EP1717510A2 - System and method for filling a vessel with a gas or a gas mixture - Google Patents
System and method for filling a vessel with a gas or a gas mixture Download PDFInfo
- Publication number
- EP1717510A2 EP1717510A2 EP06112218A EP06112218A EP1717510A2 EP 1717510 A2 EP1717510 A2 EP 1717510A2 EP 06112218 A EP06112218 A EP 06112218A EP 06112218 A EP06112218 A EP 06112218A EP 1717510 A2 EP1717510 A2 EP 1717510A2
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- EP
- European Patent Office
- Prior art keywords
- container
- filling
- filled
- gas
- filling gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- F17C5/06—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with compressed gases
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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
- F17C13/00—Details of vessels or of the filling or discharging of vessels
- F17C13/02—Special adaptations of indicating, measuring, or monitoring equipment
- F17C13/021—Special adaptations of indicating, measuring, or monitoring equipment having the height as the parameter
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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
- F17C7/00—Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
- F17C7/02—Discharging liquefied gases
- F17C7/04—Discharging liquefied gases with change of state, e.g. vaporisation
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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
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/016—Noble gases (Ar, Kr, Xe)
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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
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/016—Noble gases (Ar, Kr, Xe)
- F17C2221/017—Helium
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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
- 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
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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
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
- F17C2223/033—Small pressure, e.g. for liquefied gas
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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
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/04—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by other properties of handled fluid before transfer
- F17C2223/042—Localisation of the removal point
- F17C2223/046—Localisation of the removal point in the liquid
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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
- 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
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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
- 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
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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
- F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
- F17C2225/04—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by other properties of handled fluid after transfer
- F17C2225/042—Localisation of the filling point
- F17C2225/046—Localisation of the filling point in the liquid
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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
- 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
- F17C2227/0337—Heat exchange with the fluid by cooling
- F17C2227/0341—Heat exchange with the fluid by cooling using another fluid
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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
- 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
- F17C2227/0367—Localisation of heat exchange
- F17C2227/0369—Localisation of heat exchange in or on a vessel
- F17C2227/0376—Localisation of heat exchange in or on a vessel in wall contact
- F17C2227/0383—Localisation of heat exchange in or on a vessel in wall contact outside the vessel
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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
- F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
- F17C2250/04—Indicating or measuring of parameters as input values
- F17C2250/0404—Parameters indicated or measured
- F17C2250/0408—Level of content in the vessel
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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
- F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
- F17C2250/06—Controlling or regulating of parameters as output values
- F17C2250/0605—Parameters
- F17C2250/0626—Pressure
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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
- F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
- F17C2250/06—Controlling or regulating of parameters as output values
- F17C2250/0605—Parameters
- F17C2250/0631—Temperature
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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
- F17C2260/00—Purposes of gas storage and gas handling
- F17C2260/02—Improving properties related to fluid or fluid transfer
- F17C2260/025—Reducing transfer time
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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
- F17C2270/00—Applications
- F17C2270/05—Applications for industrial use
Definitions
- the invention relates to a method and an apparatus for filling a container with a filling gas or filling gas mixture.
- this method is suitable for inexpensively filling pressure vessels permitted for pressures of 700 bar or more.
- this is suitable Method for filling small-volume tanks, in particular gas generators for airbags, fuel tanks for gas-powered vehicles or fuel cell systems.
- Object of the present invention is therefore to provide a way to fill pressure vessels with gases or components of gas mixtures, in which the filled gas is set as accurately as possible.
- the container to be filled is flow-connected to a metering container.
- the dosing is maintained by means of a heat exchange medium to a temperature which is below the boiling point of the filling gas or the Basgaskomponente, but above its melting temperature or its pour point.
- the container to be filled is also in heat exchange with a heat exchange medium of the same or another type and is maintained at a temperature lower than the temperature in the dosing tank.
- the filling gas or the filling gas component is therefore present in the dosing container in the liquid but not in the boiling state and can be determined very accurately in its quantity.
- the liquid heat exchange medium for the dosing container and / or for the container to be filled is a liquefied gas whose boiling temperature is varied by adjusting the pressure.
- the temperature of the gas can be adjusted in a wide range according to the requirements and in particular kept at a value which is sufficiently far above the freezing point or the pour point of the filling gas, so that the filling process is not disturbed by ice deposits.
- the container to be filled with the same heat exchange medium is heated, which is also provided for controlling the temperature of the dosing, wherein the temperature difference between the containers is realized by different pressures of the heat exchange medium.
- a further embodiment of the invention provides that the container partially filled with one or more filling gas compartments is subsequently filled with a filling gas component held in the gaseous state.
- the mixing ratio of the gaseous Gugaskomponente to the other Gugaskamponenten can be advantageously adjusted by varying the gas pressure of the gaseous component.
- the filled container is then filled with a gas mixture whose composition is known with great accuracy.
