EP2532941B2 - Method for packaging NO/N2 mixtures with draining stages and prior rinsing with gas - Google Patents

Method for packaging NO/N2 mixtures with draining stages and prior rinsing with gas Download PDF

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Publication number
EP2532941B2
EP2532941B2 EP12166496.5A EP12166496A EP2532941B2 EP 2532941 B2 EP2532941 B2 EP 2532941B2 EP 12166496 A EP12166496 A EP 12166496A EP 2532941 B2 EP2532941 B2 EP 2532941B2
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European Patent Office
Prior art keywords
container
bar
gas
pressure
steps
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German (de)
French (fr)
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EP2532941B1 (en
EP2532941A1 (en
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Pierre de Villemeur
Joël Samirant
Celso Zerbinatti
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Air Liquide Sante International SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Air Liquide Sante France SA
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Air Liquide Sante International SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Air Liquide Sante France SA
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C5/00—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
    • F17C5/002—Automated filling apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/056—Small (<1 m3)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/058—Size portable (<30 l)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0639—Steels
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/014—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0146—Two-phase
    • F17C2223/0153—Liquefied gas, e.g. LPG, GPL
    • F17C2223/0161—Liquefied gas, e.g. LPG, GPL cryogenic, e.g. LNG, GNL, PLNG
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/01—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the phase
    • F17C2225/0107—Single phase
    • F17C2225/0123—Single phase gaseous, e.g. CNG, GNC
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/03—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the pressure level
    • F17C2225/036—Very high pressure, i.e. above 80 bars
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/01—Propulsion of the fluid
    • F17C2227/0128—Propulsion of the fluid with pumps or compressors
    • F17C2227/0135—Pumps
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03—Heat exchange with the fluid
    • F17C2227/0302—Heat exchange with the fluid by heating
    • F17C2227/0309—Heat exchange with the fluid by heating using another fluid
    • F17C2227/0311—Air heating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/04—Methods for emptying or filling
    • F17C2227/044—Methods for emptying or filling by purging
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2265/00—Effects achieved by gas storage or gas handling
    • F17C2265/01—Purifying the fluid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/02—Applications for medical applications
    • F17C2270/025—Breathing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/05—Applications for industrial use
    • F17C2270/059—Mass bottling, e.g. merry belts

