EP2288811B1 - Device and method for pumping a cryogenic fluid - Google Patents
Device and method for pumping a cryogenic fluid Download PDFInfo
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- EP2288811B1 EP2288811B1 EP09761888A EP09761888A EP2288811B1 EP 2288811 B1 EP2288811 B1 EP 2288811B1 EP 09761888 A EP09761888 A EP 09761888A EP 09761888 A EP09761888 A EP 09761888A EP 2288811 B1 EP2288811 B1 EP 2288811B1
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- tank
- pressure
- pump
- fluid
- cryogenic
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B15/00—Pumps adapted to handle specific fluids, e.g. by selection of specific materials for pumps or pump parts
- F04B15/06—Pumps adapted to handle specific fluids, e.g. by selection of specific materials for pumps or pump parts for liquids near their boiling point, e.g. under subnormal pressure
- F04B15/08—Pumps adapted to handle specific fluids, e.g. by selection of specific materials for pumps or pump parts for liquids near their boiling point, e.g. under subnormal pressure the liquids having low boiling points
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B23/00—Pumping installations or systems
- F04B23/02—Pumping installations or systems having reservoirs
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B2205/00—Fluid parameters
- F04B2205/01—Pressure before the pump inlet
Definitions
- the present invention relates to a device and a method for pumping a cryogenic fluid.
- the invention relates more particularly to a device for pumping a cryogenic fluid, comprising a storage tank for a cryogenic fluid containing cryogenic liquid, a cryogenic pump having a loss (NPSH) of input charge, a line of suction connecting the reservoir to the pump, the pumping device comprising a system for controlling the pressure in the reservoir to selectively maintain the pressure in the reservoir at least equal to the saturation pressure of the stored cryogenic fluid increased by the loss (NPSH) input load of the cryogenic pump and possibly also increased the value of the pressure drops due to the piping of the suction line connecting the tank to the pump.
- the invention finds a particularly advantageous application in the field of pumping low-density cryogenic fluids comprising gases such as hydrogen or helium, as well as their isotopes.
- a liquid hydrogen pump (LH2) at 700 bar has a pressure drop "NPSH" of about 250 mbar, which corresponds to a liquid hydrogen height of 35 m. It is impossible to operate the pump with a source tank installed on the pump at a height of 35m (even if it was industrially possible, the pressure losses in lines would compensate for the installation in charge of the tank). A solution is therefore to "cool" the liquid and suck this liquid under cooling. Subcooling is the process of increasing the pressure of a saturated fluid, or of reducing its temperature, at constant pressure, without waiting for the establishment of a new liquid-vapor equilibrium.
- Hydrogen under pressure is however less dense than hydrogen at atmospheric pressure.
- the density of saturated hydrogen at 1 bar absolute is 70 g / l while it is 56g / l at 7 bar absolute. Since liquid hydrogen pumps are volumetric systems, it is therefore interesting to suck up the densest possible hydrogen, thus saturated at the lowest possible pressure (the coldest), in order to optimize the quantities pumped.
- the invention described below makes it possible in particular to use a plant for pumping liquid hydrogen continuously from a source of hydrogen in liquid-gas equilibrium at a low pressure (between 1 and 12 bar) and optimize the operation of such an installation by allowing continuous operation of the pump while maximizing the density of the pumped hydrogen, thus maximizing the pumped flow rate.
- the tank is pressurized via a thermosyphon (atmospheric pressure warmer), or directly by high pressure hydrogen in bottles at room temperature.
- An object of the present invention is to overcome all or part of the disadvantages of the prior art noted above.
- the device according to the invention is essentially characterized in that the pressure control system comprises at least one of: pipe connecting a high pressure outlet of the pump to the reservoir for selectively injecting pumped cold fluid into the reservoir, a pipe connecting a source of high pressure gas to the reservoir via a gas cooling member, for selectively injecting cooled gas into the reservoir .
- the invention also relates to a method of pumping a cryogenic fluid from a cryogenic fluid reservoir comprising cryogenic liquid, the fluid being pumped via a suction line comprising a cryogenic pump having an inlet pressure drop, the method comprising a step of controlling the pressure in the reservoir to selectively maintain the pressure in the reservoir and / or in the suction line at least equal to the saturation pressure of the cryogenic fluid increased by the inlet pressure drop of the cryogenic pump and possibly also increased the value of the pressure drops due to the piping of the suction line connecting the tank to the pump.
- the method is characterized in that the step of controlling the pressure in the tank comprises introducing said cold gas into the tank at a temperature below room temperature outside the tank and preferably between between 40 ° K and 100 ° K and at a pressure between 1 and 12 bar.
- the invention may also relate to any alternative device or method comprising any combination of the above or below features.
- the device comprises a reservoir 1 of cryogenic fluid (vacuum insulated) containing a liquid-gas mixture, for example at the temperature and a pressure of between 1 and 12 bar abs.
- cryogenic fluid vacuum insulated
- the temperature and the pressure in the tank 1 are measured by corresponding sensors 101, 10.
- the lower part of the tank 1 is connected to the suction inlet of a cryogenic pump 3 by a suction line 2 vacuum insulated and comprising one or more isolation valves.
- the pump 3 comprises a gas evacuation line 4 (produced for example by heating / friction) towards the upper part of the tank 1 and provided with valves.
- the pump is connected to a high pressure discharge line 5 generally incorporating a discharge valve (high pressure outlet of the pumped fluid).
- the high-pressure discharge line 5 is connected to a cold hydrogen feed line 6 of a preferably high-inertia exchanger 10.
- the fluid passes through a cold high-pressure line 11 and then through a high-pressure atmospheric heater (or equivalent) 12 to a gas supply line 111 having an end connectable to a user U (tank or bottle for example) via a pressure regulator 13.
- the thermally isolated high-pressure discharge line 5 is also connected to the upper part of the tank 1 via a pipe 9 for pressurizing the tank 1 by cooled hydrogen coming from the pump 3.
- the pipe 9 for pressurizing the tank 1 comprises a pressure reducer 99 and / or a control valve.
- the upper end of the tank 1 is connected to a valve 20 for depressurizing the tank (towards the outside), for example via the pressurization pipe 9.
