US20180023888A1 - Method for recovering helium - Google Patents

Method for recovering helium Download PDF

Info

Publication number
US20180023888A1
US20180023888A1 US15/549,854 US201615549854A US2018023888A1 US 20180023888 A1 US20180023888 A1 US 20180023888A1 US 201615549854 A US201615549854 A US 201615549854A US 2018023888 A1 US2018023888 A1 US 2018023888A1
Authority
US
United States
Prior art keywords
nitrogen
fraction
helium
enriched fraction
enriched
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US15/549,854
Inventor
Heinz Bauer
Martin Gwinner
Andreas Bub
Christoph HERTEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
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 Linde GmbH filed Critical Linde GmbH
Assigned to LINDE AKTIENGESELLSCHAFT reassignment LINDE AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BUB, ANDREAS, GWINNER, MARTIN, BAUER, HEINZ, HERTEL, Christoph
Publication of US20180023888A1 publication Critical patent/US20180023888A1/en
Abandoned legal-status Critical Current

Links

Images

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
    • 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/028—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 characterised by the separated product stream separation of noble gases
    • F25J3/029—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 characterised by the separated product stream separation of noble gases of helium
    • 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
    • F25J3/0204—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 characterised by the feed stream
    • F25J3/0209—Natural gas or substitute natural 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/0257—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 characterised by the separated product stream separation of nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/40—Features relating to the provision of boil-up in the bottom of a column
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
    • 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
    • F25J2210/40—Air or oxygen enriched air, i.e. generally less than 30mol% of O2
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/42—Separating low boiling, i.e. more volatile components from nitrogen, e.g. He, H2, Ne
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/42—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F25J2240/12—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/42—Processes or apparatus involving steps for recycling of process streams the recycled stream being nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/02—Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids

Definitions

  • the invention relates to a method for recovering a helium product fraction from a nitrogen- and helium-containing feed fraction, wherein
  • helium product fraction be comprised of highly purified helium, the concentration and contamination of which do not exceed a value of 100 vppm, preferably of 10 vppm.
  • nitrogen- and helium-containing feed fraction be understood as a fraction, which contains 1 to 20 mol-% helium and 80 to 99 mol-% nitrogen. Further, this feed fraction can contain 0.1 to 2 mol-% methane and traces of hydrogen, argon and/or other noble gases.
  • helium is obtained almost exclusively from a mixture of volatile natural gas components, which typically contains methane and nitrogen as well as traces of hydrogen, argon and other noble gases besides helium.
  • concentration of this decontamination in helium cannot exceed a value of 100 vppm, preferably of 10 vppm.
  • the helium purification prior to the actual helium liquefaction generally consists of a combination of cryogenic—based on partial condensation—and adsorptive methods with regeneration through pressure and/or temperature changes. Based on the comparatively high product value, a helium yield as high as possible, preferably >99%, is desirable. In consequence, the helium-enriched fraction is often transferred from the liquid into the gaseous phase by pressure release and/or stripping from the liquid to the gaseous phase during the cryogenic step to remain available for further processing.
  • a nitrogen- and helium-containing feed fraction which originates, for example, from a separation process of natural gas, is first supplied to catalytic methane oxidation A and subsequently via line 2 to a drying unit B.
  • the water separated in the drying unit B is removed via line 30 .
  • the feed fraction conventionally pretreated in such way which typically has a pressure of between 10 and 40 bar, preferably between 15 and 25 bar, is supplied to the heat exchanger E 1 via line 3 and partially condensed therein against method flows yet to be explained.
  • the partially condensed feed fraction is supplied to a separator D 1 and separated therein into a first helium-enriched fraction 5 as well as a first nitrogen-enriched fraction 8 .
  • the helium-enriched fraction 5 is supplied to an adsorptive cleaning process D after preheating in the heat exchanger E 1 .
  • Such process is designed as (V)PSA and/or TSA process.
  • the helium-enriched fraction recovered therein and removed via line 6 represents the helium product fraction, the concentration of decontamination of which does not exceed a value of 100 vppm, preferably of 100 vppm.
  • this helium product fraction is supplied to a liquefaction process not illustrated in FIG. 1 .
  • the helium-containing residue gas removed from the adsorptive cleaning process D is supplied to a return compressor C via line 7 , is compressed therein to the pressure of the feed fraction 1 to be supplied to the catalytic methane oxidation A and admixed thereto via line 32 .
  • the above mentioned first nitrogen-enriched fraction 8 is expanded in valve a and supplied to the separation column T in its upper section as return flow.
  • the separation column T is preferably operated at a pressure between 7 and 20 bar, in particular between 10 and 15 bar.
  • a separation into a second helium-enriched gas fraction 9 and a second nitrogen-enriched liquid fraction 11 is implemented therein.
  • the second helium-enriched fraction 9 is preheated in heat exchanger E 1 against the feed fraction 3 to be partially condensed, and supplied to the mentioned return compressor C via control valve b, as well. Additional air is supplied thereto via line 31 .
  • the oxygen contained in the air serves as oxidation means for the catalytic methane oxidation A.
  • a sub-flow of the second nitrogen-enriched liquid fraction 11 is evaporated in heat exchanger E 1 and supplied to the separation column T as stripping gas 12 .