Definitions

  • the invention relates to a method of conditioning a NO / N 2 gas mixture in a container, in particular one or more gas bottles, comprising several successive purge and gaseous rinsing steps.
  • Gaseous NO / N 2 mixtures are commonly used to treat pulmonary vasoconstriction in adults or children, particularly in neonates with primary pulmonary hypertension or in patients undergoing cardiac surgery.
  • NO / N 2 mixtures are conventionally packaged in steel gas cylinders. Typically, these bottles contain 100 to 1000 ppm by volume of NO and nitrogen (N 2 ) for the rest. These bottles usually have a water capacity of 2 to 50 liters, which allows to introduce a total load of up to 15 m 3 of NO / N 2 mixture.
  • the packaging that is to say the bottling of these mixtures, is done in gas conditioning centers, as for example in the documents FR 2914393 and US 20030012709 .
  • the packaging of these mixtures is not always easy to achieve industrially.
  • the gaseous mixture NO / N2 is sensitive to the presence of residual oxygen-type impurities that may be present in the bottles during their filling.
  • the problem is therefore to propose an improved packaging method making it possible to eliminate all or almost all the impurities, in particular oxygen, which may be in one or more gas cylinders to receive an NO type gas mixture. / N 2 .
  • the solution of the invention is then a method for conditioning a gaseous mixture NO / N 2 in at least one container, in particular one or more gas bottles, according to claim 1.
  • the pressures given are absolute pressures.
  • the Figure 1 schematizes an embodiment of a conditioning cycle applicable in the context of the gaseous mixture conditioning process NO / N 2 of the present invention.
  • this conditioning cycle comprises several successive steps, ranging over time from T0 to T13, which are applied to each bottle and which are detailed below.
  • the successive steps a) to c) of the process of the invention have been indicated on the Figure 1 .
  • the hoses of the installation are emptied in the open air, that is to say that the internal volume of the filling hoses is put in fluid communication with the ambient atmosphere to evacuate any residual overpressure .
  • the valve (s) of gas containers connected to the hoses are closed, therefore no gas exchange takes place with the container (s). This corresponds to step d) of the process.
  • a vacuum pump is used to put the inside of the hoses in connection vacuum, that is to say at a pressure below atmospheric pressure, for example of the order of 0.15 bar , which allows to evacuate the gas residual and / or air that are there.
  • connection vacuum that is to say at a pressure below atmospheric pressure, for example of the order of 0.15 bar , which allows to evacuate the gas residual and / or air that are there.
  • This phase is also realized closed tap. Vacuuming the hoses is a safety feature that makes it possible to check the correct connection of all hoses and the absence of leaks. Indeed, in case of leakage or incorrect connection of a hose vacuum will not be established stably. This corresponds to step e) of the process schematized in Figure 1 .
  • the operator opens the valve of each bottle and the residual pressure present in each bottle then goes up to the pressure sensor, which detects said rise in pressure.
  • the residual pressure of the bottle is of the order of about 3 to 4 bar absolute.
  • each bottle is vented, that is to say that is allowed to escape the gas contained in the bottle to the outside atmosphere simply by the effect of the pressure difference between inside and outside. outside of the bottle so as to bring the internal pressure of the bottle to atmospheric pressure.
  • the bottle is rinsed with nitrogen during which its internal pressure is increased to about 10 bar.
  • the addition of nitrogen is via a gas pipeline and / or nitrogen storage under pressure so as to bring the internal pressure of the bottle to the desired pressure. This corresponds to step c) of the process of the invention.
  • the bottle is purged by depressurizing its internal volume by withdrawing the residual gas therein by means of a vacuum pump until an internal negative pressure of less than 0.2 bar abs, preferably less than 0.1 bar, for example of the order of 0.05 bar. This corresponds to a new step b) of the process of the invention.
  • the bottle is re-rinsed with nitrogen until its internal pressure is approximately 10 bar, as between T4 and T5. This corresponds to a new step c) of the process of the invention.
  • the bottle undergoes a new exhaust towards the ambient atmosphere as during times T5 and T6.
  • the gaseous residual pressure is then maintained at approximately 1.35 bar to prevent untimely entry of atmospheric contaminants. This corresponds to a new step a) of the process of the invention.
  • the bottle is further rinsed with nitrogen until its internal pressure is about 10 bar, as before. This corresponds to a new step c) of the process of the invention.
  • a gaseous premix of NO and N 2 containing an NO content of less than 10% by volume until reaching a first filling pressure P1 with P1> 1 bar, typically a P1 pressure of the order of 2 to 10 bar abs, preferably from 3 to 5 bar abs about.
  • the gaseous premix consisting of NO and N 2 contains a NO content of the order of 4% by volume.
  • nitrogen containing gas is introduced into the vessel containing the NO / N 2 premix at the first pressure P1 until a final NO / N 2 gas mixture containing a content of NO less than or equal to at 1200 ppm by volume, for example a final NO content of 200 to 800 ppm, and a second pressure P2 between P1 and 800 bar, for example here a pressure of 180 to 200 bar.
  • This method can be implemented by means of a packaging installation such as that schematized in Figure 2 equipped with a ramp 14 for packaging gas containers, that is to say, gas cylinders, comprising connecting means 15 for filling several containers 11 to 13 at a time, typically from 2 to 20 bottles concomitantly .
  • a packaging installation such as that schematized in Figure 2 equipped with a ramp 14 for packaging gas containers, that is to say, gas cylinders, comprising connecting means 15 for filling several containers 11 to 13 at a time, typically from 2 to 20 bottles concomitantly .
  • the nitrogen is stored in the tank 1 in liquid form and then withdrawn in liquid form by a cryogenic pump 2 which compresses it to a pressure of the order of 100 to 300 bar, before sending it to an atmospheric heater 3 where it is vaporized to obtain nitrogen gas.
  • a cryogenic pump 2 which compresses it to a pressure of the order of 100 to 300 bar, before sending it to an atmospheric heater 3 where it is vaporized to obtain nitrogen gas.
  • it comprises a pipe or main line 20 for conveying nitrogen from a tank 1 to the ramp 14 of conditioning.
  • the pressure in the line varies between about 100 bar immediately downstream of the collapse of the buffer capacity in the bottles and about 260 bar which corresponds to the stopping threshold of the pump.
  • the nitrogen gas is then conveyed via line 20 to a purification device 6 for removing traces of O 2 and H 2 O, for example a suitable molecular sieve, for example of the zeolite, silica gel, alumina or analog, or mixtures thereof.
  • a purification device 6 for removing traces of O 2 and H 2 O, for example a suitable molecular sieve, for example of the zeolite, silica gel, alumina or analog, or mixtures thereof.
  • the line 20 is also fluidly connected to a buffer capacity 4 for storing a portion of the nitrogen gas, as well as backup frames 5 each comprising several bottles of nitrogen.
  • the installation also comprises a cabinet 16 comprising a plurality of bottles 9 of a premix of NO / N2 containing here 4% by volume of NO, which bottles 9 are fluidly connected to the line 20 by a feed line 22.
  • premix NO / N 2 a premix of NO / N2 containing here 4% by volume of NO, which bottles 9 are fluidly connected to the line 20 by a feed line 22.
  • premix NO / N 2 .
  • the lines of NO / N2 22 and nitrogen 20 are not directly connected to each other but are connected to the block vanness 8 which in turn is connected by line 21 to the one or ramps 14.
  • the valves of the valve block 8 make it possible to choose the fluid with which the bottles 11 to 13 of the ramp 14 are filled.
  • the nitrogen lines 20 and premix lines NO / N 2 22 are thus fluidly connected firstly by the valve block 8, then a common section 21 to the filling ramp 14.
  • the valve block 8 comprises valves, control elements controlled by the control device 10.
  • Flow meters 7 make it possible to measure the quantity of N 2 and NO flowing in lines 20 and 22, and to transmit the measured information to a control device 10, such as a computer or the like.
  • the installation also includes a vent line 17 for evacuating gases to the ambient atmosphere, especially during the purge steps during which the internal volume of the container is in fluid communication with the ambient atmosphere.
  • a vacuum pump (not shown) makes it possible to operate the evacuation (s) of the containers, that is to say to reduce their internal pressure until a pressure lower than atmospheric pressure is obtained, ie ⁇ 1 bar absolute.

Description

L'invention concerne un procédé de conditionnement d'un mélange gazeux NO/N2 dans un récipient, en particulier une ou plusieurs bouteilles de gaz, comprenant plusieurs étapes de purge et de rinçage gazeux successives.The invention relates to a method of conditioning a NO / N 2 gas mixture in a container, in particular one or more gas bottles, comprising several successive purge and gaseous rinsing steps.

Les mélanges gazeux NO/N2 sont couramment utilisés pour traiter les vasoconstrictions pulmonaires chez l'adulte ou l'enfant, en particulier chez les nouveaux nés souffrant d'hypertension pulmonaire primitive ou chez les patients subissant une opération de chirurgie cardiaque.Gaseous NO / N 2 mixtures are commonly used to treat pulmonary vasoconstriction in adults or children, particularly in neonates with primary pulmonary hypertension or in patients undergoing cardiac surgery.