- the pressurization pipe 9 is also connected to a source 16 of pressurized gas such as bottles 16 at ambient temperature via a line 29 passing through the exchanger 10 with high inertia (with heat exchange) and comprising a control valve 15 ( regulator for example).
- a source 16 of pressurized gas such as bottles 16 at ambient temperature via a line 29 passing through the exchanger 10 with high inertia (with heat exchange) and comprising a control valve 15 ( regulator for example).
- the gas supply line 111 is also connected to the source 6 of high-pressure gas via a pressure reducer 14.
- a block 18 for controlling the pressure of the tank 1 receives the pressure information from the pressure sensor 100 and controls a selector 17 which selectively actuates the pressure reducer / control valve 99 of the pressurization pipe 9 and the valve 15. control of the line 29 connected to the source 16 of gas under pressure.
- a calculation block 19 determines the saturation pressure in the tank 1 as a function of the temperature detected by the valve 101 and controls the control block 19 according to the result.
- the hydrogen at the pressure, and the temperature of the tank 1 is supplied by the tank 1 to the pump 3 via the isolated line 2 under vacuum.
- the hydrogen is pumped by the pump 3 and is discharged at high pressure (between 200 and 850 bar for example) by the discharge line 5 to the exchanger 10 and the line 11 high cold pressure.
- Heater 12 increases the temperature of hydrogen to room temperature.
- the expander 14 ensures that the reservoirs 16 are at a maximum pressure.
- the upstream pressure regulator 13 controls the pressure in the pump.
- the system carries out a control of the pressure of the tank 1.
- the set pressure of the tank 1 is calculated by the calculation block 19 so that the pressure in the tank is equal to the saturation pressure of the hydrogen at the raised temperature (101) added with the loss (NPSH) of the inlet charge of the pump 3 and the pressure drops in the suction pipe 2.
- the value of the pressure drop (NPSH) is given by example by the supplier of the pump 3.
- the device according to the invention has the possibility of using, during the operation of the pump 3, hydrogen coming directly from the cold high pressure outlet 5 of the pump 3 (for example hydrogen at about 70 ° K for 450 bar pressure).
- This hydrogen supplied by the pump 3 can be expanded via the valve 99 of the pressurization pipe 9 and reinjected into the tank 1 in the form of gas and / or cold liquid.
- the device according to the invention furthermore has the possibility of using, before starting the pump 3, high-pressure bottles 16 at ambient temperature to inject cold hydrogen (by passing through the exchanger / accumulator 10) in the tank 1 in order to cool the hydrogen by pressurizing the tank 1.
- the cold accumulator (in the exchanger 10) is for example previously cold set during the operation preceding the pump 3.
- the cold accumulator can be insulated with polyurethane foam or equivalent.
- the tank 1 can be depressurized using the depressurization valve 20 of the tank 1, to cool the hydrogen remaining in the tank 1.
- the hydrogen used for the pressurization of the tank 1 is thus pre-cooled.
- the thermal stratification of the gas in the tank is then lower, its rise in pressure is slower, which increases the pumping time available before reaching the maximum operating pressure of the tank 1.
- the exchanger 10 with high inertia and preferably isolated from the outside makes it possible to have a source of cold which makes it possible to pressurize the tank 1 with cold hydrogen even when the pump 3 is not not in use (from bottles 16 or equivalent).
- Thermal inertia of the exchanger 10 and its isolation mode is determined so that its temperature preferably remains constant (+/- 10 ° C) between two phases of operation of the pump 3.
- the device described allows a greater accuracy and speed of control of the pressure of the tank 1 than in the prior art, especially with respect to a thermosiphon system.
- the figure illustrates a variant that differs from the embodiment of the figure 1 only with respect to line 4 gas evacuation.
- the other elements are designated by the same references and are not described a second time.
- line 4 for evacuation or return of hydrogen is returned to a capacity 21 called degassing.
- the return line 4 communicates with a degassing tank 21 whose level is controlled by valves 23, 24 after having been heated by an atmospheric heater 22. This configuration makes it possible to prevent the hot hydrogen from returning to the atmosphere. the cryogenic tank 1 and warms all the liquid hydrogen contained therein.
- the invention thus makes it possible to obtain an under cooling of the cryogenic fluid and an aspiration of the fluid thus sub-cooled.
- the compensation of the inlet pressure drop is thus achieved, avoiding any cavitation phenomenon in the pump 3 while the fluid is maintained at a pressure sufficiently low to maximize the density of the fluid and therefore the quantity pumped.
- control of the pressurization of the tank 1 according to the invention does not affect or little the level of liquid in the tank and thus pumping time available before reaching the maximum operating pressure of the tank 1.
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- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
Abstract
Description
La présente invention concerne un dispositif et un procédé de pompage d'un fluide cryogénique.The present invention relates to a device and a method for pumping a cryogenic fluid.
L'invention concerne plus particulièrement un dispositif de pompage d'un fluide cryogénique, comprenant un réservoir de stockage d'un fluide cryogénique contenant du liquide cryogénique, une pompe cryogénique présentant une perte (NPSH) de charge d'entrée, une ligne d'aspiration reliant le réservoir à la pompe, le dispositif de pompage comprenant un système de contrôle de la pression dans le réservoir pour sélectivement maintenir la pression dans le réservoir au moins égale à la pression de saturation du fluide cryogénique stocké augmentée de la perte (NPSH) de charge d'entrée de la pompe cryogénique et augmentée éventuellement également de la valeur des pertes de charge dues à la tuyauterie de la ligne d'aspiration reliant le réservoir à la pompe.The invention relates more particularly to a device for pumping a cryogenic fluid, comprising a storage tank for a cryogenic fluid containing cryogenic liquid, a cryogenic pump having a loss (NPSH) of input charge, a line of suction connecting the reservoir to the pump, the pumping device comprising a system for controlling the pressure in the reservoir to selectively maintain the pressure in the reservoir at least equal to the saturation pressure of the stored cryogenic fluid increased by the loss (NPSH) input load of the cryogenic pump and possibly also increased the value of the pressure drops due to the piping of the suction line connecting the tank to the pump.
L'invention trouve une application particulièrement avantageuse dans le domaine du pompage de fluides cryogéniques peu denses comprenant des gaz tels que de l'hydrogène ou de l'hélium, ainsi que leurs isotopes.The invention finds a particularly advantageous application in the field of pumping low-density cryogenic fluids comprising gases such as hydrogen or helium, as well as their isotopes.