- the object of the invention is also achieved by a device for filling a container with a filling gas or a filling gas mixture which is provided with a metering, which is in thermal contact with a heat exchange means in heat exchanger means and with a filling gas supply for supplying the filling gas or a Mountainponente in liquid or gaseous state and is equipped with a filling line for connecting the container to be filled.
- the tempered dosing container allows the supply of a liquefied filling gas or a filling gas component at a temperature below its boiling point and thus without the disturbing influences that would occur during boiling of the filling gas.
- the dosing is arranged in a provided for receiving the heat exchange means pressure vessel within the pressure vessel of the dosing is received in a bath of hillsaustausahstoff whose temperature can be adjusted by varying the pressure in the pressure vessel targeted.
- the heat transfer between the heat exchange medium and the filling gas takes place via the walls of the metering container:
- a further advantageous embodiment of the invention provides that the container to be filled is added during its filling in a fillable with a heat exchange medium bath.
- the metering container is advantageously equipped with a control device for fixing the liquid level in the metering.
- a control device for fixing the liquid level in the metering may be, for example, an overflow, or a measuring and control device which prevents the addition of filling gas above a certain filling level.
- the device 1 for filling a container 2 with a filling gas or filling gas mixture comprises a metering container 3, which is accommodated in the interior of a pressure vessel 4.
- a gas supply line 6 for supplying filling gas in the gaseous state in its upper region.
- the gas supply line 6 is connected to a vent line 7.
- Gas supply line 6 and vent line 7 can be closed or opened with valves 8.9.
- a liquid gas feed line 11 opens for supplying a liquefied filling gas.
- the liquefied gas supply line 11 is provided with a fitting 12, which can be actuated by means of a control device 13 as a function of a measured liquid level 14 in the interior of the metering container 3.
- the dosing 3 is equipped with a filling line 15, which in the operating state of the device 1 via a releasable connection means 10 establishes the flow connection to the container 2 to be filled.
- the filling line 15 is equipped with a shut-off valve 16.
- the pressure vessel 4 provided with an insulation 17, which is only partially shown here, is shut off with a supply line 18 for a heat exchange medium.
- a valve 19 is arranged, which can be controlled by means of a controller 20 in response to a measured liquid level 21 in the interior of the pressure vessel 4.
- a Gäsab In an upper region of the pressure vessel 4, a Gäsabtechnisch 22 opens.
- a device 23 for pressure control ensures the maintenance of a certain pressure in the pressure vessel. 4
- the container 2 should be filled with the most precisely metered amounts of argon and helium.
- the dosing tank 3 is first filled via the liquid gas supply line 11 with liquid argon, which was taken from a storage container, not shown here in liquid form.
- the dosing tank 3 is accommodated in the pressure tank 4 in a bath of a coolant, in the example liquid nitrogen.
- the liquid nitrogen is supplied to the pressure vessel via the supply line 18. The heat exchange between the dosing tank 3 and the liquid nitrogen bath via the walls of the dosing 3.
- the nitrogen evaporates in the pressure vessel 4 partially and thus increases the pressure in the pressure vessel 4.
- the pressure in the pressure vessel to a maintained predetermined value of, for example, about 3 bar.
- the liquid nitrogen in the pressure vessel 4 is at a temperature of about minus 187 ° C, ie at a temperature below the boiling point of argon under normal pressure conditions (minus 186 ° C) or at higher pressures, but above the melting point of Argon (minus 189 ° C) is.
- the present in the dosing 3 at a low pressure of, for example, about 1.1 bar argon is thus in the liquid, but not in the boiling state. In this state, the liquid argon is easy to handle and in particular allows the exact filling of the dosing container 4 up to a predetermined liquid level 14th
- the valve 12 is completely closed and the valve 16 is opened.
- the argon flows into the container 2.
- the container 2 is received in an insulated dip tank 25 and is also cooled with liquid nitrogen.
- the nitrogen in Tauchbad einer 25 has a lower pressure than in the pressure vessel 4, for example, atmospheric pressure, and is therefore at a lower temperature.
- the argon vapor pressure in the container 1 is always lower than in the dosing tank 2, so that the filling process is not hindered by evaporating argon.
- the liquid nitrogen in the dip tank 25 at atmospheric pressure its temperature is minus 196 ° C and the filled argon in the container 2 freezes. The resulting suction effect (cryopump effect) supports and accelerates the filling process.
- the filling of the container 1 with liquid argon is also possible if the connecting device 10 is not gas-tight, but designed in the manner of a syringe: Furthermore, instead of the previously described filling of the dosing 3 with liquid argon and argon in the gaseous state on the Gas supply 6 are introduced, which then liquefied in the dosing 3 by the heat dissipation through the container wall of the dosing 3. Instead of the metering container 3 receiving pressure vessel 4 or in addition to this, the temperature in the metering 4 can also be adjusted by another technique, such as a heat exchanger.
