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EP3132008B1 - Material aus einer zubereitung mit ferrocen - Google Patents

Material aus einer zubereitung mit ferrocen Download PDF

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Publication number
EP3132008B1
EP3132008B1 EP15717005.1A EP15717005A EP3132008B1 EP 3132008 B1 EP3132008 B1 EP 3132008B1 EP 15717005 A EP15717005 A EP 15717005A EP 3132008 B1 EP3132008 B1 EP 3132008B1
Authority
EP
European Patent Office
Prior art keywords
ferrocene
combustion
granule
hydrocarbon
fire
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15717005.1A
Other languages
English (en)
French (fr)
Other versions
EP3132008A1 (de
Inventor
James Brian Mitchell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Universite de Rennes 1
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite de Rennes 1
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Universite de Rennes 1 filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3132008A1 publication Critical patent/EP3132008A1/de
Application granted granted Critical
Publication of EP3132008B1 publication Critical patent/EP3132008B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0007—Solid extinguishing substances
    • A62D1/0014—Powders; Granules
    • 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
    • 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
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • 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
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • 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
    • C10L1/1275—Inorganic compounds sulfur, tellurium, selenium containing compounds
    • 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
    • C10L1/1291—Silicon and boron containing compounds
    • 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
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/06—Particle, bubble or droplet size