La compression d'hydrogène liquide permet de diminuer les coûts de compression par rapport à une compression d'hydrogène gazeux étant donné qu'il est plus facile de comprimer un volume de liquide incompressible qu'un volume de gaz.The compression of liquid hydrogen makes it possible to reduce the compression costs with respect to a compression of hydrogen gas since it is easier to compress a volume of incompressible liquid than a volume of gas.
La génération de cette haute pression est extrêmement coûteuse en termes d'énergie de compression. De plus, les pertes par évaporation d'hydrogène liquide dans une pompe peuvent aussi être importantes dans le cas ou la pompe n'est pas utilisée de façon optimale. La réduction des pertes (frottement et gaz) est donc un point crucial pour optimiser les coûts d'obtention de l'hydrogène haute pression.The generation of this high pressure is extremely expensive in terms of compression energy. In addition, evaporation losses of liquid hydrogen in a pump can also be significant in the case where the pump is not used optimally. The reduction of losses (friction and gas) is therefore a crucial point to optimize the costs of obtaining high pressure hydrogen.
Un des problèmes des pompes cryogéniques en général, et des pompes hydrogène liquide en particulier, réside dans le fait que le fluide à pomper est très peu dense (70g/l à 1 bar). Il est donc difficile voir impossible de fournir à la pompe la pression en aspiration nécessaire par simple installation physique du réservoir source en charge sur l'installation de pompage (pression hydrostatique). En effet, la pression en aspiration doit tenir compte de la perte de charge en entrée de la pompe (NPSH = « Net Positive Suction Head », c'est-à-dire la différence de pression entre la pression de saturation du gaz à pomper et la pression d'aspiration du fluide nécessaire pour que la pompe fonctionne en phase liquide pure, sans cavitation).One of the problems of cryogenic pumps in general, and liquid hydrogen pumps in particular, lies in the fact that the fluid to be pumped is very sparse (70 g / l at 1 bar). It is therefore difficult to see that it is impossible to supply the pump with the necessary suction pressure by simple physical installation of the source reservoir in charge on the pumping installation (hydrostatic pressure). Indeed, the suction pressure must take into account the pressure drop at the inlet of the pump (NPSH = "Net Positive Suction Head", that is to say the pressure difference between the saturation pressure of the gas at pump and the suction pressure of the fluid necessary for the pump to operate in pure liquid phase, without cavitation).
Par exemple, une pompe d'hydrogène liquide (LH2) à 700 bar possède une perte de charge « NPSH » d'environ 250 mbar, ce qui correspond à une hauteur d'hydrogène liquide de 35 m. Il est impossible de faire fonctionner la pompe avec un réservoir source installé en charge sur la pompe à une hauteur de 35m (même si c'était industriellement possible, les pertes de charge en lignes compenseraient l'installation en charge du réservoir). Une solution est donc de « sous refroidir » le liquide et aspirer ce liquide sous refroidi. Le sous refroidissement consiste à augmenter la pression d'un fluide à saturation, ou à diminuer sa température, a pression constante, sans attendre l'établissement d'un nouvelle équilibre liquide-vapeur.For example, a liquid hydrogen pump (LH2) at 700 bar has a pressure drop "NPSH" of about 250 mbar, which corresponds to a liquid hydrogen height of 35 m. It is impossible to operate the pump with a source tank installed on the pump at a height of 35m (even if it was industrially possible, the pressure losses in lines would compensate for the installation in charge of the tank). A solution is therefore to "cool" the liquid and suck this liquid under cooling. Subcooling is the process of increasing the pressure of a saturated fluid, or of reducing its temperature, at constant pressure, without waiting for the establishment of a new liquid-vapor equilibrium.
L'hydrogène sous pression est cependant moins dense que l'hydrogène à la pression atmosphérique. Par exemple, la densité de l'hydrogène saturé à 1 bar absolu est de 70 g/l alors qu'elle est de 56g/l à 7 bar absolu. Etant donné que les pompes hydrogène liquide sont des systèmes volumique, il est donc intéressant d'aspirer l'hydrogène le plus dense possible, donc saturé à la plus basse pression possible (le plus froid), ceci afin d'optimiser les quantités pompées.Hydrogen under pressure is however less dense than hydrogen at atmospheric pressure. For example, the density of saturated hydrogen at 1 bar absolute is 70 g / l while it is 56g / l at 7 bar absolute. Since liquid hydrogen pumps are volumetric systems, it is therefore interesting to suck up the densest possible hydrogen, thus saturated at the lowest possible pressure (the coldest), in order to optimize the quantities pumped.
L'invention décrite ci dessous permet notamment d'utiliser une installation de pompage d'hydrogène liquide de façon continue à partir d'une source d'hydrogène en équilibre liquide-gaz à une pression faible (comprise entre 1 et 12 bar) et d'optimiser le fonctionnement d'une telle installation en permettant un fonctionnement en continu de la pompe tout en maximisant la densité de l'hydrogène pompé, donc en maximisant le débit pompé.The invention described below makes it possible in particular to use a plant for pumping liquid hydrogen continuously from a source of hydrogen in liquid-gas equilibrium at a low pressure (between 1 and 12 bar) and optimize the operation of such an installation by allowing continuous operation of the pump while maximizing the density of the pumped hydrogen, thus maximizing the pumped flow rate.
Dans des solutions existantes, le réservoir est mis en pression par l'intermédiaire d'un thermosiphon (réchauffeur de mise en pression atmosphérique), ou directement par de l'hydrogène haute pression en bouteilles à température ambiante.In existing solutions, the tank is pressurized via a thermosyphon (atmospheric pressure warmer), or directly by high pressure hydrogen in bottles at room temperature.
Au cours du fonctionnement de ces systèmes connus, l'hydrogène à température ambiante injecté dans le ciel du réservoir réchauffe peu à peu le liquide ce qui diminue le niveau disponible de sous refroidissement.During the operation of these known systems, the hydrogen at room temperature injected into the sky of the tank gradually warms the liquid which reduces the available level of sub cooling.
