Patent Application
20230349052
The present invention relates to the general field of the high-temperature electrolysis of water (HTE), in particular the high temperature electrolysis of steam (HREV), respectively designated by the English terms “high temperature electrolysis” (HTE) and “high temperature steam electrolysis” (HTSE), the electrolysis of carbon dioxide (CO2), or even the co-electrolysis of water at high temperature (HTE) with carbon dioxide (CO2).
More precisely, the invention relates to the field of high-temperature solid-oxide electrolysers, normally designated by the acronym SOEC (standing for “solid oxide electrolyser cell”).
It also relates to the field of high-temperature solid-oxide fuel cells, normally designated by the acronym SOFC (standing for “solid oxide fuel cells”).
Thus, more generally, the invention relates to the field of solid-oxide packs of the SOEC/SOFC type operating at high temperature.
More precisely, the invention relates to an assembly comprising a solid-oxide pack of the SOEC/SOFC type and a system for the high-temperature sealed coupling of the pack, as well as a system comprising such an assembly and a furnace coupled to said pack by means of such a coupling system.
In the context of a high-temperature solid-oxide electrolyser of the SOEC type, it is a case of transforming, by means of an electric current, in one and the same electrochemical device, steam (H2O) into dihydrogen (H2) and dioxygen (O2), and/or transforming carbon dioxide (CO2) into carbon monoxide (CO) and dioxygen (O2). In the context of a high-temperature solid-oxide fuel cell of the SOFC type, the operation is the opposite in order to produce an electric current and heat while being supplied with dihydrogen (H2) and dioxygen (O2), typically with air and natural gas, namely methane (CH4). For reasons of simplicity, the following description privileges the operation of a high-temperature solid-oxide electrolyser of the SOEC type implementing the electrolysis of water. However, this operation is applicable to the electrolysis of carbon dioxide CO2, or even the co-electrolysis of water at high temperature (HTE) with carbon dioxide (CO2). In addition, this operation can be transposed to the case of a high-temperature solid-oxide fuel cell of the SOFC type.
To implement the electrolysis of water, it is advantageous to implement it at high temperature, typically between 600 and 1000° C., because it is more advantageous to electrolyse steam than liquid water and because part of the energy necessary for the reaction can be provided by heat, which is less expensive than electricity.
To implement the electrolysis of water at high temperature (HTE), a high-temperature solid-oxide electrolyser of the SOEC type consists of a pack of elementary patterns each including a solid-oxide electrolysis cell, or electrochemical cell, consisting of three anode/electrolyte/cathode layers superimposed on each other, and metal-alloy interconnection plates, also referred to as twin-pole plates or interconnectors. Each electrochemical cell is gripped between two interconnection plates. A high-temperature solid-oxide electrolyser of the SOEC type is then an alternating pack of electrochemical cells and interconnectors. A high-temperature solid-oxide fuel cell of the SOFC type consists of the same type of pack of elementary patterns. Since this high-temperature technology is reversible, the same pack can operate in electrolysis mode and produce hydrogen and oxygen from water and electricity, or in fuel cell mode and produce electricity from hydrogen and oxygen.
Each electrochemical cell corresponds to an electrolyte/electrode assembly, which is typically a multilayer ceramic assembly the electrolyte of which is formed by a central ion-conductive layer, this layer being solid, dense and gastight, and gripped between the two porous layers forming the electrodes. It should be noted that supplementary layers may exist, but which serve merely to improve one or more of the layers already described.
The interconnection devices, electrical and fluidic, are electron conductors that, from an electrical point of view, provide the connection of each electrochemical cell of an elementary pattern in the pack of elementary patterns, guaranteeing the electrical contact between one face and the cathode of one cell and between the other face and the anode of the following cell, and from a fluidic point of view, thus combining the production of each of the cells. The interconnectors thus provide the functions of bringing and collecting electric current and defining gas-circulation compartments, for distribution and/or collection.
More precisely, the main function of the interconnectors is to provide the passage of the electric current but also the circulation of the gases in the vicinity of each cell (namely: injected steam, hydrogen and oxygen extracted for the HTE electrolysis; air and fuel including the hydrogen injected and water extracted for an SOFC cell), and separating the anode and cathode compartments of two adjacent cells, which are the gas-circulation compartments at respectively the anodes and the cathodes of the cells.
In particular, for a high-temperature solid-oxide electrolyser of the SOEC type, the cathode compartment includes the steam and hydrogen, the product of the electrochemical reaction, while the anode compartment includes a draining gas, if present, and oxygen, another product of the electrochemical reaction. For a high-temperature solid-oxide fuel cell of the SOFC type, the anode compartment includes the fuel, while the cathode compartment includes the oxidant.
