Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F3/00—Biological treatment of water, waste water, or sewage
  • C02F3/28—Anaerobic digestion processes
  • C02F3/286—Anaerobic digestion processes including two or more steps
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
  • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
  • C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
  • C12M23/00—Constructional details, e.g. recesses, hinges
  • C12M23/58—Reaction vessels connected in series or in parallel
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
  • C12M45/00—Means for pre-treatment of biological substances
  • C12M45/04—Phase separators; Separation of non fermentable material; Fractionation
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
  • C12M45/00—Means for pre-treatment of biological substances
  • C12M45/06—Means for pre-treatment of biological substances by chemical means or hydrolysis
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

• the invention relates to a process for the continuous treatment of solid organic products in a hydrolysis reactor. More specifically, the invention relates to a process for the continuous treatment of solid organic products in which the residence time of the solids and the residence time of the liquids in the hydrolysis reactor are controlled and can be dissociated so as to optimize the treatment. solids. Controlled means that their values are chosen accurately by the user and are adjustable according to the needs.
• the invention also relates to a treatment plant for the continuous treatment of solid organic products. The invention has applications in any industry generating organic products, including food industries.
• Anaerobic digestion has been used for a very long time for the transformation of organic waste, soluble or solid, into biogas.
• This technique is applied to the depollution of polluting loads, such as urban or industrial waste water loaded with biodegradable organic matter, or organic products in solid form, such as sewage sludge, household waste, biowaste, waste from agro-food industries, waste from different agricultural or forestry activities, energy crops.
• Methanation is a complex biological process, involving several stages of decomposition of organic matter, including: hydrolysis, in which macromolecules are transformed into low molecular weight molecules and soluble; acidogenesis, in which low molecular weight molecules are converted to short chain organic acids, alcohols, hydrogen and other simple compounds; acetogenesis, in which the alcohols and organic acids are converted into acetic acid; methanogenesis, during which methane is formed, either from hydrogen or from acetic acid.
• the treatment of solid charges by methanation requires, when carried out in a single step, a particularly long time. This is why it is known to carry out a treatment in two stages: on the one hand, hydrolysis and acidogenesis, which can rarely be dissociated, and, on the other hand, acetogenesis and methanogenesis, which can not be separated.
• the first reaction step is the solid organic products processing step itself, the second step corresponding to the treatment of the liquid phase recovered at the end of the first treatment stage.
• the solid organic processing stage is characterized by the production of organic acids and is generally accompanied by a decrease in the alkalinity of the medium and a decrease in pH if the medium is not sufficiently buffered.
• the decrease in pH and the accumulation of organic acids result in a decrease in the overall biochemical activity of the system, such as enzymatic hydrolysis activity and acidogenic activity.
• acid methanation often leads to a rise in alkalinity, since these acids are consumed to be converted into methane.
• the treatment process capable of continuously treating solid organic products, the treatment being able to be modulated according to the nature of the solid organic products to be treated and the degradation rate of the desired solid organic products.
• the rate of degradation of solid organic products can be fixed in particular according to its final destination, the law etc.
• the invention proposes dissociating the residence times of the liquid and solid phases in the solids processing reactor, so as to be able to modulate them independently of one another in order to optimize the treatment.
• the solids processing times are much longer than those of liquid discharges.
• the liquid phase is separated from the solid phase.
• the solid phase is at least partially recycled to the solid-state treatment reactor, which makes it possible to increase the residence time of the solids.
• the liquid phase can be fed to a liquid treatment reactor to undergo anaerobic degradation of the dissolved organic compounds.
• the treated liquid resulting from this treatment can be partly introduced into the solids treatment tank to modulate the residence time of the liquids.
• a user produces solid waste and liquid waste, he can simultaneously and simultaneously process in the same place both types of waste, the interconnection between the two tanks making it possible to optimize the treatment of the products.
• solid organic solid organic.