Ceci augmente alors la pression de consigne du réservoir, ce qui a pour effet de diminuer le temps de pompage disponible avant l'atteinte de la pression maximale de fonctionnement du réservoir.This then increases the tank set pressure, which has the effect of reducing the pumping time available before reaching the maximum operating pressure of the tank.
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Un but de la présente invention est de pallier tout ou partie des inconvénients de l'art antérieur relevés ci-dessus.An object of the present invention is to overcome all or part of the disadvantages of the prior art noted above.
A cette fin, le dispositif selon l'invention, par ailleurs conforme à la définition générique qu'en donne le préambule ci-dessus, est essentiellement caractérisé en ce que le système de contrôle de la pression comprend l'un au moins parmi : une conduite reliant une sortie haute pression de la pompe au réservoir pour réinjecter sélectivement du fluide froid pompé dans le réservoir, une conduite reliant une source de gaz haute pression au réservoir via un organe de refroidissement du gaz, pour injecter sélectivement du gaz refroidi dans le réservoir.To this end, the device according to the invention, furthermore in accordance with the generic definition given in the preamble above, is essentially characterized in that the pressure control system comprises at least one of: pipe connecting a high pressure outlet of the pump to the reservoir for selectively injecting pumped cold fluid into the reservoir, a pipe connecting a source of high pressure gas to the reservoir via a gas cooling member, for selectively injecting cooled gas into the reservoir .
Par ailleurs, des modes de réalisation de l'invention peuvent comporter l'une ou plusieurs des caractéristiques suivantes :
- le système de contrôle de la pression comprend une conduite reliant une sortie haute pression de la pompe au réservoir pour réinjecter du fluide pompé dans le réservoir pendant le fonctionnement de la pompe, et une conduite reliant une source de gaz haute pression au réservoir via un organe de refroidissement, pour injecter du gaz refroidi dans le réservoir notamment lorsque la pompe est inactive,
- la conduite reliant une sortie haute pression de la pompe au réservoir comprend un détendeur pour réinjecter du gaz froid dans le réservoir,
- l'organe de refroidissement situé dans la conduite reliant la source de gaz haute pression au réservoir comprend un échangeur de chaleur apte à mettre sélectivement en échange thermique le gaz provenant de la source de gaz haute pression avec le fluide cryogénique pompé du réservoir,
- l'échangeur de chaleur comprend un accumulateur de frigories pour maintenir une puissance de refroidissement par inertie thermique entre deux utilisations de la pompe,
- la source de gaz haute pression est reliée à une sortie haute pression de la pompe via l'un au moins parmi : une vanne, un détendeur, un réchauffeur, pour permettre le remplissage sélectif de ladite source par du fluide provenant réservoir,
- le dispositif comporte une ligne d'évacuation du gaz généré par le fonctionnement de la pompe, ladite ligne d'évacuation du gaz reliant une sortie de gaz de la pompe au réservoir ou à un stockage dégazeur distinct,
- l'accumulateur de frigories comprend au moins l'un parmi : une masse d'aluminium, une masse d'eau glycolée, de cuivre ou d'alliage à base de plomb,
- l'accumulateur de frigories de l'échangeur de chaleur a une capacité calorifique massique (densité*Capacité calorifique à Pression constante) comprise entre 1400 et 4000 kJ.m-3.K-1 et une conductivité thermique comprise entre 30 et 400 W/m-K,
- le système de contrôle de la pression comprend un capteur de pression et un capteur de température du fluide cryogénique dans le réservoir et/ou dans la ligne d'aspiration, reliés à une logique de calcul et de commande pour fournir les signaux mesurés afin de commander l'injection de fluide dans le réservoir à partir de la pompe (3) (via la conduite 9) et/ou à partir de la source (16) de gaz haute pression (via la
conduite 10, 9), - le dispositif comprend une ligne d'alimentation en gaz ayant une extrémité connectable à un utilisateur et une extrémité reliée à une sortie haute pression de la pompe via au moins un réchauffeur et un détendeur,
- le système de contrôle de la pression comprend au moins un bloc de calcul et de commande apte calculer, à partir de la température mesurée par ledit capteur de température, une valeur minimale de la pression mesurée par ledit capteur de pression égale la pression de saturation du liquide ladite température augmentée de la perte (NPSH) de charge d'entrée de la pompe et des éventuelles pertes de charges dans la tuyauterie dans la ligne d'aspiration,
- le réservoir est rempli de fluide cryogénique saturé avec sa vapeur, le fluide cryogénique est de préférence un fluide peu dense tel que de l'hydrogène ou de l'hélium,
- le gaz de la source de gaz haute pression provient du réservoir.
- the pressure control system comprises a pipe connecting a high pressure outlet of the pump to the reservoir to reinject pumped fluid into the reservoir during operation of the pump, and a pipe connecting a source of high pressure gas to the reservoir via an organ cooling system, for injecting cooled gas into the reservoir, especially when the pump is inactive,
- the pipe connecting a high-pressure outlet of the pump to the tank comprises an expander for reinjecting cold gas into the tank,
- the cooling member located in the pipe connecting the source of high pressure gas to the tank comprises a heat exchanger able to selectively heat exchange the gas from the source of high pressure gas with the cryogenic fluid pumped from the tank,
- the heat exchanger comprises a cold accumulator for maintaining cooling power by thermal inertia between two uses of the pump,
- the source of high pressure gas is connected to a high pressure outlet of the pump via at least one of: a valve, a pressure reducer, a heater, to allow the selective filling of said source with fluid from the reservoir,
- the device comprises a gas evacuation line generated by the operation of the pump, said gas evacuation line connecting a gas outlet of the pump to the tank or to a separate degassing storage,
- the cold accumulator comprises at least one of: an aluminum mass, a brine, copper or lead-based alloy mass,
- the heat exchanger accumulator has a mass heat capacity (density * Heat capacity at constant pressure) of between 1400 and 4000 kJ.m-3.K-1 and a thermal conductivity of between 30 and 400 W / mK
- the pressure control system comprises a pressure sensor and a temperature sensor of the cryogenic fluid in the reservoir and / or in the suction line, connected to a calculation and control logic for supplying the measured signals in order to control injecting fluid into the reservoir from the pump (3) (via line 9) and / or from the source (16) of high pressure gas (via
line 10, 9), - the device comprises a gas supply line having a user-connectable end and an end connected to a high pressure outlet of the pump via at least one heater and a pressure reducer,
- the pressure control system comprises at least one calculation and control block capable of calculating, from the temperature measured by said temperature sensor, a minimum value of the pressure measured by said pressure sensor equal to the saturation pressure of the liquid said increased temperature of the loss (NPSH) of the pump inlet charge and any pressure losses in the piping in the suction line,
- the reservoir is filled with cryogenic fluid saturated with its vapor, the cryogenic fluid is preferably a low density fluid such as hydrogen or helium,
- the gas from the source of high pressure gas comes from the tank.