Ces mélanges NO/N2 sont classiquement conditionnés dans des bouteilles de gaz en acier. Typiquement, ces bouteilles contiennent de 100 à 1000 ppm en volume de NO et de l'azote (N2) pour le reste. Ces bouteilles ont habituellement une contenance en eau de 2 à 50 litres, ce qui permet d'y introduire une charge totale pouvant aller jusqu'à 15 m3 de mélange NO/N2.These NO / N 2 mixtures are conventionally packaged in steel gas cylinders. Typically, these bottles contain 100 to 1000 ppm by volume of NO and nitrogen (N 2 ) for the rest. These bottles usually have a water capacity of 2 to 50 liters, which allows to introduce a total load of up to 15 m 3 of NO / N 2 mixture.

Le conditionnement, c'est-à-dire la mise en bouteille de ces mélanges, se fait dans des centres de conditionnement de gaz, comme par exemple dans les documents FR 2914393 et US 20030012709 .The packaging, that is to say the bottling of these mixtures, is done in gas conditioning centers, as for example in the documents FR 2914393 and US 20030012709 .

Toutefois, compte-tenu de la faible teneur en NO dans le mélange, à savoir typiquement de l'ordre de quelques centaines de ppm en volume, le conditionnement de ces mélanges n'est pas toujours aisé à réaliser au plan industriel. En particulier, le mélange gazeux NO/N2 est sensible à la présence d'impuretés résiduelles de type oxygène susceptibles d'être présentes dans les bouteilles lors de leur remplissage.However, given the low content of NO in the mixture, typically of the order of a few hundred ppm by volume, the packaging of these mixtures is not always easy to achieve industrially. In particular, the gaseous mixture NO / N2 is sensitive to the presence of residual oxygen-type impurities that may be present in the bottles during their filling.

En effet, il est primordial de pouvoir s'assurer que les bouteilles ont été, avant leur remplissage, correctement débarrassées de toutes les impuretés gazeuses qu'elles sont susceptibles de contenir, en particulier de l'oxygène qui peut réagir avec le NO pour former du NO2 toxique.Indeed, it is essential to be able to ensure that the bottles were, before filling, properly cleaned of any gaseous impurities they may contain, in particular oxygen which can react with the NO to form toxic NO 2 .

Dit autrement, si la purge et le nettoyage du volume interne des bouteilles n'est pas correctement opéré, les mélanges NO/N2 produits ne seront pas conformes aux spécifications et devront être mis au rebut.In other words, if the purging and cleaning of the internal volume of the bottles is not properly carried out, the NO / N 2 mixtures produced will not comply with the specifications and must be discarded.

Par ailleurs, on connait le document US 6152192 qui enseigne un procédé de remplissage d'un récipient de gaz avec un gaz ou mélange gazeux, notamment O2, N2, He, Ar, CO2, ou d'autres gaz, dans lequel le récipient, préalablement au remplissage, est soumis à des étapes de purge avec mise en communication fluidique avec l'atmosphère ambiante, de mise sous vide avec une pompe à vide et de rinçage gazeux durant laquelle un gaz y est introduit. Ce cycle de purge peut être répété plusieurs fois.Moreover, we know the document US 6152192 which teaches a method of filling a gas container with a gas or gas mixture, in particular O 2 , N 2 , He, Ar, CO 2 , or other gases, in which the container, prior to filling, is subjected to purge steps with fluid communication with the ambient atmosphere, evacuation with a vacuum pump and gaseous rinsing during which a gas is introduced therein. This purge cycle can be repeated several times.

Un enseignement similaire est donné par le document US 20030070724 .Similar teaching is given by the document US 20030070724 .

Le problème est dès lors de proposer un procédé de conditionnement amélioré permettant d'éliminer la totalité ou quasi totalité des impuretés, en particulier de l'oxygène, susceptibles de se trouver dans une ou plusieurs bouteilles de gaz devant recevoir un mélange gazeux de type NO/N2.The problem is therefore to propose an improved packaging method making it possible to eliminate all or almost all the impurities, in particular oxygen, which may be in one or more gas cylinders to receive an NO type gas mixture. / N 2 .

La solution de l'invention est alors un procédé de conditionnement d'un mélange gazeux NO/N2 dans au moins un récipient, en particulier une ou plusieurs bouteilles de gaz, selon la revendication 1.The solution of the invention is then a method for conditioning a gaseous mixture NO / N 2 in at least one container, in particular one or more gas bottles, according to claim 1.

Selon le cas, le procédé de l'invention peut comprendre l'une ou plusieurs des caractéristiques techniques suivantes :