• the liquid treated at the outlet of the liquid waste treatment tank is characterized by a low content of residual organic pollution and a high alkalinity. Feeding the solids treatment tank treated liquid, through which said liquid will percolate or be mixed, allows to evacuate the solubilized elements from hydrolysis and acidogenesis.
• the high alkalinity of the treated liquid makes it possible to counteract the drop in alkalinity due to acidogenesis within the mass of solids, which makes it possible to maintain the solubilization and acidogenesis rate of said solids. solid at a high level. It is thus possible to regulate the alkalinity in the solids treatment tank by controlling the treated liquid recycling rate to the alkalinity level at the outlet of the tank. It is also possible to add alkaline compounds to the treated liquid reinjected. The liquid that has passed through the solids treatment tank is then loaded into soluble molecules derived from acidogenesis and is returned to the anaerobic treatment tank of the liquid discharges.
• the subject of the invention is therefore a process for the continuous treatment of solid organic products in which solid organic products are treated in a hydrolysis reactor, characterized in that a fraction of treated liquid is introduced into the hydrolysis reactor. in order to modify the liquid residence time in the hydrolysis reactor and
• a fraction of treated solids leaving the hydrolysis reactor is reintroduced into said hydrolysis reactor, so as to modify the time of residence of the solid organic products in the hydrolysis reactor according to a desired degradation rate of the solid organic products.
• Solid organic products are all types of waste that can undergo hydrolysis and acidogenesis.
• the solid organic products may comprise biodegradable solid organic material and / or biodegradable soluble material.
• hydrolysis reactor or solids processing tank is meant a reactor in which the solid organic products undergo hydrolysis and / or acidogenesis so as to be at least partially degraded to alcohols and organic acids.
• the treated liquid fraction is acetogenized liquid and / or methanogenesis so as to no longer contain organic alcohols or acids, or negligible amounts.
• the liquid residence time is the time spent by the liquid phase in the hydrolysis reactor.
• the hydrolysis rate of the solid organic products is modulated in the hydrolysis reactor.
• the residence time of the solid organic products is the time spent by the solid phase in the hydrolysis reactor.
• the degradation rate that is, the degree of treatment of solid organic products, can be varied as needed.
• Solids treated means the solid phase resulting from the phase separation at the outlet of the hydrolysis reactor.
• the treated liquid fraction can be recovered at the outlet of a methanation reactor in which the liquid phase leaving the hydrolysis reactor, and / or a liquid effluent, is treated.
• the content of biodegradable solid organic matter and soluble organic matter biodegradable products is characterized solid organics to be treated, and the content of proteins, sugars, greases and fibers in said biodegradable solid organic material and in said biodegradable soluble organic matter is determined so as to adapt the hydrolysis constant in the hydrolysis reactor features solid organic products to be treated.
• characteristics of the solid organic products to be treated is meant the content of biodegradable solid organic matter and biodegradable soluble organic matter as well as the content of proteins, sugars, fats and fibers of each of them.
• the working concentration of solid biodegradable organic material and the working concentration of soluble biodegradable organic matter in the hydrolysis reactor are set according to the nature of the solid organic products to be treated.
• the organic matter concentration refers to the average concentration in the hydrolysis reactor, in kilograms of organic matter per kilogram of solid organic products (kgMO / kg).
• Solid organic products are by nature the content of biodegradable solid organic matter and biodegradable soluble organic matter.
• the working concentration of solid biodegradable organic material is between 0.005 and 0.3 kgMO / kg, so as to have a good compromise between the effectiveness of the biological reaction and the ease of pumping and stirring of the medium.
• the working concentration is also a function of the input concentration of the waste to be treated.
• the working concentration of soluble organic biodegradable material is low compared to the working concentration of solid organic biodegradable material, and in particular less than 0.005 kg of MO per kg of reactor so that there is no too many molecules inhibiting the hydrolysis reaction in the hydrolysis reactor.
• the dimensions of the hydrolysis reactor and the fraction of treated solids to be reintroduced into said hydrolysis reactor are determined as a function of the biodegradable solid organic matter content of the solid organic products to be treated and of their protein content, of sugars, in fat and fiber, the content of biodegradable soluble organic matter of the solid organic products to be treated and their content of proteins, sugars, fats and fibers, the hydrolysis constant in the hydrolysis reactor, the solid biodegradable organic material working concentration, the soluble biodegradable organic material working concentration, and the degree of hydrolysis of the desired biodegradable material.