L'invention concerne également un procédé de pompage d'un fluide cryogénique d'un réservoir de fluide cryogénique comprenant du liquide cryogénique, le fluide étant pompé via une ligne d'aspiration comprenant une pompe cryogénique présentant une perte de charge d'entrée, le procédé comprenant une étape de contrôle de la pression dans le réservoir pour sélectivement maintenir la pression dans le réservoir et/ou dans la ligne d'aspiration au moins égale la pression de saturation du fluide cryogénique augmentée de la perte de charge d'entrée de la pompe cryogénique et augmentée éventuellement également de la valeur des pertes de charge dues à la tuyauterie de la ligne d'aspiration reliant le réservoir à la pompe.The invention also relates to a method of pumping a cryogenic fluid from a cryogenic fluid reservoir comprising cryogenic liquid, the fluid being pumped via a suction line comprising a cryogenic pump having an inlet pressure drop, the method comprising a step of controlling the pressure in the reservoir to selectively maintain the pressure in the reservoir and / or in the suction line at least equal to the saturation pressure of the cryogenic fluid increased by the inlet pressure drop of the cryogenic pump and possibly also increased the value of the pressure drops due to the piping of the suction line connecting the tank to the pump.
Selon une particularité avantageuse le procédé est caractérisé en ce que l'étape de contrôle de la pression dans le réservoir comprend une introduction de gaz dit froid dans le réservoir à une température inférieure à la température ambiante à l'extérieur du réservoir et de préférence comprise entre 40°K et 100°K et à une pression comprise entre 1 et 12 bar.According to an advantageous feature, the method is characterized in that the step of controlling the pressure in the tank comprises introducing said cold gas into the tank at a temperature below room temperature outside the tank and preferably between between 40 ° K and 100 ° K and at a pressure between 1 and 12 bar.
Par ailleurs, des modes de réalisation de l'invention peuvent comporter l'une ou plusieurs des caractéristiques suivantes :
- le gaz froid introduit dans le réservoir pour contrôler la pression dans le réservoir est fourni par l'une au moins parmi : une conduite reliant une sortie haute pression de la pompe au réservoir, une conduite reliant une source de gaz haute pression au réservoir via un organe de refroidissement du gaz,
- l'introduction de gaz froid dans le réservoir est fourni sélectivement par une conduite reliant une sortie haute pression de la pompe au réservoir lorsque la pompe est en fonctionnement et par une conduite reliant une source de gaz haute pression au réservoir via un organe de refroidissement du gaz lorsque la pompe est arrêtée,
- le gaz froid fourni par la conduite reliant une sortie haute pression de la pompe au réservoir est obtenu par détente du fluide provenant de la sortie haute pression de la pompe, et en ce que l'organe de refroidissement du gaz provenant de la source de gaz haute pression utilise des frigories du fluide pompé du réservoir.
- the cold gas introduced into the tank to control the pressure in the tank is provided by at least one of: a pipe connecting a high pressure outlet of the pump to the tank, a pipe connecting a source of high pressure gas to the tank via a gas cooling member,
- the introduction of cold gas into the tank is selectively provided by a pipe connecting a high pressure outlet of the pump to the tank when the pump is in operation and by a pipe connecting a source of high pressure gas to the tank via a cooling member of the gas when the pump is stopped,
- the cold gas supplied by the pipe connecting a high pressure outlet of the pump to the tank is obtained by expansion of the fluid coming from the high pressure outlet of the pump, and in that the cooling member of the gas coming from the gas source High pressure uses frigories of the fluid pumped from the tank.
L'invention peut concerner également tout dispositif ou procédé alternatif comprenant toute combinaison des caractéristiques ci-dessus ou ci-dessous.The invention may also relate to any alternative device or method comprising any combination of the above or below features.
D'autres particularités et avantages apparaîtront à la lecture de la description ci-après, faite en référence aux figures dans lesquelles :
- la
figure 1 représente une vue schématique illustrant la structure et le fonctionnement d'un dispositif de pompage d'un fluide cryogénique selon un premier exemple de réalisation de l'invention, - la
figure 2 représente une vue schématique illustrant la structure et le fonctionnement d'un dispositif de pompage d'un fluide cryogénique selon un second exemple de réalisation de l'invention.
- the
figure 1 represents a schematic view illustrating the structure and operation of a device for pumping a cryogenic fluid according to a first embodiment of the invention, - the
figure 2 is a schematic view illustrating the structure and operation of a device for pumping a cryogenic fluid according to a second embodiment of the invention.