- the metered addition of a further gas which can be supplied in the liquid or gaseous state takes place.
- gaseous helium is introduced via the gas supply line 6 into the metering tank 3.
- the control of the amount of gas supplied takes place by regulating the pressure in the gas supply line 6 or in the metering 3.
- the helium remains in the metering 3 in the gaseous state.
- the addition of helium can take place after the cached in the dosing 3 Argon has been completely filled in the container;
- the supply of helium on the gas supply line 6 already make during the argon filling of the container 2 and thus to accelerate the filling of the container 2 in total as a result of the gas pressure.
- shut-off valve 16 After completion of the Heliumbe Chelfung the shut-off valve 16 is closed, the container 2 is closed and separated from the connecting device 10. The metering container 3 is depressurized by opening the valve 9, and the device 1 is available for filling a further container available.
- the container 1 can be decoupled from the device 1 in a different procedure even after filling with argon and transported to a..weiteren filling device in which then the Heliumb, e hypolEung done. Because of the low argon vapor pressure in the container 1 escapes during transport almost no argon from the container 2, even if it is not closed for the transport process. This approach has the advantage that existing helium-Follanlagen could be used for this purpose.
- the device 1 is also suitable for filling containers with gas mixtures, which consist of more than two components. In this case, the individual components are added successively in the manner described above. The device 1 enables accurate and rapid filling of containers 2 with low filling pressure and an exactly predictable final pressure.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren sowie eine Vorrichtung zum Befüllen eines Behälters mit einem Füllgas oder Füllgasgemisch.The invention relates to a method and an apparatus for filling a container with a filling gas or filling gas mixture.
Um Gase mit einer hohen Speicherdichte lagern zu können, erfolgt die Speicherung entweder in flüssigem Zustand oder gasförmig unter hohen Drücken. Die Lagerung im flüssigen Zustand ermöglicht zwar eine sehr hohe Speicherdichte, sie ist jedoch nur unter inkaufnahme mehr oder minder großer Abdampfverluste möglich, die auch bei gut wärmeisolierten Behältern unvermeidlich sind. Zur Druckspeicherung von Gasen wurden bislang überwiegend Kompressoren eingesetzt, die.einen Betriebsdruck im Druckbehälter von etwa 200 bis 300 bar erlauben. Die Kompressoren sind jedoch in Bau und Betrieb sehr aufwendig, zudem führen neuere Anwendungen, beispielsweise Anwendungen in der Brennstoffzellentechnik oder Gasgeneratoren für Airbags, zum Bedürfnis nach weitaus höheren Drücken von 700 bar oder mehr. Derartige Drücke sind mit konventioneller Kompressionstechnik nicht oder nur mit unvertretbar hohem Aufwand zu realisieren.In order to store gases with a high storage density, storage takes place either in the liquid state or in gaseous form under high pressures. Although the storage in the liquid state allows a very high storage density, but it is only possible with the purchase of more or less large evaporation losses, which are unavoidable even with well-insulated containers. Up to now compressors have mainly been used for pressure storage of gases, which allow an operating pressure in the pressure vessel of about 200 to 300 bar. However, the compressors are very complex in construction and operation, also lead newer applications, such as applications in fuel cell technology or gas generators for airbags, the need for much higher pressures of 700 bar or more. Such pressures can not be realized with conventional compression technology or only with unacceptably high costs.
Aus der
Bei der Befüllung mit verflüssigtem Gas tritt jedoch das Problem auf, dass die Handhabung des im siedenden Zustand vorliegenden Füllgases mit großen Schwierigkeiten verbunden ist. Insbesondere ist eine exakte Bestimmung der eingefüllten Stoffmenge und sornit - im Falle eines Gasgemisches - eine genaue Angabe des Mischungsverhältnisses der einzelnen Gaskomponenten im befüllten Behälter kaum zu bewerkstelligen.When filling with liquefied gas, however, the problem arises that the handling of the filling gas present in the boiling state is associated with great difficulties. In particular, an exact determination of the amount of substance charged and sornit - in the case of a gas mixture - a precise indication of the mixing ratio of the individual gas components in the filled container can hardly be accomplished.
Aufgabe der vorliegenden Erfindung ist es demnach, eine Möglichkeit zur Befüllung von Druckbehältern mit Gasen oder Komponenten von Gasgemischen anzugeben, bei der die eingefüllte Gasmenge möglichst genau festgelegt ist.Object of the present invention is therefore to provide a way to fill pressure vessels with gases or components of gas mixtures, in which the filled gas is set as accurately as possible.
