WO2016174317A1 - Production of helium from a gas stream containing hydrogen - Google Patents

Production of helium from a gas stream containing hydrogen Download PDF

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Publication number
WO2016174317A1
WO2016174317A1 PCT/FR2015/052633 FR2015052633W WO2016174317A1 WO 2016174317 A1 WO2016174317 A1 WO 2016174317A1 FR 2015052633 W FR2015052633 W FR 2015052633W WO 2016174317 A1 WO2016174317 A1 WO 2016174317A1
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WO
WIPO (PCT)
Prior art keywords
helium
volume
stream
nitrogen
hydrogen
Prior art date
Application number
PCT/FR2015/052633
Other languages
French (fr)
Inventor
Bertrand DEMOLLIENS
Jean-Marc Tsevery
Original Assignee
L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
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Publication date
Application filed by L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude filed Critical L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority to EA201792303A priority Critical patent/EA035014B1/en
Priority to US15/742,146 priority patent/US20180238618A1/en
Publication of WO2016174317A1 publication Critical patent/WO2016174317A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B23/00—Noble gases; Compounds thereof
    • 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
    • F25J3/061—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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/066—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation 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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0685—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of noble gases
    • F25J3/069—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation 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
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0003—Chemical processing
    • C01B2210/0004—Chemical processing by oxidation
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C01B2210/0014—Physical processing by adsorption in solids
    • C01B2210/0021—Temperature swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0029—Obtaining noble gases
    • C01B2210/0031—Helium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0053—Hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0068—Organic compounds
    • C01B2210/007—Hydrocarbons
    • 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
    • F25J2205/82—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
    • F25J2210/04—Mixing or blending of fluids with the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/30—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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/20—Integration in an installation for liquefying or solidifying a fluid stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop

Definitions

  • the present invention relates to a process for producing helium from a source gas stream comprising at least helium, methane, nitrogen and hydrogen.
  • Helium is obtained commercially almost exclusively from a mixture of volatile components of natural gas, this mixture comprising, as well as helium, typically methane and nitrogen and traces of hydrogen, argon and other noble gases.
  • this mixture comprising, as well as helium, typically methane and nitrogen and traces of hydrogen, argon and other noble gases.
  • helium is made available as a component of the gas that accompanies mineral oil, or as part of the production of natural gas. It is theoretically possible to obtain helium in the atmosphere, but it is not economical because of the low concentrations (typical concentration of helium in the air of the order of 5.2 ppmv).
  • the concentration of impurities in the helium stream to be liquefied must not exceed a value of 1000 ppm by volume, preferably 10 ppmv.
  • the liquefaction process of helium is connected downstream of a helium purification process.
  • This is generally composed of a combination of cryogenic processes, generally based on partial condensation, and adsorption processes, the regeneration in the case of the latter being possible due to the variation of temperature and or pressure.
  • a process for purifying helium such that, in addition to the purified helium, nitrogen of requisite purity - in which the sum of the impurities is less than 1% by volume - can be obtained.
  • nitrogen of requisite purity - in which the sum of the impurities is less than 1% by volume - can be obtained.
  • only a portion, typically from 5% to 70%, preferably from 10% to 50%, of the nitrogen present in the mixture to be purified is brought to the desired purity.
  • the remaining nitrogen is released into the atmosphere along with methane as a low pressure gas, either directly or after an oxidation step, preferably carried out in a torch or incinerator.
  • This process for obtaining a pure helium fraction from a starting fraction comprising at least helium, methane and nitrogen comprises the following successive stages:
  • the starting fraction is subjected to a methane and nitrogen removal
  • step c) the compressed fraction is subjected to nitrogen removal, and d) the helium-rich fraction obtained in step c) is subjected to adsorption purification to produce a fraction.
  • this method does not make it possible to treat gas streams containing a high hydrogen content, typically more than 6% by volume of hydrogen.
  • FIG. 1 Another type of helium purification process known from the prior art is illustrated in FIG.
  • a gaseous stream 1 ' comprising nitrogen, methane, helium and hydrogen, for example originating from the outlet of a nitrogen rejection unit (NRU) 15 following the treatment of a stream of natural gas to remove nitrogen from this natural gas, is introduced into a compressor 2 '. Once this gas is compressed, it is introduced into a 3 'helium concentrator device.
  • NRU nitrogen rejection unit
  • the hydrogen contained in the gas stream is removed by means of a system 4' in which hydrogen and oxygen react.
  • the gas stream is then purified by means of an alternating pressure adsorption (PSA) process.
  • PSA alternating pressure adsorption
  • a gas stream 6 'from PSA 6' containing predominantly helium is then liquefied in a helium liquefaction device 7 '.
  • the liquefied helium is sent to an 8 'helium storage system.
  • liquid nitrogen stored in the device 10 ' is used to feed the helium concentrator device 3'.
  • the gaseous stream 12 'containing a majority of nitrogen and a small amount of helium is purified by means of a purification means 13' eliminating the impurities contained in the gas stream 12 'in order to produce a gaseous stream 14' of recycling sent to the compressor 2 'after having been mixed with the gas mixture the initial to be treated.
  • a purge implemented at the 3 'helium concentrator contains methane. It must then be treated using a methane oxidation device to meet environmental requirements. It is necessary to have an air separation unit 11 '(in English ASU) which produces the liquid nitrogen to the specification compatible with the 8' helium storage (of the order of ppm of methane).
  • the inventors of the present invention have then bridged a solution to solve the problems raised above.
  • the subject of the present invention is a process for producing helium from a source gas stream comprising at least helium, methane, nitrogen and hydrogen, comprising at least the following successive stages:
  • PSA pressure swing adsorption
  • the subject of the present invention is: A process as defined above characterized in that the source gas stream comprises from 40% to 95% by volume of nitrogen, from 0.05% to 40% by volume of helium, from 50 ppmv to 5% by volume of methane and from 1% to 10% by volume of hydrogen, preferably from 5% by volume to 10% by volume of hydrogen.
  • a process as defined above comprising a step prior to step a) of producing the source gas stream to be treated by means of a nitrogen extraction unit or a natural gas liquefaction unit, said unit producing a stream of liquid nitrogen implemented in step d) allowing the partial condensation of the stream from step c) to produce a stream of liquid nitrogen and a gas stream comprising predominantly helium.
  • step a) is between Bara and Bara, preferably between Bara and Bara.
  • a process as defined above characterized in that the stream of liquid nitrogen from step d) comprises more than 98.5% by volume of nitrogen.
  • step b) consists in bringing the gas stream coming from step a) into contact with oxygen and a catalytic bed comprising particles of at least one selected metal. among copper, platinum, palladium, osmium, iridium, ruthenium and rhodium, supported by a chemically inert carrier with respect to carbon dioxide and water so as to react with methane and hydrogen with oxygen.
  • a process as defined above characterized in that it comprises an additional step f) liquefaction of the helium from step e).
  • a process as defined above characterized in that the liquid nitrogen from step d) cools the liquefied helium in step f).
  • a plant for producing helium from a source gas mixture comprising methane, helium, hydrogen and nitrogen comprising at least one compressor directly receiving the source gas mixture, at least one means for removing hydrogen and methane, at least one nitrogen removal and helium concentration device, and at least one helium purification means located downstream of the nitrogen removal and helium concentration, characterized in that the means for removing hydrogen and methane is located downstream of said at least one compressor and upstream of the nitrogen removal device and helium concentration.