To implement the electrolysis of steam at high temperature (HTE), steam (H2O) is injected into the cathode compartment. Under the effect of the electric current applied to the cell, the dissociation of the water molecules in the form of steam is achieved at the interface between the hydrogen electrode (cathode) and the electrolyte: this dissociation produces dihydrogen gas (H2) and oxygen ions (O2-). The dihydrogen (H2) is collected and discharged at the outlet of the hydrogen compartment. The oxygen ions (O2-) migrate through the electrolyte and recombine as dioxygen (O2) at the interface between the electrolyte and the oxygen electrode (anode). A draining gas, such as air, can circulate at the anode and thus collect the oxygen generated in gaseous form at the anode.
To provide the operation of a solid-oxide fuel cell (SOFC), air (oxygen) is injected into the cathode compartment of the cell and hydrogen into the anode compartment. The oxygen of the air will dissociate into O2- ions. These ions will migrate in the electrolyte of the cathode to the anode to oxidise the hydrogen and form water with a simultaneous production of electricity. In an SOFC cell, just as in SOEC electrolysis, the steam is located in the dihydrogen (H2) compartment. Only the polarity is reversed.
By way of illustration,
This reaction is implemented electrochemically in the cells of the electrolyser. As shown diagrammatically in
The electrochemical reactions take place at the interface between each of the electron conductors and the ion conductor.
At the cathode 2, the half reaction is as follows:
At the anode 4, the half reaction is as follows:
The electrolyte 3, interposed between the two electrodes 2 and 4, is the site of migration of the O2- ions under the effect of the electrical field created by the difference in potential imposed between the anode 4 and the cathode 2.
As illustrated between parentheses on
An elementary electrolyser, or electrolysis reactor, consists of an elementary cell as described above, with a cathode 2, an electrolyte 3 and an anode 4, and two interconnectors that fulfil the functions of electrical, hydraulic and thermal distribution.
To increase the outputs of hydrogen and oxygen produced, stacking a plurality of elementary electrolysis cells one on the other, separated by interconnectors, is known. The assembly is positioned between two end interconnection plates that support the electrical feeds and gas feeds of the electrolyser (electrolysis reactor).
A high-temperature solid-oxide electrolyser of the SOEC type thus comprises at least one, and generally a plurality of, electrolysis cells stacked one on the other, each elementary cell being formed by an electrolyte, a cathode and an anode, the electrolyte being interposed between the anode and the cathode.
As indicated previously, the fluidic and electrical interconnection devices that are in electrical contact with one or more electrodes in general fulfil the functions of bringing and collecting electric current and delimit one or more gas-circulation compartments.
Thus, the function of the so-called cathode compartment is the distribution of the electric current and steam as well as the recovery of the hydrogen at the cathode in contact.
The function of the so-called anode compartment is the distribution of the electric current and the recovery of the oxygen produced at the anode in contact, optionally by means of a draining gas.
The interconnector 5 is a component made from metallic alloy that provides the separation between the cathode 50 and anode 51 compartments, defined by the volumes lying between the interconnector 5 and the adjacent cathode 2.1 and between the interconnector 5 and the adjacent anode 4.2 respectively. It also provides the distribution of the gases to the cells. Steam is injected into each elementary pattern in the cathode compartment 50. The collection of the hydrogen produced and of the residual steam at the cathode 2.1, 2.2 is implemented in the cathode compartment 50 downstream of the cell C1, C2 after dissociation of the steam by the latter. The collection of the oxygen produced at the anode 4.2 is implemented in the anode compartment 51 downstream of the cell C1, C2 after dissociation of the steam by the latter. The interconnector 5 provides the passage of the current between the cells C1 and C2 by direct contact with the adjacent electrodes, i.e. between the anode 4.2 and the cathode 2.1.
The operating conditions of a high-temperature solid-oxide electrolyser (SOEC) being very similar to those of a solid-oxide fuel cell (SOFC), the same technological constraints are found again.
Thus, the correct operation of such solid-oxide packs of the SOEC/SOFC type operating at high temperature mainly requires satisfying the points stated below.
First of all, it is necessary to have electrical insulation between two successive interconnectors, otherwise the electrochemical cell would be short-circuited, but also good electrical contact and a sufficient contact surface between a cell and an interconnector. The lowest ohmic resistance possible is sought between cells and interconnectors.
Moreover, it is necessary to have impermeability between the anode and cathode compartments otherwise there would be a recombination of the gases produced, causing a reduction in yield and especially the appearance of hot spots damaging the pack.
Finally, it is essential to have a good distribution of the gases both at the inlet and in recovery of the products otherwise there will be a loss of efficiency, non-homogeneity of pressure and temperature in the various elementary patterns, or even degradations damaging to the electrochemical cells.