Definitions

  • the invention relates to the field of hydrocarbon combustion. More particularly, the invention relates to the reduction of fumes from the combustion of hydrocarbons and the reduction of undesirable combustion products.
  • PICs incomplete combustion products
  • Fumes resulting from incomplete hydrocarbon combustion include many chemical compounds, such as, for example, polycyclic and aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), English «Volatile Organic Compounds'), unburned fuels and other products of combustion in addition to solid particles commonly known as soot and which contain carbon as well as possibly oxygen and hydrogen, in addition to the impurities present in them. fuels before combustion. Some of these elements are detrimental to the health of people. It is therefore important to be able to limit their emission.
  • PAHs polycyclic and aromatic hydrocarbons
  • VOCs volatile organic compounds
  • PAHs polycyclic aromatic hydrocarbons
  • English «Volatile Organic Compounds' Unburned fuels and other products of combustion in addition to solid particles commonly known as soot and which contain carbon as well as possibly oxygen and hydrogen, in addition to the impurities present in them. fuels before combustion.
  • Fires of automobile tire stocks can burn for very long periods of time and release enormous smoke, especially because of the presence of air in such a stack.
  • Household and other garbage burning fires have similar characteristics of duration and pollution.
  • the demand WO 2013/032447 teaches a fire extinguishing material suitable for rapid release of extinguishing gas, in the form of microcapsules having an inorganic shell encapsulating an iron component such as ferrocene or particulate ferrocene derivatives.
  • the demand FR 2,602,977 teaches a method and device for extinguishing a fire plume in a flammable liquid obtained by spreading on the sheet a compact layer of spheres of uniform diameter made of a material resistant to high temperatures (eg steel, aerated concrete), optionally association with an extinguishing powder.
  • a material resistant to high temperatures eg steel, aerated concrete
  • Ferrocene also called iron dicyclopentadienyl
  • Fe (C 5 H 5 ) 2 It belongs to the family of metallocenes. Ferrocene is itself a flammable compound and its addition in a fire leads to a red emission of smoke due to the formation of iron oxide particles.
  • the mode of diffusion is important and greatly conditions the efficiency of the process. Poor propagation of ferrocene on fire results in limited action. If ferrocene is spilled before the start of fire, its diffusion is not homogeneous and leads to a limited efficiency.
  • Dispersion using a device similar to the one previously mentioned and used for extinguishing purposes does not respond optimally to homogeneous diffusion. High temperatures quickly damage container capsules and diffusion is not controlled.
  • a direct diffusion of ferrocene on a fire also does not allow to be effective, it can not then reach the base of the flames, being itself flammable.
  • the invention improves the state of the art by providing a granule of material comprising a preparation made of a homogeneous mixture of an organometallic compound which is a set of ferrocene particles and / or a derivative of the ferrocene between 10 and 30% of the total material component granulate and an inert flame retardant material, where the material is porous and where its largest dimension is between 10 and 30mm.
  • the granule is hollow and its density is such that it floats on the surface of an oil or a hydrocarbon.
  • the inert flame retardant material is plaster or refractory clay.
  • homogeneous mixture is understood to mean a mixture in which each of the components is present in substantially identical proportions throughout the preparation.
  • the granule of material is spherical, elliptical, rectangular, square, or chip-shaped.
  • the granule of material is adapted to progressively release the ferrocene particles in the form of steam and under the effect of heat when it is positioned on the surface of a hydrocarbon on fire.
  • the granule of material is adapted in particular to a progressive release of the ferrocene particles, in the vapor phase, in the form of ferrocene vapor, because of the progressive degradation of the inert flame retardant material under the effect of the heat emitted by the hydrocarbon fire.
  • the modules represented are functional units, which correspond or not to physically distinguishable units. For example, these modules or some of them are grouped into a single component. In contrast, according to other embodiments, some modules are composed of separate physical entities.
  • the figure 1 illustrates a granule P1 of material consisting of a preparation made of a mixture of F ferrocene particles (iron dicyclopentadienyl; Fe (C 5 H 5 ) 2 ) and / or F particles of a ferrocene derivative and a matrix of inert flame retardant material FPM according to a particular and non-limiting embodiment of the invention.
  • F ferrocene particles iron dicyclopentadienyl; Fe (C 5 H 5 ) 2
  • FPM inert flame retardant material
  • the inert flame retardant material matrix FPM of the material consists of plaster (also called “plaster-of-Paris” or hydrated calcium sulfate).
  • the use of the material in the form of granules thus formed allows a homogeneous diffusion (diffusion) of ferrocene at the base of the flames of a hydrocarbon fire, with a view to improving combustion and appreciably reducing fumes. particles and / or undesirable compounds.
  • ferrocene is a crystalline compound that evaporates from 100 ° C. Its melting temperature is 174 ° C. and its boiling point is 249 ° C. when its vapor pressure is equal to atmospheric pressure, under standard atmospheric conditions. It is also a flammable substance in the air whose combustion leads to the appearance of iron oxide particles. Ferrocene is very stable at high temperatures up to 500 ° C.
  • Heavy oils mixing various hydrocarbon compounds, such as aliphatic or aromatic compounds, for example, are characterized by boiling temperatures between 50 ° C and 400 ° C.
  • the ferrocene present on the surface of a burning hydrocarbon can evaporate from the surface and join the flame zone, in the vapor phase, to act as a catalyst for combustion.
  • Other Less stable compounds such as, for example, pentacarbonyl Fe (CO) 5 , could not evaporate towards the zone of flames but would merge, in the form of iron or solid iron oxide, with the hydrocarbons by pyrolysis.
  • the conditioning of ferrocene P1 granules consist of a preparation made of a homogeneous mixture of F particles of ferrocene and flame retardant plaster FPM, allows a homogeneous diffusion in the area fire and increased efficiency as a catalyst for combustion.
  • the entry of the ferrocene according to the granular packaging mode protects it from the high temperatures of the flame zone, going beyond 1000 ° C, during the spreading phase.
  • the diffusion of ferrocene according to the embodiment of the invention is therefore gradual and slow, which allows the efficiency of the process.
  • the ferrocene is gradually released from the granules, in the form of steam.
  • the ferrocene vapors thus liberated mix with the vapors of the hydrocarbons on fire.
  • the combustion being in practice a combustion of the vapors.
  • the plaster casing present in the granules protects the ferrocene particles from high temperatures during a step of crossing the zone of the flames during a spreading operation. Plaster then acting as a thermal insulator preventing too rapid temperature rise of the ferrocene particles.
  • the ferrocene can be placed on the surface of a hydrocarbon layer before the birth of a fire or after the start of a fire.
  • the plaster is replaced by refractory clay which has similar properties of thermal insulation.
  • the plaster is replaced by zeolite powder.
  • the granular structure makes it possible to operate by gradually adding predetermined amounts of ferrocene until a combustion quality is obtained which is sufficient to reduce the emission of smoke and or undesirable particles during a hydrocarbon fire.
  • the level of ferrocene included in a granule is 10 to 30% of the total material, thus allowing the granules not to degrade too rapidly and to sufficiently protect the ferrocene particles during the diffusion phase to then operate as a combustion catalyst.
  • Such a proportion of ferrocene in the granules causes an approximate proportion of the order of 0.5% in the mixture of ferrocene vapors and hydrocarbons on fire.
  • the granules P1 are spherical, elliptical, rectangular, square, or chip-shaped, or any other form allowing easy spreading while acting as a temporary protective thermal barrier particles ferrocene to improve their diffusion on the hydrocarbon, making it as homogeneous as possible.
  • the P1 granules have a maximum dimension of 30 mm, providing mechanical characteristics suitable for simple and rapid spreading on a hydrocarbon web.
  • the slow diffusion of ferrocene vapors carried out by the diffusion of ferrocene mixed with an inert flame retardant material in the form of granules, tablets or pellets, for example, also allows a consequent reduction of the fumes of fumes and unwanted particles during a fire of solids, such as in particular rubber (non-limiting example).
  • the figure 2 illustrates a granule P2 similar to the granule P1, seen in section, whose hollow structure allows it to float (or float better) on the surface of a liquid hydrocarbon web.
  • the hollow portion of the granule P2 comprises air, aimed at reducing its density and supplying oxygen to the combustion.
  • the granules are manufactured according to manufacturing methods that are well known to those skilled in the field of the manufacture of granules or tablets and implement, for example, a pelletisation method.
  • granules comprising ferrocene are obtained by pelletizing, by mixing and moistening a plaster and ferrocene powder. Centrifugal movement within a drying chamber produces agglomerates that combine to form compact granules. Some characteristics of the granules can be improved or realized by means of direct granulation or granulation layer by layer, for example.
  • the figure 3 represents a granule P1 comprising ferrocene F and plaster FPM according to a particular and non-limiting embodiment of the invention, on the surface of a CO hydrocarbon compound on fire. Combustion of hydrocarbon CO generates VOC vapors from hydrocarbon combustion. A slow and gradual release of FV ferrocene vapor is effected from the P1 granulate, under the effect of heat. FV vapors are then advantageously mixed with OV vapors and operate as a combustion catalyst effect, resulting in a consequent reduction of fumes and unwanted particles.
  • pellets attached to floating elements and comprising a mixture of plaster and ferrocene, made according to a particular and non-limiting embodiment of the invention. , resulted in a 90-95% reduction in fume emissions from a light crude oil fire in a small container.
  • This experiment was carried out in a content of 165 centimeters in diameter comprising 80 liters of light crude oil with 32 pellets with a diameter of 27 mm each.
  • the figure 4 is a graphical representation illustrating soot emission rates from a hydrocarbon fire as a function of the level of ferrocene F present in the vapor phase and released due to the temperature rise of the pellets P1 or P2 dispersed at the fire surface.
  • the concentration of ferrocene in the vapor phase is expressed on the figure 4 as a percentage of the FV ferrocene vapors with respect to all the vapors present and composed of the sum of the VOC hydrocarbon compound vapors and the FV ferrocene vapors.
  • the invention is not limited to the plaster and ferrocene formulation described above but to any formulation comprising ferrocene or ferrocene derivative particles mixed with an inert flame retardant matrix acting as a temporary thermal barrier to protect the ferrocene during homogeneous diffusion on the surface of a hydrocarbon and then allowing their release for operation as a combustion catalyst and reduce fumes and / or undesirable particles.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Inorganic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (4)