• the fraction of treated liquid to be reintroduced into the hydrolysis reactor as a function of the content of biodegradable soluble organic matter of the solid organic products to be treated is determined from the working concentration of soluble organic matter that is soluble in the hydrolysis reactor, the biodegradable solid organic matter content of the solid organic products to be treated, the feed rate of the solid organic products to be treated in the hydrolysis reactor, and the degree of hydrolysis of the desired biodegradable material.
• the invention also relates to an installation for the continuous treatment of solid organic products comprising
• a feed pipe for solid organic products able to supply the hydrolysis reactor continuously with solid organic products to be treated
• Phase separation means capable of separating a liquid phase from a solid phase at the output of the hydrolysis reactor
• Controlled supply means of the hydrolysis reactor treated liquid.
• controlled means that the treated liquid supply as the reinjection of a fraction of the solid phase is at a desired rate, which can be changed at any time according to the needs.
• the installation according to the invention may also comprise
• an anaerobic digestion reactor capable of supplying the methanisation reactor with liquid waste to be treated;
• controlled re-injection means of a treated liquid fraction leaving the methanation reactor in the hydrolysis reactor are controlled re-injection means of a treated liquid fraction leaving the methanation reactor in the hydrolysis reactor.
• the plant according to the invention is used to implement the process for treating solid organic products according to the invention.
• FIG. 2 Graph showing the comparative evolution of pH over time in hydrolysis reactors for different liquid residence times
• FIG. 3 Graph showing the comparative evolution of the amount of total volatile fatty acids measured in the hydrolysis reactors as a function of time for different liquid residence times;
• FIG. 4 Graph showing the comparative evolution of the degradation of the organic matter over time as a function of the inoculum present in the hydrolysis reactor;
• FIG. 5 Schematic representation of an example of an installation used to implement the treatment method according to the invention.
• TSL liquid residence time
• TSS solid residence time
• the third reactor was not fed with water from outside, so the TSL in this reactor can be considered infinite.
• the water percolating into the third reactor is constantly reintroduced.
• Liquid phase samples are also taken from the reactors to measure the pH (Figure 2) and the characteristics of the effluent, including the concentration of volatile fatty acids (Figure 3), which are the products of acidogenesis potentially inhibitory.
• the pH level and the amount of volatile fatty acids are a function of the liquid residence time used. In all three reactors, the performances initials are similar and it is only when volatile fatty acids and pH are differentiated that the degradation performance of organic matter diverges.
• This experiment shows that the best degradation performance of solid organic products is a function, on the one hand, of the presence of a liquid stream having the properties of a water treated by anaerobic digestion, which makes it possible at the same time to trace the pH and to lower the concentration of volatile fatty acids, these two elements being clearly inhibitors of the hydrolysis reaction, and, on the other hand, the level of flow rate applied for this flow of liquid, the adjustment of which allows to improve the rate of hydrolysis.
• This experiment therefore shows the advantage of the dissociation of the liquid residence time and of the solid residence time in the solid-state treatment reactor, and the need to adapt the hydraulic residence time to the rate of degradation of the solids since the speed The degradation of solid organic products is equal to the rate of production of the molecules that inhibit the reaction.
• Both reactors operate with the same applied organic load, ie 2.5 kg of organic material introduced per cubic meter of reactor per day.
• Table 1 shows the removal efficiencies of the organic matter, in percentage of degraded organic matter, in the two reactors during the two experiments, after 30 days of stabilized operation, that is to say during where performance is established and no longer changes over time.
• the first hydrolysis reactor is filled with anaerobic inoculum, ie digestate recovered from the first experiment, in a proportion representing about 10% of the organic matter of the introduced waste.
• the second hydrolysis reactor is not inoculated.
• Figure 4 shows the organic matter curves remaining in the two hydrolysis reactors, as a percentage of the amount of initial organic material, as a function of time.
• Solid organic waste already contains its own inoculum, already having enzymatic systems suitable for hydrolysis. This result goes against many lessons indicating that continuous recycling of bacteria is the only beneficial phenomenon to improve the treatment of solids.