  • Such stripping gas supply causes the separation process taking place in separation column T and determines the helium content of the second helium-enriched fraction 9 .
  • At least a sub-flow of the second nitrogen-enriched fraction 11 is evaporated in heat exchanger E 1 against the feed fraction to be partially condensed 3 under a pressure of less than 5 bar, preferably of less than 3 bar.
  • This method serves to set a temperature as low as possible in separator D 1 .
  • a sub-flow of the second nitrogen-enriched fraction 11 is supplied to a circulation container D 2 via control valve c.
  • the liquid fraction removed therefrom via line 14 is supplied to heat exchanger E 1 under the above mentioned low pressure, at least partially evaporated therein, and resupplied to the circulation container D 2 .
  • a nitrogen-enriched gas fraction 15 is removed from the top of circulation container D 2 , preheated in heat exchanger E 1 against the feed fraction to be partially condensed 3 , and subsequently resupplied as regeneration gas to the above mentioned drying unit B, which is an adsorptive drying process, as a rule.
  • This loaded regeneration gas is removed from the process via line 16 .
  • the sub-flow 13 of the second nitrogen-enriched fraction 11 which is not supplied to the circulation container D 2 , can be supercooled in heat exchanger E 1 and can be generated as supercooled liquid via control valve d and line 17 .
  • an otherwise required generation or provision of liquefied nitrogen (LIN), as the case may be, can be refrained from.
  • a sub-flow of liquid fraction 14 removed from the circulation container D 2 can be removed in the above described manner via control valve d and line 17 .
  • the coldness required for the partial condensation of the feed fraction 3 can principally be provided by preheating cold, gaseous decomposition products as well as the above described evaporation of liquid fraction 14 , which was removed from the circulation container D 2 .
  • the larger the stripping gas quantity 12 evaporated in heat exchanger E 1 the lower can be the quantity of liquid fraction 14 removed from the circulation container D 2 . It must, however, be ensured that heat exchange and temperature of flow 12 are suitable for cooling and partially condensing feed fraction 3 . If the content of flow 12 in the heat turnover in heat exchanger E 1 becomes too large, the temperature in separator D 1 increases undesirably.
  • the quantity of the stripping gas 12 supplied to separation column T is selected according to the invention to such amount that a third nitrogen-enriched fraction 20 can be removed from separation column T in the section of its bottom, wherein such fraction contains at least 30%, preferably at least 50% of the nitrogen contained in the first nitrogen-enriched fraction 8 .
  • These nitrogen contents are achieved in that a larger stripping gas quantity 12 is boiled up in the bottom of separation column T than would be required for the actual stripping process in separation column T.
  • a further nitrogen-enriched fraction can be recovered in separation column T under increased pressure.
  • This further or third nitrogen-enriched fraction can be condensed to a pressure after preheating in heat exchanger E 1 , which is above the pressure of column T by 4 to 20 bar, preferably by 5 to 15 bar.
  • the nitrogen-enriched fraction 21 is cooled in heat exchanger E 1 and subsequently work-performing expanded in expansion device X.
  • the expanded nitrogen-enriched fraction 22 is subsequently preheated against the feed fraction to be partially condensed 3 in heat exchanger E 1 and admixed to the above described nitrogen-enriched fraction 15 .
  • Such work-performing expansion X which increases thermo-dynamic efficiency of the process, is optional, facilitates or increases the quantity of the cooled liquid (LIN) removed via line 17 , however.