  • l'étape b) de mise sous vide est opérée par soutirage de gaz au moyen d'une pompe à vide.
  • séquence d'étapes a), b) et c) est immédiatement suivie d'une séquence d'étapes a) et c) ou d'une séquence d'étapes a), c) et a).
  • lors des étapes c), le gaz inerte servant à opérer le rinçage gazeux est de l'azote.
  • plusieurs récipients de gaz sont soumis simultanément aux étapes a) à c).
  • subséquemment à la mise en oeuvre d'au moins deux séquences d'étapes a) et c), on introduit dans le ou les récipients successivement :
    1. i) un prémélange gazeux formé de NO et de N2 contenant une teneur en NO inférieure à 10% en volume jusqu'à atteindre une première pression P1 avec P1 > 1 bar absolu;
    2. ii) de l'azote gazeux jusqu'à obtenir, par mélange de l'azote avec ledit prémélange NO/N2, un mélange gazeux final NO/N2 contenant une teneur en NO inférieure ou égale à 1200 ppm en volume et une deuxième pression P2 comprise entre P1 et 800 bar.
  • l'étape c) de rinçage gazeux comprend l'introduction d'azote gazeux dans le ou les récipients jusqu'à obtenir une pression de rinçage comprise entre 2 et 20 bar au sein du ou desdits récipients, de préférence entre 2 et 12 bar.
  • durant l'étape a) de purge, le volume interne du récipient est maintenu en communication fluidique avec l'atmosphère tant que la pression interne du récipient est supérieure à une pression minimale de purge (Pmin) telle que : 3,5 bar > Pmin > 1 bar, de préférence entre 1,1 et 3 bar environ.
  • durant au moins une étape b) de mise sous vide, le volume interne du récipient est mis en dépression jusqu'à atteindre un niveau de pression inférieur à 0,5 bar, de préférence inférieur à 0,2 bar.
  • il comprend, préalablement à l'étape a), une étape d) de mise sous vide et une étape e) de purge d'au moins un flexible reliant la rampe de remplissage à un récipient de gaz.
  • durant l'étape c) de rinçage gazeux, on stoppe l'introduction de gaz inerte dans ledit au moins un récipient lorsque la pression dans ledit au moins un récipient atteint une valeur comprise entre 2 et 20 bar, de préférence entre 3 et 10 bar.
  • on stoppe la mise en communication fluidique avec l'atmosphère ambiante lors de l'étape a) de purge lorsque la pression dans le volume interne du récipient atteint une valeur comprise entre 1 et 1,5 bar.
  • la première pression P1 est comprise entre 2 et 10 bar, de préférence inférieure ou égale à 5 bar.
  • la deuxième pression est comprise entre 100 et 700 bar, de préférence d'au moins 200 bar.
  • le prémélange gazeux formé de NO et de N2 contient une teneur en NO inférieure ou égale à 8% en volume, de préférence une teneur en NO inférieure ou égale à 5% en volume.
  • le prémélange gazeux formé de NO et de N2 contient une teneur en NO de l'ordre de 4% en volume et la première pression P1 est de l'ordre de 2 à 10 bar abs, par exemple de l'ordre de 2 à 5 bar abs.
  • le mélange gazeux final NO/N2 contient une teneur en NO inférieure ou égale à 1000 ppm en volume, de préférence le mélange gazeux final NO/N2 contient une teneur en NO comprise entre 200 et 1000 ppm en volume, de préférence encore entre 200 et 800 ppm en volume.
  • il est mis en oeuvre par le biais d'une rampe de conditionnement de récipients de gaz comprenant des moyens de raccordement permettant de remplir plusieurs récipients à la fois.
  • le récipient est une bouteille de gaz, de préférence une bouteille de gaz à corps en acier, en aluminium ou un alliage d'aluminium.
Depending on the case, the method of the invention may comprise one or more of the following technical characteristics:
  • step b) of evacuation is operated by gas withdrawal by means of a vacuum pump.
  • sequence of steps a), b) and c) is immediately followed by a sequence of steps a) and c) or a sequence of steps a), c) and a).
  • during steps c), the inert gas used to carry out the gaseous rinsing is nitrogen.
  • several gas containers are simultaneously subjected to steps a) to c).
  • after the implementation of at least two sequences of steps a) and c), is introduced into the container or containers successively:
    1. i) a gaseous premix consisting of NO and N 2 containing an NO content of less than 10% by volume until a first pressure P1 is reached with P1> 1 bar absolute;
    2. ii) nitrogen gas to obtain, by mixing nitrogen with said premix NO / N 2, a final gas mixture NO / N 2 containing a NO x content less than or equal to 1200 ppm by volume and a second P2 pressure between P1 and 800 bar.
  • step c) gaseous rinsing comprises the introduction of nitrogen gas into the container or containers to obtain a rinsing pressure of between 2 and 20 bar within the said container or containers, preferably between 2 and 12 bar.
  • during the purging step a), the internal volume of the container is maintained in fluid communication with the atmosphere as long as the internal pressure of the container is greater than a minimum purge pressure (Pmin) such that: 3.5 bar> Pmin > 1 bar, preferably between 1.1 and 3 bar approximately.
  • during at least one step b) of evacuation, the internal volume of the container is depressurized to reach a pressure level of less than 0.5 bar, preferably less than 0.2 bar.
  • it comprises, prior to step a), a step d) of evacuation and a step e) purge at least one hose connecting the filling ramp to a gas container.
  • during step c) of gaseous rinsing, the introduction of inert gas into said at least one container is stopped when the pressure in said at least one container reaches a value between 2 and 20 bar, preferably between 3 and 10 bar .
  • stopping the fluidic communication with the ambient atmosphere during the purge step a) when the pressure in the internal volume of the container reaches a value between 1 and 1.5 bar.
  • the first pressure P1 is between 2 and 10 bar, preferably less than or equal to 5 bar.
  • the second pressure is between 100 and 700 bar, preferably at least 200 bar.
  • the gaseous premix of NO and N 2 contains an NO content of less than or equal to 8% by volume, preferably an NO content of less than or equal to 5% by volume.
  • the gaseous premix consisting of NO and N 2 contains a NO content of the order of 4% by volume and the first pressure P1 is of the order of 2 to 10 bar abs, for example of the order of 2 to 5 bar abs.
  • the final gas mixture NO / N 2 contains an NO content of less than or equal to 1000 ppm by volume, preferably the final gas mixture NO / N 2 contains a content in NO between 200 and 1000 ppm by volume, more preferably between 200 and 800 ppm by volume.
  • it is implemented by means of a gas container conditioning ramp comprising connecting means for filling several containers at a time.
  • the container is a gas cylinder, preferably a gas cylinder with steel body, aluminum or aluminum alloy.

Dans le cadre de la présente invention, les pressions données sont des pressions absolues.In the context of the present invention, the pressures given are absolute pressures.

L'invention va maintenant être mieux comprise grâce à la description donnée ci-après en référence aux Figures annexées parmi lesquelles :

  • la Figure 1 schématise un mode de réalisation d'un cycle de conditionnement selon la présente invention et
  • la Figure 2 représente le schéma d'une installation de mise en oeuvre du procédé de l'invention.
The invention will now be better understood thanks to the description given hereinafter with reference to the appended figures among which:
  • the Figure 1 schematically an embodiment of a conditioning cycle according to the present invention and
  • the Figure 2 represents the diagram of an installation for implementing the method of the invention.