The incoming and outgoing gases in a high-temperature electrolysis pack (SOEC) or fuel cell (SOFC) operating a high temperature can be managed by means of suitable devices of a furnace such as the one illustrated with reference to
The furnace 10 thus includes cold parts PF and hot parts PC, the latter comprising the furnace hearth 11, a looped tube 12 for managing the entries and exits of gas and the pack 20, also referred to as a stack, for high-temperature electrolysis (SOEC) or fuel cell (SOFC).
The gas feed and outlet devices are usually coupled at the cold parts PF, in particular by double-ring mechanical clamping couplings, surface sealing couplings by VCR® metal joint, welded connections or sealed partition passages.
In the case of double-ring mechanical clamping couplings, the two rings separate the tube sealing and clamping functions. The front ring creates a seal while the rear ring makes it possible to advance the front ring axially and applies effective clamping of the tube radially. This principle makes it possible to obtain very good tube clamping and very good impermeability to gas leakages. In addition, installing same is easy and it has very good resistance to fatigue caused by vibrations. Dismantling is easy in the case of absence of welding. However, its major drawbacks are precisely its absence of resistance to high temperatures so that the rear ring, the front ring and the tube may be welded together by diffusion welding making it impossible to dismantle the join.
In the case of surface sealing couplings by a VCR® metal joint, the seal is obtained when the joint is compressed by two rims during the clamping of a male nut and a hexagonal body with a female nut. This principle affords a very good seal, the possibility of using differential joints (nickel, copper, stainless steel, etc.) according to the most suitable configuration, and easy mounting/dismantling with change of the joint during these operations. However, this solution is not suitable at high temperature, since the operation thereof allows a maximum temperature of only approximately 537° C.
In the case of welded connections, a total seal is obtained by welding the tubes together by a method of the TIG type (standing for “tungsten inert gas”) or by orbital welder, i.e. a TIG method coupled with a rotary nozzle. However, welding operations on a stack 20 mounted in a furnace 10 are very complicated because of the reduced accessibility for being able to weld the tubes on the periphery.
Finally, there is a coupling system resistant to a temperature of approximately 870° C., using gastight partition passages for sensors, probes, electrical signals and tubes to pass. These gastight partition passages are in the form of a threaded coupling made from 316L stainless steel that is screwed onto the wall of a pipe, of a vessel or of a cover. Depending on the version thereof, these passages accommodate one or more through elements, of various types, sizes and diameters. These passages therefore enable elements to pass without discontinuity and do not allow the gastight joining of two elements.
The couplings of the gas feed and outlet devices at the cold parts PF of the furnace 10 constitute a major drawback since these cold parts PF are remote from the heating elements of the furnace 10 and encumbered by the peripherals such as the exchangers, the insulators, the condensers, among other things. This involves privileging the production of the connections in the hot parts PF while wishing to make them easy to dismantle and reuse.
In addition, the use of the chamber of the furnace 10 for preheating the inlet gas also leads to implementing the looped tube 12, with a length of approximately 2.5 to 3 m, to use the radiation of the heating elements of the furnace 10, which adds complexity in the curvatures to ensure that the tubes arrive at the correct place in a confined space.
Furthermore, if it is wished to be able to dismantle the pack 20 to be able to operate it at another place, then conferring on it a character of the “Plug & Play” (PnP) type, it would be necessary first of all to break the connections mechanically, for example by means of a metal saw, and to prepare the new connections to put the pack 20 on another furnace, which greatly complicates the manipulations.
Finally, it should be noted that such a pack 20 is very fragile and it is necessary to implement the fewest possible operations during a change of location. Thus, it is necessary in particular to be able to avoid vibrations and impacts and also to avoid turning it over.
The coupling solutions mentioned previously do not make it possible to meet the requirements stated above. In particular, double-ring mechanical clamping couplings weld at high temperature. Welds do not meet the problem mentioned because of the complexity of welding (difficult access) and they do not avoid the cutting of tubes for dismantling.
The coupling solutions of the prior art do not make it possible to remove the pack 20 from a furnace 10 to be able to reconnect to another furnace 10, i.e. to have a “Plug & Play” character, without the breaking the joins mechanically, which obliges the operators responsible for the mounting/dismantling to perform tedious work of bending, coupling and adaptation.
From the French patent application FR 3 061495 A1, an example is known of a demountable gastight system for connecting at high temperature in SOEC/SOFC mode. A mica joint is used between a smooth base and a threaded base to obtain demountable and reusable gastight connections. This system makes it possible to solve high-temperature coupling but may however involve an excessively high leakage rate. In addition, the mica joint may leave residues following the thermal cycling that it is then necessary to eliminate before mounting another joint.
There is still a need for improving the known coupling solutions of the prior art for a high-temperature electrolysis pack (SOEC) or fuel cell (SOFC).