Abstract

A method for recovering a helium product fraction (6) from a nitrogen- and helium-containing feed fraction (3) is described, wherein the nitrogen- and helium-containing feed fraction (3) is partially condensed (E1), separated into a first helium-enriched fraction (5) and a first nitrogen-enriched fraction (8) and the former is cleaned again in an adsorptive manner.
According to the invention, the separation is carried out in a separation column (T), which is supplied with the first nitrogen-enriched fraction (8) as return flow and with a sub-flow of the second nitrogen-enriched fraction as stripping gas (12), wherein the stripping gas quantity (12) is set such that a third nitrogen-enriched fraction (20), which contains at least 30% of the nitrogen contained in the first nitrogen-enriched fraction (8), can be recovered in the separation column (T).

Description

  • The invention relates to a method for recovering a helium product fraction from a nitrogen- and helium-containing feed fraction, wherein
      • the nitrogen- and helium-containing feed fraction is partially condensed and separated into a first helium-enriched fraction and a first nitrogen-enriched fraction,
      • the first helium-enriched fraction is subjected to an adsorptive cleaning process and the helium-enriched fraction recovered therefrom represents the helium product fraction,
      • the first nitrogen-enriched fraction is separated into a second helium-enriched fraction and a second nitrogen-enriched fraction, and
      • the second helium-enriched fraction is preheated against the nitrogen- and helium-containing feed fraction to be partially condensed, condensed and admixed to the nitrogen- and helium-containing feed fraction to be partially condensed.
  • The term “helium product fraction” be comprised of highly purified helium, the concentration and contamination of which do not exceed a value of 100 vppm, preferably of 10 vppm.
  • The term “nitrogen- and helium-containing feed fraction” be understood as a fraction, which contains 1 to 20 mol-% helium and 80 to 99 mol-% nitrogen. Further, this feed fraction can contain 0.1 to 2 mol-% methane and traces of hydrogen, argon and/or other noble gases.
  • Currently, helium is obtained almost exclusively from a mixture of volatile natural gas components, which typically contains methane and nitrogen as well as traces of hydrogen, argon and other noble gases besides helium. To avoid separation by freezing of undesired decontamination during helium liquification, the concentration of this decontamination in helium cannot exceed a value of 100 vppm, preferably of 10 vppm.
  • The helium purification prior to the actual helium liquefaction generally consists of a combination of cryogenic—based on partial condensation—and adsorptive methods with regeneration through pressure and/or temperature changes. Based on the comparatively high product value, a helium yield as high as possible, preferably >99%, is desirable. In consequence, the helium-enriched fraction is often transferred from the liquid into the gaseous phase by pressure release and/or stripping from the liquid to the gaseous phase during the cryogenic step to remain available for further processing.
  • A method implication is known from U.S. Pat. No. 5,167,125, wherein a nitrogen-enriched flow, which has elevated pressure and contains helium, is separated by using a pressure drop in a helium-containing flow of average pressure and a nitrogen-enriched flow of lower pressure. Such separation is implemented in a rectification column, which has a reboiler and a condenser.
  • It is the object of the present invention to specify a generic method for recovering a helium product fraction, which facilitates generation of at least a partial quantity of the nitrogen-enriched flow accruing during separation at the same pressure as the helium-containing flow, to be able to subsequently supply the nitrogen-enriched flow to a work-performing expansion.
  • For the solution of said object, a generic method for recovering a helium product fraction is suggested, which is characterized in that
      • the separation of the first nitrogen-enriched fraction into a second helium-enriched fraction and a second nitrogen-enriched fraction is implemented in a separation column, to which the first nitrogen-enriched fraction is supplied as return flow,
      • a sub-flow of the second nitrogen-enriched fraction evaporates and the separation column is supplied as stripping gas,
      • at least a sub-flow of the second nitrogen-enriched fraction is evaporated against the nitrogen- and helium-containing feed fraction to be partially condensed under a pressure of less than 5 bar,
      • a third nitrogen-enriched fraction is removed from the separation column,
      • wherein the stripping gas quantity is set such that the third nitrogen-enriched fraction contains at least 30% of the nitrogen contained in the first nitrogen-enriched fraction, and
      • the third nitrogen-enriched fraction serves at least partially to cool the nitrogen- and helium-containing feed fraction to be partially condensed.
  • Further advantageous embodiments of the method according to the invention for recovering a helium product fraction, which represent subject matters of the dependent claims are characterized in that
      • the third nitrogen-enriched fraction is at least partially work-performing expanded (X),
      • the separation column is operated with a pressure of 7 to 20 bar, preferably of 10 to 15 bar,
      • the third nitrogen-enriched fraction contains at least 50% of the nitrogen contained in the first nitrogen-enriched fraction,
      • at least a sub-flow of the second nitrogen-enriched fraction is evaporated against the nitrogen- and helium-containing feed fraction to be partially condensed under a pressure of less than 3 bar, and/or
      • the adsorptive cleaning process is a (V)PSA and/or TSA process.
  • The method according to the invention for recovering a helium product fraction as well as further advantageous embodiments thereof are explained in further detail by means of the embodiment example represented in FIG. 1.
