Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
  • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
  • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
  • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
  • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen

Definitions

• the invention relates to the field of methods for producing liquid hydrocarbons comprising a Fischer-Tropsch synthesis step. It relates more particularly to an improved Fischer-Tropsch synthesis process which makes it possible to maximize production and minimize production costs.
• Fischer-Tropsch synthesis is a reaction which makes it possible to synthesize liquid paraffinic, olefinic hydrocarbons and / or oxygenated derivatives from a synthesis gas, the latter being for example obtained from natural gas or coal. This reaction, exploited industrially in Europe during the Second World War and also in South Africa since the 1950s, has found a spectacular revival of interest since the 1980s to 1990, following the evolution of the oil and gas costs, but also for environmental reasons.
• One of the concerns of those skilled in the art implementing such methods is to maximize the rate of conversion of the reactants, that is to say to maximize the rate of conversion of carbon monoxide to liquid hydrocarbons. It is often difficult to maximize the conversion rate of the reactants in a single reactor and in a single pass, that is to say in a single pass of said reactants in said reactor. Indeed, by seeking a high level of conversion, the functioning of the catalyst used during the synthesis can be degraded taking into account the operating conditions and, in particular, the high partial pressures of water. For example, a marked decrease in the selectivity of products having at least five carbon atoms can be observed when, using a cobalt-based catalyst, the conversion level of carbon monoxide is pushed beyond about 80% by weight.
• one solution may consist in carrying out said synthesis in several stages, for example by using several reactors in series.
• Another solution can consist in carrying out the Fischer-Tropsch synthesis in a single reactor by implementing an internal recycling loop around said reactor, which can make it possible to maintain a level of conversion by moderate pass, for example of the order of 60 to 70% by weight, while achieving a high overall conversion level, for example greater than or equal to 90% conversion.
• the usage ratio is generally defined as the stoichiometric ratio (or molar ratio) between the hydrogen and the carbon monoxide consumed by the Fischer-Tropsch synthesis.
• the usage ratio is generally variable. This ratio may depend on the nature of the catalyst as well as the operating conditions used during the synthesis. This usage ratio can change over time, depending for example on the stability of the catalyst. This usage ratio can also reflect the selectivity of the catalyst. For example, in the case of a Fischer-Tropsch process using a cobalt-based catalyst and aimed at producing long-chain paraffinic hydrocarbons, the usage ratio can vary between 2.0 and 2.3 in moles.
• the ratio between hydrogen and carbon monoxide introduced into a reaction zone where a Fischer-Tropsch synthesis is carried out plays on the reaction mechanisms of said synthesis, in particular on the kinetics and the selectivity of the catalyst used.
• An object of the invention therefore relates to a process for the production of liquid hydrocarbons by Fischer-Tropsch synthesis comprising a step (a) of generating a synthesis gas essentially comprising carbon monoxide and hydrogen, a step ( b) Fischer-Tropsch synthesis, from a feed comprising at least part of the synthesis gas, allowing the production of an effluent comprising liquid synthetic hydrocarbons and at least one gaseous effluent, a step (c ) of condensation of the gaseous effluent obtained during step (b), a step (d) of separation of the condensed effluent during step (c) making it possible to obtain a gaseous effluent enriched in carbon monoxide and in hydrogen, an aqueous phase and liquid hydrocarbons, and a step (e) of recycling at least part of the enriched gaseous effluent obtained during step (d) to step (b) of synthesis Fischer-Tropsch, in which: 1) two ratios are determined molar concentrations
• margin error is a function of the regulation system implemented and the response times of the adjustment means. Said margin of error is less than or equal to plus or minus 5%, preferably less than or equal to plus or minus 2%, more preferably less than or equal to plus or minus 1%, for example less than or equal to plus or minus minus 0.5%.
• the determination of the molar concentrations of hydrogen and of carbon monoxide can be carried out using any means known to those skilled in the art, such as for example chromatographic analyzes. These A1 and A2 concentration ratios can then be determined by simple calculation from the concentration measurements.
• A1 corresponds to a molar ratio of hydrogen and carbon monoxide concentrations in the feed of step (b) of Fischer-Tropsch synthesis.
• This feed is generally a mixture comprising the synthesis gas produced in step (a) and the effluent enriched with hydrogen and carbon monoxide recycled during step (e).
• A2 corresponds, for its part, to a molar ratio of hydrogen and carbon monoxide concentrations in any of the gaseous effluents obtained during steps (b) to (e).