La Figure 1 schématise un mode de réalisation d'un cycle de conditionnement applicable dans le cadre du procédé de conditionnement de mélange gazeux NO/N2 de la présente invention.The Figure 1 schematizes an embodiment of a conditioning cycle applicable in the context of the gaseous mixture conditioning process NO / N 2 of the present invention.

Comme on le voit, ce cycle de conditionnement comporte plusieurs étapes successives, s'échelonnant au fil du temps de T0 à T13, qui sont appliquées à chaque bouteille et qui sont détaillées ci-après. Les étapes a) à c) successives du procédé de l'invention ont été indiquées sur la Figure 1.As can be seen, this conditioning cycle comprises several successive steps, ranging over time from T0 to T13, which are applied to each bottle and which are detailed below. The successive steps a) to c) of the process of the invention have been indicated on the Figure 1 .

Entre T0 et T1, les flexibles de l'installation sont vidés à l'air libre, c'est-à-dire que le volume interne des flexibles de remplissage est mis en communication fluidique avec l'atmosphère ambiante pour évacuer toute surpression résiduelle éventuelle. Durant cette phase, le ou les robinets de récipients de gaz connectés aux flexibles sont fermés, donc aucun échange de gaz n'a lieu avec le ou les récipients. Ceci correspond à l'étape d) du procédé.Between T0 and T1, the hoses of the installation are emptied in the open air, that is to say that the internal volume of the filling hoses is put in fluid communication with the ambient atmosphere to evacuate any residual overpressure . During this phase, the valve (s) of gas containers connected to the hoses are closed, therefore no gas exchange takes place with the container (s). This corresponds to step d) of the process.

Entre T1 et T2, on utilise une pompe à vide pour mettre l'intérieur des flexibles en dépression de branchement, c'est-à-dire à une pression inférieure à la pression atmosphérique, par exemple de l'ordre de 0,15 bar, ce qui permet d'évacuer le gaz résiduel et/ou l'air qui s'y trouvent. Cette phase est donc aussi réalisée robinet fermée. La mise sous vide des flexibles est une sécurité qui permet de vérifier le bon raccordement de tous les flexibles et l'absence de fuite. En effet, en cas de fuite ou de raccordement incorrect d'un flexible le vide ne sera pas établi de manière stable. Ceci correspond à l'étape e) du procédé schématisé en Figure 1.Between T1 and T2, a vacuum pump is used to put the inside of the hoses in connection vacuum, that is to say at a pressure below atmospheric pressure, for example of the order of 0.15 bar , which allows to evacuate the gas residual and / or air that are there. This phase is also realized closed tap. Vacuuming the hoses is a safety feature that makes it possible to check the correct connection of all hoses and the absence of leaks. Indeed, in case of leakage or incorrect connection of a hose vacuum will not be established stably. This corresponds to step e) of the process schematized in Figure 1 .

Entre T2 et T3, l'opérateur ouvre le robinet de chaque bouteilles et la pression résiduelle présente dans chaque bouteille remonte alors jusqu'au capteur de pression, lequel détecte ladite remontée de pression. Typiquement, la pression résiduelle de la bouteille est de l'ordre d'environ 3 à 4 bar absolus. Après T2, aucun rinçage gazeux du récipient avec de l'azote n'a encore eu lieu. Ceci correspond à l'étape f) du procédé schématisé en Figure 1.Between T2 and T3, the operator opens the valve of each bottle and the residual pressure present in each bottle then goes up to the pressure sensor, which detects said rise in pressure. Typically, the residual pressure of the bottle is of the order of about 3 to 4 bar absolute. After T2, no gaseous flushing of the vessel with nitrogen has yet occurred. This corresponds to step f) of the process schematized in Figure 1 .

Entre T3 et T4, commence le traitement proprement dit de chaque bouteille. Plus précisément, chaque bouteille est à mise à l'atmosphère, c'est-à-dire qu'on laisse s'échapper le gaz contenu dans la bouteille vers l'atmosphère extérieur sous le simple effet de la différence de pression entre intérieur et extérieur de la bouteille de manière à porter la pression interne de la bouteille à la pression atmosphérique. Ceci correspond à l'étape a) du procédé de l'invention. A T4, la pression interne de la bouteille de gaz est donc sensiblement égale à la pression atmosphérique (1 atm = environ 1 bar absolu), c'est-à-dire de l'ordre de 1 à 1,5 bar abs.Between T3 and T4, the actual processing of each bottle begins. More specifically, each bottle is vented, that is to say that is allowed to escape the gas contained in the bottle to the outside atmosphere simply by the effect of the pressure difference between inside and outside. outside of the bottle so as to bring the internal pressure of the bottle to atmospheric pressure. This corresponds to step a) of the process of the invention. At T4, the internal pressure of the gas cylinder is therefore substantially equal to the atmospheric pressure (1 atm = about 1 bar absolute), that is to say of the order of 1 to 1.5 bar abs.

Entre T4 et T5, la bouteille subit un rinçage avec de l'azote pendant lequel sa pression interne est portée à environ 10 bar. L'adjonction d'azote se fait via une canalisation de gaz et/ou un stockage d'azote sous pression de manière à porter la pression interne de la bouteille à la pression désirée. Ceci correspond à l'étape c) du procédé de l'invention.Between T4 and T5, the bottle is rinsed with nitrogen during which its internal pressure is increased to about 10 bar. The addition of nitrogen is via a gas pipeline and / or nitrogen storage under pressure so as to bring the internal pressure of the bottle to the desired pressure. This corresponds to step c) of the process of the invention.