En se référant à présent à la
La partie inférieure du réservoir 1 est reliée à l'entrée d'aspiration d'une pompe 3 cryogénique par une ligne 2 d'aspiration isolée sous vide et comprenant une ou plusieurs vannes d'isolation.The lower part of the
La pompe 3 comprend une ligne 4 d'évacuation du gaz (produit par exemple échauffement/frottement) vers la partie supérieure du réservoir 1 et munie de vannes.The pump 3 comprises a gas evacuation line 4 (produced for example by heating / friction) towards the upper part of the
La pompe est reliée à une ligne 5 de refoulement haute pression incorporant généralement un clapet de refoulement (sortie haute pression du fluide pompé). La ligne 5 de refoulement haute pression est reliée à une ligne 6 d'alimentation en hydrogène froid d'un l'échangeur 10 de préférence à grande inertie. En sortie de l'échangeur 10 le fluide transite dans une ligne 11 haute pression froide puis au travers d'un réchauffeur 12 atmosphérique (ou équivalent) haute pression jusqu'à une ligne 111 d'alimentation en gaz ayant une extrémité connectable à un utilisateur U (réservoir ou bouteille par exemple) via un régulateur 13 de pression.The pump is connected to a high
La ligne 5 isolée thermiquement de refoulement haute pression est reliée également à la partie supérieure du réservoir 1 via une conduite 9 de pressurisation du réservoir 1 par hydrogène refroidi issu de la pompe 3. La conduite 9 de pressurisation du réservoir 1 comprend un détendeur 99 et/ou une vanne de contrôle. L'extrémité supérieure du réservoir 1 est reliée à une vanne 20 de dépressurisation du réservoir (vers l'extérieur), par exemple via la conduite 9 de pressurisation.The thermally isolated high-
La conduite 9 de pressurisation est également reliée à une source 16 de gaz sous pression telle que des bouteilles 16 à température ambiante via une ligne 29 transitant par l'échangeur 10 à grande inertie (avec échange thermique) et comprenant une vanne 15 de contrôle (détendeur par exemple).The pressurization pipe 9 is also connected to a
La ligne 111 d'alimentation en gaz est également reliée à la source 6 de gaz à haute pression via un détendeur 14.The
Un bloc 18 de contrôle de la de la pression du réservoir 1 reçoit l'information de pression du capteur 100 de pression et pilote un sélecteur 17 qui actionne sélectivement le détendeur/vanne de contrôle 99 de la conduite 9 de pressurisation ainsi que la vanne 15 de contrôle de la ligne 29 reliée à la source 16 de gaz sous pression. Un bloc 19 de calcul détermine la pression de saturation dans le réservoir 1 en fonction de la température relevée par le clapet 101 et commande le bloc 19 de contrôle en fonction du résultat.A
Dans un exemple de fonctionnement possible avec un réservoir 1 d'hydrogène liquide sous refroidi, l'hydrogène à la pression, et à la température du réservoir 1 est fourni par le réservoir 1 à la pompe 3 par l'intermédiaire de la ligne 2 isolée sous vide. L'hydrogène est pompé par la pompe 3 et est évacué à haute pression (entre 200 et 850 bar par exemple) par la ligne 5 de refoulement vers l'échangeur 10 puis la ligne 11 haute pression froide.In an example of possible operation with a
Le réchauffeur 12 augmente la température de l'hydrogène jusqu'à la température ambiante.
Le détendeur 14 s'assure que les réservoirs 16 sont à une pression maximale. Le régulateur de pression amont 13 contrôle la pression dans la pompe.The
Selon l'invention, le système réalise un contrôle de la pression du réservoir 1. La pression de consigne du réservoir 1 est calculée par le bloc de calcul 19 pour que la pression dans le réservoir soit égale à la pression de saturation de l'hydrogène à la température relevée (101) additionnée de la perte (NPSH) de charge d'entrée de la pompe 3 et des pertes de charge dans la tuyauterie 2 d'aspiration 2. La valeur de la perte de charge (NPSH) est donnée par exemple par le fournisseur de la pompe 3.According to the invention, the system carries out a control of the pressure of the
Le dispositif selon l'invention a la possibilité d'utiliser, pendant le fonctionnement de la pompe 3, de l'hydrogène provenant directement de la sortie 5 haute pression froide de la pompe 3 (par exemple de l'hydrogène à environ 70°K pour 450 bar de pression). Cet hydrogène fourni par la pompe 3 peut être détendu via la vanne 99 de la conduite 9 de pressurisation et réinjecté dans le réservoir 1 sous la forme de gaz et/ou liquide froid.The device according to the invention has the possibility of using, during the operation of the pump 3, hydrogen coming directly from the cold
Le dispositif selon l'invention a de plus la possibilité d'utiliser, avant un démarrage la pompe 3, des bouteilles haute pression 16 à température ambiante pour injecter de l'hydrogène froid (par passage dans l'échangeur/accumulateur 10) dans le réservoir 1 afin de sous refroidir l'hydrogène en pressurisant le réservoir 1.The device according to the invention furthermore has the possibility of using, before starting the pump 3, high-
L'accumulateur de froid (dans l'échangeur 10) est par exemple préalablement mis en froid lors du fonctionnement précédant de la pompe 3. L'accumulateur de froid peut être isolé par de la mousse polyuréthane ou équivalent.The cold accumulator (in the exchanger 10) is for example previously cold set during the operation preceding the pump 3. The cold accumulator can be insulated with polyurethane foam or equivalent.
Ceci permet d'éviter toute cavitation à l'aspiration de la pompe 3.This makes it possible to avoid any cavitation at the suction of the pump 3.
Lorsque la pompe 3 est arrêtée, le réservoir 1 peut être dépressurisé à l'aide de la vanne 20 de dépressurisation du réservoir 1, pour refroidir l'hydrogène restant dans le réservoir 1.When the pump 3 is stopped, the
Selon une particularité avantageuse de l'invention, l'hydrogène servant à la pressurisation du réservoir 1 est ainsi pré-refroidi. La stratification thermique du gaz du réservoir est alors plus faible, sa montée en pression est plus lente, ce qui augmente le temps de pompage disponible avant l'atteinte de la pression maximale de fonctionnement du réservoir 1.According to an advantageous feature of the invention, the hydrogen used for the pressurization of the
De plus, l'échangeur 10 à inertie élevée et de préférence isolé de l'extérieur permet de disposer d'une source de froid qui permet de mettre en pression le réservoir 1 avec de l'hydrogène froid même lorsque la pompe 3 n'est pas en service (à partir de bouteilles 16 ou équivalent). L'inertie thermique de l'échangeur 10 et son mode d'isolation est déterminé de manière à ce que sa température reste de préférence constante (+/- 10°C) entre deux phases de fonctionnement de la pompe 3.In addition, the
Le dispositif décrit permet une précision et une rapidité de contrôle de la pression du réservoir 1 plus grandes que selon l'art antérieur, notamment par rapport à un système par thermosiphon.The device described allows a greater accuracy and speed of control of the pressure of the
La figure illustre une variante qui se distingue du mode de réalisation de la
Dans la réalisation de la
L'invention permet d'obtenir ainsi un sous refroidissement du fluide cryogénique et une aspiration du fluide ainsi sous-refroidi. La compensation de perte de charge d'entrée est ainsi réalisée, évitant tout phénomène de cavitation dans la pompe 3 tandis que le fluide est maintenu une pression suffisamment faible pour rendre maximum la densité du fluide et donc la quantité pompée.The invention thus makes it possible to obtain an under cooling of the cryogenic fluid and an aspiration of the fluid thus sub-cooled. The compensation of the inlet pressure drop is thus achieved, avoiding any cavitation phenomenon in the pump 3 while the fluid is maintained at a pressure sufficiently low to maximize the density of the fluid and therefore the quantity pumped.
