Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
  • C10L1/1216—Inorganic compounds metal compounds, e.g. hydrides, carbides
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
  • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
  • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
  • C10L1/1208—Inorganic compounds elements
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
  • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
  • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
  • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02D—CONTROLLING COMBUSTION ENGINES
  • F02D41/00—Electrical control of supply of combustible mixture or its constituents
  • F02D41/0025—Controlling engines characterised by use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02D—CONTROLLING COMBUSTION ENGINES
  • F02D41/00—Electrical control of supply of combustible mixture or its constituents
  • F02D41/02—Circuit arrangements for generating control signals
  • F02D41/021—Introducing corrections for particular conditions exterior to the engine
  • F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
  • F02D41/027—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus
  • F02D41/029—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus the exhaust gas treating apparatus being a particulate filter
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N2430/00—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
  • F01N2430/04—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by adding non-fuel substances to combustion air or fuel, e.g. additives
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N9/00—Electrical control of exhaust gas treating apparatus
  • F01N9/002—Electrical control of exhaust gas treating apparatus of filter regeneration, e.g. detection of clogging

Definitions

• the present invention relates to a method of operating an internal combustion engine, in particular diesel, fueled by a fuel containing a regeneration catalyst of a particulate filter. This process applies to motor vehicles equipped with a catalyzed particulate filter to suppress black fumes from the engine exhaust.
• DPF particulate filters
• the regeneration of the FAP is done by periodically increasing the temperature upstream of the FAP, at a temperature sufficient to cause the combustion of soot and thus regenerate the FAP.
• This temperature is typically higher than 650 ° C and fuel is therefore usually burned in the engine (post injection) or on an oxidation catalyst upstream of the FAP to achieve this thermal level.
• the temperature of the diesel engine exhaust gases is generally much lower, typically below 400 ° C.
• the temperature of the exhaust gas tends to fall further with new combustion technologies such as HCCI type homogeneous combustion. It is also very low, often less than 250 ° C when the vehicle is used in certain conditions as in urban use.
• a second important parameter is the duration of the regeneration of the FAP, that is to say the time during which the temperature upstream of the FAP must be maintained at a high level.
• duration of the regeneration of the FAP that is to say the time during which the temperature upstream of the FAP must be maintained at a high level.
• a catalyst that promotes this regeneration is generally used according to two main principles:
• the FAP is then called catalyzed or called Catalyst Soot Filter (CSF).
• CSF Catalyst Soot Filter
• the catalyst is generally composed of a noble metal, such as platinum and transition metal oxides such as alumina or reducible oxides such as oxides based on cerium, cerium and zirconium or more generally rare earths. This technology is currently widely implemented on recent vehicles meeting the Euro 5 standard in Europe;
• FAP regeneration additive vectorized by the fuel supplying the engine or Fuel Borne Catalyst (FBC).
• FBC Fuel Borne Catalyst
• BCF additives are known, in particular those based on cerium and / or iron. This technology is currently also installed on diesel vehicles.
• the second principle is generally more efficient and can regenerate the FAP in all driving conditions, especially urban, and more economical and more environmentally friendly.
• the major disadvantage of the FBC technology lies in the complexity of its implementation, in particular to ensure a concentration of additive as constant as possible in the fuel as is currently implemented on vehicles equipped with this technology. Typically, it will be sought to maintain a concentration of additive that does not significantly evolve in the fuel, that is to say typically with concentration differences of less than 20% or even less than 10%.
• the object of the invention is to propose a process whose implementation is less complex and therefore less expensive than for known methods.
• the method of the invention is a method of operating an internal combustion engine of a vehicle equipped with an exhaust system comprising a catalyzed particle filter (CSF) in which the engine is powered with a fuel containing a regeneration catalyst of the particulate filter and characterized in that the catalyst concentration in the fuel varies in a discontinuous manner.
• CSF catalyzed particle filter
• the process of the invention makes it possible to regenerate CSF efficiently, especially at low temperature, without requiring the complex systems of the prior art to maintain the concentration in the fuel at a constant value.