  • Via line 1, a nitrogen- and helium-containing feed fraction, which originates, for example, from a separation process of natural gas, is first supplied to catalytic methane oxidation A and subsequently via line 2 to a drying unit B. The water separated in the drying unit B is removed via line 30. The feed fraction conventionally pretreated in such way, which typically has a pressure of between 10 and 40 bar, preferably between 15 and 25 bar, is supplied to the heat exchanger E1 via line 3 and partially condensed therein against method flows yet to be explained. Via line 4, the partially condensed feed fraction is supplied to a separator D1 and separated therein into a first helium-enriched fraction 5 as well as a first nitrogen-enriched fraction 8.
  • The helium-enriched fraction 5 is supplied to an adsorptive cleaning process D after preheating in the heat exchanger E1. Such process is designed as (V)PSA and/or TSA process. The helium-enriched fraction recovered therein and removed via line 6, represents the helium product fraction, the concentration of decontamination of which does not exceed a value of 100 vppm, preferably of 100 vppm. As a rule, this helium product fraction is supplied to a liquefaction process not illustrated in FIG. 1.
  • The helium-containing residue gas removed from the adsorptive cleaning process D is supplied to a return compressor C via line 7, is compressed therein to the pressure of the feed fraction 1 to be supplied to the catalytic methane oxidation A and admixed thereto via line 32.
  • The above mentioned first nitrogen-enriched fraction 8 is expanded in valve a and supplied to the separation column T in its upper section as return flow. The separation column T is preferably operated at a pressure between 7 and 20 bar, in particular between 10 and 15 bar. A separation into a second helium-enriched gas fraction 9 and a second nitrogen-enriched liquid fraction 11 is implemented therein. The second helium-enriched fraction 9 is preheated in heat exchanger E1 against the feed fraction 3 to be partially condensed, and supplied to the mentioned return compressor C via control valve b, as well. Additional air is supplied thereto via line 31. The oxygen contained in the air serves as oxidation means for the catalytic methane oxidation A.
  • A sub-flow of the second nitrogen-enriched liquid fraction 11 is evaporated in heat exchanger E1 and supplied to the separation column T as stripping gas 12. Such stripping gas supply causes the separation process taking place in separation column T and determines the helium content of the second helium-enriched fraction 9.
  • At least a sub-flow of the second nitrogen-enriched fraction 11 is evaporated in heat exchanger E1 against the feed fraction to be partially condensed 3 under a pressure of less than 5 bar, preferably of less than 3 bar. This method serves to set a temperature as low as possible in separator D1. In the embodiment example illustrated in FIG. 1, a sub-flow of the second nitrogen-enriched fraction 11 is supplied to a circulation container D2 via control valve c. The liquid fraction removed therefrom via line 14 is supplied to heat exchanger E1 under the above mentioned low pressure, at least partially evaporated therein, and resupplied to the circulation container D2.
  • A nitrogen-enriched gas fraction 15 is removed from the top of circulation container D2, preheated in heat exchanger E1 against the feed fraction to be partially condensed 3, and subsequently resupplied as regeneration gas to the above mentioned drying unit B, which is an adsorptive drying process, as a rule. This loaded regeneration gas is removed from the process via line 16.
  • The sub-flow 13 of the second nitrogen-enriched fraction 11, which is not supplied to the circulation container D2, can be supercooled in heat exchanger E1 and can be generated as supercooled liquid via control valve d and line 17. By means of this configuration of the method according to the invention, an otherwise required generation or provision of liquefied nitrogen (LIN), as the case may be, can be refrained from.
  • Alternative or supplemental to the method implementation illustrated in FIG. 1, a sub-flow of liquid fraction 14 removed from the circulation container D2 can be removed in the above described manner via control valve d and line 17.
  • The coldness required for the partial condensation of the feed fraction 3 can principally be provided by preheating cold, gaseous decomposition products as well as the above described evaporation of liquid fraction 14, which was removed from the circulation container D2. Generally, the following is true: the larger the stripping gas quantity 12 evaporated in heat exchanger E1, the lower can be the quantity of liquid fraction 14 removed from the circulation container D2. It must, however, be ensured that heat exchange and temperature of flow 12 are suitable for cooling and partially condensing feed fraction 3. If the content of flow 12 in the heat turnover in heat exchanger E1 becomes too large, the temperature in separator D1 increases undesirably.
  • The quantity of the stripping gas 12 supplied to separation column T is selected according to the invention to such amount that a third nitrogen-enriched fraction 20 can be removed from separation column T in the section of its bottom, wherein such fraction contains at least 30%, preferably at least 50% of the nitrogen contained in the first nitrogen-enriched fraction 8. These nitrogen contents are achieved in that a larger stripping gas quantity 12 is boiled up in the bottom of separation column T than would be required for the actual stripping process in separation column T.
  • Opposed to the method mentioned and described in U.S. Pat. No. 5,167,125, a further nitrogen-enriched fraction can be recovered in separation column T under increased pressure. This further or third nitrogen-enriched fraction can be condensed to a pressure after preheating in heat exchanger E1, which is above the pressure of column T by 4 to 20 bar, preferably by 5 to 15 bar. After removing the condensation heat in heat exchanger E2, the nitrogen-enriched fraction 21 is cooled in heat exchanger E1 and subsequently work-performing expanded in expansion device X. The expanded nitrogen-enriched fraction 22 is subsequently preheated against the feed fraction to be partially condensed 3 in heat exchanger E1 and admixed to the above described nitrogen-enriched fraction 15. Such work-performing expansion X, which increases thermo-dynamic efficiency of the process, is optional, facilitates or increases the quantity of the cooled liquid (LIN) removed via line 17, however.