De plus, le contrôle de la pressurisation du réservoir 1 selon l'invention n'affecte pas ou peu le niveau de liquide dans le réservoir et donc temps de pompage disponible avant l'atteinte de la pression maximale de fonctionnement du réservoir 1.In addition, the control of the pressurization of the
Claims (9)
- Device for pumping a cryogenic fluid, comprising a tank (1) for storing a cryogenic fluid, containing cryogenic liquid and in particular a liquid-gas mixture, a cryogenic pump (3) having an inlet head loss (NPSH), a suction line (2) connecting the tank (1) to the pump (3), the pumping device comprising a pressure control system (9, 18, 19) in the tank (1) for selectively keeping the pressure in the tank (1) at least equal to the saturation pressure of the stored cryogenic fluid plus the inlet head loss (NPSH) of the cryogenic pump and optionally also plus the value of the head losses due to the piping of the suction line (2) connecting the tank (1) to the pump (3), characterised in that the pressure control system (9, 18, 19) comprises a pipe (9) connecting a high-pressure outlet of the pump (3) to the tank (1) so as to re-inject pumped cold fluid selectively into the tank (1), the pipe (9) which connects a high-pressure outlet (5) of the pump (3) to the tank (1) comprising an expansion valve (99) for re-injecting "cold" fluid into the tank (1) in gaseous and/or liquid form.
- Device according to claim 1, characterised in that the pressure control system (9, 18, 19) comprises a pipe (9, 29) connecting a high-pressure gas source (16) to the tank (1) via a cooling member (10), so as to inject cooled gas into the tank (1), in particular when the pump (3) is inactive.
- Device according to either claim 1 or claim 2, characterised in that the cooling member (10) located in the pipe (9, 10) which connects the high-pressure gas source (16) to the tank (1) comprises a heat exchanger (10) adapted to place the gas from the high-pressure gas source (16) selectively in a heat-exchange relationship with the cryogenic fluid pumped from the tank (1).
- Device according to claim 3, characterised in that the heat exchanger (10) comprises a cold energy accumulator so as to maintain a cooling power through thermal inertia between two uses of the pump (3).
- Device according to any one of claims 1 to 4, characterised in that the high-pressure gas source (16) is connected to a high-pressure outlet of the pump (3) via at least one of a valve, an expansion valve (14) and a heater (10, 12), so as to allow said source (16) to be selectively filled with fluid from the tank (1).
- Device according to any one of claims 1 to 5, characterised in that it comprises a discharge line (4) for discharging the gas generated by the operation of the pump (3), said gas discharge line (4) connecting a gas outlet of the pump (3) to the tank (1) or to a separate degassing storage facility (21).
- Method for pumping a cryogenic fluid from a cryogenic fluid tank (1) containing cryogenic liquid and in particular a liquid-gas mixture, the fluid being pumped via a suction line (2) comprising a cryogenic pump (3) having an inlet head loss (NPSH), the method comprising a step of controlling the pressure in the tank (1) so as selectively to keep the pressure in the tank or in the suction line (2) at least equal to the saturation pressure of the cryogenic fluid plus the inlet head loss (NPSH) of the cryogenic pump and optionally also plus the value of the head losses due to the piping of the suction line (2) connecting the tank (1) to the pump (3), characterised in that the step of controlling the pressure in the tank (1) involves introducing "cold" fluid into the tank (1) at a temperature lower than the ambient temperature outside the tank (1) and at a pressure of between 1 and 12 bar, the cold fluid being introduced into the tank (1) selectively by a pipe (9) connecting a high-pressure outlet (5) of the pump (3) to the tank (1) when the pump (3) is operating and by a pipe (9, 29) connecting a high-pressure gas source (16) to the tank (1) via a gas cooling member (10) when the pump (3) is switched off.
- Pumping method according to claim 7, characterised in that the cold fluid supplied by the pipe (9) connecting a high-pressure outlet of the pump (3) to the tank (1) is obtained by expanding the fluid from the high-pressure outlet (5) of the pump (3), and in that the cooling member (10) which cools the gas from the high-pressure gas source (16) uses the cold energy of the fluid pumped from the tank (3).