Diese Aufgabe wird durch ein Verfahren mit den Merkmalen des Patentanspruchs 1 sowie durch eine Vorrichtung mit den Merkmalen des Patentanspruchs 6 gelöst.This object is achieved by a method having the features of
Nach den erfindungsgemäßen Verfahren ist also der zu befüllende Behälter mit einem Dosierbehälter strömungsverbunden. Der Dosierbehälter wird mittels eines Wärmeaustauschmittels auf eine Temperatur gehalten, die unterhalb der Siedetemperatur des Füllgases bzw. der Füllgaskomponente, jedoch oberhalb seiner Schmelztemperatur bzw. seines Stockpunktes liegt. Gleichzeitig befindet sich auch der zu befüllende Behälter in Wärmeaustausch mit einem Wärmeaustauschmittel der gleichen oder einer anderen Art und wird auf eine Temperatur, die niedriger ist als die Temperatur im Dosierbehälter, gehalten. Das Füllgas oder die Füllgaskomponente liegt im Dosierbehälter also im flüssigen, jedoch nicht im siedenden Zustand vor und kann in seiner Menge sehr genau bestimmt werden. Zugleich verhindert die niedrigere Temperatur im zu füllenden Behälter eine Verdampfung des Gases beim Befüllen und begünstigt aufgrund des Kryopumpeneffekts die Förderung des Gases aus dem Dosierbehälter in den zu befüllenden Behälter.According to the method of the invention, therefore, the container to be filled is flow-connected to a metering container. The dosing is maintained by means of a heat exchange medium to a temperature which is below the boiling point of the filling gas or the Füllgaskomponente, but above its melting temperature or its pour point. At the same time, the container to be filled is also in heat exchange with a heat exchange medium of the same or another type and is maintained at a temperature lower than the temperature in the dosing tank. The filling gas or the filling gas component is therefore present in the dosing container in the liquid but not in the boiling state and can be determined very accurately in its quantity. At the same time prevents the lower temperature in the container to be filled evaporation of the gas during filling and favors the promotion of the gas from the dosing into the container to be filled due to the cryopump effect.
Vorteilhafterweise handelt es sich bei dem VlJärmeaustauschmittel für den Dosierbehälter und oder für den zu befüllenden Behälter um ein verflüssigtes Gas, dessen Siedetemperatur durch Einstellung des Drucks variiert wird. Dadurch kann die Temperatur des Gases in einem weiten Bereich entsprechend den Erfordernissen genau eingestellt und insbesondere auf einen Wert gehalten werden, der hinreichend weit oberhalb des Gefrierpunktes bzw. des Stockpunktes des Füllgases liegt, damit der Füllprozess nicht durch Eisablagerungen gestört wird.Advantageously, the liquid heat exchange medium for the dosing container and / or for the container to be filled is a liquefied gas whose boiling temperature is varied by adjusting the pressure. As a result, the temperature of the gas can be adjusted in a wide range according to the requirements and in particular kept at a value which is sufficiently far above the freezing point or the pour point of the filling gas, so that the filling process is not disturbed by ice deposits.
In einer zweckmäßigen Ausgestaltung der Erfindung ist vorgesehen, dass der zu befüllende Behälter mit dem gleichen Wärmeaustauschmittel temperiert wird, das auch zur Temperierung des Dosierbehälters vorgesehen ist, wobei die Temperaturdifferenz zwischen den Behältern durch unterschiedliche Drücke des Wärmeaustauschmittels realisiert wird.In an advantageous embodiment of the invention, it is provided that the container to be filled with the same heat exchange medium is heated, which is also provided for controlling the temperature of the dosing, wherein the temperature difference between the containers is realized by different pressures of the heat exchange medium.
Eine weiter ausgestaltende Ausführungsform der Erfindung sieht vor, dass der mit einer oder mehreren Füllgaskompcanenteln teilweise befüllte Behälter anschließend mit einer im gasförmigen Zustand gehaltenen Füllgaskomponente befüllt wird. Das Mischungsverhältnis der gasförmigen Füllgaskomponente zu den übrigen Füllgaskamponenten kann vorteilhaft durch Variation des Gasdrucks der gasförmigen Komponente eingestellt werden. Im erwärmten Zustand ist der befüllte Behälter dann mit einem Gasgemisch befüllt, dessen Zusammensetzung mit großer Genauigkeit bekannt ist.A further embodiment of the invention provides that the container partially filled with one or more filling gas compartments is subsequently filled with a filling gas component held in the gaseous state. The mixing ratio of the gaseous Füllgaskomponente to the other Füllgaskamponenten can be advantageously adjusted by varying the gas pressure of the gaseous component. In the heated state, the filled container is then filled with a gas mixture whose composition is known with great accuracy.