• the essential feature of the process of the invention is that the catalyst concentration in the fuel varies in a discontinuous manner.
• this concentration is not constant but it is variable in time and it varies more in a non-continuous manner. So it can take in a very short time or instantly different values. It can be zero and vary in ranges which can for example vary by a factor of 0 to 30, more particularly from 0 to 20. Even more particularly these ranges can range from 0 to 15 and in particular from 0 to 5.
• This concentration can also stay constant at a certain value for a certain period of time and then go in a very short time or instantly at another value to remain constant for another period of time.
• the method of the invention can be implemented according to different variants.
• the process is carried out under conditions such that during the CSF loading period, the concentration of catalyst in the fuel varies one more time in an increasing manner. It thus passes from a value V 0 which can be zero to a value V n such that V n > Vo.
• filter loading period is meant the period during which the exhaust gas circulates inside the CSF and where it is gradually loaded into soot. This is all periods of engine operation outside the filter regeneration period.
• the concentration of catalyst in the fuel varies several times more and more. It thus passes from a value V 0 which can be zero to a value V n and then to another value V n + i, these values being such that V n + i> V n > Vo.
• the method is implemented in such a way that during the loading period of the particulate filter, the catalyst concentration in the fuel varies one or more times in a decreasing manner. It can thus go from a value V 0 which is not zero to a value V n and possibly to another value V n + i, these values being such that V n + i ⁇ V n ⁇ Vo.
• the number of times the variation occurs may not be limited.
• the catalyst concentration in the fuel can be varied several times increasing or decreasing during the CSF loading period, which concentration can be zero over a period of time.
• the invention can be used with any type of CSF regeneration catalyst. These catalysts are well known. More particularly and by way of example only, this catalyst may be in the form of a colloidal dispersion.
• the colloids of this colloidal dispersion may be based on a compound of a rare earth and / or a metal selected from groups MA, IVA, VIIA, VIII, IB, MB, IIIB and IVB of the periodic table.
• They may be more particularly based on cerium and / or iron compounds.
• Colloidal dispersions that include detergent compositions can also be used.
• colloidal dispersions examples include those described in patent applications EP 671205, WO 97/19022, WO 01/10545 and WO 03/053560, the latter two notably describing dispersions based on cerium and iron compounds respectively. these dispersions additionally containing an amphiphilic agent.
• WO 2010/150040 which describes a colloidal dispersion based on an iron compound, an amphiphilic agent and a detergent composition comprising a quaternary ammonium salt.
• the quaternary ammonium salt may be the reaction product:
• the quaternizing agent may comprise dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates; hydrocarbon-substituted epoxides in combination with an acid or mixtures thereof.
• Catalyzed PAFs are also well known. They generally comprise a catalyst based on at least one metal selected from platinum or platinum group metals, such as palladium. Combinations of platinum with these metals or these metals between them are of course possible.
• the catalyst metal may be incorporated in the filter or deposited thereon in a known manner. It can be for example included in a coating (washcoat) itself disposed on the filter.
• This coating may be chosen from alumina, titanium oxide, silica, spinels, zeolites, silicates, crystalline aluminum phosphates or their mixtures. Alumina can be particularly used.
• the washcoat may also contain reducible materials capable of directly or indirectly assisting the combustion of soot. Mention may be made, for example, of materials based on cerium oxide such as ceria, mixed oxides based on cerium and zirconium, optionally doped, or even oxides of manganese.
• the FAP catalyst is a catalyst for assisting in the combustion of soot, it is therefore present on the filter in a relatively small amount, that is to say generally in an amount of plus 70 g / ft 3 (2.5 g / dm 3 ).
• This quantity is expressed in mass of metal element, for example in weight of platinum, with respect to the volume of the FAP. This amount may more particularly be at most 60 g / ft 3 (2.1 g / dm 3 ) and even more particularly at most 50 g / ft 3 (1.8 g / dm 3 ).