Entre T5 et T6, l'azote contenu dans la bouteille est à nouveau échappé à l'atmosphère, ce qui permet d'éliminer les impuretés éventuellement présentes dans la bouteille. Ceci correspond à une nouvelle étape a) du procédé de l'invention.Between T5 and T6, the nitrogen contained in the bottle is again escaped to the atmosphere, which eliminates any impurities in the bottle. This corresponds to a new step a) of the process of the invention.

Entre T6 et T7, la bouteille est purgée par mise en dépression de son volume interne par soutirage du gaz résiduel qui s'y trouve au moyen d'une pompe à vide jusqu'à obtenir une dépression interne inférieure à 0,2 bar abs, de préférence inférieure à 0,1 bar, par exemple de l'ordre de 0,05 bar. Ceci correspond à une nouvelle étape b) du procédé de l'invention.Between T6 and T7, the bottle is purged by depressurizing its internal volume by withdrawing the residual gas therein by means of a vacuum pump until an internal negative pressure of less than 0.2 bar abs, preferably less than 0.1 bar, for example of the order of 0.05 bar. This corresponds to a new step b) of the process of the invention.

Entre T7 et T8, la bouteille subit un nouveau rinçage à l'azote jusqu'à porter sa pression interne à 10 bar environ, comme entre T4 et T5. Ceci correspond à une nouvelle étape c) du procédé de l'invention.Between T7 and T8, the bottle is re-rinsed with nitrogen until its internal pressure is approximately 10 bar, as between T4 and T5. This corresponds to a new step c) of the process of the invention.

Entre T8 et T9, la bouteille subit un nouvel échappement vers l'atmosphère ambiant comme pendant les temps T5 et T6. La pression résiduelle gazeuse est alors maintenue à environ 1,35 bar pour éviter une entrée intempestive de contaminants atmosphériques. Ceci correspond à une nouvelle étape a) du procédé de l'invention.Between T8 and T9, the bottle undergoes a new exhaust towards the ambient atmosphere as during times T5 and T6. The gaseous residual pressure is then maintained at approximately 1.35 bar to prevent untimely entry of atmospheric contaminants. This corresponds to a new step a) of the process of the invention.

Entre T9 et T10, la bouteille subit encore un rinçage supplémentaire à l'azote jusqu'à porter sa pression interne à 10 bar environ, comme précédemment. Ceci correspond à une nouvelle étape c) du procédé de l'invention.Between T9 and T10, the bottle is further rinsed with nitrogen until its internal pressure is about 10 bar, as before. This corresponds to a new step c) of the process of the invention.

Entre T10 et T11, l'azote est échappé à l'atmosphère, comme entre T8 et T9 et entre T5 et T6, mais en maintenant cette fois une pression résiduelle interne de l'ordre de 3 bar. Ceci correspond à une nouvelle étape a) du procédé de l'invention.Between T10 and T11, the nitrogen is escaped to the atmosphere, as between T8 and T9 and between T5 and T6, but this time maintaining an internal residual pressure of the order of 3 bar. This corresponds to a new step a) of the process of the invention.

Entre T11 et T12, on introduit dans la bouteille, un prémélange gazeux formé de NO et de N2 contenant une teneur en NO inférieure à 10% en volume jusqu'à atteindre une première pression de remplissage P1 avec P1 > 1 bar, typiquement une pression P1 de l'ordre de 2 à 10 bar abs, préférentiellement de 3 à 5 bar abs environ. Avantageusement, le prémélange gazeux formé de NO et de N2 contient une teneur en NO de l'ordre de 4 % en volume.Between T11 and T12, is introduced into the bottle, a gaseous premix of NO and N 2 containing an NO content of less than 10% by volume until reaching a first filling pressure P1 with P1> 1 bar, typically a P1 pressure of the order of 2 to 10 bar abs, preferably from 3 to 5 bar abs about. Advantageously, the gaseous premix consisting of NO and N 2 contains a NO content of the order of 4% by volume.

Entre T12 et T 13, on introduit ensuite dans le récipient contenant le prémélange NO/N2 à la première pression P1, de l'azote gazeux jusqu'à obtenir un mélange gazeux final NO/N2 contenant une teneur en NO inférieure ou égale à 1200 ppm en volume, par exemple une teneur finale de NO de 200 à 800 ppm, et une deuxième pression P2 comprise entre P1 et 800 bar, par exemple ici une pression de 180 à 200 bar.Between T12 and T 13, nitrogen containing gas is introduced into the vessel containing the NO / N 2 premix at the first pressure P1 until a final NO / N 2 gas mixture containing a content of NO less than or equal to at 1200 ppm by volume, for example a final NO content of 200 to 800 ppm, and a second pressure P2 between P1 and 800 bar, for example here a pressure of 180 to 200 bar.

Ce procédé peut être mis en oeuvre par le biais d'une installation de conditionnement comme celle schématisée en Figure 2 équipée d'une rampe 14 de conditionnement de récipients de gaz, c'est-à-dire de bouteilles de gaz, comprenant des moyens de raccordement 15 permettant de remplir plusieurs récipients 11 à 13 à la fois, typiquement de 2 à 20 bouteilles concomitamment.This method can be implemented by means of a packaging installation such as that schematized in Figure 2 equipped with a ramp 14 for packaging gas containers, that is to say, gas cylinders, comprising connecting means 15 for filling several containers 11 to 13 at a time, typically from 2 to 20 bottles concomitantly .