Die Aufgabe der Erfindung wird auch durch eine Vorrichtung zum Befüllen eines Behälters mit einem Füllgas oder einem Füllgasgemisch gelöst, die mit einem Dosierbehälter versehen ist, der an Wärmetauscherflächen mit einem Wärmeaustauschmittel in thermischen Kontakt steht und mit einer Füllgaszuführung zur Zuführung des Füllgases oder einer Füllgaskomponente im flüssigen oder gasförmigen Zustand und mit einer Füllleitung zum Anschließen des zu befüllenden Behälters ausgerüstet ist. Der temperierte Dosierbehälter ermöglicht die Zuführung eines verflüssigten Füllgases oder einer Füllgaskomponente bei einer Temperatur unterhalb seines Siedepunktes und somit ohne die störenden Einflüsse, die beim Sieden des Füllgases auftreten würden.The object of the invention is also achieved by a device for filling a container with a filling gas or a filling gas mixture which is provided with a metering, which is in thermal contact with a heat exchange means in heat exchanger means and with a filling gas supply for supplying the filling gas or a Füllgaskomponente in liquid or gaseous state and is equipped with a filling line for connecting the container to be filled. The tempered dosing container allows the supply of a liquefied filling gas or a filling gas component at a temperature below its boiling point and thus without the disturbing influences that would occur during boiling of the filling gas.
Bei einer besonders zweckmäßige Ausgestaltung der erfindungsgemäßen Vorrichtung ist der Dosierbehälter in einem zur Aufnahme des Wärmeaustauschmittels vorgesehenen Druckbehälter angeordnet, Innerhalb des Druckbehälters ist der Dosierbehälter in einem Bad aus Wärmeaustausahmittel aufgenommen, dessen Temperatur durch Variation des Drucks im Druckbehälter zielgerichtet eingestellt werden kann. Die Wärmeübertragung zwischen dem Wärmeaustauschmittel und dem Füllgas erfolgt über die Wände des Dosierbehälters:In a particularly advantageous embodiment of the device according to the invention the dosing is arranged in a provided for receiving the heat exchange means pressure vessel within the pressure vessel of the dosing is received in a bath of Wärmeaustausahmittel whose temperature can be adjusted by varying the pressure in the pressure vessel targeted. The heat transfer between the heat exchange medium and the filling gas takes place via the walls of the metering container:
Eine weiter vorteilhafte Ausgestaltung der Erfindung sieht vor, dass auch der zu befüllende Behälter während seiner Befüllung in einem mit einem Wärmeaustauschmittel befüllbaren Bad aufgenommen ist.A further advantageous embodiment of the invention provides that the container to be filled is added during its filling in a fillable with a heat exchange medium bath.
Um die Zugabe des Füllgases bzw, der Füllgaskomponente möglichst zuverlässig steuern zu können, ist der Dosierbehälter vorteilhafterweise mit einer Kontrolleinrichtung zur Festlegung des Flüssigkeitspegels im Dosierbehälter ausgerüstet. Dabei kann es sich beispielsweise um einen Überlauf, handeln, oder um eine Mess- und Steuereinrichtung, die die Zugabe von Füllgas ab einer bestimmten Füllhöhe unterbindet.In order to control the addition of the filling gas or the filling gas component as reliably as possible, the metering container is advantageously equipped with a control device for fixing the liquid level in the metering. This may be, for example, an overflow, or a measuring and control device which prevents the addition of filling gas above a certain filling level.
Anhand der Zeichnung (Fig. 1) soll ein Ausführungsbeispiel der Erfindung näher erläutert werden.Reference to the drawing (Fig. 1), an embodiment of the invention will be explained in more detail.