• FIG. 5 is schematically represented a solid organic product processing line according to the invention, in which concomitantly, additional liquid discharges may be treaties.
• the installation comprises a hydrolysis reactor 10 capable of receiving solid organic products D 0 to be treated.
• a methanation reactor 11 is able to treat liquids directly from liquid discharges D 9 , and / or from the liquid phase D 3 recovered at the outlet of the hydrolysis reactor.
• the hydrolysis reactor 10 may be an anaerobic or aerobic digestion reactor.
• the methanation reactor 11 is an anaerobic digestion reactor.
• a separator 12 collects a mass of waste D at least partially treated at the outlet of the hydrolysis reactor 10, so as to separate the liquid phase D 3 from the solid phase D 2 .
• the liquid phase D 3 is conveyed towards the methanation reactor 11, where it is treated at the same time as liquid discharges.
• the liquid phase D 3 can be treated in another methanation reactor.
• the solid phase D2 may be wholly or partly conveyed out of the treatment chain.
• the installation comprises means 13 for reinjecting a fraction of treated solids D 5 into the hydrolysis reactor 10.
• the reinjection means 13 comprise a channel capable of conveying the fraction of treated solids D 5 from an evacuation pipe of the solid phase 14 in the hydrolysis reactor 10, or directly from the separator 12.
• the reinjection means also comprise flow control means adapted to modulate the feed rate of treated solids D 5 as needed. Adjusting the treated solids streams D 4 , D 5 makes it possible to adjust the TSS in the solids processing reactor.
• the treated liquid D 6 at the outlet of the methanation reactor 11 is characterized by a low content of residual organic pollution and a high alkalinity, due to the different biochemical reactions that have taken place during the transformation into methane of the soluble organic compounds.
• a treated liquid fraction D 8 from the treated liquid D 6 from the methanation reactor is used to supply the hydrolysis reactor 10, through which it will percolate or be mixed, and cause the solubilized elements resulting from the hydrolysis and acidogenesis.
• the remainder of the treated liquid phase D 7 is discharged out of the treatment system.
• the plant for the treatment of solid organic products comprises controlled reinjection means 16 of a treated liquid fraction D 8 capable of bringing said fraction D 8 from an evacuation pipe 15 of the treated liquid to the hydrolysis reactor 10, or directly from the methanation reactor 11.
• the reinjection means 16 also comprise flow control means adapted to modulate the feed rate of the fraction of treated liquids D 8 , that is, to say the flow, according to the needs. Adjusting the treated liquid flows D 7, D 8 makes it possible to adjust the TSL in the solid-state treatment reactor 10.
• a solid / liquid separator 12 for example a centrifuge, makes it possible not only to control the TSS, but also to adjust, via the treated solid fraction reinjected D5, the dry matter content in the hydrolysis reactor. 10, dry matter among which found a high density of microorganisms, the concentration of which in the solids processing reactor favors the rate of biological reaction.
• separator 12 it is possible not to provide separator 12 itself, while keeping the phase separation step.
• the solid in the case where the solid is sufficiently heterogeneous to form a layer through which the liquid can flow without causing solid, or percolate, the solid can be directly removed from the reactor by a suitable extraction system, such as an Archimedean screw pump or other, liquid being the percolation residue, or leachate leaving the hydrolysis reactor 10.
• an adjustable fraction of treated liquid Ds is reused to redilute or percolate through the mass of solid organic products contained in the hydrolysis reactor 10.
• the evacuation level of the soluble organic acid compounds is thus adjusted and Raises the pH in the hydrolysis reactor.
• the high alkalinity of the treated liquid fraction D 8 makes it possible to counteract the drop in alkalinity due to acidogenesis within the mass of solid organic products, and thus to maintain the rate of solubilization and acidogenesis of said organic products. solid at a high level.
• This method of treatment thus makes it possible, on the one hand, to treat liquid Dg and solid Do discharges together by anaerobic digestion, and to optimize the solids treatment phase by adjusting both the residence time of the solids and the time of residence of liquids.
• the liquid D 3 having passed through the hydrolysis reactor 10 and recovered at the exit of the separator 12 is loaded with soluble molecules originating from the acidogenesis and is returned to the methanation reactor 11.
• the liquid treatment reactor 11 is a high-load anaerobic digestion reactor, capable of tolerating a certain amount of suspended solids, and more particularly a fixed bed having a continuous declogging system such as that described in the application FR2885126.
• the liquid and solid are separated by any known means so as to separate in two streams solids and liquids which are then treated according to the steps described above.