Claims (7)

1. A method for recovering a helium product fraction from a nitrogen- and helium-containing feed fraction, wherein
the nitrogen- and helium-containing feed fraction is partially condensed and separated into a first helium-enriched fraction and a first nitrogen-enriched fraction,
the first helium-enriched fraction is subjected to an adsorptive cleaning process and the helium-enriched fraction recovered therefrom represents the helium product fraction,
the first nitrogen-enriched fraction is separated into a second helium-enriched fraction and a second nitrogen-enriched fraction, and
the second helium-enriched fraction is preheated against the nitrogen- and helium-containing feed fraction to be partially condensed, condensed and admixed to the nitrogen- and helium-containing feed fraction to be partially condensed,
characterized, in that
the separation of the first nitrogen-enriched fraction into a second helium-enriched fraction and a second nitrogen-enriched fraction is implemented in a separation column, to which the first nitrogen-enriched fraction is supplied as return flow,
a sub-flow of the second nitrogen-enriched fraction evaporates and the separation column is supplied as stripping gas,
at least a sub-flow of the second nitrogen-enriched fraction is evaporated against the nitrogen- and helium-containing feed fraction to be partially condensed under a pressure of less than 5 bar,
a third nitrogen-enriched fraction is removed from the separation column,
wherein the stripping gas quantity is set such that the third nitrogen-enriched fraction contains at least 30% of the nitrogen contained in the first nitrogen-enriched fraction, and
the third nitrogen-enriched fraction serves at least partially to cool the nitrogen- and helium-containing feed fraction to be partially condensed.
2. The method according to claim 1, characterized in that the third nitrogen-enriched fraction is at least partially work-performing expanded.
3. The method according to claim 1, characterized in that the separation column is operated under a pressure of 7 to 20 bar.
4. The method according to claim 1, characterized in that the third nitrogen-enriched fraction contains at least 50% of the nitrogen contained in the first nitrogen-enriched fraction.
5. The method according to claim 1, characterized in that at least a sub-flow of the second nitrogen-enriched fraction is evaporated against the nitrogen- and helium-containing feed fraction to be partially condensed under a pressure of less than 3 bar.
6. The method according to claim 1, characterized in that the adsorptive cleaning process is a (V)PSA and/or TSA process.
7. The method according to claim 3, characterized in that the separation column is operated under a pressure of 10 to 15 bar.
US15/549,854 2015-02-10 2016-01-26 Method for recovering helium Abandoned US20180023888A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102015001664.4A DE102015001664A1 (en) 2015-02-10 2015-02-10 Helium recovery process
DE102015001664.4 2015-02-10
PCT/EP2016/000131 WO2016128111A1 (en) 2015-02-10 2016-01-26 Method for recovering helium

Publications (1)

Publication Number Publication Date
US20180023888A1 true US20180023888A1 (en) 2018-01-25

Family

ID=55273198

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/549,854 Abandoned US20180023888A1 (en) 2015-02-10 2016-01-26 Method for recovering helium

Country Status (6)

Country Link
US (1) US20180023888A1 (en)
AU (1) AU2016218602B2 (en)
CA (1) CA2976341C (en)
DE (1) DE102015001664A1 (en)
RU (1) RU2689252C2 (en)
WO (1) WO2016128111A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3096900B1 (en) * 2019-06-06 2021-10-01 Air Liquide Helium purification process and unit

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5351491A (en) * 1992-03-31 1994-10-04 Linde Aktiengesellschaft Process for obtaining high-purity hydrogen and high-purity carbon monoxide
US5771714A (en) * 1997-08-01 1998-06-30 Praxair Technology, Inc. Cryogenic rectification system for producing higher purity helium
DE10007440A1 (en) * 2000-02-18 2001-08-23 Linde Ag Recovering a helium pure fraction from a stream containing at least methane, nitrogen and helium comprises using two-stage purifying process
US20080272340A1 (en) * 2005-02-01 2008-11-06 Daphne Koh Method for Producing Syngas with Low Carbon Dioxide Emission

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3205669A (en) * 1960-08-15 1965-09-14 Phillips Petroleum Co Recovery of natural gas liquids, helium concentrate, and pure nitrogen
SU1645796A1 (en) * 1989-01-26 1991-04-30 Всесоюзный научно-исследовательский институт природных газов Process of simultaneous production of heliun ethan and heavier hydrocarbons
US5167125A (en) 1991-04-08 1992-12-01 Air Products And Chemicals, Inc. Recovery of dissolved light gases from a liquid stream
US5257505A (en) * 1991-04-09 1993-11-02 Butts Rayburn C High efficiency nitrogen rejection unit
DE10106484A1 (en) * 2001-02-13 2002-08-14 Linde Ag Simultaneous recovery of helium and nitrogen pure fractions from process stream containing methane, nitrogen and helium, involves partially condensing process stream, and further processing
DE102005010054A1 (en) * 2005-03-04 2006-09-07 Linde Ag Process for simultaneously recovering a helium and a nitrogen pure fraction
DE102008007925A1 (en) * 2008-02-07 2009-08-13 Linde Aktiengesellschaft Separating helium, comprises condensing helium-containing fraction, separating into e.g. helium-enriched gas fraction, condensing the gas fraction, evaporating liquid fraction, separating into e.g. helium-rich gas fraction and heating
DE102011010634A1 (en) * 2011-02-08 2012-08-09 Linde Aktiengesellschaft A method of separating trace components from a fraction containing at least nitrogen and helium
DE102012008446A1 (en) * 2012-04-26 2013-10-31 Linde Aktiengesellschaft Method for obtaining pure helium-fraction from helium-containing, methane- and nitrogen-rich feed fraction, involves condensing feed fraction at ten bar pressure, which is separated into helium-depleted fraction and helium-rich fraction
DE102013007208A1 (en) * 2013-04-25 2014-10-30 Linde Aktiengesellschaft Process for recovering a methane-rich liquid fraction
DE102013012656A1 (en) * 2013-07-30 2015-02-05 Linde Aktiengesellschaft A method of separating unwanted components from a helium stream

