1265337B (en) * 1963-09-09 1968-04-04 Hitachi Ltd Process for the low temperature separation of coke oven gas
DE1272943B (en) * 1961-06-01 1968-07-18 Air Liquide Process for cooling a gas mixture to a low temperature
US3596472A (en) * 1967-12-20 1971-08-03 Messer Griesheim Gmbh Process for liquefying natural gas containing nitrogen
US3857251A (en) * 1971-12-27 1974-12-31 Technigaz Lng storage tank vapor recovery by nitrogen cycle refrigeration with refrigeration make-up provided by separation of same vapor
US3894856A (en) * 1969-07-22 1975-07-15 Airco Inc Liquefaction of natural gas with product used as adsorber
US4017283A (en) * 1971-11-17 1977-04-12 Sulzer Brothers Limited Method and plant for making up nitrogen vaporization losses in nitrogen-containing liquified natural gas carrying tankers
US5505232A (en) * 1993-10-20 1996-04-09 Cryofuel Systems, Inc. Integrated refueling system for vehicles
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EP1715267A1 (en) * 2005-04-22 2006-10-25 Air Products And Chemicals, Inc. Dual stage nitrogen rejection from liquefied natural gas
CN102994184A (en) * 2012-12-03 2013-03-27 中国石油集团工程设计有限责任公司 Device and method for co-production of liquefied natural gas and liquid nitrogen
EP3907453A1 (en) * 2020-05-07 2021-11-10 Cryocollect Cooling device for installation for liquefying gas

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US2677945A (en) * 1948-01-21 1954-05-11 Chemical Foundation Inc Transportation of natural gas
US2595284A (en) * 1948-12-31 1952-05-06 Us Interior Method and apparatus for treatment of gaseous hydrocarbon mixtures
US2959022A (en) * 1949-08-04 1960-11-08 Lee S Twomey Manipulation of nitrogen-contaminated natural gases
US2663169A (en) * 1949-08-04 1953-12-22 Lee S Twomey Manipulation of nitrogen-contaminated natural gases
US2696088A (en) * 1949-08-04 1954-12-07 Lee S Twomey Manipulation of nitrogen-contaminated natural gases
US2812646A (en) * 1949-08-04 1957-11-12 Lee S Twomey Manipulation of nitrogen-contaminated natural gases
US2690060A (en) * 1949-08-22 1954-09-28 Phillips Petroleum Co Fractional distillation
US2716332A (en) * 1950-04-20 1955-08-30 Koppers Co Inc Systems for separating nitrogen from natural gas
US2685181A (en) * 1952-04-30 1954-08-03 Emily C Schlitt Separation of the constituents of gaseous mixtures
US2823523A (en) * 1956-03-26 1958-02-18 Inst Gas Technology Separation of nitrogen from methane
US3257813A (en) * 1960-08-03 1966-06-28 Conch Int Methane Ltd Liquefaction of gases
US3205669A (en) * 1960-08-15 1965-09-14 Phillips Petroleum Co Recovery of natural gas liquids, helium concentrate, and pure nitrogen
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US3224207A (en) * 1962-02-12 1965-12-21 Conch Int Methane Ltd Liquefaction of gases
DE1265337B (en) * 1963-09-09 1968-04-04 Hitachi Ltd Process for the low temperature separation of coke oven gas
US3596472A (en) * 1967-12-20 1971-08-03 Messer Griesheim Gmbh Process for liquefying natural gas containing nitrogen
US3894856A (en) * 1969-07-22 1975-07-15 Airco Inc Liquefaction of natural gas with product used as adsorber
US4017283A (en) * 1971-11-17 1977-04-12 Sulzer Brothers Limited Method and plant for making up nitrogen vaporization losses in nitrogen-containing liquified natural gas carrying tankers
US3857251A (en) * 1971-12-27 1974-12-31 Technigaz Lng storage tank vapor recovery by nitrogen cycle refrigeration with refrigeration make-up provided by separation of same vapor
US5505232A (en) * 1993-10-20 1996-04-09 Cryofuel Systems, Inc. Integrated refueling system for vehicles
US20080066493A1 (en) * 2004-07-12 2008-03-20 Cornelis Buijs Treating Liquefied Natural Gas
WO2006005746A1 (en) * 2004-07-12 2006-01-19 Shell Internationale Research Maatschappij B.V. Treating liquefied natural gas
WO2006005748A1 (en) * 2004-07-12 2006-01-19 Shell Internationale Research Maatschappij B.V. Treating liquefied natural gas
AU2005261727B2 (en) * 2004-07-12 2008-07-10 Shell Internationale Research Maatschappij B.V. Treating liquefied natural gas
US20080066492A1 (en) * 2004-07-12 2008-03-20 Cornelis Buijs Treating Liquefied Natural Gas
WO2006094969A1 (en) * 2005-03-09 2006-09-14 Shell Internationale Research Maatschappij B.V. Method for the liquefaction of a hydrocarbon-rich stream
US20080173043A1 (en) * 2005-03-09 2008-07-24 Sander Kaart Method For the Liquefaction of a Hydrocarbon-Rich Stream
US20070245771A1 (en) * 2005-04-22 2007-10-25 Spilsbury Christopher G Dual stage nitrogen rejection from liquefied natural gas
WO2006111721A1 (en) * 2005-04-22 2006-10-26 Air Products And Chemicals, Inc. Dual stage nitrogen rejection from liquefied natural gas
EP1715267A1 (en) * 2005-04-22 2006-10-25 Air Products And Chemicals, Inc. Dual stage nitrogen rejection from liquefied natural gas
US7520143B2 (en) 2005-04-22 2009-04-21 Air Products And Chemicals, Inc. Dual stage nitrogen rejection from liquefied natural gas
CN102994184A (en) * 2012-12-03 2013-03-27 中国石油集团工程设计有限责任公司 Device and method for co-production of liquefied natural gas and liquid nitrogen
EP3907453A1 (en) * 2020-05-07 2021-11-10 Cryocollect Cooling device for installation for liquefying gas

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