• Xo to Xs concentration of biodegradable solid organic matter in streams 0 to 8 (in kgMO / kg);
• X'o to X' ⁇ concentration of inert solid (non-biodegradable) in streams 0 to 8 (in kg / kg); So at Ss: concentration of soluble organic matter in streams 0 to
• the solid residence time, TSS is understood as the average time spent by an inert substance, that is to say non-biodegradable, of concentration X 'in the assembly comprising the hydrolysis reactor 10 and the separator 12. .
• the TSS can be expressed as follows:
• TSS - R yi ⁇ 1
• the TSS depends on two parameters: the total mass of the reactor M R and the fraction of treated solids recycled in the reactor 10, the parameters c and t being intrinsic properties of the separator 12.
• the system is characterized from a system of simple algebraic equations derived from the mass balances associated with the operation of the installation in continuous mode, as well as from the Expert knowledge acquired on the kinetics of hydrolysis and solubilization of biodegradable organic matter.
• the yield p is defined as being the rate of reduction of organic solid between the entry and the exit, that is to say the flow of digestate D 4 :
• the material balance on the biodegradable solid organic material is based on the non-accumulation of biodegradable organic material in the balance chamber, defined as the hydrolysis reactor; it is written as follows:
• D 8 Xs consists of the fraction of treated liquid reinjected from the methanation reactor 11. It is therefore possible to assume that this flow represents a negligible contribution of biodegradable solid organic matter by relative to the input streams D 0 X 0 and to the recycling stream D 5 X 5 representing the fraction of treated solid organic products reinjected into the hydrolysis reactor.
• the balance sheet is therefore reduced to:
• Equation 1 The system consisting of Equations 1, 2 and 3 involves the following variables:
• D 0 , Xo, SO, t, c are input data that do not vary; p is the treatment goal;
• M R , Ds and s are the sizing parameters; Xi and Si: respectively are the working concentration of biodegradable solid organic material and soluble in the reactor, which must be adjusted to optimal values; k: is the hydrolysis constant, which depends on the nature of the solid organic products to be treated.
• the sizing method therefore proposes: setting the desired working concentration Xi in the hydrolysis reactor; to deduce the Si concentration desirable in the hydrolysis reactor; to propose a value of k, which depends on the nature of the solid organic products to be treated; to complete the calculation by deducing M R , D 8 and s from equations 1, 2 and 3.
• Xi is set so as to obtain a good compromise between the efficiency of the biological reaction and the ease of pumping and stirring of the medium; this value also depends on the input nature of the solid organic products to be treated, if they are more or less concentrated.
• the value chosen is between 0.005 and 0.3 kg of organic matter per kg of reactor, the value of 0.005 corresponding to the lower limit below which the efficiency of the biological reaction is low, and 0.3 corresponding to the upper limit above from which the pumping and mixing of the product are compromised.
• f is chosen so that the concentration of soluble organic matter remains low in front of Xi: 0.001 ⁇ / ⁇ 0.2
• the kinetic constant k depends on the nature of the solid organic products to be treated. It is known that the hydrolysis constant of solid organic compounds varies depending on whether it is sugars, proteins or fats.
• the hydrolysis constant associated with the degradation of organic matter as a whole can be calculated according to the formula next :
• Table 2 shows, by way of example, the recommended values for the various hydrolysis constants at a temperature of 37.degree.
• TSL 0.4 days
• TSS I 5.6 days

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Zoology (AREA)
• Bioinformatics & Cheminformatics (AREA)
• Wood Science & Technology (AREA)
• Microbiology (AREA)
• Genetics & Genomics (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Biochemistry (AREA)
• General Engineering & Computer Science (AREA)
• Biotechnology (AREA)
• Biomedical Technology (AREA)
• Sustainable Development (AREA)
• General Chemical & Material Sciences (AREA)
• Analytical Chemistry (AREA)
• Clinical Laboratory Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Biodiversity & Conservation Biology (AREA)
• Hydrology & Water Resources (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Treatment Of Sludge (AREA)
• Processing Of Solid Wastes (AREA)
• Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=39496015

Family Applications (1)

Country Status (4)

Cited By (1)

Families Citing this family (5)

Family Cites Families (7)

• 2007
  • 2007-09-11 FR FR0757492A patent/FR2920761B1/fr active Active
• 2008
  • 2008-09-10 EP EP08836087A patent/EP2190791A2/de not_active Withdrawn
  • 2008-09-10 WO PCT/FR2008/051612 patent/WO2009044076A2/fr active Application Filing
• 2010
  • 2010-02-19 TN TNP2010000083A patent/TN2010000083A1/fr unknown

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events