  • An installation as defined above characterized in that it further comprises a helium liquefaction device downstream of the helium purification means.
  • FIG. 2 illustrates an embodiment of a method according to the invention.
  • a source gas stream 1 containing at least helium, nitrogen, hydrogen and methane is treated by a process of the present invention to produce a pure helium stream, typically containing more than 99.9% % by volume of helium.
  • the source stream 1 comes for example from a unit 2 of nitrogen extraction (in English, nitrogen rejection unit, NRU) located downstream of a cryogenic unit for treating natural gas.
  • the source current 1 is introduced into a compressor 3 making it possible to compress the gas stream 4 at a pressure of between 15 bara (absolute bar) and 35 bara, preferably between 20 bara and 25 bara.
  • the temperature is the ambient temperature where the installation is located.
  • the gas stream 4 is introduced into a unit 5 for eliminating hydrogen and methane.
  • This unit 5 consists for example of one to several reactors in series containing a catalyst between grids. This catalyst is typically Pd / Al 2 O 3. A catalytic oxidation between oxygen and oxidants (hydrogen / methane) is created.
  • a high hydrogen content at the inlet makes it possible to operate at a high temperature and to co-oxidize the methane (for example, with 2% of hydorgene, the temperature rises to about 200 ° C. which is not sufficient not to oxidize methane).
  • the hydrogen and methane contained in the initial source stream 1 to be treated are oxidized by the oxygen of unit 5.
  • This gas stream 6 comprises mainly nitrogen and helium.
  • the outgoing gas (against ambient air or cooling water) is cooled before being sent to the adsorption unit 7. Part of the water then condenses directly in a condensate recuperator. Part of the heat produced can be recovered for use in another process
  • the gaseous stream 6 is then treated in an adsorption unit 7, such as an alternating-temperature adsorption unit (TSA), in order to eliminate water and carbon dioxide from the gaseous stream 6.
  • an adsorption unit 7 such as an alternating-temperature adsorption unit (TSA)
  • TSA alternating-temperature adsorption unit
  • a gaseous stream 8 essentially comprising nitrogen and helium (that is to say comprising less than 5 ppm by volume of methane, less than 1 ppm by volume of hydrogen, less than 0.1 ppm by volume of carbon dioxide and less than 0.1 ppm by volume of water).
  • the gaseous stream 8 is treated in a unit 9 for purifying nitrogen and concentrating helium.
  • This unit 9 comprises at least one heat exchanger in which the gas stream is cooled from ambient temperature (0 ° C - 40 ° C for example) to a temperature between -180 ° C and -195 ° C.
  • the gaseous flow is for example introduced into a phase separator pot generating a liquid flow 10 and a gaseous stream 11.
  • the liquid stream contains 98.8% by volume of nitrogen.
  • This liquid flow 10 is sent to a storage device 12 of liquid nitrogen. It does not contain methane.
  • the gaseous stream 11 contains from 80% by volume to 95% by volume of helium and from 5% by volume to 20% by volume of nitrogen. Stream 11 is sent to a helium purification unit 13.
  • This purification unit 13 is for example an alternating pressure adsorption unit (in English PSA) and produces two streams. One 14, containing 99.9% by volume of helium and another containing the remainder of the elements (essentially nitrogen). The gas stream 15 is introduced into a compressor 16 and then mixed with the source gas stream 1 to be treated, this is a regeneration loop of the unit 13.
  • the helium rich stream 14 may be supplied to a helium liquefaction unit 17 producing a liquid helium stream 18 directed to a storage device 19.
  • the pure liquid nitrogen stored in the nitrogen storage device 12 can be used to maintain the temperature of the helium storage device 19.
  • a stream of liquid nitrogen produced by the nitrogen extraction unit 2 is introduced into the unit 9 for purifying nitrogen and concentrating helium. This makes it possible to obtain the necessary cooling capacity and thereby avoid the investment of a dedicated air separation unit contrary to the process illustrated in FIG.
  • Another refrigerant present at the site for example LNG
  • a high pressure fluid can be used (by Thomson expansion or turbines) to create the necessary cold.
  • the simultaneous oxidation of hydrogen and methane occurs before the helium concentration.
  • the TSA 7 then operates under pressure which guarantees a better efficiency (a reduction of the necessary volume of adsorbents as well as a reduction of the heat consumption at the level of the regeneration heater).
  • the purge from the cryogenic helium concentration unit 9 no longer contains methane (which has been oxidized beforehand).
  • Liquid nitrogen without methane can therefore be produced from unit 9. It is sufficient to integrate this unit 9 with the Helium concentration unit 2 (NRU or natural gas liquefaction unit) to obtain the cooling capacity required. This avoids the investment of a dedicated air separation unit (ASU).
  • ASU dedicated air separation unit
  • a stream 21 previously expanded in the unit 9 containing nitrogen and helium is extracted from said unit 9 and then sent to a compressor 3 and / or 16.
  • Helium from the expansion of the liquid nitrogen unit 9 is recycled to increase the percentage of helium produced.
  • the stream 21 comprises between 40% and 50% by volume of helium and between 50% and 60% by volume of nitrogen.
  • Helium 1 1 is preconcentrated at about 90% to PSA 13 (rather than
  • waste gas pressure (in English (offgas) of the PSA 13 can also be reduced compared with that of the process illustrated in FIG. 1 since they can return directly to the compressor 16 without first going through a drying unit.

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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The invention relates to a method for producing helium from a source gas stream (1) including at least helium, methane, nitrogen and hydrogen, comprising at least the following consecutive steps: step a): injecting said source gas stream (1) into at least one compressor (3); step b): eliminating the hydrogen and the methane by reacting the stream (4) obtained from step a) with oxygen; step c): eliminating at least the impurities from step b) by temperature swing adsorption (TSA); step d): partially condensing the stream (8) obtained from step c) in order to produce a stream (10) of liquid nitrogen and a gas stream (11) comprising mostly helium; step e): purifying the gas stream (11) obtained from step d) in order to increase the helium content by pressure swing adsorption (PSA) by eliminating the nitrogen and the impurities contained in the gas stream (11) obtained from step d).

Description

Production d'hélium à partir d'un courant gazeux  Helium production from a gaseous stream
contenant de l'hydrogène La présente invention concerne un procédé de production d'hélium à partir d'un courant gazeux source comprenant au moins de l'hélium, du méthane, de l'azote et de l'hydrogène.  The present invention relates to a process for producing helium from a source gas stream comprising at least helium, methane, nitrogen and hydrogen.
L'hélium est obtenu commercialement pratiquement exclusivement à partir d'un mélange de composants volatils du gaz naturel, ce mélange comprenant, ainsi que de l'hélium, typiquement du méthane et de l'azote et des traces d'hydrogène, de l'argon et d'autres gaz nobles. Au cours de la production de l'huile minérale, l'hélium est mis à disposition en tant que composant du gaz qui accompagne l'huile minérale, ou dans le cadre de la production de gaz naturel. Il est théoriquement possible d'obtenir de l'hélium dans l'atmosphère, mais ce n'est pas économique en raison des faibles concentrations (concentration typique de l'hélium dans l'air de l'ordre de 5,2 ppmv).  Helium is obtained commercially almost exclusively from a mixture of volatile components of natural gas, this mixture comprising, as well as helium, typically methane and nitrogen and traces of hydrogen, argon and other noble gases. During the production of mineral oil, helium is made available as a component of the gas that accompanies mineral oil, or as part of the production of natural gas. It is theoretically possible to obtain helium in the atmosphere, but it is not economical because of the low concentrations (typical concentration of helium in the air of the order of 5.2 ppmv).