• A2 is calculated from measurements carried out on any gaseous flow originating from the gaseous effluent obtained during step (b) and directed towards the effluent recycled during step (e). These streams generally have hydrogen and carbon monoxide concentrations in the same proportions.
• the concentration ratio A2 can be calculated on the basis of measurements carried out on at least one of the following effluents: the gaseous effluent obtained during step (b), - the cooled effluent obtained during step (c), preferably on the gaseous part of this effluent, - the gaseous effluent enriched in carbon monoxide and in hydrogen obtained during step (d), or - the effluent recycled to step (b) Fischer-Tropsch synthesis.
• the concentrations of hydrogen and / or carbon monoxide in the synthesis gas obtained in step (a) are adjusted so as to maintain the difference between the two substantially constant A1 and A2 reports.
• This adjustment can be carried out by any means known to a person skilled in the art, such as, for example, by means of a regulation system or an automaton connected, on the one hand, to the means for measuring the concentrations of hydrogen and of monoxide of carbon on the basis of which the ratios A1 and A2 are calculated, and on the other hand to means for adjusting the hydrogen and / or carbon monoxide concentrations in the synthesis gas obtained in step (a)
• the regulation of the process of the invention makes adjustments in step (a) of the process in order to enrich the synthesis gas with carbon monoxide or to deplete it in hydrogen so as to minimize or keep constant the difference between A1 and A2.
• the regulation of the process of the invention makes adjustments at the level of step (a) of the process in order to enrich the synthesis gas with hydrogen or to deplete it in carbon monoxide so as to equalize A1 and A2.
• the implementation of the method of the invention advantageously makes it possible to avoid having to carry out the regulation with respect to a given value of the usage ratio.
• the regulation is done by minimization or maintenance at a constant value of the difference between two concentration ratios, " in this case those measured by A1 and A2.
• one adjusts the hydrogen and / or carbon monoxide concentrations in the synthesis gas obtained in step (a) so as to maintain substantially constant between the two ratios A1 and A2
• the concentrations of hydrogen and / or carbon monoxide in the synthesis gas obtained in step (a) can be adjusted so as to keep the difference between the two ratios A1 and A2 constant.
• the difference between the two ratios A1 and A2 at a constant value less than 0.5, preferably less than 0.2.
• This mode makes it possible to adjust the selectivity of the reaction to obtain the desired product distribution.
• the aging of the catalyst over time can induce a variation in the usage ratio giving rise to a modification of the distribution of the products.
• the usage ratio in the reaction zone of step (b) of Fischer-Tropsch synthesis can vary over time.
• this usage ratio tends to increase over time, which may reflect a certain deactivation of the catalyst, and more particularly a decrease in its selectivity for long chain hydrocarbon products.
• the usage ratio can increase with temperature, which favors the formation of light products to the detriment of heavy products. There can therefore also be an impact of any change in capacity, in terms of modification of spatial speed and / or modification of operating temperature, on the usage ratio in the Fischer-Tropsch synthesis reaction zone.
• the method of the invention is implemented so as to regulate the operating conditions in order to regulate the H2 / CO concentration ratio to a level corresponding to a required usage ratio in accordance with a targeted product distribution.
• the present invention can advantageously be implemented in the processes for converting natural gas into liquid hydrocarbons, processes known by the Anglo-Saxon name “gas to liquid”, or abbreviated as GTL. These processes present a natural gas recovery route which makes it possible, among other things, to produce very good quality diesel fuels, sulfur-free, from natural gas. These methods generally use a catalyst based on cobalt or iron, preferably based on cobalt. Step (a):
• the method of the invention therefore comprises a step (a) of generation of the synthesis gas essentially comprising carbon monoxide and hydrogen.
• This generation of a synthesis gas can be carried out from natural gas, from coal or obtained by any other transformation route known to those skilled in the art, for example by decomposition of methanol in the presence of a copper-based catalyst.
• the generation of a synthesis gas is carried out from natural gas.
• this step (a) may include a step of steam reforming of methane or a step of partial oxidation of the methane, or a combination of these two steps, such as the autothermal reforming process, for example, the ⁇ ATR process sold by the company TOPSOE.
• This first step may include a combination of a methane vapor reforming step with a methane partial oxidation step.
• this embodiment provides a means of adjusting the concentrations of hydrogen and carbon monoxide in the synthesis gas, in particular the concentration ratio of hydrogen and carbon monoxide, H2 / CO. These means generally result from the implementation of a reaction for converting carbon monoxide in the presence of water into carbon dioxide and into hydrogen.
