Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
  • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
  • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
  • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
  • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
  • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
  • F25J3/04418—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system with thermally overlapping high and low pressure columns
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
  • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
  • F25J3/04763—Start-up or control of the process; Details of the apparatus used
  • F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
  • F25J3/04854—Safety aspects of operation
  • F25J3/0486—Safety aspects of operation of vaporisers for oxygen enriched liquids, e.g. purging of liquids
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
  • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
  • F25J3/04763—Start-up or control of the process; Details of the apparatus used
  • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
  • F25J3/04872—Vertical layout of cold equipments within in the cold box, e.g. columns, heat exchangers etc.
  • F25J3/04884—Arrangement of reboiler-condensers
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
  • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
  • F25J3/04763—Start-up or control of the process; Details of the apparatus used
  • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
  • F25J3/04896—Details of columns, e.g. internals, inlet/outlet devices
  • F25J3/04933—Partitioning walls or sheets
  • F25J3/04939—Vertical, e.g. dividing wall columns
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2250/00—Details related to the use of reboiler-condensers
  • F25J2250/02—Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2250/00—Details related to the use of reboiler-condensers
  • F25J2250/20—Boiler-condenser with multiple exchanger cores in parallel or with multiple re-boiling or condensing streams
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
  • F25J2290/44—Particular materials used, e.g. copper, steel or alloys thereof or surface treatments used, e.g. enhanced surface
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S62/00—Refrigeration
  • Y10S62/902—Apparatus
  • Y10S62/903—Heat exchange structure