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5351491A (en) * 1992-03-31 1994-10-04 Linde Aktiengesellschaft Process for obtaining high-purity hydrogen and high-purity carbon monoxide
US5771714A (en) * 1997-08-01 1998-06-30 Praxair Technology, Inc. Cryogenic rectification system for producing higher purity helium
DE10007440A1 (en) * 2000-02-18 2001-08-23 Linde Ag Recovering a helium pure fraction from a stream containing at least methane, nitrogen and helium comprises using two-stage purifying process
US20080272340A1 (en) * 2005-02-01 2008-11-06 Daphne Koh Method for Producing Syngas with Low Carbon Dioxide Emission

Also Published As

Publication number Publication date
RU2015124169A (en) 2017-01-10
RU2689252C2 (en) 2019-05-24
DE102015001664A1 (en) 2016-08-11
AU2016218602B2 (en) 2021-04-08
RU2015124169A3 (en) 2018-10-29
CA2976341A1 (en) 2016-08-18
CA2976341C (en) 2023-07-11
WO2016128111A1 (en) 2016-08-18
AU2016218602A1 (en) 2017-08-31

Similar Documents

Publication Publication Date Title
US7201019B2 (en) Light gas component separation from a carbon dioxide mixture
CN110307695B (en) Method and device for manufacturing product nitrogen and product argon
TWI687633B (en) Oxygen production system and oxygen production method
US5363656A (en) Ultra-high purity nitrogen and oxygen generator
RU2486131C2 (en) Method of producing helium
JPH06207775A (en) Low-temperature air separating method for manufacturing nitrogen having no carbon monoxide
US20140208798A1 (en) Apparatus and Integrated Process for Separating a Mixture of Carbon Dioxide and at Least One Other Gas and for Separating Air by Cryogenic Distillation
CN101360964A (en) Cryogenic process system with extended bonnet filter
JP2007064617A (en) Method of manufacturing krypton and/or xenon by cryogenic air separation
CA2976341C (en) Method for recovering helium
JP4206083B2 (en) Argon production method using cryogenic air separator
KR101238063B1 (en) Nitrogen generating device and apparatus for use therefor
US20210310733A1 (en) Method for recycling argon
US20180051215A1 (en) Method for removing nitrogen from a hydrocarbon-rich fraction
JP4960277B2 (en) Method for producing ultra-high purity oxygen
US20110209498A1 (en) Process for separating off nitrogen
US3073093A (en) Process and apparatus for purifying gases
FR2971044A1 (en) Method for separating gas containing carbon dioxide to produce carbon dioxide enriched liquid flow in agro-food industry, involves sending part of liquid flow to exchanger, where part of flow is vaporized before being sent to lower part
JP2721591B2 (en) Ultra high purity nitrogen production equipment
JP4430351B2 (en) Fluorine compound gas separation and purification equipment
JP2009299930A (en) Air separating method and device used for the same
KR102010087B1 (en) Method for producing argon from air
JPH05306885A (en) Pressure type air separating device
JP3095238B2 (en) Ultra high purity nitrogen production equipment
CA2597328A1 (en) Method for separating trace components from a nitrogen-rich stream

Legal Events

Date Code Title Description
AS Assignment

Owner name: LINDE AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BAUER, HEINZ;GWINNER, MARTIN;BUB, ANDREAS;AND OTHERS;SIGNING DATES FROM 20170918 TO 20170920;REEL/FRAME:043680/0326

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION