EP3322949B1 - Production of helium from a stream of natural gas - Google Patents
Production of helium from a stream of natural gas Download PDFInfo
- 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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- helium
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- 239000001307 helium Substances 0.000 title claims description 69
- 229910052734 helium Inorganic materials 0.000 title claims description 69
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title claims description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 52
- 239000003345 natural gas Substances 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- 239000007789 gas Substances 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 6
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003507 refrigerant Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 17
- 238000000605 extraction Methods 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 230000036961 partial effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 5
- 239000007792 gaseous phase Substances 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000002371 helium Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
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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
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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
- F25J3/0228—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
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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
- F25J3/0228—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
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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
- F25J3/0228—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
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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
- F25J3/0228—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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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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- Mechanical Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Separation By Low-Temperature Treatments (AREA)
Description
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 et de l'azote.The present invention relates to a process for producing helium from a source gas stream comprising at least helium, methane and nitrogen.
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.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.
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).During the production of mineral oil, 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).
Le gaz naturel brut peut contenir un grand nombre d'impuretés gênantes à retirer. L'azote en est un exemple. A partir d'une certaine concentration d'azote dans le gaz naturel, celui-ci n'est typiquement pas vendable à cause de son faible pouvoir calorifique. Pour retirer l'azote on utilise le plus souvent un procédé cryogénique mis en œuvre dans une unité appelée unité de rejet d'azote [en anglais : Nitrogen Rejection Unit (NRU)].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).
Si en plus de l'azote, il y a de l'hélium dans le gaz naturel, il y a un intérêt économique à extraire un courant riche en hélium séparément pour produire de l'hélium et le commercialiser. Typiquement, on concentre l'hélium dans le procédé cryogénique pour finalement le purifier dans un procédé par adsorption type PSA (en anglais Pressure Swing Adsorption).If in addition to nitrogen there is helium in the natural gas, there is an economic interest in extracting a helium-rich stream separately to produce helium and market it. Typically, the helium is concentrated in the cryogenic process to finally purify it in a process by PSA type adsorption (in English Pressure Swing Adsorption).
Plusieurs solutions existent aujourd'hui pour l'extraction de l'hélium dans une NRU, en particulier dans une unité NRU dite à double colonne.Several solutions exist today for the extraction of helium in an NRU, in particular in a so-called double-column NRU unit.
Il est possible d'ajouter une colonne pour distiller l'azote et l'hélium, tel que cela est décrit dans le brevet
- Complexification de l'installation.
- Consommation énergétique augmentée à cause du besoin en réfrigération (cycle) lié à cette colonne.
- Complexity of the installation.
- Increased energy consumption due to the need for refrigeration (cycle) linked to this column.
D'autres solutions existent en utilisant des condensations partielles et/ou des vaporisations instantanées (flashs) successives mais celles-ci ne permettent en général pas d'avoir à la fois une forte teneur en hélium et un haut rendement. Un tel exemple est décrit dans le brevet
Il existe donc un besoin de résoudre les problèmes décrits ci-dessus.There is therefore a need to solve the problems described above.
C'est pourquoi la présente invention a pour objet un procédé de production d'un courant gazeux d'hélium à partir d'un courant gazeux source comprenant au moins de l'hélium, du méthane, et de l'azote, comprenant au moins les étapes suivantes :
- Etape a) : introduction dudit courant gazeux source dans une unité de rejet d'azote à double colonne, ladite double colonne comprenant une colonne de distillation à haute pression, une colonne de distillation à basse pression et un condenseur mettant en relation la colonne à haute pression avec la colonne à basse pression ;
- Etape b) : extraction en sortie dudit condenseur d'au moins une partie d'un mélange produit en tête de colonne à haute pression ;
- Etape c) : détente dudit mélange issu de l'étape b) à une pression intermédiaire comprise entre 8 bars et 20 bars absolus
- Etape d) : séparation du mélange issu de l'étape c) dans un premier pot séparateur de phases en une phase liquide et une phase gazeuse enrichie en hélium ;
- Etape e) : condensation au moins partielle de ladite phase gazeuse enrichie en hélium dans un échangeur de chaleur ;
- Etape f) : séparation du courant issu de l'étape e) dans un deuxième pot séparateur de phases en une phase liquide et une phase gazeuse contenant plus de 50% en volume d'hélium.
- Step a): introduction of said source gas stream into a double column nitrogen rejection unit, said double column comprising a high pressure distillation column, a low pressure distillation column and a condenser connecting the high pressure column pressure with low pressure column;
- Stage b): extraction at the outlet of said condenser of at least part of a mixture produced at the top of the high pressure column;
- Stage c): expansion of said mixture resulting from stage b) at an intermediate pressure of between 8 bars and 20 bars absolute
- Step d): separation of the mixture resulting from step c) in a first phase separator pot into a liquid phase and a gaseous phase enriched in helium;
- Step e): at least partial condensation of said helium-enriched gaseous phase in a heat exchanger;
- Step f): separation of the stream from step e) in a second phase separator pot into a liquid phase and a gaseous phase containing more than 50% by volume of helium.
Selon d'autres modes de réalisation, la présente invention a aussi pour objet :
- Un procédé tel que défini ci-dessus caractérisé en ce qu'il comprend une étape g) : utilisation, comme réfrigérant, de la phase liquide après détente issue de l'étape f) dans ledit échangeur de chaleur mis en œuvre à l'étape e).
- Un procédé tel que défini ci-dessus caractérisé en ce qu'au cours de l'étape g), ladite phase liquide est vaporisée à une pression comprise entre 0,1 bar et 3 bar absolus.
- Un procédé tel que défini ci-dessus caractérisé en ce qu'au cours de l'étape a) le courant gazeux est introduit dans la colonne à haute pression à au moins deux niveaux d'alimentation, la fraction vapeur de la première alimentation étant plus faible que la fraction vapeur de la seconde et la première alimentation étant introduite à un niveau plus élevée de ladite colonne à haute pression que la seconde .
- Un procédé tel que défini ci-dessus comprenant une étape h) : extraction de la phase gazeuse issue de l'étape f) comme produit riche en hélium, contenant au moins 75% en volume d'hélium.
- Un procédé tel que défini ci-dessus caractérisé en ce que la température en sortie de condenseur à l'étape b) est comprise entre - 150°C et - 165°C.
- Un procédé tel que défini ci-dessus caractérisé en ce que la pression dans la colonne à haute pression est comprise entre 20 bars absolus et 50 bars absolus et la pression dans la colonne à basse pression est comprise entre 1 bar absolu et 5 bars absolus.
- Un procédé tel que défini ci-dessus caractérisé en ce que la température de mise en œuvre de l'étape c) est comprise entre - 160°C et - 180°C.
- Un procédé tel que défini ci-dessus caractérisé en que la température de mise en œuvre de l'étape e) est comprise entre - 180°C et - 210°C.
- Un procédé tel que défini ci-dessus caractérisé en ce que la phase liquide issue de l'étape d) est introduite dans la colonne à basse pression de ladite unité de rejet.
- Un procédé tel que défini ci-dessus comprenant une étape supplémentaire de production d'un courant enrichi en azote comprenant moins de 2% en volume de méthane à partir d'un courant gazeux issu de la tête de la colonne à basse pression.
- Un procédé tel que défini ci-dessus caractérisé en ce que courant gazeux source comprend de 20% en volume à 80 % en volume de méthane, de 20% en volume à 80% en volume d'azote et de 0% en volume à 2% en volume d'hélium.
- A method as defined above characterized in that it comprises a step g): use, as refrigerant, of the liquid phase after expansion from step f) in said heat exchanger implemented in step e).
- A method as defined above characterized in that during step g), said liquid phase is vaporized at a pressure of between 0.1 bar and 3 bar absolute.
- A process as defined above characterized in that during step a) the gas stream is introduced into the high pressure column at at least two feed levels, the vapor fraction of the first feed being more lower than the vapor fraction of the second and the first feed being introduced at a higher level of said high pressure column than the second.
- A process as defined above comprising a step h): extraction of the gaseous phase resulting from step f) as a product rich in helium, containing at least 75% by volume of helium.
- A process as defined above characterized in that the temperature at the condenser outlet in step b) is between -150°C and -165°C.
- A process as defined above characterized in that the pressure in the high pressure column is between 20 bar absolute and 50 bar absolute and the pressure in the low pressure column is between 1 bar absolute and 5 bar absolute.
- A method as defined above characterized in that the temperature for implementing step c) is between -160°C and -180°C.
- A method as defined above characterized in that the temperature for implementing step e) is between -180°C and -210°C.
- A method as defined above characterized in that the liquid phase resulting from step d) is introduced into the low pressure column of the said rejection unit.
- A process as defined above comprising an additional step of producing a nitrogen-enriched stream comprising less than 2% by volume of methane from a gas stream from the top of the low-pressure column.
- A process as defined above characterized in that the source gas stream comprises from 20% by volume to 80% by volume of methane, from 20% by volume to 80% by volume of nitrogen and from 0% by volume to 2 % by volume of helium.
La solution objet de la présente invention permet de séparer un courant composé de méthane, d'azote et d'hélium en trois courants de méthane pur, azote pur et riche en hélium.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.
La présente invention permet de résoudre le problème des solutions par condensation partielle en obtenant à la fois un fort rendement (>85%) et une forte teneur en hélium (>50%) et ceci sans utiliser une colonne dédiée à la séparation de l'hélium.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.
L'intégration de l'extraction d'hélium dans une unité NRU avec un schéma à double colonne permet de minimiser le coût des équipements et la consommation énergétique de l'unité d'extraction d'hélium (helium rejection unit, HRU) sans pénaliser la consommation et le cout d'installation des autres équipements de la NRU.The integration of helium extraction in an NRU unit with a double column scheme makes it possible to minimize the cost of equipment and the energy consumption of the helium extraction unit (helium rejection unit, HRU) without penalizing consumption and installation cost of other NRU equipment.
Le procédé objet de l'invention consiste en une unité NRU double colonne dans lequel on condense totalement (ou presque en raison de la présence d'incondensables) au niveau du condenseur de la colonne à haute pression HP. Le liquide produit en tête de cette colonne HP est en partie utilisé comme reflux de la colonne HP et en partie destiné à être utilisé comme reflux de la colonne à basse pression BP.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.
La particularité de l'invention est de détendre le liquide produit et non utilisé comme reflux de la colonne HP à une pression intermédiaire pour ainsi « flasher» ou vaporiser instantanément (par gaz de « flash », on entend : vapeur instantanée) tout l'hélium désiré dans un premier pot séparateur d'hélium (contrôle du rendement) puis d'effectuer une condensation partielle du gaz dudit « flash » (ou vapeur instantanée) pour obtenir un gaz ayant une forte teneur en hélium dans un deuxième pot séparateur d'hélium.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.
On pourra avantageusement produire le froid nécessaire à la condensation partielle du « flash » (vapeur instantanée) issu du premier pot séparateur d'hélium en vaporisant à basse pression le liquide de cuve du deuxième pot séparateur d'hélium.It will be possible advantageously to produce the cold necessary for the partial condensation of the “flash” (instantaneous steam) coming from the first helium separator pot by vaporizing the bottom liquid of the second helium separator pot at low pressure.
Le procédé objet de la présente invention est illustré sur la
Sur la
Le courant gazeux source 1 comprend pour 100% en volume, par exemple, de 20% en volume à 80% en volume de méthane, de 20% en volume à 80% en volume d'azote et de 1 ppmen volume à 1% en volume d'hélium.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.
La pression de la colonne à haute pression est par exemple de 30 bara et la pression dans la colonne à basse pression est par exemple de 2 bara.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.
Le principe d'une unité à double colonne est largement décrit dans l'état de la technique, par exemple dans le document de
Le terme unité de rejet d'azote est relatif à un dispositif dans lequel l'azote et le méthane sont séparés rectification cryogénique.The term nitrogen rejection unit relates to a device in which nitrogen and methane are separated cryogenic rectification.
Pour augmenter le rendement en hélium on peut en outre faire une introduction multiple dans la colonne à haute pression 5 : une partie (3d) du courant 3 étant introduite majoritairement sous forme liquide et une partie (3c) est introduite majoritairement sous forme gazeuse en cuve de colonne 5 pour vaporiser l'hélium qui serait autrement entraîné dans le méthane liquide.To increase the yield of helium, it is also possible to make a multiple introduction into the high pressure column 5: a part (3d) of the
Une partie 9 du courant liquide 11 sortant du condenseur 8 situé en partie basse de la colonne 7 à basse pression est utilisé comme reflux dans la partie haute 10 de la colonne 5 à haute pression. Dans un schéma NRU double colonne classique, le reste du liquide 11 est refroidi puis détendu pour être directement utilisé comme reflux de la colonne basse pression. L'objet de la présente invention consiste à utiliser une partie 12 dudit courant liquide 11 pour en extraire l'hélium avant de l'utiliser comme reflux de la colonne à basse pression.A
Ce courant liquide 11 contient typiquement moins de 2% en volume de méthane, plus de 95% en volume d'azote et de 0,5% en volume à 3% en volume d'hélium.This
La température du courant liquide 12 est par exemple comprise entre - 150°C et - 165°C.The temperature of the
Ce courant liquide 12 est détendu à une pression intermédiaire à l'aide, par exemple, d'une vanne 13. Cette pression intermédiaire est typiquement de l'ordre de 8 bara à 15 bara. Par exemple 12 bara.This
Par cette détente, le courant liquide a été vaporisé, c'est-à-dire que du gaz a été formé instantanément (il s'agit de gaz de « flash »). Le courant 14 ainsi produit contient une majorité de liquide et une minorité de gaz. Ce gaz est enrichi en hélium. Ce gaz enrichi en hélium comporte au moins 80% en volume de l'hélium contenu dans le courant liquide 12. Le courant diphasique 14 est introduit dans un premier pot 15 séparateur de phases. Le pot 15 produit un courant liquide 16 et un courant gazeux 17. Le courant gazeux 17 contient plus de 80% en volume de l'hélium contenu dans le courant source 1.Through this expansion, the liquid stream was vaporized, ie gas was formed instantaneously (this is “flash” gas). The
Néanmoins, ce courant gazeux 17 contient de l'azote. Le courant liquide 16 contenant une majorité d'azote, mais aussi de l'hélium et du méthane est introduit dans la partie haute 18 de la colonne 7 à basse pression après avoir été détendu, par exemple à l'aide d'une vanne 19 afin de servir de reflux de la colonne 7 à basse pression. Le courant 20 en sortie de la tête 21 de la colonne 7 est introduit dans un échangeur de chaleur 22 ou 2 afin de produire un courant 23 riche en azote voire pur en azote ne contenant pas d'hélium et contenant moins de 1,5% en volume de méthane.Nevertheless, this
Le courant gazeux 17 enrichi en hélium contient typiquement plus de 70% en volume d'azote, plus de 5% en volume d'hélium et moins de 2% en volume de méthane, par exemple 90% en volume d'azote, de 8% à 10% en volume d'hélium et moins de 0,5% en volume de méthane. Ce courant gazeux 17 est introduit dans un échangeur 24 de chaleur afin d'être condensé au moins partiellement. Le mélange 25 ainsi condensé est introduit dans un deuxième pot séparateur de phases 26. En tête du séparateur 26, un courant gazeux 27 est extrait. Ce courant gazeux 27 comporte plus de 50% en volume d'hélium, de préférence plus de 60% en volume d'hélium et plus particulièrement plus de 70% en volume d'hélium. Le courant gazeux 27 peut, optionnellement repasser dans un échangeur de chaleur 24.The helium-enriched
La phase liquide 28 issue du séparateur 26 sert à refroidir l'échangeur 24 après avoir été détendu à une pression inférieure à 3 bara, par exemple à l'aide d'un détendeur tel qu'une vanne 29. Ce courant liquide 28 est pur en azote, par exemple il contient plus de 99% en volume d'azote.The
Grâce à l'installation 31 comprenant l'unité 6 de rejet d'azote et l'unité 30 d'extraction d'hélium telle qu'illustrée en
Claims (12)
- Process for producing a helium gas stream (27) from a source gas stream (1) comprising at least helium, methane and nitrogen, comprising at least the following steps:step a) : introducing said source gas stream (1) into a double-column nitrogen rejection unit (6), said double column comprising a high-pressure distillation column (5), a low-pressure distillation column (7) and a condenser (8) linking the high-pressure column (5) with the low-pressure column (7);step b) : extracting at the outlet of said condenser (8) at least one part (12) of a mixture (11) produced at the top of the high-pressure column (5);step c): expanding said mixture resulting from step b) to an intermediate pressure of between 8 bar and 20 bar absolute;step d): separating the mixture (14) resulting from step c) in a first phase separator vessel (15) into a liquid phase (16) and a helium-enriched gas phase (17);step e) : at least partially condensing said helium-enriched gas phase (17) in a heat exchanger (24) ;step f): separating the stream (25) resulting from step e) in a second phase separator vessel (26) into a liquid phase (28) and a gas phase (27) containing more than 50% by volume of helium.
- Process according to the preceding claim, characterized in that it comprises a step g): using, as refrigerant, the liquid phase (28) after expansion resulting from step f) in said heat exchanger (24) used in step e).
- Process according to Claim 2, characterized in that, during step g), said liquid phase (28) is vaporized at a pressure of between 0.1 bar and 3 bar absolute.
- Process according to one of the preceding claims, characterized in that, during step a), the gas stream is introduced into the high-pressure column (5) at at least two feed levels, the vapor fraction of the first feed (3d) being smaller than the vapor fraction of the second (3c) and the first feed (3d) being introduced at a higher level of said high-pressure column (5) than the second (3c).
- Process according to one of the preceding claims, comprising a step h): extracting the gas phase (27) resulting from step f) as helium-rich product containing at least 75% by volume of helium.
- Process according to the preceding claim, characterized in that the temperature at the outlet of the condenser (8) in step b) is between -150°C and -165°C.
- Process according to the preceding claim, characterized in that the pressure in the high-pressure column (5) is between 20 bar absolute and 50 bar absolute and the pressure in the low-pressure column is between 1 bar absolute and 5 bar absolute.
- Process according to any one of the preceding claims, characterized in that the temperature at which step c) is carried out is between -160°C and -180°C.
- Process according to any one of the preceding claims, characterized in that the temperature at which step e) is carried out is between -180°C and -210°C.
- Process according to any one of the preceding claims, characterized in that the liquid phase (16) resulting from step d) is introduced into the low-pressure column (7) of said rejection unit (6).
- Process according to any one of the preceding claims, comprising an additional step of producing a nitrogen-enriched stream (23) comprising less than 2% by volume of methane from a gas stream (20) from the top (21) of the low-pressure column (7).
- Process according to any one of the preceding claims, characterized in that said source gas stream (1) comprises from 20% by volume to 80% by volume of methane, from 20% by volume to 80% by volume of nitrogen and from 0% by volume to 2% by volume of helium.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1556739A FR3038973B1 (en) | 2015-07-16 | 2015-07-16 | HELIUM PRODUCTION FROM NATURAL GAS CURRENT |
PCT/FR2016/051786 WO2017009573A1 (en) | 2015-07-16 | 2016-07-12 | Production of helium from a stream of natural gas |
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EP3322949A1 EP3322949A1 (en) | 2018-05-23 |
EP3322949B1 true EP3322949B1 (en) | 2022-02-23 |
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EP16750950.4A Active EP3322949B1 (en) | 2015-07-16 | 2016-07-12 | Production of helium from a stream of natural gas |
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US (1) | US20180209725A1 (en) |
EP (1) | EP3322949B1 (en) |
FR (1) | FR3038973B1 (en) |
PL (1) | PL3322949T3 (en) |
RU (1) | RU2717666C2 (en) |
WO (1) | WO2017009573A1 (en) |
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RU2736682C1 (en) * | 2020-06-05 | 2020-11-19 | Андрей Владиславович Курочкин | Natural gas preparation unit with helium extraction |
CN111981767B (en) * | 2020-08-20 | 2024-03-08 | 中国石油工程建设有限公司 | Natural gas single-tower cryogenic helium extraction device and method |
Family Cites Families (9)
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SU127270A1 (en) * | 1959-05-18 | 1959-11-30 | Л.С. Бабе | Method of extracting gels from natural gas |
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 (en) * | 2008-10-07 | 2010-11-26 | Technip France | PROCESS FOR THE PRODUCTION OF LIQUID AND GASEOUS NITROGEN CURRENTS, A HELIUM RICH GASEOUS CURRENT AND A DEAZOTE HYDROCARBON CURRENT, AND ASSOCIATED PLANT. |
WO2010042266A1 (en) * | 2008-10-07 | 2010-04-15 | Exxonmobil Upstream Research Company | Helium recovery from natural gas integrated with ngl recovery |
RU2502545C1 (en) * | 2012-08-08 | 2013-12-27 | Открытое акционерное общество "Газпром" | Method of natural gas processing and device to this end |
-
2015
- 2015-07-16 FR FR1556739A patent/FR3038973B1/en not_active Expired - Fee Related
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2016
- 2016-07-12 US US15/744,987 patent/US20180209725A1/en not_active Abandoned
- 2016-07-12 PL PL16750950.4T patent/PL3322949T3/en unknown
- 2016-07-12 RU RU2018103764A patent/RU2717666C2/en active
- 2016-07-12 WO PCT/FR2016/051786 patent/WO2017009573A1/en active Application Filing
- 2016-07-12 EP EP16750950.4A patent/EP3322949B1/en active Active
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FR3038973B1 (en) | 2019-09-27 |
WO2017009573A1 (en) | 2017-01-19 |
RU2018103764A (en) | 2019-07-31 |
EP3322949A1 (en) | 2018-05-23 |
FR3038973A1 (en) | 2017-01-20 |
RU2717666C2 (en) | 2020-03-24 |
US20180209725A1 (en) | 2018-07-26 |
PL3322949T3 (en) | 2022-07-25 |
RU2018103764A3 (en) | 2019-10-29 |
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