Afin d'éviter la congélation indésirable lors d'un processus de liquéfaction de l'hélium, la concentration des impuretés dans le courant d'hélium à liquéfier ne doit pas dépasser une valeur de 1000 ppm en volume, de préférence de 10 ppmv.  In order to avoid unwanted freezing during a liquefaction process of helium, the concentration of impurities in the helium stream to be liquefied must not exceed a value of 1000 ppm by volume, preferably 10 ppmv.
Pour cette raison, le processus de liquéfaction de l'hélium est connecté en aval d'un procédé de purification d'hélium. Celui-ci se compose généralement d'une combinaison de procédés cryogéniques, généralement basée sur la condensation partielle, et des procédés d'adsorption, la régénération dans le cas de ce dernier étant possible grâce à la variation de température et ou de pression.  For this reason, the liquefaction process of helium is connected downstream of a helium purification process. This is generally composed of a combination of cryogenic processes, generally based on partial condensation, and adsorption processes, the regeneration in the case of the latter being possible due to the variation of temperature and or pressure.
Dans de nombreux cas, il est avantageux de mettre en œuvre un procédé de purification de l'hélium de telle sorte que, en plus de l'hélium purifié, de l'azote de pureté requise - dans laquelle la somme des impuretés est inférieure à 1 % en volume - peut être obtenu. En général, seule une portion, typiquement de 5% à 70%, de préférence de 10% à 50%, de l'azote présent dans le mélange à purifier est amenée à la pureté désirée. L'azote restant est libéré dans l'atmosphère en même temps que le méthane sous forme de gaz basse pression, soit directement, soit après une étape d'oxydation, de préférence mis en œuvre dans une torche ou un incinérateur. In many cases, it is advantageous to employ a process for purifying helium such that, in addition to the purified helium, nitrogen of requisite purity - in which the sum of the impurities is less than 1% by volume - can be obtained. In general, only a portion, typically from 5% to 70%, preferably from 10% to 50%, of the nitrogen present in the mixture to be purified is brought to the desired purity. The remaining nitrogen is released into the atmosphere along with methane as a low pressure gas, either directly or after an oxidation step, preferably carried out in a torch or incinerator.
Un exemple connu de procédé de l'état de la technique pour l'obtention d'une fraction d'hélium pur à partir d'une fraction de départ comprenant au moins de l'hélium, du méthane et de l'azote est décrit dans la demande de brevet AU2013200075.  A known example of a method of the state of the art for obtaining a pure helium fraction from a starting fraction comprising at least helium, methane and nitrogen is described in US Pat. patent application AU2013200075.
Ce procédé d'obtention d'une fraction d'hélium pur à partir d'une fraction de départ comprenant au moins de l'hélium, du méthane et de l'azote comprend les étapes successives suivantes :  This process for obtaining a pure helium fraction from a starting fraction comprising at least helium, methane and nitrogen comprises the following successive stages:
a) la fraction de départ est soumise à une élimination de méthane et d'azote,  a) the starting fraction is subjected to a methane and nitrogen removal,
b) la fraction issue de a) qui se compose essentiellement d'hélium et d'azote est comprimée,  (b) the fraction from (a) that consists essentially of helium and nitrogen is compressed,
c) la fraction comprimée est soumise à une élimination d'azote, et d) la fraction riche en hélium obtenu à l'étape c) est soumise à une purification par adsorption pour produire une fraction.  c) the compressed fraction is subjected to nitrogen removal, and d) the helium-rich fraction obtained in step c) is subjected to adsorption purification to produce a fraction.
L'élimination précoce de la fraction de méthane contenue dans le courant gazeux initial à traiter impose la mise en œuvre de deux étapes cryogéniques indépendantes nécessaires, les coûts d'investissement et d'exploitation sont donc importants.  The early removal of the methane fraction contained in the initial gaseous stream to be treated requires the implementation of two independent cryogenic steps required, investment and operating costs are therefore important.
Par ailleurs, une partie de l'azote contenue dans le courant gazeux initial à traité est perdu avec l'éthane éliminé à la première étape. Or, le recyclage d'azote pour d'autres applications est un élément clé à l'échelle industrielle, car l'azote, en particulier l'azote liquide est très valorisable.  On the other hand, a part of the nitrogen contained in the initial gas stream to be treated is lost with the ethane removed in the first stage. However, nitrogen recycling for other applications is a key element on an industrial scale, since nitrogen, in particular liquid nitrogen, is highly valuable.
En outre, ce procédé ne permet pas de traiter les flux gazeux contenant une forte teneur en hydrogène, typiquement plus de 6% en volume d'hydrogène.  In addition, this method does not make it possible to treat gas streams containing a high hydrogen content, typically more than 6% by volume of hydrogen.
Un autre type de procédé de purification d'hélium connu de l'art antérieur est illustré par la figure 1 . Un flux gazeux 1 ' comprenant de l'azote, du méthane, de l'hélium et de l'hydrogène, par exemple provenant de la sortie d'une unité 15' de rejet d'azote (NRU en anglais, nitrogen rejection unit) suite au traitement d'un flux de gaz naturel pour éliminer l'azote de ce gaz naturel, est introduit dans un compresseur 2'. Une fois ce gaz comprimé, il est introduit dans un dispositif concentrateur d'hélium 3'. Another type of helium purification process known from the prior art is illustrated in FIG. A gaseous stream 1 'comprising nitrogen, methane, helium and hydrogen, for example originating from the outlet of a nitrogen rejection unit (NRU) 15 following the treatment of a stream of natural gas to remove nitrogen from this natural gas, is introduced into a compressor 2 '. Once this gas is compressed, it is introduced into a 3 'helium concentrator device.
En sortie de ce dispositif 3', l'hydrogène contenu dans le flux gazeux est éliminé au moyen d'un système 4' dans lequel réagissent hydrogène et de l'oxygène.  At the outlet of this device 3 ', the hydrogen contained in the gas stream is removed by means of a system 4' in which hydrogen and oxygen react.
A l'issue de cette étape, le flux gazeux est alors purifié au moyen 5' d'un procédé d'adsorption à pression alternée (PSA en anglais). Un flux gazeux 6', provenant du PSA 6', contenant majoritairement de l'hélium est alors liquéfié dans un dispositif 7' de liquéfaction d'hélium. L'hélium liquéfié est envoyé dans un système de stockage d'hélium 8'. Ledit système de stockage 8' étant refroidi par de l'azote liquide 9' issu d'un dispositif de stockage d'azote liquide 10' alimenté par une unité de séparation d'air 1 1 '.  At the end of this step, the gas stream is then purified by means of an alternating pressure adsorption (PSA) process. A gas stream 6 'from PSA 6' containing predominantly helium is then liquefied in a helium liquefaction device 7 '. The liquefied helium is sent to an 8 'helium storage system. Said storage system 8 'being cooled by liquid nitrogen 9' from a liquid nitrogen storage device 10 'fed by an air separation unit 11'.
Par ailleurs l'azote liquide stocké dans le dispositif 10' sert à alimenter le dispositif concentrateur d'hélium 3'.  In addition, the liquid nitrogen stored in the device 10 'is used to feed the helium concentrator device 3'.