• the concentration of regeneration catalyst mass in the fuel, especially when it is in the form of a colloidal dispersion will advantageously be between 0 and 30 ppm, this content being expressed in metal element such as iron in the case of a colloidal dispersion based on iron.
• the catalyst content of the soot emitted by the engine, expressed as a mass of metal element may be between 0 and 8%, depending on the content of regeneration catalyst of the fuel, the fuel consumption of the vehicle and its production of soot.
• the vehicle will operate with a fuel containing a variable content of regeneration catalyst, this content may be zero over certain periods.
• the soot produced by the engine will be more or less rich in active elements for the regeneration of CSF depending on the rate of additive fuel.
• soot loading of the CSF will be done alternately by soot that is not additive or additive in a variable concentration of catalyst. regeneration.
• the fuel used during the periodic regeneration of the CSF may be additive or non-additive.
• Regeneration is then classically controlled by the ECU of the vehicle according to the technology chosen by the manufacturer.
• the advantage of the invention is that the additive can be introduced into the fuel by simple systems, less expensive than those known and whose dosing strategy is simpler and faster to implement on the vehicle.
• Particularly preferred are systems that do not require interfacing with the ECU electronic central system of the vehicle so as to simplify its implementation on the vehicle.
• a first embodiment is to manually add a dose of additive, usually liquid, which is poured into the fuel tank of the vehicle.
• the additive dose is calculated so that the content of active ingredient for the regeneration of the CSF is sufficient to promote the combustion of the soot entrapped in the CSF.
• the iron element content of the fuel just after manual additivation may advantageously be between 2 and 30 ppm by weight of iron metal, more particularly between 5 and 20 ppm by weight of iron metal.
• This simple way makes it possible to add the fuel when it is necessary: in particular at regular frequency when the vehicle is used mainly in town - for example by adding it every 1000 to 3000 km.
• This means can also be used when the indicator light of the dashboard of the vehicle signals a defect of the means of depollution.
• FIG. 1 illustrates an example of a regeneration catalyst concentration profile in the fuel that can be obtained when a dose of additive is added regularly to the tank here every 2200 km (or 44 hours of taxiing). ).
• a fixed fuel consumption of 6 1/100 km was considered, a fixed speed of 50 km / h or a fixed fuel consumption of 3 l / h.
• the iron content increases sharply from 0 to 15 ppm.
• the figure also mentions the regeneration periods of the CSF (stars in the figure) - the regenerations being done at regular intervals of 700 km or every 14 hours of operation. It can be noted, for example, that the soot loading of the CSF corresponding to the first regeneration was done with a vehicle operating 50% of the time with a non-additive fuel and 50% of the time with an additive fuel at 15 ppm iron weight.
• Example 1 below illustrates the benefit obtained by means of a regeneration engine test of a CSF carried out under these loading conditions.
• soot loading of the CSF is done with a fuel whose concentration of additive is variable and that the benefit is obtained by implementing a very simple system of pouring every 2200 km here (44 hours here) a additive dose manually into the tank.
• Another embodiment can be used by equipping the vehicle with means for introducing the simple and autonomous regeneration catalyst, that is to say without connection with the central ECU of the vehicle.
• This means may consist in the introduction of a small FBC catalyst tank, typically 1 L or less, of a metering pump for injecting at regular intervals a given amount of additive into the fuel tank.
• the pump can be less complicated and therefore less expensive since the quantity injected will be fixed.
• No interfacing with the ECU is necessary since the pump can be programmed to inject for example at regular intervals (time interval as every 5 to 10 hours and / or kilometer interval as every 1000 to 3000 km).
• Local devices on the pump such as a power-up or GPS chip may indicate to the pump that the vehicle is driving or giving the distance covered by the vehicle.
• the downstream exhaust line is a commercial line consisting of an oxidation catalyst containing a platinum-alumina washcoat followed by a commercial CSF containing a platinum-alumina washcoat (volume total of filter 3 L).
• the fuel used is a commercial fuel meeting the standard
• the fuel is additive by the amount of FBC additive making it possible to achieve different iron metal content expressed as ppm mass relative to the mass of the fuel.