• Step (a) for generating a synthesis gas may include means dedicated to adjusting the concentrations of hydrogen and / or carbon monoxide in the synthesis gas.
• these means can be injection means with controlled flow of water and / or carbon dioxide.
• step (a) comprises an autothermal reforming
• the injection of water vapor at a controlled flow rate is particularly well suited.
• step (a) of generation of a synthesis gas is followed by a step (a 1 ) dedicated to the adjustment of the concentrations of hydrogen and / or of monoxide carbon in the synthesis gas.
• This step (a ') can be carried out from a supply of all or part of the synthesis gas produced in step (a).
• step (a 1 ) is carried out using a supply of part of the synthesis gas produced in step (a), which can range from 1 and 50% by weight, preferably 10 to 30 % by weight of the synthesis gas produced in step (a).
• this step (a ′) may include the implementation of a means for extracting hydrogen or carbon monoxide, such as, for example, a membrane which preferentially extracts hydrogen from a mixture comprising hydrogen and carbon monoxide.
• This step (a ′) may include the implementation of means allowing a make-up of hydrogen or carbon monoxide, such as, for example, a make-up line of hydrogen coming from an annexed catalytic reforming unit.
• This adjustment can also be carried out by means of the regulation system which constitutes one of the objects of the invention.
• the ratio of H2 / CO concentrations at the output of step (a 1 ) can be equal to, higher or lower than the H2 / CO concentration ratio in the synthesis gas from step (a).
• step (a 1 ) makes it possible to improve the regulation of the H2 / CO concentration ratio of the feed to the reaction section of step (b). Indeed, even if it is often possible to adjust this H2 / CO concentration ratio directly during step (a) of synthesis gas generation, the regulatory actions on this step (a) can exhibit significant response times which may prove to be too slow for establishing effective regulation, or even incompatible with the regulation system of the present invention.
• the preferred embodiment implementing a step (a 1 ) provides flexibility in the operation of the method of the invention. The adjustments made at this stage (a ') are simple and rapid corrective actions, which considerably improves the overall performance of the process of the invention.
• Step (b) of Fischer-Tropsch synthesis of the process according to the invention is carried out using a feed comprising at least part of the synthesis gas originating from steps (a) or (a 1 ) and allowing production an effluent comprising synthetic liquid hydrocarbons and at least one gaseous effluent.
• step (b) Thanks to the H2 / CO concentration ratio regulation system in step (b), the operation of this Fischer-Tropsch synthesis step is optimized.
• Step (b) of Fischer-Tropsch synthesis is carried out in a reaction zone comprising one or more suitable reactors, the technology of which is known to those skilled in the art.
• suitable reactors the technology of which is known to those skilled in the art.
• These can be, for example, multitubular fixed bed reactors, mobile bed reactors or bubble column type reactors, known in English under the name of "slurry bubble column", or abbreviated as "SBC” .
• step (b) implements one or more reactors of the bubble column type. Since synthesis is highly exothermic, this mode of realization allows, among other things, to improve the thermal control of the reactor, in particular in the case of high capacity units.
• the catalyst used in this step (b) is generally any catalytic solid known to those skilled in the art allowing the Fischer-Tropsch synthesis to be carried out.
• the catalyst used in this step (b) comprises cobalt or iron, more preferably cobalt.
• the catalyst used in this step (b) is generally a supported catalyst.
• the support can be, for example, based on alumina, silica or titanium.
• the temperature and pressure conditions are variable and adapted to the catalyst used in this step (b).
• the pressure can generally be between 0.1 and 10 MPa.
• the temperature can generally be between 200 and 400 ° C.
• the temperature is preferably between approximately 200 and 250 ° C. and the pressure is preferably between approximately 1 and 4 MPa.
• the feed of step (b) of the invention comprises carbon monoxide and hydrogen with a ratio of H2 / CO molar concentrations which can be between 0.5 and 3, preferably between 1 and 2 , 5, more preferably between 2.0 and 2.3.
• the liquid effluent from step (b) comprising the synthetic liquid hydrocarbons is generally intended to be treated in various purification and / or conversion steps with a view to producing, for example, fuels and in particular diesel fuel very high quality.
• a gaseous effluent obtained during step (b) is condensed.
• This effluent can comprise all or part of the effluent obtained during step (b).
• This condensation step can be carried out so as to reach a temperature ranging from -20 to 300 ° C, preferably ranging from 0 to 200 ° C, more preferably ranging from 30 to 60 ° C.