  1. Werkstoffgranulat, umfassend eine Zubereitung, hergestellt aus einem homogenen Gemisch einer metallorganischen Verbindung, die ein Verbund von Partikeln (F) von Ferrocen (F) und/oder einem Ferrocenderivat ist, zwischen 10 und 30 Prozent des gesamten das Granulat bildenden Materials und einem inerten feuerhemmenden Material (FPM), dadurch gekennzeichnet, dass der Werkstoff porös ist, und dadurch, dass seine größte Abmessung zwischen 10 und 30 mm beträgt.
  2. Werkstoffgranulat nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass das inerte feuerhemmende Material (FPM) Gips oder feuerfester Ton ist.
  3. Werkstoffgranulat nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Granulat (P2) hohl ist und dass seine Dichte derart ist, dass es auf der Oberfläche eines Öls oder eines Kohlenwasserstoffs schwimmt.
  4. Werkstoffgranulat nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es in Form eines kugelförmigen, elliptischen, rechteckigen, quadratischen Elements oder in Form eines Spans vorliegt.
EP15717005.1A 2014-04-17 2015-04-17 Material aus einer zubereitung mit ferrocen Active EP3132008B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1400923A FR3020068B1 (fr) 2014-04-17 2014-04-17 Materiau constitue d'une preparation comprenant un compose organometallique et une matiere ignifuge inerte
PCT/EP2015/058459 WO2015158922A1 (fr) 2014-04-17 2015-04-17 Materiau constitue d'une preparation comprenant du ferrocene