Die Vorrichtung 1 zum Befüllen eines Behälters 2 mit einem Füllgas oder Füllgasgemisch umfasst einen Dosierbehälter 3, der im Innern eines Druckbehälters 4 aufgenommen ist. In den Dosierbehälter 3 mündet in seinem oberen Bereich eine Gaszuleitung 6 zum Zuführen von Füllgas im gasförmigen Zustand ein. Die Gaszuleitung 6 ist mit einer Entlüftungsleitung 7 verbunden. Gaszuleitung 6 und Entlüftungsleitung 7 können mit Armaturen 8,9 geschlossen oder geöffnet werden. In einen mittleren Bereich des Dosierbehälters 3 mündet eine Flüssiggaszuleitung 11 zum Zuführen eines verflüssigten Füllgases ein. Die Flüssiggaszuleitung 11 ist mit einer Armatur 12 versehen, die mittels einer Steuereinrichtung 13 in Abhängigkeit von einem gemessenen Flüssigkeitspegel 14 im Innern des Dosierbehälters 3 ansteuerbar ist. Ferner ist der Dosierbehälter 3 mit einer Füllleitung 15 ausgerüstet, die im Betriebszustand der Vorrichtung 1 über eine lösbare Verbindungseinrichtung 10 die Strömungsverbindung zum zu befüllenden Behälter 2 herstellt. Die Füllleitung 15 ist mit einer Absperrarmatur 16 ausgerüstet.The
Der mit einer - hier nur teilweise dargestellten - Isolierung 17 versehene Druckbehälter 4 ist mit einer Zuleitung 18 für ein Wärmeaustauschmedium ausgertistet. In der Zuleitung 18 ist eine Armatur 19 angeordnet, die mittels einer Steuerung 20 in Abhängigkeit von einem gemessenen Flüssigkeitspegel 21 im Innern des Druckbehälters 4 gesteuert werden kann. In einem oberen Bereich des Druckbehälters 4 mündet eine Gäsableitung 22 ein. Eine Einrichtung 23 zur Druckkontrolle gewährleistet die Aufrechterhaltung eines bestimmten Drucks im Druckbehälter 4.The
Die Funktionsweise der Vorrichtung 1 soll anhand eines Beispiels nun näher erläutert werden. Im Beispiel soll der Behälter 2 mit möglichst exakt dosierten Mengen von Argon und Helium befüllt werden. Hierzu wird zunächst der Dosierbehälter 3 überdie Flüssiggaszuleitung 11 mit flüssigem Argon befüllt, das aus einem hier nicht gezeigten Vorratsbehälter in flüssiger Form entnommen wurde. Um zu gewährleisten, dass das Argon im Dosierbehälter 3 im flüssigen Zustand vorliegt, ist der Dosierbehälter 3 im Druckbehälter 4 in einem Bad aus einem Kühlmittel, im Beispiel flüssiger Stickstoff, aufgenommen. Der flüssige Stickstoff wird dem Druckbehälter über die Zuleitung 18 zugeführt. Der Austausch von Wärme zwischen Dosierbehälter 3 und dem Flüssigstickstoffbad erfolgt über die Wände des Dosierbehälters 3. Beim Wärmeübergang verdampft der Stickstoff im Druckbehälter 4 teilweise und erhöht damit den Druck im Druckbehälter 4. Mittels der Einrichtung 23 zur Druckregelung, wird der Druck im Druckbehälter auf einen vorgegebenen Wert von beispielsweise etwa 3 bar aufrechterhalten. Bei diesem Druck liegt der Flüssigstickstoff im Druckbehälter 4 bei einer Temperatur von ca. minus 187°C vor, also bei einer Temperatur, die unterhalb des Siedepunktes von Argon unter Normaldruckbedingungen (minus 186°C) oder bei höheren Drücken, jedoch oberhalb des Schmelzpunktes von Argon (minus 189°C) liegt. Das im Dosierbehälter 3 bei einem geringen Überdruck von beispielsweise ca. 1,1 bar vorliegende Argon liegt damit im flüssigen, jedoch nicht im siedenden Zustand vor. In diesem Zustand ist das flüssige Argon leicht zu handhaben und ermöglicht insbesondere die exakte Befüllung des Dosierbehälters 4 bis zu einem vorgegebenen Flüssigkeitspegel 14.The operation of the
Wenn der Dosierbehälter 3 auf diese Weise mit einer definierten Flüssigargonmenge befüllt ist, wird die Armatur 12 vollständig geschlossen und die Armatur 16 geöffnet. Das Argon fließt in den Behälter 2. Der Behälter 2 ist in einem isolierten Tauchbadbehälter 25 aufgenommen und wird ebenfalls mit flüssigem Stickstoff gekühlt. Der Stickstoff hat im Tauchbadbehälter 25 jedoch einen geringeren Druck als im Druckbehälter 4, beispielsweise Atmosphärendruck, und liegt demzufolge bei einer niedrigeren Temperatur vor. Dadurch ist der Argondampfdruck im Behälter 1 stets niedriger als im Dosierbehälter 2, sodass der Befüllvorgang nicht durch verdampfendes Argon behindert wird. Liegt der Flüssigstickstoff im Tauchbadbehälter 25 bei atmosphärischem Druck vor, beträgt seine Temperatur minus 196°C und das eingefüllte Argon im Behälter 2 friert aus. Die hierdurch erzeugte Sogwirkung (Kryopumpeneffekt) unterstützt und beschleunigt den Befüllvorgang.If the
Die Befüllung des Behälters 1 mit flüssigem Argon ist im übrigen auch dann möglich, wenn die Verbindungseinrichtung 10 nicht gasdicht, sondern nach Art einer Spritze ausgebildet ist: Weiterhin kann anstelle der zuvor beschriebenen Befüllung des Dosierbehälters 3 mit flüssigem Argon auch Argon im gasförmigen Zustand über die Gaszuleitung 6 herangeführt werden, welches sich dann im Dosierbehälter 3 durch die Wärmeabfuhr über die Behälterwand des Dosierbehälters 3 verflüssigt. Anstelle des den Dosierbehälter 3 aufnehmenden Druckbehälters 4 oder ergänzend zu diesem kann die Temperatur im Dosierbehälter 4 auch durch eine andere Technik, etwa durch eine Wärmetauscher, eingestellt werden.The filling of the