Definitions

• the invention relates to the field of cryogenic separation of air, and more generally to cryogenic processes in which a liquid bath rich in oxygen must be vaporized.
• the cryogenic distillation of the air is ensured in distillation columns and in the tank of some of these columns an oxygen-rich liquid is collected, in particular in the low pressure column of a column system, such as a double air separation column.
• This oxygen-rich liquid is continuously vaporized to ensure reboiling of the column, by means of a vaporizer installed in the tank and supplied with a heat transfer fluid such as nitrogen gas collected at the top of the column.
• This vaporization of oxygen gradually leads to a gradual increase in the concentration of the liquid bath treated by the vaporizer in impurities heavier than oxygen.
• these compounds mention may be made of light hydrocarbons, CO 2 and nitrogen oxides.
• This concentration is dangerous in the long term because one can then reach a threshold from which, in certain areas of the vaporizer where the liquid oxygen is completely vaporized, a deposit of hydrocarbons in the pure state can occur on the vaporizer leading to combustion. said hydrocarbons.
• This combustion can propagate to aluminum which, for reasons of cost and energy efficiency, generally constitutes the basic material of the vaporizer.
• the accumulation of inert compounds can also be dangerous when these compounds solidify in an amount such that they block the channels of the vaporizer. It is then necessary to stop the installation to restore its proper functioning.
• a partial solution to this problem could be to replace the aluminum vaporizer with a copper vaporizer, which does not risk igniting on contact with hydrocarbons.
• this solution would be expensive, in particular because the exchanger should have substantially larger dimensions, with equal performance, than an aluminum exchanger.
• Another solution consists in purging part of the oxygen-rich liquid. Such a purge occurs naturally if the installation is used to produce liquid oxygen or gaseous oxygen at high pressure by a process called "internal compression", or gaseous oxygen at low pressure. But if the oxygen is withdrawn from the column above the vaporizer (which is the case in installations producing krypton or xenon), or if the liquid oxygen withdrawn is only partially vaporized and if its part not vaporized is returned to the column, the problem arises identically.
• the purge flow can be as low as 0.01% of the total treated air flow. But in current practice, the purge flow is 0.1 to 0.2% of the total flow of treated air. The lower the purge flow, for an initial purity of air, the more one takes the risk of a dangerous accumulation of hydrocarbons and other impurities in the oxygen-rich liquid. It is generally estimated that with a purge flow rate greater than or equal to 10% of the total treated air flow, there is no longer any danger in using an aluminum vaporizer.
• the object of the invention is to propose an alternative solution to that which has just been written, in which any risk of explosion of any vaporizer would be eliminated, and which would be easier to manage, while making it possible not to reject definitively outside the installation only a minimum quantity of treated air.
• the subject of the invention is a process for treating a bath of liquid containing at least 70 mol%. of oxygen collected at the bottom of a column or of a cryogenic distillation column element forming part of a column system used for the separation of air, according to which a vaporization of said liquid bath is carried out continuously by means of at least a first vaporizer in aluminum and a part of said bath of oxygen-rich liquid is purged in order to avoid an excessive accumulation of flammable impurities in said bath, said purged part is sent in at least a second vaporizer, the oxygen vaporized by said second vaporizer is returned in said cryogenic distillation column, and in that one purges part of the bath of oxygen-rich liquid treated by said second vaporizer characterized in that the second vaporizer is by its construction and / or its material less flammable than the first vaporizer .
• a vaporization of said liquid bath is carried out continuously by means of at least a first vaporizer in aluminum and a part of said bath of oxygen-rich liquid
• the oxygen-rich liquid treated by said second vaporizer is purged at a flow rate equal to at most 1% of the total air flow supplying the distillation column system.
• the oxygen-rich liquid treated by said second vaporizer is purged at a flow rate equal to at most 0.2% of the air flow supplying said distillation column.
• a cryogenic distillation column or column element in the tank of which is disposed at least a first aluminum vaporizer for the treatment of a bath of liquid rich in oxygen, comprising purging means for bringing a part of said bath into at least a second vaporizer, means for returning the oxygen vaporized by said second vaporizer to said column, and means for purging a part of said bath sent into said second vaporizer characterized in that the second vaporizer is by its construction and / or its material less flammable than the first vaporizer.
• the cryogenic distillation column or column element comprises a partition dividing its tank into a first and a second compartment, in that said at least first vaporizer is arranged in the first compartment, in that said at least second vaporizer is arranged in the second compartment, and in that said partition has a height such that it allows the supply of the second compartment with oxygen-rich liquid from the first compartment by overflow.
• cryogenic distillation column or column element characterized in that it comprises means for measuring the level of liquid enriched in oxygen present in the compartments defined by the partition.
• an air distillation apparatus comprising a cryogenic distillation column according to claim 6, 7, 8 or 9, characterized in that the column in the tank of which the first vaporizer is the low pressure column of a double column comprising a medium pressure column and the low pressure column thermally connected to each other by means of the first vaporizer and comprising means for sending a nitrogen-enriched gas from the medium pressure column to the first vaporizer and possibly the second vaporizer.
• the basic idea of the invention consists in purging the aluminum vaporizer (s) conventionally used by sending the liquid purged in at least one other vaporizer made of a metal such as copper which can be placed either inside or outside the column.
• the copper vaporizer can safely tolerate large concentrations of impurities in the oxygen-rich liquid it processes, and only a minimal amount of liquid can be purged from this copper vaporizer.
• the vaporized oxygen is returned to the column, and an excellent material balance is obtained from the operation of cryogenic separation of the initial mixture (generally air), while retaining a very satisfactory operating safety of the installation.
• copper is just one example of a metal that can be used to make up the other vaporizer; any other metal with comparable thermal conductivity and flammability characteristics could be used.
• FIG. 2 which shows schematically front view in longitudinal section (Figure 2a) and top view in cross section ( Figure 2b) a portion of cryogenic air distillation column equipped with a second embodiment of a device according to the invention.
• FIG. 1 represents a portion of an installation 1 for cryogenic air distillation, comprising, as is known, two superimposed columns.
• the lower part of this installation is composed of a medium pressure column 2, and the upper part of installation 1 is composed of a low pressure column 3. These two columns are separated by a partition 4.
• a very liquid bath rich in oxygen 5 (at least 70%; contents of 95% or more are commonly obtained) is collected in the lower part of the low pressure column 3.
• This lower part of the low pressure column 3 also contains an aluminum vaporizer 6 . Its function is to ensure vaporization of the liquid oxygen contained in the liquid 5, so as to reboil the low pressure column 3. Inside this vaporizer, heat exchanges are ensured by means of nitrogen.