L'azote est stocké dans le réservoir 1 sous forme liquide puis soutiré sous forme liquide par une pompe cryogénique 2 qui le comprime à une pression de l'ordre de 100 à 300 bar, avant de l'envoyer vers un réchauffeur atmosphérique 3 où il est vaporisé de manière à obtenir de l'azote gazeux. Comme on le voit, elle comprend une canalisation ou ligne principale 20 permettant de véhiculer de l'azote depuis un réservoir 1 jusqu'à la rampe 14 de conditionnement. En fait, la pression dans la ligne varie entre environ 100 bar immédiatement en aval de l'écroulement de la capacité tampon dans les bouteilles et environ 260 bar qui correspond au seuil d'arrêt de la pompe.The nitrogen is stored in the tank 1 in liquid form and then withdrawn in liquid form by a cryogenic pump 2 which compresses it to a pressure of the order of 100 to 300 bar, before sending it to an atmospheric heater 3 where it is vaporized to obtain nitrogen gas. As can be seen, it comprises a pipe or main line 20 for conveying nitrogen from a tank 1 to the ramp 14 of conditioning. In fact, the pressure in the line varies between about 100 bar immediately downstream of the collapse of the buffer capacity in the bottles and about 260 bar which corresponds to the stopping threshold of the pump.

L'azote gaz est ensuite véhiculé par la ligne 20 vers un dispositif de purification 6 permettant d'éliminer les traces de O2 et H2O, par exemple un tamis moléculaire adapté, par exemple de type zéolite, gel de silice, alumine ou analogue, ou leurs mélanges.The nitrogen gas is then conveyed via line 20 to a purification device 6 for removing traces of O 2 and H 2 O, for example a suitable molecular sieve, for example of the zeolite, silica gel, alumina or analog, or mixtures thereof.

Il est à noter que la ligne 20 est aussi reliée fluidiquement à une capacité tampon 4 permettant de stocker une partie de l'azote gazeux, ainsi qu'à des cadres de secours 5 comprenant chacun plusieurs bouteilles d'azote.It should be noted that the line 20 is also fluidly connected to a buffer capacity 4 for storing a portion of the nitrogen gas, as well as backup frames 5 each comprising several bottles of nitrogen.

Par ailleurs, l'installation comprend également une armoire 16 comprenant plusieurs bouteilles 9 d'un prémélange de NO/N2 contenant ici 4% en volume de NO, lesquels bouteilles 9 sont reliées fluidiquement à la ligne 20 par une ligne d'alimentation 22 en prémélange NO/N2. En fait, les lignes de NO/N2 22 et d'azote 20 ne sont pas reliées directement l'une à l'autre mais elles sont reliées au bloc à vanness 8 qui est lui relié par la ligne 21 à la ou aux rampes 14. Les vannes du bloc à vannes 8 permettent de choisir le fluide avec lequel on remplit les bouteilles 11 à 13 de la rampe 14. Les lignes d'azote 20 et de prémélange NO/N2 22 sont donc reliées fluidiquement d'abord par le bloc à vannes 8, puis un tronçon commun 21 à la rampe de remplissage 14. Le bloc à vannes 8 comprend des vannes, des éléments de pilotage commandés par le dispositif de pilotage 10...Furthermore, the installation also comprises a cabinet 16 comprising a plurality of bottles 9 of a premix of NO / N2 containing here 4% by volume of NO, which bottles 9 are fluidly connected to the line 20 by a feed line 22. premix NO / N 2 . In fact, the lines of NO / N2 22 and nitrogen 20 are not directly connected to each other but are connected to the block vanness 8 which in turn is connected by line 21 to the one or ramps 14. The valves of the valve block 8 make it possible to choose the fluid with which the bottles 11 to 13 of the ramp 14 are filled. The nitrogen lines 20 and premix lines NO / N 2 22 are thus fluidly connected firstly by the valve block 8, then a common section 21 to the filling ramp 14. The valve block 8 comprises valves, control elements controlled by the control device 10.

Des débitmètres 7 permettent de mesurer la quantité de N2 et de NO circulant dans les lignes 20 et 22, et de transmettre les informations mesurées à un dispositif de pilotage 10, tel un ordinateur ou analogue.Flow meters 7 make it possible to measure the quantity of N 2 and NO flowing in lines 20 and 22, and to transmit the measured information to a control device 10, such as a computer or the like.

L'installation comprend également une ligne de mise à l'atmosphère 17 permettant d'évacuer les gaz vers l'atmosphère ambiante, notamment pendant la ou les étapes de purge durant laquelle le volume interne du récipient est mis en communication fluidique avec l'atmosphère ambiante.The installation also includes a vent line 17 for evacuating gases to the ambient atmosphere, especially during the purge steps during which the internal volume of the container is in fluid communication with the ambient atmosphere.

Une pompe à vide (non montrée) permet d'opérer la ou les mises sous vide des récipients, c'est-à-dire de faire diminuer leur pression interne jusqu'à obtenir une pression inférieure à la pression atmosphérique, i.e. < 1 bar absolu.A vacuum pump (not shown) makes it possible to operate the evacuation (s) of the containers, that is to say to reduce their internal pressure until a pressure lower than atmospheric pressure is obtained, ie <1 bar absolute.

Claims (12)