Publications (2)

Publication Number Publication Date
EP3132008A1 EP3132008A1 (de) 2017-02-22
EP3132008B1 true EP3132008B1 (de) 2019-09-11

Family

ID=51225595

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15717005.1A Active EP3132008B1 (de) 2014-04-17 2015-04-17 Material aus einer zubereitung mit ferrocen

Country Status (5)

Country Link
US (1) US9951286B2 (de)
EP (1) EP3132008B1 (de)
CA (1) CA2944271A1 (de)
FR (1) FR3020068B1 (de)
WO (1) WO2015158922A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116510225A (zh) * 2023-05-31 2023-08-01 上海应用技术大学 一种抑烟型环保泡沫灭火剂及制备方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US607292A (en) * 1898-07-12 Johannes stocker
US4197913A (en) * 1978-07-10 1980-04-15 Olin Corporation Use of phosphogypsum for fire suppression
FR2602977B1 (fr) * 1986-08-25 1990-01-12 Commissariat Energie Atomique Procede et dispositif d'extinction d'une nappe de feu dans un liquide inflammable
DE3729930A1 (de) * 1987-09-07 1989-03-16 Dieter Georg Mueller Fluessige katalysator-komplexe
US5713964A (en) 1993-10-25 1998-02-03 Exxon Chemical Patents Inc. Low smoke composition and firefighter training process
WO2004014489A1 (en) 2002-08-09 2004-02-19 Jutabha, Sally Fire extinguishing ball
CN1695752A (zh) * 2004-05-13 2005-11-16 景中兴 新型森林灭火剂配方及工艺
FR2935907B1 (fr) * 2008-09-18 2010-11-12 Elie Gosse Procede de lutte contre le feu par projection d'un produit.
CN101372642B (zh) * 2008-10-29 2012-07-04 陈士进 一种高效燃煤节能助燃剂及其制备方法
WO2013032447A1 (en) * 2011-08-30 2013-03-07 Empire Technology Development Llc Ferrocene /carbon dioxide releasing system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
FR3020068A1 (fr) 2015-10-23
EP3132008A1 (de) 2017-02-22
US9951286B2 (en) 2018-04-24
US20170037335A1 (en) 2017-02-09
WO2015158922A1 (fr) 2015-10-22
FR3020068B1 (fr) 2017-12-15
CA2944271A1 (fr) 2015-10-22

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