• this liquid oxygen purged through line 9 is introduced into a heat exchanger 10.
• this exchanger 10 is located outside the cryogenic separation installation. It consists of a tank 11 at the bottom of which is deposited oxygen-rich liquid 12. The lower part of the tank 11 also contains a copper vaporizer 13, the role of which is to ensure the boiling of oxygen enclosed by the bath 12.
• This copper vaporizer 13 is, like the aluminum vaporizer 6 of the cryogenic separation installation 1, supplied with gaseous nitrogen taken from the middle column pressure, by means of a pipe 14. This gaseous nitrogen condenses in the copper vaporizer 13, and a pipe 15 ensures its evacuation from the vaporizer 13 and its return to the medium pressure column 2.
• a pipe 16 pricked on the upper part of the exchanger 10 ensures the return of gaseous oxygen in the low pressure column 3, while a pipe 17 ensures a purge of a fraction of the liquid 12, this fraction therefore constituting the only quantity of liquid rich in oxygen discharged of the whole installation.
• the copper vaporizer 13 can be replaced by a copper vaporizer or another metal such as aluminum but which is by its construction less flammable than the vaporizer 6, for example the second vaporizer can be a tubular vaporizer.
• the second vaporizer is located inside the cold box which is used to isolate the column system 1.
• the flow of oxygen-rich liquid 5 sent via line 9 into the exchanger 10 is an operating parameter of the installation which can be controlled at will by the user. If one wishes to ensure that, whatever the initial cleanliness of the air treated by the distillation installation 1, there is absolutely no danger of finding in this liquid 5 an excessive concentration of impurities, the flow rate of liquid 5 sent in line 9 must be greater than or equal to 10% of the total amount of air treated by column 1. Of course, if we treat air having initially a relatively high purity, we can be satisfied with a Significantly lower purge flow.
• a purge flow of the oxygen-rich liquid 5 towards the exchanger 10 of at least 0.5% is accepted as constituting a good synthesis between economic considerations (which recommend a low flow so as not to give too large a size to the exchanger 10) and safety considerations (which recommend a high purge flow to be sure not to exceed in the oxygen-rich liquid 5 of the low pressure column 3 too high concentrations of impurities).
• the other important parameter of the installation according to the invention that must be adjusted is the purge flow rate of the oxygen-rich liquid 12 present inside the exchanger 10, and discharged through line 17. It is this purge flow which represents the only part of the materials treated by the installation which will be evacuated and definitively lost if it does not undergo subsequent treatment. It is, of course, advantageous to limit this purge flow to the lowest possible value, compatible with the security requirements of the operation of the installation, and in particular of the exchanger 10. As the vaporizer 13 of this exchanger 10 is made of copper, it is able to withstand very substantially higher concentrations of flammable impurities than an aluminum vaporizer would do.
• the size of the exchanger 10 and of the copper vaporizer 13 which contains it depends closely on the flow rate of oxygen-rich liquid 5 which they are required to treat. The higher this flow rate, the larger the exchanger 10 and the vaporizer 13. If the space available outside of column 1 is relatively limited, the exchanger 10 can only be given a small footprint: under these conditions the installation can only treat a flow of liquid rich in fairly limited oxygen 5. This type of installation as shown in FIG. 1 is therefore rather to be recommended in cases where the air treated by the cryogenic separation column 1 originally has an already relatively high purity. Otherwise, it may be recommended to use an installation according to the invention as shown in FIG. 2.
• the tank of the low pressure column 3 is divided into two compartments by a partition 18 of height H.
• the partition 18 is wedge-shaped, the first compartment 19 represents approximately three quarters of the lower part of the low pressure column 3, and the second compartment 20 represents the remaining quarter.
• the first compartment 19 is installed at least one (or, as in the example shown, several) vaporizer 21, 22, 23 made of aluminum, and in compartment 20 is installed at least one vaporizer 24 made of copper.
• the height H of the partition 18 is calculated in such a way that the oxygen-rich liquid 5 present in the first compartment 19, when the low pressure column 3 operates in steady state, overflows over the partition 18 to pass into the second compartment 20.
• This flow of liquid 5 flowing from the first compartment 19 into the second compartment 20 therefore represents the purge flow rate of the oxygen-rich liquid.
• the purged liquid forms a bath 5 'which is treated by the copper vaporizer 24. Under the effect of this treatment, the bath 5' is enriched in impurities.
• the vaporizer 24 being made of copper, this enrichment in impurities is tolerable without deteriorating the conditions of safety of the operation of the installation.
• a line 25 purges the liquid 5 ′ rich in oxygen and in impurities present in the second compartment 20, in a similar manner to the line 17 of the first embodiment of the invention shown in FIG. 1.
• the copper vaporizer 24 can be as large as the interior space of the low pressure column 3 allows, in relation to the size of the aluminum vaporizer (s) 21, 22, 23 necessary for the treatment of the oxygen-rich bath 5.
• L the installation is preferably provided with means making it possible to detect the levels reached by the oxygen-rich liquid 5, 5 'in the compartments 19, 20 defined by the partition 18. In this way, the operation of the installation can be controlled, in particular by regulating the purge flow rate circulating in line 25, so as in particular to avoid any return of liquid oxygen 5 ′ concentrated in impurities from the second compartment 20 into the first compartment 19.
• a flow of gaseous oxygen (not illustrated) is withdrawn from the lower part of the low pressure column 3 and heats up in the exchange line of the device to form a gaseous product.
• the device can also produce liquid products.
• the inside of column 3 a configuration such that the deconcentrated liquid oxygen in impurities descending from column 3 goes favorably in the first compartment 19 containing the or the aluminum vaporizers 21, 22, 23. Likewise, it is recommended to favor the mixing of this liquid oxygen deconcentrated in impurities with the liquid oxygen 5 already present in the first compartment 19.
• the different vaporizers can be operated not with nitrogen gas taken from the top of the medium pressure column 2, but with air or any other heat transfer fluid, the supply would be independent of the rest of the cryogenic separation column 1.
• the invention is applicable to any type of cryogenic distillation column in the tank from which an oxygen-rich liquid requiring purging is collected, the double column installation which has been described being only a preferred example. .

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• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Mechanical Engineering (AREA)
• Thermal Sciences (AREA)
• General Engineering & Computer Science (AREA)
• Separation By Low-Temperature Treatments (AREA)

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• 2003
  • 2003-04-10 FR FR0350097A patent/FR2853723B1/fr not_active Expired - Fee Related
• 2004
  • 2004-03-29 EP EP04724040A patent/EP1616139A1/de not_active Withdrawn
  • 2004-03-29 WO PCT/FR2004/050132 patent/WO2004092670A1/fr active Application Filing
  • 2004-03-29 US US10/552,124 patent/US7380414B2/en not_active Expired - Fee Related
• 2008
  • 2008-05-07 US US12/116,672 patent/US20080289361A1/en not_active Abandoned

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