EP3322949B1 - Production d'hélium à partir d'un courant de gaz naturel - Google Patents

Production d'hélium à partir d'un courant de gaz naturel Download PDF

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Publication number
EP3322949B1
EP3322949B1 EP16750950.4A EP16750950A EP3322949B1 EP 3322949 B1 EP3322949 B1 EP 3322949B1 EP 16750950 A EP16750950 A EP 16750950A EP 3322949 B1 EP3322949 B1 EP 3322949B1
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EP
European Patent Office
Prior art keywords
helium
volume
column
pressure
process according
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Application number
EP16750950.4A
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German (de)
English (en)
French (fr)
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EP3322949A1 (fr
Inventor
Paul Terrien
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication of EP3322949A1 publication Critical patent/EP3322949A1/fr
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    • 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
    • F25J3/0233—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 CnHm with 1 carbon atom or more
    • 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
    • F25J3/0238—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 CnHm with 2 carbon atoms or more
    • 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
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
    • F25J2200/06—Processes or apparatus using separation by rectification in a dual pressure main column system in a classical double column flow-sheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • 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
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/60—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (a mixture of) 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids

Definitions

  • the present invention relates to a process for producing helium from a source gas stream comprising at least helium, methane and nitrogen.
  • Helium is obtained commercially almost exclusively from a mixture of the 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.
  • helium is made available as a component of the gas that accompanies the mineral oil, or as part of the production of natural gas. It is theoretically possible to obtain helium from the atmosphere, but it is not economical due to the low concentrations (typical concentration of helium in air around 5.2 ppmv).
  • Raw natural gas can contain a large number of troublesome impurities to remove.
  • An example is nitrogen. From a certain concentration of nitrogen in the natural gas, it is typically not salable because of its low calorific value. To remove the nitrogen, most often a cryogenic process is used, carried out in a unit called a Nitrogen Rejection Unit (NRU).
  • NRU Nitrogen Rejection Unit
  • the helium is concentrated in the cryogenic process to finally purify it in a process by PSA type adsorption (in English Pressure Swing Adsorption).
  • the solution that is the subject of the present invention makes it possible to separate a stream composed of methane, nitrogen and helium into three streams of pure methane, pure nitrogen and rich in helium.
  • the present invention makes it possible to solve the problem of solutions by partial condensation by obtaining both a high yield (>85%) and a high helium content (>50%) and this without using a column dedicated to the separation of the helium.
  • the process that is the subject of the invention consists of a double-column NRU unit in which condensing is completely (or almost due to the presence of incondensables) at the level of the condenser of the high-pressure column HP.
  • the liquid produced at the top of this HP column is partly used as reflux of the HP column and partly intended to be used as reflux of the low-pressure column LP.
  • the particularity of the invention is to expand the liquid produced and not used as reflux of the HP column to an intermediate pressure in order to "flash” or vaporize instantaneously (by “flash” gas we mean: instantaneous vapor) all the desired helium in a first helium separator pot (yield control) then to carry out a partial condensation of the gas of said "flash" (or instantaneous vapor) to obtain a gas having a high helium content in a second separator pot helium.
  • a source gas stream 1 comprising at least helium, methane, and nitrogen is introduced at a pressure of approximately 50 bar absolute into a heat exchanger 2.
  • the stream 3 at the outlet of said exchanger 2 is expanded using, for example, a valve 4 before being introduced into a high pressure column 5 of a double column unit 6 comprising a distillation column 5 at high pressure, a column of distillation 7 at low pressure and a condenser 8 connecting the column 5 at high pressure with the column 7 at low pressure.
  • the source gas stream 1 comprises for 100% by volume, for example, from 20% by volume to 80% by volume of methane, from 20% by volume to 80% by volume of nitrogen and from 1 ppm by volume to 1% by volume of helium.
  • the pressure of the high pressure column is for example 30 bara and the pressure in the low pressure column is for example 2 bara.
  • the term nitrogen rejection unit relates to a device in which nitrogen and methane are separated cryogenic rectification.
  • a part (3d) of the stream 3 being introduced mainly in liquid form and a part (3c) is introduced mainly in gaseous form in the tank.
  • column 5 to vaporize the helium that would otherwise be entrained in the liquid methane.
  • a part 9 of the liquid stream 11 leaving the condenser 8 located in the lower part of the low pressure column 7 is used as reflux in the upper part 10 of the high pressure column 5.
  • the rest of the liquid 11 is cooled then expanded to be used directly as reflux of the low-pressure column.
  • the object of the present invention consists in using a part 12 of said liquid stream 11 to extract the helium therefrom before using it as reflux of the low pressure column.
  • This liquid stream 11 typically contains less than 2% by volume of methane, more than 95% by volume of nitrogen and from 0.5% by volume to 3% by volume of helium.
  • the temperature of the liquid stream 12 is for example between -150°C and -165°C.
  • This liquid stream 12 is expanded to an intermediate pressure using, for example, a valve 13.
  • This intermediate pressure is typically around 8 bara to 15 bara. For example 12 bara.
  • the stream 14 thus produced contains a majority of liquid and a minority of gas.
  • This gas is enriched with helium.
  • This helium-enriched gas comprises at least 80% by volume of the helium contained in the liquid stream 12.
  • the two-phase stream 14 is introduced into a first pot 15 phase separator.
  • the pot 15 produces a liquid stream 16 and a gas stream 17.
  • the gas stream 17 contains more than 80% by volume of the helium contained in the source stream 1.
  • this gas stream 17 contains nitrogen.
  • the liquid stream 16 containing a majority of nitrogen, but also helium and methane is introduced into the upper part 18 of the column 7 at low pressure after having been expanded, for example using a valve 19 in order to serve as reflux of column 7 at low pressure.
  • the stream 20 at the outlet of the head 21 of the column 7 is introduced into a heat exchanger 22 or 2 in order to produce a stream 23 rich in nitrogen or even pure in nitrogen containing no helium and containing less than 1.5% in volume of methane.
  • the helium-enriched gas stream 17 typically contains more than 70% by volume of nitrogen, more than 5% by volume of helium and less than 2% by volume of methane, for example 90% by volume of nitrogen, of 8 % to 10% by volume helium and less than 0.5% by volume methane.
  • This gas stream 17 is introduced into a heat exchanger 24 in order to be at least partially condensed.
  • the mixture 25 thus condensed is introduced into a second phase separator pot 26.
  • a gas stream 27 is extracted.
  • This gas stream 27 comprises more than 50% by volume of helium, preferably more than 60% by volume of helium and more particularly more than 70% by volume of helium.
  • the gas stream 27 can optionally pass through a heat exchanger 24.
  • the liquid phase 28 coming from the separator 26 is used to cool the exchanger 24 after having been expanded to a pressure below 3 bara, for example using a pressure reducer such as a valve 29.
  • This liquid stream 28 is pure in nitrogen, for example it contains more than 99% by volume of nitrogen.
  • the installation 31 comprising the nitrogen rejection unit 6 and the helium extraction unit 30 as illustrated in figure 1 and according to a method that is the subject of the invention as described above, with a source stream 1 containing approximately 50% by volume of nitrogen, 50% by volume of methane and 0.3% by volume of helium, a purity is obtained of helium in the stream 27 of about 74% by volume and a helium yield of about 91%.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation By Low-Temperature Treatments (AREA)
EP16750950.4A 2015-07-16 2016-07-12 Production d'hélium à partir d'un courant de gaz naturel Active EP3322949B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1556739A FR3038973B1 (fr) 2015-07-16 2015-07-16 Production d'helium a partir d'un courant de gaz naturel
PCT/FR2016/051786 WO2017009573A1 (fr) 2015-07-16 2016-07-12 Production d'hélium à partir d'un courant de gaz naturel