- Pumping method according to either claim 7 or claim 8, characterised in that the cold fluid is introduced into the tank at a temperature of between 40 °K and 100 °K.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0853168A FR2931213A1 (en) | 2008-05-16 | 2008-05-16 | DEVICE AND METHOD FOR PUMPING A CRYOGENIC FLUID |
| PCT/FR2009/050844 WO2009150337A2 (en) | 2008-05-16 | 2009-05-07 | Device and method for pumping a cryogenic fluid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2288811A2 EP2288811A2 (en) | 2011-03-02 |
| EP2288811B1 true EP2288811B1 (en) | 2012-02-15 |
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ID=40083678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09761888A Active EP2288811B1 (en) | 2008-05-16 | 2009-05-07 | Device and method for pumping a cryogenic fluid |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US9546645B2 (en) |
| EP (1) | EP2288811B1 (en) |
| JP (1) | JP5313338B2 (en) |
| CN (1) | CN102027236B (en) |
| AT (1) | ATE545784T1 (en) |
| FR (1) | FR2931213A1 (en) |
| WO (1) | WO2009150337A2 (en) |
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| US8543245B2 (en) * | 2009-11-20 | 2013-09-24 | Halliburton Energy Services, Inc. | Systems and methods for specifying an operational parameter for a pumping system |
| US8365551B2 (en) * | 2010-12-09 | 2013-02-05 | General Electric Company | Vacuum insulator for a refrigerator appliance |
| US20140190187A1 (en) | 2013-01-07 | 2014-07-10 | Hebeler Corporation | Cryogenic Liquid Conditioning and Delivery System |
| EP2989370B1 (en) * | 2013-04-22 | 2019-07-17 | Chart Inc. | Liquid natural gas cooling on the fly |
| US9347615B2 (en) * | 2013-09-13 | 2016-05-24 | Air Products And Chemicals, Inc. | Low-loss cryogenic fluid supply system and method |
| FR3022233B1 (en) * | 2014-06-12 | 2019-06-07 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | DEVICE AND METHOD FOR SUPPLYING FLUID |
| US9828987B2 (en) * | 2015-01-30 | 2017-11-28 | Caterpillar Inc. | System and method for priming a pump |
| DE102017008210B4 (en) * | 2017-08-31 | 2020-01-16 | Messer France S.A.S. | Device and method for filling a mobile refrigerant tank with a cryogenic refrigerant |
| FR3089600B1 (en) * | 2018-12-06 | 2021-03-19 | Air Liquide | Cryogenic fluid storage tank |
| FR3089599B1 (en) * | 2018-12-06 | 2020-11-13 | Air Liquide | Cryogenic fluid storage tank |
| US12215680B2 (en) * | 2019-12-16 | 2025-02-04 | Praxair Technology, Inc. | Portable, cryogenic fluid pump apparatus with associated instrumentation, conduit legs and accessories |
| MX2022011213A (en) * | 2020-03-10 | 2022-10-07 | Chart Inc | DEVICE, SYSTEM AND METHOD FOR MEASURING LIQUID DENSITY. |
| CN112811382B (en) * | 2021-02-07 | 2025-04-22 | 中国海洋石油集团有限公司 | A closed oil unloading device for a crude oil tanker |
| US12092093B2 (en) | 2022-03-08 | 2024-09-17 | Air Products And Chemicals, Inc. | Apparatus and method for cryogenic pump cooldown |
| CN118775244B (en) * | 2024-07-17 | 2025-09-16 | 中山先进低温技术研究院 | Liquid hydrogen pump test system based on hydrogen liquefier |
| CN119878514A (en) * | 2025-02-24 | 2025-04-25 | 中国科学院理化技术研究所 | Controllable transmission system of cryogenic liquid pump cavitation |
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| US3632235A (en) * | 1969-06-09 | 1972-01-04 | Carl A Grenci | Cryogenic pump system |
| FR2439881A1 (en) * | 1978-10-23 | 1980-05-23 | Air Liquide | METHOD AND DEVICE FOR STARTING A CRYOGENIC LIQUID PUMP |
| FR2506400B1 (en) * | 1981-05-19 | 1986-03-21 | Air Liquide | METHOD AND PLANT FOR PUMP TRANSFER OF A CRYOGENIC LIQUID |
| US5243821A (en) * | 1991-06-24 | 1993-09-14 | Air Products And Chemicals, Inc. | Method and apparatus for delivering a continuous quantity of gas over a wide range of flow rates |
| US5360139A (en) * | 1993-01-22 | 1994-11-01 | Hydra Rig, Inc. | Liquified natural gas fueling facility |
| FR2707371B1 (en) * | 1993-07-08 | 1995-08-11 | Air Liquide | Installation for supplying gas under high pressure. |
| DE19717267B4 (en) * | 1997-04-24 | 2008-08-14 | Alstom | Process for the preparation of refrigerated liquefied gas |
| DE10107187A1 (en) * | 2001-02-15 | 2002-08-29 | Linde Ag | Gas station for cryogenic media |
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| US20030213246A1 (en) * | 2002-05-15 | 2003-11-20 | Coll John Gordon | Process and device for controlling the thermal and electrical output of integrated micro combined heat and power generation systems |
| JP2003148695A (en) * | 2001-11-12 | 2003-05-21 | Toho Gas Co Ltd | Liquefied natural gas pressurizer |
| US6564579B1 (en) * | 2002-05-13 | 2003-05-20 | Black & Veatch Pritchard Inc. | Method for vaporizing and recovery of natural gas liquids from liquefied natural gas |
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| FR2855598B1 (en) * | 2003-05-28 | 2005-10-07 | Air Liquide | METHOD AND INSTALLATION FOR SUPPLYING PRESSURE GAS RELIEF BY CRYOGENIC LIQUID VAPORIZATION |
| GB0320474D0 (en) * | 2003-09-01 | 2003-10-01 | Cryostar France Sa | Controlled storage of liquefied gases |
| US20050076639A1 (en) * | 2003-10-14 | 2005-04-14 | Shirk Mark A. | Cryogenic cogeneration system |
| FR2866929B1 (en) * | 2004-03-01 | 2008-04-04 | Air Liquide | SYSTEM FOR PUMPING A CRYOGENIC FLUID |
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| FR2891347B1 (en) * | 2005-09-28 | 2007-11-02 | Air Liquide | METHOD AND DEVICE FOR FILLING A PRESSURIZED GAS IN A RESERVOIR |
| DE102006019993B3 (en) * | 2006-04-26 | 2007-12-27 | Daimlerchrysler Ag | Compressed gas e.g. hydrogen, storage for e.g. fuel cell vehicle, has cooling device provided for heat transfer medium, where part of gas is supplied as heat transfer medium to cooling device through branching of filling device |
-
2008
- 2008-05-16 FR FR0853168A patent/FR2931213A1/en active Pending
-
2009
- 2009-05-07 JP JP2011508977A patent/JP5313338B2/en not_active Expired - Fee Related
- 2009-05-07 US US12/993,009 patent/US9546645B2/en active Active
- 2009-05-07 WO PCT/FR2009/050844 patent/WO2009150337A2/en not_active Ceased
- 2009-05-07 AT AT09761888T patent/ATE545784T1/en active
- 2009-05-07 EP EP09761888A patent/EP2288811B1/en active Active
- 2009-05-07 CN CN2009801174794A patent/CN102027236B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US9546645B2 (en) | 2017-01-17 |
| JP2011521180A (en) | 2011-07-21 |
| CN102027236B (en) | 2013-11-13 |
| CN102027236A (en) | 2011-04-20 |
| FR2931213A1 (en) | 2009-11-20 |
| ATE545784T1 (en) | 2012-03-15 |
| WO2009150337A2 (en) | 2009-12-17 |
| JP5313338B2 (en) | 2013-10-09 |
| EP2288811A2 (en) | 2011-03-02 |
| WO2009150337A3 (en) | 2010-02-18 |
| US20110070103A1 (en) | 2011-03-24 |
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