  1. Method for packaging an NO/N2 gas mixture in at least one container, characterised in that:
    - prior to the introduction of said NO/N2 mixture, said at least one container is subjected to at least:
    a) one purging step during which the internal volume of the container is brought into fluidic communication with the ambient atmosphere,
    b) a step of applying a vacuum during which the internal volume of the container is subjected to negative pressure,
    c) a gas flushing step during which an inert gas is introduced into said at least one container, and
    - said at least one container is subjected to steps a) and c) several times in succession prior to the introduction of said NO/N2 mixture into said at least one container, two successive sequences of steps a) and c) being separated by a sequence of steps a), b) and c), and
    - subsequently to the implementation of at least two sequences of steps a) and c), a gas mixture formed from NO and N2 is introduced into the container or containers.
  2. Method according to the preceding claim, characterised in that a sequence of steps a), b) and c) is immediately followed by a sequence of steps a) and c) or a sequence of steps a), c) and a).
  3. Method according to one of the preceding claims, characterised in that during steps c) the inert gas used to carry out the gas flushing is nitrogen.
  4. Method according to one of the preceding claims, characterised in that a plurality of gas containers are simultaneously subjected to steps a) to c).
  5. Method according to one of the preceding claims, characterised in that, subsequently to the implementation of at least two sequences of steps a) and c), the following are successively introduced into the container or containers:
    i) a gas premix formed from NO and N2 having an NO content of less than 10% by volume, until a first pressure P1 is obtained where P1 > 1 bar absolute;
    ii) nitrogen gas until, by mixing nitrogen with said NO/N2 premix, a final NO/N2 gas mixture is obtained having an NO content that is less than or equal to 1200 ppm by volume and a second pressure P2 of between P1 and 800 bar.
  6. Method according to one of the preceding claims, characterised in that the gas flushing step c) comprises the introduction of nitrogen gas into the container or containers until a flushing pressure of between 2 and 20 bar is obtained within said container or containers, preferably between 2 and 12 bar.
  7. Method according to one of the preceding claims, characterised in that, during the purging step a), the internal volume of the container is kept in fluidic communication with the atmosphere as long as the internal pressure of the container is greater than a minimum purge pressure (Pmin) such that: 3.5 bar > Pmin > 1 bar, preferably between about 1.1 and 3 bar.
  8. Method according to one of the preceding claims, characterised in that, during at least one step b) of applying a vacuum, the internal volume of the container is subjected to negative pressure until a pressure level of less than 0.5 bar, preferably less than 0.2 bar, is achieved.
  9. Method according to one of the preceding claims, characterised in that it comprises, prior to step a), a step d) of applying a vacuum and a step e) of purging at least one hose connecting the filling pipe to a gas container.
  10. Method according to one of the preceding claims, characterised in that the final NO/N2 gas mixture has an NO content of less than or equal to 1000 ppm by volume, preferably the final NO/N2 gas mixture has an NO content of between 200 and 1000 ppm by volume, more preferably between 200 and 800 ppm by volume.
  11. Method according to one of the preceding claims, characterised in that, during the step c) of gas flushing, the introduction of inert gas into said at least one container is stopped when the pressure in said at least one container reaches a level between 2 and 20 bar, preferably between 3 and 10 bar.
  12. Method according to one of the preceding claims, characterised in that the provision of fluidic communication with the ambient atmosphere during purging step a) is stopped when the pressure in the internal volume of the container reaches a level between 1 and 1.5 bar.
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2976258B1 (en) * 2011-06-09 2014-09-05 Air Liquide INSTALLATION OF PACKAGING OF NO TO MASS FLOWMETERS
FR2976259B1 (en) * 2011-06-09 2013-07-05 Air Liquide PROCESS FOR CONDITIONING A NO / N2 GAS MIXTURE

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5485827A (en) † 1990-12-05 1996-01-23 The General Hospital Corporation Methods and devices for treating plumonary vasoconstriction and asthma
US6152192A (en) † 1998-02-11 2000-11-28 Welding Company Of America Controller for system for filling gas cylinders with single gas or gas mixture
US20030070724A1 (en) † 2001-09-26 2003-04-17 Shock Robert F. Computer controlled apparatus and method of filling cylinders with gas
US20100330207A1 (en) † 2009-06-30 2010-12-30 Ikaria Holdings, Inc. Methods of treating term and near-term neonates having hypoxic respiratory failure associated with clinical or echocardiographic evidence of pulmonary hypertension

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5540251A (en) * 1994-02-01 1996-07-30 Mayeaux; Paul H. Precision gas blender
US5476115A (en) * 1994-03-10 1995-12-19 Praxair Technology, Inc. Automatic gas blending system
US5826632A (en) * 1997-05-30 1998-10-27 The Boc Group, Inc. Dynamic gas cylinder filling process
US7334708B2 (en) * 2001-07-16 2008-02-26 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Integral blocks, chemical delivery systems and methods for delivering an ultrapure chemical
US20060060139A1 (en) * 2004-04-12 2006-03-23 Mks Instruments, Inc. Precursor gas delivery with carrier gas mixing
US7328726B2 (en) * 2006-01-20 2008-02-12 Air Products And Chemicals, Inc. Ramp rate blender
FR2914393B1 (en) * 2007-03-27 2009-07-17 Air Liquide METHOD AND DEVICE FOR PREPARING GAS BOTTLES UNDER PRESSURE.
US7621302B2 (en) * 2007-09-28 2009-11-24 Airgas, Inc. Coriolis dosing system for filling gas cylinders
FR2976259B1 (en) * 2011-06-09 2013-07-05 Air Liquide PROCESS FOR CONDITIONING A NO / N2 GAS MIXTURE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5485827A (en) † 1990-12-05 1996-01-23 The General Hospital Corporation Methods and devices for treating plumonary vasoconstriction and asthma
US6152192A (en) † 1998-02-11 2000-11-28 Welding Company Of America Controller for system for filling gas cylinders with single gas or gas mixture
US20030070724A1 (en) † 2001-09-26 2003-04-17 Shock Robert F. Computer controlled apparatus and method of filling cylinders with gas
US20100330207A1 (en) † 2009-06-30 2010-12-30 Ikaria Holdings, Inc. Methods of treating term and near-term neonates having hypoxic respiratory failure associated with clinical or echocardiographic evidence of pulmonary hypertension

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BRANSON R.D. ET AL: "Inhaled nitric oxide: delivery systems and monitoring", RESPIRATORY CARE, vol. 44, no. 3, March 1999 (1999-03-01), pages 281 - 307 †

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BR102012013702B1 (en) 2022-04-26
CN102814155B (en) 2016-09-07
US20120312416A1 (en) 2012-12-13
EP2532941B1 (en) 2014-07-02
EP2532941A1 (en) 2012-12-12
BR102012013702B8 (en) 2022-05-24
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CN102814155A (en) 2012-12-12
FR2976260A1 (en) 2012-12-14

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