• the FBC additive used is an additive based on a colloidal dispersion of iron particles such as dispersion C of Example 3 of the patent application WO 2010/150040, the iron element content of this additive being 4. , 3% mass of iron metal.
• the iron content of the additive fuel is controlled by the
• the test is carried out in two successive steps: a CSF soot loading step, followed by a regeneration step thereof.
• the conditions of these two stages are strictly identical for the different tests, apart from the fuel used (additive or not).
• the loading phase is carried out by operating the engine at a speed of 3000 rpm and using a torque of 45 Nm for approximately 6 hours. This loading phase is stopped when 12 g of particles (or soot) are loaded into the CSF. During this phase the temperature of the gases upstream of the CSF is 230-235 ° C. Under these conditions the particle emissions are about 2 g / h.
• the CSF is disassembled and weighed to control the mass of charged particles during this phase.
• the CSF is then reassembled on the bench and warmed by the engine which is reset for 30 minutes in the operating conditions of the load (3000 rpm / 45 Nm).
• the engine conditions are then modified (torque 80 Nm / 2200 rpm) and a post-injection is controlled by the central electronic engine unit (ECU), which allows the temperature upstream of the CSF to be raised to 500 ° C and to start its regeneration. These conditions are maintained for 60 minutes, this time being counted from the start of the post-injection.
• ECU central electronic engine unit
• the fuel used during the regeneration is the last fuel used for the CSF loading phase.
• the regeneration efficiency of CSF is measured by two parameters:
• % burned soot (t) ((DPc-DPt) / (Dpc-Dpr)) * % total burnt soot
• test 1 Three reference tests (not in accordance with the invention) were carried out either with a non-additive fuel (test 1) or using an additive fuel throughout the loading of the CSF and its regeneration (test 10 with a rate of additive fuel at 15 ppm iron and test 1 1 with a fuel additivation rate at 3 ppm iron).
• tests were carried out using a non-additive fuel at the start of charging the CSF (Fuel No. 1) and an additive fuel (Fuel No. 2) at the end of charging (tests 2 to 5 and 8 to 9) or in the reverse order ie fuel additive at the beginning of loading and not additive (tests 6 to 7).
• Each of the tests represents either a respective loading time without and with added fuel or a change in the amount of FBC additive in the fuel.
• Table 1 compares the results obtained during the regeneration of the CSF by expressing the% of soot burned in total, ie at the end of the regeneration period (1 hour) or at the beginning of the regeneration (20 minutes).
• test 1 when a non-additive fuel is used (test 1), the regeneration is not total (60% after 1 hour) and it is also much slower (39% regeneration after 20 minutes). minutes).
• the loading of the CSF using an alternation of non-additive fuel then additive (or reverse) can greatly increase the regenerative efficiency of the CSF.
• the test 2 represents the loading conditions of the CSF described for the loading of the CSF during its first regeneration in FIG.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Combustion & Propulsion (AREA)
• General Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Processes For Solid Components From Exhaust (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Exhaust Gas After Treatment (AREA)
• Catalysts (AREA)
• Exhaust Gas Treatment By Means Of Catalyst (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Output Control And Ontrol Of Special Type Engine (AREA)
• Filtering Of Dispersed Particles In Gases (AREA)

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• 2011
  • 2011-03-17 FR FR1100799A patent/FR2972766B1/fr not_active Expired - Fee Related
• 2012
  • 2012-03-15 US US14/004,832 patent/US20140048029A1/en not_active Abandoned
  • 2012-03-15 EP EP12708549.6A patent/EP2686410A1/de not_active Withdrawn
  • 2012-03-15 WO PCT/EP2012/054549 patent/WO2012123540A1/fr active Application Filing
  • 2012-03-15 KR KR1020137026987A patent/KR101605597B1/ko active IP Right Grant
  • 2012-03-15 JP JP2013558434A patent/JP2014511960A/ja active Pending
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• 2016
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