Le flux gazeux 12' contenant une majorité d'azote et une faible quantité d'hélium est purifié au moyen d'un moyen de purification 13' éliminant les impuretés contenues dans le flux gazeux 12' afin de produire un flux gazeux 14' de recyclage envoyé au compresseur 2' après avoir été mélangé avec le mélange gazeux l ' initial à traiter.  The gaseous stream 12 'containing a majority of nitrogen and a small amount of helium is purified by means of a purification means 13' eliminating the impurities contained in the gas stream 12 'in order to produce a gaseous stream 14' of recycling sent to the compressor 2 'after having been mixed with the gas mixture the initial to be treated.
Lorsque le taux d'hydrogène est élevé, typiquement plus de 4% en volume voire 6%, l'appoint d'air au niveau du système d'élimination d'hydrogène 4' dans lequel réagissent hydrogène et de l'oxygène est important. Une grande quantité d'azote et d'argon est alors introduite à ce niveau-là, ce qui dimensionne le système 5' PSA.  When the hydrogen content is high, typically more than 4% by volume or even 6%, the addition of air at the hydrogen removal system 4 'in which hydrogen and oxygen react is important. A large amount of nitrogen and argon is then introduced at this level, which sizes the 5 'PSA system.
Une purge mise en œuvre au niveau du concentrateur d'hélium 3' contient du méthane. Il faut alors la traiter au moyen d'un dispositif d'oxydation du méthane pour satisfaire les exigences environnementales. Il est nécessaire d'avoir une unité de séparation d'air 1 1 ' (en anglais ASU) qui produit l'azote liquide à la spécification compatible avec les stockages d'hélium 8' (de l'ordre du ppm de méthane). A purge implemented at the 3 'helium concentrator contains methane. It must then be treated using a methane oxidation device to meet environmental requirements. It is necessary to have an air separation unit 11 '(in English ASU) which produces the liquid nitrogen to the specification compatible with the 8' helium storage (of the order of ppm of methane).
Les inventeurs de la présente invention ont alors mis au pont une solution permettant de résoudre les problèmes soulevés ci-dessus.  The inventors of the present invention have then bridged a solution to solve the problems raised above.
La présente invention a pour objet un procédé de production d'hélium à partir d'un courant gazeux source comprenant au moins de l'hélium, du méthane, de l'azote et de l'hydrogène, comprenant au moins les étapes successives suivantes :  The subject of the present invention is a process for producing helium from a source gas stream comprising at least helium, methane, nitrogen and hydrogen, comprising at least the following successive stages:
Etape a) : introduction dudit courant gazeux source dans au moins un compresseur;  Step a): introducing said source gas stream into at least one compressor;
Etape b) : élimination de l'hydrogène et du méthane par réaction du courant issu de l'étape a) avec de l'oxygène ;  Step b): elimination of hydrogen and methane by reacting the stream from step a) with oxygen;
Etape c) : élimination au moins des impuretés issues de l'étape b) par adsorption à température alternée (TSA) ;  Step c): removal of at least impurities from step b) by alternating-temperature adsorption (TSA);
Etape d) : condensation partielle du courant issu de l'étape c) afin de produire un courant d'azote liquide et un courant gazeux comprenant majoritairement de l'hélium ;  Step d): partial condensation of the stream resulting from stage c) in order to produce a stream of liquid nitrogen and a gas stream mainly comprising helium;
Etape e) : purification du courant gazeux issu de l'étape d) afin d'augmenter la teneur en hélium par adsorption à pression alternée (PSA) en éliminant l'azote et les impuretés contenues dans le courant gazeux issu de l'étape d).  Step e): purification of the gas stream from step d) in order to increase the helium content by pressure swing adsorption (PSA) by eliminating the nitrogen and the impurities contained in the gas stream from step d ).
Selon d'autres modes de réalisation, la présente invention a pour objet: Un procédé tel que défini précédemment caractérisé en ce que le courant gazeux source comprend de 40% à 95% en volume d'azote, de 0,05% à 40% en volume d'hélium, de 50 ppmv à 5% en volume de méthane et de 1 % à 10% en volume d'hydrogène, de préférence de 5% en volume à 10% en volume d'hydrogène.  According to other embodiments, the subject of the present invention is: A process as defined above characterized in that the source gas stream comprises from 40% to 95% by volume of nitrogen, from 0.05% to 40% by volume of helium, from 50 ppmv to 5% by volume of methane and from 1% to 10% by volume of hydrogen, preferably from 5% by volume to 10% by volume of hydrogen.
Un procédé tel que défini précédemment caractérisé en ce que le courant gazeux source comprend de 40% à 60% en volume d'azote, de 30% à 50% en volume d'hélium, de 50 ppmv à 5% en volume de méthane et de 1 % à 10% en volume d'hydrogène, de préférence de 5% en volume à 10% en volume d'hydrogène. Un procédé tel que défini précédemment comprenant une étape préalablement à l'étape a) de production du courant gazeux source à traiter au moyen d'une unité d'extraction d'azote ou d'une unité de liquéfaction de gaz naturel, ladite unité produisant un courant d'azote liquide mis en œuvre à l'étape d) permettant la condensation partielle du courant issu de l'étape c) afin de produire un courant d'azote liquide et un courant gazeux comprenant majoritairement de l'hélium. A process as defined above characterized in that the source gas stream comprises from 40% to 60% by volume of nitrogen, from 30% to 50% by volume of helium, from 50 ppm to 5% by volume of methane and from 1% to 10% by volume of hydrogen, preferably from 5% by volume to 10% by volume of hydrogen. A process as defined above comprising a step prior to step a) of producing the source gas stream to be treated by means of a nitrogen extraction unit or a natural gas liquefaction unit, said unit producing a stream of liquid nitrogen implemented in step d) allowing the partial condensation of the stream from step c) to produce a stream of liquid nitrogen and a gas stream comprising predominantly helium.
Un procédé tel que défini précédemment caractérisé en ce que la pression à l'issue de l'étape a) est comprise entre 15 Bara et 35 Bara, de préférence entre 20 Bara et 25 Bara.  A process as defined above characterized in that the pressure at the end of step a) is between Bara and Bara, preferably between Bara and Bara.
Un procédé tel que défini précédemment caractérisé en ce que le courant gazeux issu de l'étape b) comprend moins de 1 ppm en volume d'hydrogène et moins de 1 ppm en volume de méthane.  A process as defined above characterized in that the gaseous stream from step b) comprises less than 1 ppm by volume of hydrogen and less than 1 ppm by volume of methane.
Un procédé tel que défini précédemment caractérisé en ce que lesdites impuretés contenues dans le courant gazeux issu de l'étape b) comprennent majoritairement du dioxyde de carbone et de l'eau.  A process as defined above characterized in that said impurities contained in the gas stream from step b) mainly comprise carbon dioxide and water.
Un procédé tel que défini précédemment caractérisé en ce que le courant d'azote liquide issu de l'étape d) comprend plus de 98,5% en volume d'azote.  A process as defined above characterized in that the stream of liquid nitrogen from step d) comprises more than 98.5% by volume of nitrogen.
Un procédé tel que défini précédemment caractérisé en ce que ledit courant gazeux issu de l'étape d) comprend entre 80% en volume et 95% en volume d'hélium.  A process as defined above characterized in that said gaseous stream from step d) comprises between 80% by volume and 95% by volume of helium.
Un procédé tel que défini précédemment caractérisé en ce que ledit courant gazeux issu de l'étape e) comprend au moins 99,9% en volume d'hélium.  A process as defined above characterized in that said gaseous stream from step e) comprises at least 99.9% by volume of helium.
Un procédé tel que défini précédemment caractérisé en ce que l'étape b) consiste en la mise en contact du courant gazeux issu de l'étape a) avec de l'oxygène et un lit catalytique comportant des particules d'au moins un métal choisi parmi le cuivre, le platine, le palladium, l'osmium, l'iridium, le ruthénium et le rhodium, supporté par un support inerte chimiquement vis-à-vis du dioxyde de carbone et de l'eau de sorte à faire réagir le méthane et l'hydrogène avec l'oxygène. Un procédé tel que défini précédemment caractérisé en ce qu'il comprend une étape supplémentaire f) de liquéfaction de l'hélium issu de l'étape e). A process as defined above characterized in that step b) consists in bringing the gas stream coming from step a) into contact with oxygen and a catalytic bed comprising particles of at least one selected metal. among copper, platinum, palladium, osmium, iridium, ruthenium and rhodium, supported by a chemically inert carrier with respect to carbon dioxide and water so as to react with methane and hydrogen with oxygen. A process as defined above characterized in that it comprises an additional step f) liquefaction of the helium from step e).
Un procédé tel que défini précédemment caractérisé en ce que l'azote liquide issu de l'étape d) refroidit l'hélium liquéfié à l'étape f).  A process as defined above characterized in that the liquid nitrogen from step d) cools the liquefied helium in step f).
Une Installation de production d'hélium à partir d'un mélange de gaz source comprenant du méthane, de l'hélium, de l'hydrogène et de l'azote comprenant au moins un compresseur recevant directement le mélange de gaz source, au moins un moyen d'élimination d'hydrogène et de méthane, au moins un dispositif d'élimination d'azote et de concentration d'hélium, et au moins un moyen de purification en hélium situé en aval du dispositif d'élimination d'azote et de concentration d'hélium, caractérisée en ce que le moyen d'élimination d'hydrogène et de méthane est situé en aval dudit au moins un compresseur et en amont du dispositif d'élimination d'azote et de concentration d'hélium.  A plant for producing helium from a source gas mixture comprising methane, helium, hydrogen and nitrogen comprising at least one compressor directly receiving the source gas mixture, at least one means for removing hydrogen and methane, at least one nitrogen removal and helium concentration device, and at least one helium purification means located downstream of the nitrogen removal and helium concentration, characterized in that the means for removing hydrogen and methane is located downstream of said at least one compressor and upstream of the nitrogen removal device and helium concentration.
Une Installation telle que définie précédemment caractérisée en ce qu'elle comprend en outre un dispositif de liquéfaction d'hélium en aval du moyen de purification en hélium.  An installation as defined above characterized in that it further comprises a helium liquefaction device downstream of the helium purification means.
L'invention sera décrite de manière plus détaillée en se référant à la figure 2 qui illustre un mode de mise en œuvre d'un procédé selon l'invention.  The invention will be described in more detail with reference to FIG. 2 which illustrates an embodiment of a method according to the invention.
Un courant gazeux source 1 contenant au moins de l'hélium, de l'azote, de l'hydrogène et du méthane est traité par un procédé objet de la présente invention afin de produire un flux d'hélium pur, typiquement contenant plus de 99,999% en volume d'hélium. Le courant source 1 provient par exemple d'une unité 2 de d'extraction d'azote (en anglais, nitrogen rejection unit, NRU) située en aval d'une unité cryogénique de traitement du gaz naturel.  A source gas stream 1 containing at least helium, nitrogen, hydrogen and methane is treated by a process of the present invention to produce a pure helium stream, typically containing more than 99.9% % by volume of helium. The source stream 1 comes for example from a unit 2 of nitrogen extraction (in English, nitrogen rejection unit, NRU) located downstream of a cryogenic unit for treating natural gas.
Le courant source 1 est introduit dans un compresseur 3 permettant de comprimer le courant gazeux 4 à une pression comprise entre 15 Bara (Bars absolu) et 35 Bara, de préférence entre 20 bara er 25 Bara. La température est la température ambiante où se situe l'installation.  The source current 1 is introduced into a compressor 3 making it possible to compress the gas stream 4 at a pressure of between 15 bara (absolute bar) and 35 bara, preferably between 20 bara and 25 bara. The temperature is the ambient temperature where the installation is located.
Le courant gazeux 4 est introduit dans une unité 5 d'élimination d'hydrogène et de méthane. Cette unité 5 consiste par exemple en un à plusieurs réacteurs en série contenant un catalyseur entre des grilles. Ce catalyseur est typiquement du Pd/AI2O3. Une oxydation catalytique entre l'oxygène et les comburants (hydrogène/ méthane) se crée. The gas stream 4 is introduced into a unit 5 for eliminating hydrogen and methane. This unit 5 consists for example of one to several reactors in series containing a catalyst between grids. This catalyst is typically Pd / Al 2 O 3. A catalytic oxidation between oxygen and oxidants (hydrogen / methane) is created.
L'hydrogène réagit avec l'oxygène pour former de l'eau. Cette réaction étant exothermique, la température s'élève.  Hydrogen reacts with oxygen to form water. This reaction being exothermic, the temperature rises.
Pour oxyder le méthane également, des températures plus élevées sont requises. Un fort taux d'hydrogène à l'entrée permet d'opérer à une température élevée et de co-oxyder le méthane (par exemple, avec 2% d'hydorgène, la température s'élève à 200°C environ ce qui ne suffit pas pour oxyder le méthane).  To oxidize methane also, higher temperatures are required. A high hydrogen content at the inlet makes it possible to operate at a high temperature and to co-oxidize the methane (for example, with 2% of hydorgene, the temperature rises to about 200 ° C. which is not sufficient not to oxidize methane).
Ainsi l'hydrogène et le méthane contenus dans le courant source 1 initial à traiter sont oxydés par l'oxygène de l'unité 5.  Thus, the hydrogen and methane contained in the initial source stream 1 to be treated are oxidized by the oxygen of unit 5.
Des impuretés telles que l'eau et le dioxyde de carbone sont donc produites dans le courant gazeux 6 en sortie de l'unité 5. Ce courant gazeux 6 comprend majoritairement de l'azote et de l'hélium.  Impurities such as water and carbon dioxide are therefore produced in the gas stream 6 at the outlet of the unit 5. This gas stream 6 comprises mainly nitrogen and helium.
On refroidit le gaz sortant (contre l'air ambiant ou eau de refroidissement) avant de l'envoyer dans l'unité d'adsorption 7. Une partie de l'eau se condense alors directement dans un récupérateur de condensais. Une partie de la chaleur produite peut être récupérée pour être utilisée dans un autre procédé  The outgoing gas (against ambient air or cooling water) is cooled before being sent to the adsorption unit 7. Part of the water then condenses directly in a condensate recuperator. Part of the heat produced can be recovered for use in another process
Le courant gazeux 6 est alors traité dans une unité d'adsorption 7, telle qu'une unité d'adsorption à température alternée (TSA en anglais), afin d'éliminer l'eau et le dioxyde de carbone du courant gazeux 6. Il en résulte un courant gazeux 8 comprenant essentiellement de l'azote et de l'hélium (c'est-à- dire comprenant moins de 5 ppm en volume de méthane, moins de 1 ppm en volume d'hydrogène, moins de 0,1 ppm en volume de dioxyde de carbone et moins de 0,1 ppm en volume d'eau). Le courant gazeux 8 est traité dans une unité 9 d'épuration d'azote et de concentration d'hélium.  The gaseous stream 6 is then treated in an adsorption unit 7, such as an alternating-temperature adsorption unit (TSA), in order to eliminate water and carbon dioxide from the gaseous stream 6. this results in a gaseous stream 8 essentially comprising nitrogen and helium (that is to say comprising less than 5 ppm by volume of methane, less than 1 ppm by volume of hydrogen, less than 0.1 ppm by volume of carbon dioxide and less than 0.1 ppm by volume of water). The gaseous stream 8 is treated in a unit 9 for purifying nitrogen and concentrating helium.