Nachdem das flüssige Argon in den Behälter 2 eingefüllt wurde, erfolgt die Zudosierung eines weiteren Gases, das im flüssigen oder gasförmigen Zustand zugeführt werden kann. Im Beispiel wird gasförmiges Helium über die Gaszuleitung 6 in den Dosierbehälter 3 eingebracht. Die Kontrolle über die zugeführte Gasmenge erfolgt dabei durch Regelung des Drucks in der Gaszuleitung 6 oder im Dosierbehälter 3. Das Helium bleibt im Dosierbehälter 3 im gasförmigen Zustand. Die Zudosierung des Heliums kann erfolgen, nachdem das im Dosierbehälter 3 zwischengespeicherte Argon vollständig in den Behälter eingefüllt worden ist; es ist jedoch auch möglich, die Zuführung des Heliums über die Gaszuleitung 6 bereits während der Argon-Befüllung des Behälters 2 vorzunehmen und damit infolge des Gasdrucks die Befüllung des Behälters 2 insgesamt zu beschleunigen.After the liquid argon has been introduced into the
Nach Abschluss der Heliumbefülfung wird die Absperrarmatur 16 geschlossen, der Behälter 2 verschlossen und von der Verbindungseinrichtung 10 getrennt. Der Dosierbehälter 3 wird durch Öffnen des Armatur 9 druckentlastet, und die Vorrichtung 1 steht zur Befüllung eines weiteren Behälters zur Verfügung.After completion of the Heliumbefülfung the shut-off
Der Behälter 1 kann in einer anderen Vorgehensweise auch nach der Befüllung mit Argon von der Vorrichtung 1 abgekoppelt und zu einer..weiteren Abfüllvorrichtung transportiert werden, in der dann die Heliumb,efülEung erfolgt. Wegen des niedrigen Argon-Dampfdrucks im Behälter 1 entweicht beim Transport nahezu kein Argon aus dem Behälter 2, auch wenn dieser für den Transportvorgang nicht verschlossen wird. Diese Vorgehensweise hat den Vorteil, dass bereits vorhandene Helium-Follanlagen hierfür genutzt werden könnten. Die Vorrichtung 1 eignet sich auch zur Befüllung von Behältern mit Gasgemischen, die aus mehr als zwei Komponenten bestehen. In diesem Falle werden die einzelnen Komponenten sukzessive in der zuvor beschriebenen Weise zudosiert. Die Vorrichtung 1 ermöglicht eine genaue und schnelle Befüllung von Behältern 2 mit niedrigem Befülldruck und einem genau vorausberechenbaren Enddruck.The
- 1. Vorrichtung1. Device
- 2. Behälter2. container
- 3. Dosierbehälter3. dosing tank
- 4. Druckbehälter4. pressure vessel
- 5. -5. -
- 6. Gaszuleitung6. Gas supply
- 7. Entlüfturlgsleitung7. Discharge line
- 8. Armatur8. fitting
- 9. Armatur9. fitting
- 10. Verbindungseinrichtung10. Connection device
- 11. Flüs$iggaszuleitung11. Liquid gas supply
- 12. Armatur12. faucet
- 13. Steuereinrichtung13. Control device
- 14. Flüssigkeitspegel14. Liquid level
- 15. Fülleitung15. Filling line
- 16. Armatur16th fitting
- 17. Isolierung17. Insulation
- 18. Zuleitung18. Supply line
- 19. Ventil19th valve
- 20. Steuerung20. Control
- 21. Flüssigkeitspegel21. Liquid level
- 22. Gasableitung22. Gas discharge
- 23. Einrichtung zur Druckkontrolle23. Device for pressure control
- 24.-24.-
- 25. Tauchbadbehälter25th dip tank
Claims (9)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE102005019413A DE102005019413A1 (en) | 2005-04-25 | 2005-04-25 | Process to charge an automotive airbag cartridge with gas under defined conditions of temperature and pressure |
Publications (3)
Publication Number | Publication Date |
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EP1717510A2 true EP1717510A2 (en) | 2006-11-02 |
EP1717510A3 EP1717510A3 (en) | 2008-07-09 |
EP1717510B1 EP1717510B1 (en) | 2011-09-14 |
Family
ID=36273435
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP06112218A Not-in-force EP1717510B1 (en) | 2005-04-25 | 2006-04-04 | System and method for filling a vessel with a gas or a gas mixture |
Country Status (4)
Country | Link |
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EP (1) | EP1717510B1 (en) |
CN (2) | CN100552278C (en) |
AT (1) | ATE524691T1 (en) |
DE (1) | DE102005019413A1 (en) |
Families Citing this family (11)