• the condensation step (c) is carried out so as to condense at least part of the effluent sent in said step, which makes it possible to obtain a two-phase flow.
• the condensed part can represent at most 50%, preferably at most 15% by weight, of the part of the effluent sent in the condensation step.
• the condensation step (c) can be implemented by any means known to those skilled in the art, such as, for example, an air condenser or a conventional water heat exchanger, preferably by an air condenser.
• the separation zone in which the separation step (d) is implemented can be equipped by any means known to those skilled in the art, such as, for example, by one or more separation tanks.
• step (e) at least part of the gaseous effluent enriched in carbon monoxide and in hydrogen obtained during step (d) is recycled to step (b) of synthesis Fischer-Tropsch synthesis.
• the part of the enriched gaseous effluent recycled to stage (b) of Fischer-Tropsch synthesis may comprise at least 50% by volume, preferably at least 75% by volume, more preferably at least 85% by volume effluent enriched in carbon monoxide and hydrogen obtained during step (d).
• the part of the enriched effluent recycled to step (b) can have a flow rate ranging from 0 (excluded) to 2 times, preferably from 0.5 to 1.5 times that of the synthesis gas obtained from step (a) or (a ').
• the part of the effluent enriched in carbon monoxide and in hydrogen is compressed by any means known to those skilled in the art at a pressure which can range from 0.1 to 10 MPa, preferably from 1 to 4 MPa, more preferably from 2 to 3 MPa.
• step (e) of recycling can comprise means for extracting carbon dioxide.
• These means can be any means known to those skilled in the art, such as, for example, washing with an aqueous solution of amines.
• the carbon dioxide extraction can be partial or total. This extraction can be carried out on all or part of the recycled enriched effluent.
• the recycled enriched effluent can optionally be reheated or cooled by any means known to those skilled in the art.
• three embodiments of the method of the invention are illustrated in Figures 1, 2 and 3.
• Figure 1 schematically shows an embodiment corresponding to a basic version of the method of the invention.
• FIG. 2 schematically represents a preferred embodiment of the process of the invention in which a separate step (a ') for adjusting the ratio of the concentrations of hydrogen and carbon monoxide is carried out after step (a ) generation of synthesis gas.
• FIG. 3 schematically represents another preferred embodiment in which step (a 1 ) of adjusting the ratio of the concentrations of hydrogen and of carbon monoxide is carried out only on part of the synthesis gas produced during step (a).
• Figure 4 shows, in the context of the example below, the impact of the H2 / CO molar ratio on the conversion of carbon monoxide.
• FIG. 5 represents, within the framework of the example below, the impact of the H2 / CO molar ratio on the selectivity of hydrocarbons having at least five carbon atoms.
• a hydrocarbon feedstock is sent via a conduit 1 to a synthesis gas generation zone 2, said gas then being sent into a conduit 3.
• the generation zone 2 is equipped with means for adjusting the hydrogen and carbon monoxide concentrations of the synthesis gas thus produced.
• These means are represented schematically by a hydrogen supply pipe 4 equipped with a valve 5 and a hydrogen discharge pipe 6 equipped with a valve 7.
• the two valves 5 and 7 can be operated at distance by a programmable controller 51.
• the synthesis gas is sent via the pipe 3 and a pipe 11 into a Fischer-Tropsch synthesis reactor 12.
• This reactor is equipped with a discharge pipe 13 for an effluent comprising liquid hydrocarbons to purification and / or conversion steps not shown.
• a gaseous effluent is also evacuated via a line 21 of the Fischer-Tropsch synthesis reactor 12. This gaseous effluent is directed to a cooling unit 22. The cooled effluent is directed through a conduit 31 to separation means, in this case a separator flask 32. An aqueous effluent enriched with water is drawn off at the bottom of this flask by a conduit 33. A liquid effluent enriched in hydrocarbons is also drawn off through a pipe 34. At the head of the separator tank, an effluent enriched in carbon monoxide and hydrogen is discharged through a pipe 35.
• Part of the enriched effluent is sent, via a conduit 41, to a compressor 42.
• the other part of the enriched effluent is discharged via a conduit 43.
• the part of the enriched and compressed effluent is sent, via a conduit 44, to means 45 for extracting carbon dioxide before being recycled into the Fischer-Tropsch synthesis reactor via a conduit 46 by via the conduit 11.
• the carbon dioxide is extracted via a conduit 47.
• a programmable controller 51 makes it possible to regulate the opening and closing of the valves 5 and 7 as a function of the measurements of hydrogen and carbon monoxide concentrations carried out using chromatographic analyzers 52 and 53 located respectively on the conduits 11 and 41. Valves 5 and 7, and analyzers 52 and 53 are connected to the programmable controller 51 respectively via lines 54, 55, 56 and 57.
• Figure 2 includes elements already shown in Figure 1.
• the embodiment represented in FIG. 2 comprises means 61 for adjusting the ratio of the concentrations of hydrogen and carbon monoxide in the synthesis gas, said means being dissociated from the zone 2 for generation of the synthesis gas. These adjustment means are connected to the synthesis gas generation zone 2 via a conduit 62.
• FIG. 2 The means (4, 5, 6 and 7) used to adjust the hydrogen and carbon monoxide concentrations in FIG. 1 are replaced in FIG. 2 by a supply pipe 63 in hydrogen equipped with a valve 64 and a hydrogen discharge pipe 65 fitted with a valve 66.
• the two valves 64 and 66 are operated remotely by a programmable controller.
• the programmable controller 51 makes it possible to regulate the opening and closing of the valves 64 and 66 as a function of the hydrogen and monoxide concentration measurements.
• carbon produced by chromatographic analyzers 52 and 53 which are, in this embodiment, located respectively on the conduits 1 1 and 43.
• the valves 64 and 66, and the analyzers 52 and 53 are connected to the programmable controller 51 respectively via lines 54, 55, 56 and 57.
• Figure 3 includes elements already shown in Figure 2. Unlike the embodiment of Figure 2, the adjustment means 61 of the ratio of the concentrations of hydrogen and carbon monoxide in the synthesis gas are directly connected to the synthesis gas pipe 3 via a supply pipe 71 and a discharge pipe 72.
• step of adjusting the ratio of the concentrations of hydrogen and carbon monoxide is implemented only on part of the synthesis gas produced during step (a).
• the programmable controller 51 makes it possible to regulate the opening and closing of the valves 64 and 66 as a function of the measurements of hydrogen and carbon monoxide concentrations carried out using chromatographic analyzers 52 and 53 which are , in this case, located respectively on the conduits 11 and 46.
• the valves 64 and 66, and the analyzers 52 and 53 are connected to the programmable controller 51 respectively via the lines 54, 55, 56 and 57.
• the diagram in Figure 3 served as the basis for these examples.
• the reaction section of the Fischer-Tropsch synthesis used in these examples was supplied with a synthesis gas comprising hydrogen and carbon monoxide.
• This synthesis gas is produced by a generation device and an adjustment device making it possible either to maintain constant, or to adjust to a value determined by a programmable controller, the H2 / CO concentration ratio of hydrogen and monoxide. of carbon from this synthesis gas.
• the recycling rate defined by the ratio of the flow rate in the recycling loop to the flow rate of synthesis gas leaving the synthesis gas generation zone, is maintained around a value equal to 1.0.
• the Fischer-Tropsch synthesis reaction is carried out at 220 ° C.
• the Fischer-Tropsch reaction section is fed with a synthesis gas having a H2 / CO molar concentration ratio equal to 2.0.
• the Fischer-Tropsch reaction section is fed with a synthesis gas having a H2 / CO molar concentration ratio equal to 2.2.
• the method implemented corresponds to the diagram in FIG. 3 in which the regulation system according to the invention (adjustment means 61, automaton 51, valves 64 and 66) is not implemented (comparative cases).
• the Fischer-Tropsch reaction section is supplied with a synthesis gas having a ratio of H2 / CO molar concentrations regulated by, inter alia, the adjustment means 61, the automaton 51 and to valves 64 and 66 according to the invention ( Figure 3).
• Figure 4 shows the impact of the H2 / CO concentration ratio on the conversion of carbon monoxide.
• Figure 5 shows the impact of the H2 / CO concentration ratio on the selectivity of hydrocarbons having at least five carbon atoms.
• the regulation method according to the invention not only allows stable operation, but it also makes it possible, simply, quickly and precisely, to adjust the ratio of H2 / CO concentrations in the reactor to a level approximately equal to the usage ratio. .
• This operation thus makes it possible to obtain a good compromise between the conversion of carbon monoxide and the selectivity to hydrocarbons having at least 5 carbon atoms.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2005
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  • 2005-05-17 WO PCT/FR2005/001234 patent/WO2005123882A1/fr active Application Filing
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