Cette unité 9 comprend au moins un échangeur de chaleur dans lequel le courant gazeux est refroidi depuis la température ambiante (0°C - 40°C par exemple) jusqu'à une température comprise entre -180°C et -195°C. En sortie de cet échangeur de chaleur, le flux gazeux est par exemple introduit dans un pot séparateur de phase générant un flux liquide 10 et un courant gazeux 1 1 . Le flux liquide 10 contient 98,8% en volume d'azote. Ce flux liquide 10 est envoyé vers un dispositif de stockage 12 d'azote liquide. Il ne contient pas de méthane. This unit 9 comprises at least one heat exchanger in which the gas stream is cooled from ambient temperature (0 ° C - 40 ° C for example) to a temperature between -180 ° C and -195 ° C. At the outlet of this heat exchanger, the gaseous flow is for example introduced into a phase separator pot generating a liquid flow 10 and a gaseous stream 11. The liquid stream contains 98.8% by volume of nitrogen. This liquid flow 10 is sent to a storage device 12 of liquid nitrogen. It does not contain methane.
Le courant gazeux 1 1 contient de 80% en volume à 95% en volume d'hélium et de 5% en volume à 20% en volume d'azote. Le courant 1 1 est envoyé dans une unité 13 de purification en hélium.  The gaseous stream 11 contains from 80% by volume to 95% by volume of helium and from 5% by volume to 20% by volume of nitrogen. Stream 11 is sent to a helium purification unit 13.
Cette unité 13 de purification est par exemple une unité d'adsorption à pression alternée (en anglais PSA) et produit deux courants. L'un 14, contenant 99,9% en volume d'hélium et un autre 15 contenant le reste des éléments (essentiellement de l'azote). Le courant gazeux 15 est introduit dans un compresseur 16 puis mélangé au courant gazeux source 1 à traiter, il s'agit là d'une boucle de régénération de l'unité 13.  This purification unit 13 is for example an alternating pressure adsorption unit (in English PSA) and produces two streams. One 14, containing 99.9% by volume of helium and another containing the remainder of the elements (essentially nitrogen). The gas stream 15 is introduced into a compressor 16 and then mixed with the source gas stream 1 to be treated, this is a regeneration loop of the unit 13.
Le courant 14 riche en hélium peut être envoyé vers une unité 17 de liquéfaction d'hélium produisant un courant 18 d'hélium liquide dirigé vers un dispositif de stockage 19. L'azote liquide pur 10 stocké dans le dispositif de stockage d'azote 12 peut être utilisé pour maintenir la température du dispositif 19 de stockage d'hélium.  The helium rich stream 14 may be supplied to a helium liquefaction unit 17 producing a liquid helium stream 18 directed to a storage device 19. The pure liquid nitrogen stored in the nitrogen storage device 12 can be used to maintain the temperature of the helium storage device 19.
Selon un mode préféré de réalisation, un courant 20 d'azote liquide produit par l'unité 2 d'extraction d'azote est introduit dans l'unité 9 d'épuration d'azote et de concentration d'hélium. Cela permet d'obtenir la puissance frigorifique nécessaire et par là d'éviter l'investissement d'une unité de séparation d'air dédiée contrairement au procédé illustré sur la figure 1 .  According to a preferred embodiment, a stream of liquid nitrogen produced by the nitrogen extraction unit 2 is introduced into the unit 9 for purifying nitrogen and concentrating helium. This makes it possible to obtain the necessary cooling capacity and thereby avoid the investment of a dedicated air separation unit contrary to the process illustrated in FIG.
On peut également utiliser un autre fluide frigorigène présent sur le site (par exemple du LNG) ou utiliser un fluide haute pression que l'on détend (par détente joule Thomson ou turbines) pour créer le froid nécessaire.  Another refrigerant present at the site (for example LNG) can also be used or a high pressure fluid can be used (by Thomson expansion or turbines) to create the necessary cold.
Des avantages d'un procédé tel qu'illustré à la figure 2 objet de la présente invention par rapport au procédé illustré à la figure 1 sont décrits ci- après.  Advantages of a method as illustrated in Figure 2 object of the present invention compared to the method illustrated in Figure 1 are described below.
L'oxydation simultanée de l'hydrogène et du méthane a lieu avant la concentration en hélium. Le TSA 7 fonctionne alors sous pression ce qui garantit une meilleure efficacité (une réduction du volume d'adsorbants nécessaire ainsi qu'une réduction de la consommation de chaleur au niveau du réchauffeur de régénération). La purge provenant de l'unité 9 cryogénique de concentration en hélium ne contient plus de méthane (qui a été oxydé au préalable). The simultaneous oxidation of hydrogen and methane occurs before the helium concentration. The TSA 7 then operates under pressure which guarantees a better efficiency (a reduction of the necessary volume of adsorbents as well as a reduction of the heat consumption at the level of the regeneration heater). The purge from the cryogenic helium concentration unit 9 no longer contains methane (which has been oxidized beforehand).
De l'azote liquide 10 sans méthane peut donc être produit à partir de l'unité 9. Il suffit d'intégrer cette unité 9 avec l'unité 2 de concentration d'Hélium (NRU ou unité de liquéfaction du gaz naturel) pour obtenir la puissance frigorifique nécessaire. Cela permet d'éviter l'investissement d'une unité de séparation d'air (en anglais ASU) dédiée.  Liquid nitrogen without methane can therefore be produced from unit 9. It is sufficient to integrate this unit 9 with the Helium concentration unit 2 (NRU or natural gas liquefaction unit) to obtain the cooling capacity required. This avoids the investment of a dedicated air separation unit (ASU).
Selon un mode particulier de l'invention, un courant 21 préalablement détendu dans l'unité 9 contenant de l'azote et de l'hélium est extrait de ladite unité 9 puis envoyé vers un compresseur 3 et/ou 16. Ainsi de l'hélium issu de la détente de l'azote liquide de l'unité 9 est recyclé afin d'augmenter le pourcentage d'hélium produit.  According to one particular embodiment of the invention, a stream 21 previously expanded in the unit 9 containing nitrogen and helium is extracted from said unit 9 and then sent to a compressor 3 and / or 16. Thus, Helium from the expansion of the liquid nitrogen unit 9 is recycled to increase the percentage of helium produced.
Par exemple le courant 21 comporte entre 40% et 50% en volume d'hélium et entre 50% et 60% en volume d'azote.  For example, the stream 21 comprises between 40% and 50% by volume of helium and between 50% and 60% by volume of nitrogen.
Le rendement de l'unité 13 PSA et sa taille sont également grandement améliorés. L'hélium 1 1 est préconcentré à environ 90% au PSA 13 (plutôt que The performance of the PSA unit 13 and its size are also greatly improved. Helium 1 1 is preconcentrated at about 90% to PSA 13 (rather than
70% dans le procédé de la figure 1 et avec un fort taux d'hydrogène. Les impuretés argon et oxygène sont également en quantité bien plus faibles70% in the process of Figure 1 and with a high hydrogen content. Argon and oxygen impurities are also much lower
(puisque l'argon et l'oxygène se condensent en même temps que l'azote). (since argon and oxygen condense together with nitrogen).