Publications (2)

Publication Number Publication Date
EP3322949A1 EP3322949A1 (fr) 2018-05-23
EP3322949B1 true EP3322949B1 (fr) 2022-02-23

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP16750950.4A Active EP3322949B1 (fr) 2015-07-16 2016-07-12 Production d'hélium à partir d'un courant de gaz naturel

Country Status (6)

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US (1) US20180209725A1 (ru)
EP (1) EP3322949B1 (ru)
FR (1) FR3038973B1 (ru)
PL (1) PL3322949T3 (ru)
RU (1) RU2717666C2 (ru)
WO (1) WO2017009573A1 (ru)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2736682C1 (ru) * 2020-06-05 2020-11-19 Андрей Владиславович Курочкин Установка подготовки природного газа с извлечением гелия
CN111981767B (zh) * 2020-08-20 2024-03-08 中国石油工程建设有限公司 一种天然气单塔深冷提氦装置和方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU127270A1 (ru) * 1959-05-18 1959-11-30 Л.С. Бабе Способ извлечени гели из природного газа
US4701201A (en) * 1986-09-24 1987-10-20 Union Carbide Corporation Process to produce cold helium gas for liquefaction
US4701200A (en) * 1986-09-24 1987-10-20 Union Carbide Corporation Process to produce helium gas
US4948405A (en) * 1989-12-26 1990-08-14 Phillips Petroleum Company Nitrogen rejection unit
GB2298034B (en) * 1995-02-10 1998-06-24 Air Prod & Chem Dual column process to remove nitrogen from natural gas
US5771714A (en) * 1997-08-01 1998-06-30 Praxair Technology, Inc. Cryogenic rectification system for producing higher purity helium
FR2936864B1 (fr) * 2008-10-07 2010-11-26 Technip France Procede de production de courants d'azote liquide et gazeux, d'un courant gazeux riche en helium et d'un courant d'hydrocarbures deazote et installation associee.
WO2010042266A1 (en) * 2008-10-07 2010-04-15 Exxonmobil Upstream Research Company Helium recovery from natural gas integrated with ngl recovery
RU2502545C1 (ru) * 2012-08-08 2013-12-27 Открытое акционерное общество "Газпром" Способ переработки природного газа и устройство для его осуществления

Also Published As

Publication number Publication date
FR3038973B1 (fr) 2019-09-27
WO2017009573A1 (fr) 2017-01-19
RU2018103764A (ru) 2019-07-31
EP3322949A1 (fr) 2018-05-23
FR3038973A1 (fr) 2017-01-20
RU2717666C2 (ru) 2020-03-24
US20180209725A1 (en) 2018-07-26
PL3322949T3 (pl) 2022-07-25
RU2018103764A3 (ru) 2019-10-29

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