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CN101315545B (en) * | 2008-06-27 | 2010-06-09 | 浙江大学 | Three-level charging-up system for hydrogenation station high-efficiency hydrogenation |
JP5332933B2 (en) * | 2009-06-17 | 2013-11-06 | トヨタ自動車株式会社 | Hydrogen filling system |
CN102494514B (en) * | 2011-12-09 | 2014-10-15 | 张立永 | Freezing reactor |
SG11201509425QA (en) | 2013-05-17 | 2015-12-30 | Entegris Inc | Preparation of high pressure bf3/h2 mixtures |
CN104075104B (en) * | 2014-06-24 | 2016-02-10 | 北京控制工程研究所 | Satellite electric propulsion system hot supercharging xenon charging method |
DE102014112059A1 (en) * | 2014-08-22 | 2016-02-25 | Proton Motor Fuel Cell Gmbh | Fuel cell system reaction gas container with optimized space utilization |
EP3443257A1 (en) * | 2016-04-15 | 2019-02-20 | Scott Technologies, Inc. | Real time analysis logging of various gases and contaminants for specific breathing air cyclinders |
ITUA20163553A1 (en) * | 2016-05-18 | 2017-11-18 | Vrv S P A | STORAGE CONTAINER, TRANSPORT AND DISTRIBUTION OF LIQUID OR LIQUEFIED GAS |
CN107747678A (en) * | 2017-11-13 | 2018-03-02 | 国网内蒙古东部电力有限公司检修分公司 | A kind of extremely cold area high voltage electric equipment mixed gas making-up air device |
CN109444218B (en) * | 2018-12-17 | 2024-02-20 | 西南科技大学 | Improved environment state simulation device in oxidation kinetics reaction and use method |
CN111425755A (en) * | 2019-12-13 | 2020-07-17 | 凯馺国际股份有限公司 | Filling equipment and filling method for gas in steel cylinder for bubble water machine |
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WO1999005465A1 (en) | 1997-07-24 | 1999-02-04 | Winterlab Limited | Process for preparing ice substitutes |
WO2002066884A1 (en) | 2001-02-20 | 2002-08-29 | Messer Griesheim Gmbh | Method and device for filling pressure containers with low-boiling permanent gases or gas mixtures |
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NL6512548A (en) * | 1965-09-28 | 1967-03-29 | ||
DE1501291A1 (en) * | 1966-12-24 | 1969-12-04 | Max Planck Gesellschaft | Device for refilling a helium bath at temperatures below the? Point and operating procedures for this |
DE3714424C1 (en) * | 1987-04-30 | 1988-06-09 | Messerschmitt Boelkow Blohm | Storage of noble gas for electrical space propulsion |
JPH10259898A (en) * | 1997-01-14 | 1998-09-29 | Daikin Ind Ltd | Method for transferring and filling liquefied gas |
US5960633A (en) * | 1998-05-14 | 1999-10-05 | Limbach; John N. | Apparatus and method for transporting high value liquified low boiling gases |
EP1353112A1 (en) * | 2002-04-10 | 2003-10-15 | Linde Aktiengesellschaft | Cryogenic liquid transfer method |
FR2840971B1 (en) * | 2002-06-12 | 2004-08-06 | Air Liquide | METHOD FOR STORING IN THE GASEOUS PHASE OF A COMPRESSIBLE FLUID AND CORRESPONDING STORAGE DEVICE |
US6688115B1 (en) * | 2003-01-28 | 2004-02-10 | Air Products And Chemicals, Inc. | High-pressure delivery system for ultra high purity liquid carbon dioxide |
-
2005
- 2005-04-25 DE DE102005019413A patent/DE102005019413A1/en not_active Withdrawn
-
2006
- 2006-01-27 CN CNB200680013915XA patent/CN100552278C/en not_active Expired - Fee Related
- 2006-04-04 EP EP06112218A patent/EP1717510B1/en not_active Not-in-force
- 2006-04-04 AT AT06112218T patent/ATE524691T1/en active
- 2006-04-24 CN CN2006100751307A patent/CN1854596B/en not_active Expired - Fee Related
Patent Citations (4)
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EP0033386A1 (en) | 1980-01-31 | 1981-08-12 | Messer Griesheim Gmbh | Process for transporting and storing permanent gases |
DE19704362C1 (en) | 1997-02-05 | 1998-01-02 | Linde Ag | Vehicle tank filling device for cryogenic fuel |
WO1999005465A1 (en) | 1997-07-24 | 1999-02-04 | Winterlab Limited | Process for preparing ice substitutes |
WO2002066884A1 (en) | 2001-02-20 | 2002-08-29 | Messer Griesheim Gmbh | Method and device for filling pressure containers with low-boiling permanent gases or gas mixtures |
Also Published As
Publication number | Publication date |
---|---|
EP1717510A3 (en) | 2008-07-09 |
DE102005019413A1 (en) | 2006-10-26 |
EP1717510B1 (en) | 2011-09-14 |
ATE524691T1 (en) | 2011-09-15 |
CN1854596A (en) | 2006-11-01 |
CN101180495A (en) | 2008-05-14 |
CN100552278C (en) | 2009-10-21 |
CN1854596B (en) | 2010-06-09 |
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