II n'y a également plus de dioxyde de carbone ni d'eau à traiter dans le gaz entrant. La pression du gaz résiduaire (en anglais (offgas) du PSA 13 peut également être réduite par rapport à celle du procédé illustré à la figure 1 car ils peuvent revenir directement au compresseur 16 sans passer auparavant par une unité de séchage.  There is also no more carbon dioxide or water to be treated in the incoming gas. The waste gas pressure (in English (offgas) of the PSA 13 can also be reduced compared with that of the process illustrated in FIG. 1 since they can return directly to the compressor 16 without first going through a drying unit.
Tous ces points permettent d'améliorer le rendement du PSA 13 ce qui dimensionne la ligne de retour et le compresseur 3 du courant 1 à traiter (la consommation énergétique du compresseur est réduite.)  All these points make it possible to improve the efficiency of the PSA 13 which dimensions the return line and the compressor 3 of the current 1 to be treated (the energy consumption of the compressor is reduced.)
Le tableau ci-dessous récapitule les compositions des courants gazeux entrant dans l'unité de purification en hélium (élément numéroté 13 de la figure 2 et 5' de la figure 1 ). Courant The table below summarizes the compositions of the gas streams entering the helium purification unit (element numbered 13 of FIG. 2 and 5 'of FIG. 1). Current
Figure 1 Figure 2 gazeux  Figure 1 Figure 2 Gaseous
Composition Composition
He mol% 69,48% 89,9697% He mol% 69.48% 89.9697%
N2 mol% 29,94% 9,9979%N2 mol% 29.94% 9.9979%
CH4 ppm v 1 1CH4 ppm v 1 1
Ar ppm v 2 658 181Ar ppm v 2,658,181
H2 ppm v <0.5 <0.5H2 ppm v <0.5 <0.5
Ne ppm v 300 300Do not ppm v 300 300
CO ppm v 0 0CO ppm v 0 0
02 ppm v 2 703 14302 ppm to 2 703 143
H2O saturé 0H2O saturated 0
CO2 ppmv 355 <0.1CO2 ppmv 355 <0.1
Total mol% 100% 100% Total mol% 100% 100%
Débit (sec) Nm3/h 4806 3713 Flow rate (sec) Nm3 / h 4806 3713
Pression bars a 23,55 23,45 Pressure bars at 23.55 23.45
Température °C 47 47 Temperature ° C 47 47
Tableau : Composition des gaz entrants dans le PSA Table: Composition of the incoming gases in the PSA

Claims

Revendications claims
1 . Procédé de production d'hélium à partir d'un courant gazeux source (1 ) comprenant au moins de l'hélium, du méthane, de l'azote et de l'hydrogène, comprenant au moins les étapes successives suivantes : 1. A process for producing helium from a source gas stream (1) comprising at least helium, methane, nitrogen and hydrogen, comprising at least the following successive stages:
Etape a) : introduction dudit courant gazeux source (1 ) dans au moins un compresseur (3);  Step a): introducing said source gas stream (1) into at least one compressor (3);
Etape b) : élimination de l'hydrogène et du méthane par réaction du courant (4) issu de l'étape a) avec de l'oxygène ;  Step b): elimination of hydrogen and methane by reacting the stream (4) from step a) with oxygen;
Etape c) : élimination au moins des impuretés issues de l'étape b) par adsorption à température alternée (TSA) ;  Step c): removal of at least impurities from step b) by alternating-temperature adsorption (TSA);
Etape d) : condensation partielle du courant (8) issu de l'étape c) afin de produire un courant (10) d'azote liquide et un courant (1 1 ) gazeux comprenant majoritairement de l'hélium ;  Step d): partial condensation of the stream (8) from step c) to produce a stream (10) of liquid nitrogen and a stream (1 1) gas comprising predominantly helium;
Etape e) : purification du courant gazeux (1 1 ) issu de l'étape d) afin d'augmenter la teneur en hélium par adsorption à pression alternée (PSA) en éliminant l'azote et les impuretés contenues dans le courant gazeux (1 1 ) issu de l'étape d).  Step e): purification of the gas stream (1 1) from step d) in order to increase the helium content by pressure swing adsorption (PSA) by eliminating the nitrogen and the impurities contained in the gas stream (1 1) from step d).
2. Procédé selon la revendication précédente caractérisé en ce que le courant gazeux source (1 ) comprend de 40% à 95% en volume d'azote, de 0,05% à 40% en volume d'hélium, de 50 ppmv à 5% en volume de méthane et de 1 % à 10% en volume d'hydrogène, de préférence de 5% en volume à 10% en volume d'hydrogène. 2. Method according to the preceding claim characterized in that the source gas stream (1) comprises from 40% to 95% by volume of nitrogen, from 0.05% to 40% by volume of helium, from 50 ppmv to 5% by volume. % by volume of methane and from 1% to 10% by volume of hydrogen, preferably from 5% by volume to 10% by volume of hydrogen.
3. Procédé selon la revendication 2 caractérisé en ce que le courant gazeux source (1 ) comprend de 40% à 60% en volume d'azote, de 30% à 50% en volume d'hélium, de 50 ppmv à 5% en volume de méthane et de 1 % à 10% en volume d'hydrogène, de préférence de 5% en volume à 10% en volume d'hydrogène. 3. Process according to claim 2, characterized in that the source gas stream (1) comprises from 40% to 60% by volume of nitrogen, from 30% to 50% by volume of helium, from 50 ppm to 5% by weight. volume of methane and 1% to 10% by volume of hydrogen, preferably 5% by volume to 10% by volume of hydrogen.
4. Procédé selon l'une des revendications précédentes comprenant une étape préalablement à l'étape a) de production du courant gazeux source (1 ) à traiter au moyen d'une unité (2) d'extraction d'azote ou d'une unité de liquéfaction de gaz naturel, ladite unité (2) produisant un courant (20) d'azote liquide mis en œuvre à l'étape d) permettant la condensation partielle du courant (8) issu de l'étape c) afin de produire un courant d'azote liquide (10) et un courant gazeux (1 1 ) comprenant majoritairement de l'hélium. 4. Method according to one of the preceding claims comprising a step prior to step a) of producing the source gas stream (1) to be treated by means of a nitrogen extraction unit (2) or a natural gas liquefaction unit, said unit (2) producing a stream (20) of liquid nitrogen implemented in stage d) allowing partial condensation of the stream (8) resulting from stage c) in order to produce a stream of liquid nitrogen (10) and a gaseous stream (1 1) comprising mainly helium.
5. Procédé selon la revendication précédente caractérisé en ce que la pression à l'issue de l'étape a) est comprise entre 15 Bara et 35 Bara, de préférence entre 20 Bara et 25 Bara. 5. Method according to the preceding claim characterized in that the pressure at the end of step a) is between Bara and Bara, preferably between Bara and Bara.
6. Procédé selon la revendication précédente caractérisé en ce que le courant gazeux (6) issu de l'étape b) comprend moins de 1 ppm en volume d'hydrogène et moins de 1 ppm en volume de méthane. 6. Method according to the preceding claim characterized in that the gas stream (6) from step b) comprises less than 1 ppm by volume of hydrogen and less than 1 ppm by volume of methane.
7. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que lesdites impuretés contenues dans le courant gazeux (6) issu de l'étape b) comprennent majoritairement du dioxyde de carbone et de l'eau. 7. Method according to any one of the preceding claims characterized in that said impurities contained in the gas stream (6) from step b) mainly comprise carbon dioxide and water.
8. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le courant d'azote liquide issu de l'étape d) comprend plus de 98,5% en volume d'azote. 8. Method according to any one of the preceding claims, characterized in that the liquid nitrogen stream from step d) comprises more than 98.5% by volume of nitrogen.
9. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que ledit courant gazeux issu de l'étape d) comprend entre 80% en volume et 95% en volume d'hélium. 9. Method according to any one of the preceding claims characterized in that said gaseous stream from step d) comprises between 80% by volume and 95% by volume of helium.
10. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que ledit courant gazeux issu de l'étape e) comprend au moins 99,9% en volume d'hélium. 10. Method according to any one of the preceding claims characterized in that said gaseous stream from step e) comprises at least 99.9% by volume of helium.
1 1 . Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape b) consiste en la mise en contact du courant gazeux issu de l'étape a) avec de l'oxygène et un lit catalytique comportant des particules d'au moins un métal choisi parmi le cuivre, le platine, le palladium, l'osmium, l'iridium, le ruthénium et le rhodium, supporté par un support inerte chimiquement vis-à-vis du dioxyde de carbone et de l'eau de sorte à faire réagir le méthane et l'hydrogène avec l'oxygène. 1 1. Process according to any one of the preceding claims, characterized in that step b) consists in bringing the gas stream coming from step a) into contact with oxygen and a catalytic bed comprising particles of at least a metal chosen from copper, platinum, palladium, osmium, iridium, ruthenium and rhodium, supported by a carrier that is chemically inert with respect to carbon dioxide and water so that react methane and hydrogen with oxygen.
12. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce qu'il comprend une étape supplémentaire f) de liquéfaction de l'hélium issu de l'étape e). 12. Method according to any one of the preceding claims characterized in that it comprises an additional step f) liquefaction of the helium from step e).
13. Procédé selon la revendication précédente caractérisé en ce que l'azote liquide issu de l'étape d) refroidit l'hélium liquéfié à l'étape f). 13. Method according to the preceding claim characterized in that the liquid nitrogen from step d) cools the liquefied helium in step f).
14. Installation de production d'hélium à partir d'un mélange de gaz source (1 ) comprenant du méthane, de l'hélium, de l'hydrogène et de l'azote comprenant au moins un compresseur (3) recevant directement le mélange de gaz source (1 ), au moins un moyen (5) d'élimination d'hydrogène et de méthane, au moins un dispositif (9) d'élimination d'azote et de concentration d'hélium, et au moins un moyen de purification (13) en hélium situé en aval du dispositif (9) d'élimination d'azote et de concentration d'hélium, caractérisée en ce que le moyen (5) d'élimination d'hydrogène et de méthane est situé en aval dudit au moins un compresseur (3) et en amont du dispositif (9) d'élimination d'azote et de concentration d'hélium. 14. Installation for producing helium from a mixture of source gas (1) comprising methane, helium, hydrogen and nitrogen comprising at least one compressor (3) directly receiving the mixture of source gas (1), at least one means (5) for removing hydrogen and methane, at least one device (9) for eliminating nitrogen and helium concentration, and at least one means for purification (13) in helium located downstream of the device (9) for removing nitrogen and helium concentration, characterized in that the means (5) for removing hydrogen and methane is located downstream of said at least one compressor (3) and upstream of the device (9) for removing nitrogen and concentrating helium.
15. Installation selon la revendication précédente caractérisée en ce qu'elle comprend en outre un dispositif (17) de liquéfaction d'hélium en aval du moyen de purification (13) en hélium. 15. Installation according to the preceding claim characterized in that it further comprises a device (17) for liquefying helium downstream of the purification means (13) in helium.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018002247A1 (en) * 2018-03-20 2019-09-26 Linde Aktiengesellschaft Extraction of helium or helium and neon from natural gas

Families Citing this family (8)

* 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
FR3104564B1 (en) 2019-12-12 2022-03-04 Air Liquide Gas purification method and device
RU2740992C1 (en) * 2020-05-28 2021-01-22 Андрей Владиславович Курочкин Apparatus for concentrating and purifying helium
CN112023618A (en) * 2020-07-22 2020-12-04 中国石油天然气股份有限公司西南油气田分公司成都天然气化工总厂 Crude helium refining system and method
CN112093782A (en) * 2020-07-31 2020-12-18 辉门环新（安庆）粉末冶金有限公司 Nitrogen purification system and nitrogen purification method
CN111964354B (en) * 2020-08-10 2021-09-10 中船重工鹏力（南京）超低温技术有限公司 Method for separating and purifying helium gas by removing methane and nitrogen
CN113144821A (en) * 2021-04-27 2021-07-23 大连理工大学 Multi-technology integrated separation process for producing high-purity helium gas from helium-rich natural gas liquefaction tail gas
CN113247873B (en) * 2021-06-02 2022-07-01 四川杰瑞恒日天然气工程有限公司 Recovery system and method for helium in natural gas

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5787730A (en) * 1996-08-23 1998-08-04 Praxair Technology, Inc. Thermal swing helium purifier and process
JP2012031049A (en) * 2010-07-07 2012-02-16 Sumitomo Seika Chem Co Ltd Method and apparatus for purifying helium gas
JP2012162444A (en) * 2011-01-21 2012-08-30 Sumitomo Seika Chem Co Ltd Refining method and refining apparatus of helium gas
DE102012000147A1 (en) * 2012-01-05 2013-07-11 Linde Aktiengesellschaft Method for obtaining a helium pure fraction

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4659351A (en) * 1986-01-29 1987-04-21 Air Products And Chemicals, Inc. Combined process to produce liquid helium, liquid nitrogen, and gaseous nitrogen from a crude helium feed
US4666481A (en) * 1986-03-10 1987-05-19 Union Carbide Corporation Process for producing liquid helium
JP3277340B2 (en) * 1993-04-22 2002-04-22 日本酸素株式会社 Method and apparatus for producing various gases for semiconductor manufacturing plants
US5339641A (en) * 1993-07-07 1994-08-23 Praxair Technology, Inc. Cryogenic liquid nitrogen production system
US9791210B2 (en) * 2012-08-02 2017-10-17 Air Products And Chemicals, Inc. Systems and methods for recovering helium from feed streams containing carbon dioxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5787730A (en) * 1996-08-23 1998-08-04 Praxair Technology, Inc. Thermal swing helium purifier and process
JP2012031049A (en) * 2010-07-07 2012-02-16 Sumitomo Seika Chem Co Ltd Method and apparatus for purifying helium gas
JP2012162444A (en) * 2011-01-21 2012-08-30 Sumitomo Seika Chem Co Ltd Refining method and refining apparatus of helium gas
DE102012000147A1 (en) * 2012-01-05 2013-07-11 Linde Aktiengesellschaft Method for obtaining a helium pure fraction
AU2013200075A1 (en) 2012-01-05 2013-07-18 Aktiengesellschaft, Linde Process for obtaining a pure helium fraction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018002247A1 (en) * 2018-03-20 2019-09-26 Linde Aktiengesellschaft Extraction of helium or helium and neon from natural gas

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