The aim of the invention is to at least partially remedy the requirements mentioned above and the drawbacks relating to the embodiments of the prior art.
It aims in particular to implement an optimised design of coupling of a high-temperature electrolysis (SOEC) or fuel cell (SOFC) pack. In particular, it aims to produce in the hot part, i.e. inside the chamber of a furnace, and in line with the gas inlets and outlets, demountable and reusable connections that are gastight at 860°. This system must be able to be integrated in a pack having a character of the “Plug & Play” (PnP) type (self-clamping system), as described in the French patent application FR 3 045 215 A1.
Thus, the object of the invention, according to one of the aspects thereof, is an assembly, comprising:
The assembly according to the invention may furthermore include one or more of the following features taken in isolation or in accordance with all possible technical combinations.
The clamping base may include a first support surface, located in the first internal pipe. The support base may include a second support surface. The first and second support surfaces may then be in contact with each other in accordance with a contact of the plane-on plane type, formed in the direction of flow of the gas.
Moreover, the support base may include a housing, on the first end thereof, to at least partially house the seal.
The clamping base and the support base may be produced from the same material as said at least one of the top and bottom clamping plates.
Furthermore, the seal may be formed by a flexible metal joint in a C shape, comprising a core consisting of a metal helical spring with contiguous turns, a first metal envelope in which the spring is embedded.
The metal helical spring may have contiguous or non-contiguous turns. A spring with non-contiguous turns can provide more flexibility.
The flexible metal joint in a C shape may include a second metal envelope in which the first envelope is embedded. The presence of a second envelope may be advantageous since it will make it possible to follow any surface defects, giving rise to a better seal. Preferably, the second envelope is made from a more ductile material than the first envelope.
The first envelope may for example be made from a nickel-based superalloy. The second envelope may for example be made from gold or copper.
The assembly may include a top end plate and a bottom end plate, between which the plurality of electrochemical cells and the plurality of intermediate interconnectors are clamped.
In addition, said at least one of the top and bottom clamping plates may advantageously be manufactured by an additive manufacturing technique, in particular being produced from refractory austenitic steel, in particular of AISI 310 type.
Moreover, said at least one of the top and bottom clamping plates may have a thickness of between 20 and 30 mm, in particular of the order of 25 mm.
In addition, another object of the invention, according to another of the aspects thereof, is a system, characterised in that it includes:
The support base may be welded, in particular by welding of the TIG type and/or by arc welding, on the end of said at least one gas inlet and/or outlet tube, in line therewith.
The invention will be able to be understood better from the reading of the following detailed description of non-limitative example embodiments thereof, as well as from the examination of the schematic partial figures of the accompanying drawing, on which:
In all these figures, identical references can designate identical or similar elements.
In addition, the various parts shown in the figures are not necessarily shown to a uniform scale, to make the figures more legible.
Furthermore, it should be noted that all the constituents (anode/electrolyte/cathode) of a given electrochemical cell are preferentially ceramic. The operating temperature of a pack of the high-temperature SOEC/SOFC type is more typically between 600 and 1000° C.
In addition, any terms “top” and “bottom” are to be understood here according to the normal direction of orientation of a pack of the SOEC/SOFC type when in its configuration of use.
With reference to
Advantageously, the assembly 80 according to the invention has a structure similar to that of the assembly described in the French patent application FR 3 045 215 A1, apart from the presence here of a coupling system 90 gastight at high temperature, i.e. the pack 20 has a character of the “Plug & Play” (PnP) type.
Thus, in a manner that is common to the various embodiments of the invention described hereinafter, and as can be seen in
This pack 20 includes a plurality of electrochemical cells 41 each formed by a cathode, an anode and an electrolyte interposed between the cathode and the anode, and a plurality of intermediate interconnectors 42 each arranged between two adjacent electrochemical cells 41. This assembly of electrochemical cells 41 and intermediate interconnectors 42 may also be designated by stack.
In addition, the pack 20 includes a top end plate 43 and a bottom end plate 44, respectively also referred to as top stack end plate 43 and bottom stack end plate 44, between which the plurality of electrochemical cells 41 and the plurality of intermediate interconnectors 42 are clamped, i.e. between which the stack is located.
Moreover, the assembly 80 also includes a system 60 for clamping the solid-oxide pack 20 of the SOEC/SOFC type, including a top clamping plate 45 and a bottom clamping plate 46, between which the solid-oxide pack 20 of the SOEC/SOFC type is clamped.
Each clamping plate 45, 46 of the clamping system 60 includes four clamping orifices 54.
In addition, the clamping system 60 furthermore includes four clamping rods 55, or tie rods, extending through a clamping orifice 54 in the top clamping plate 45 and through a corresponding clamping orifice 54 in the bottom clamping plate 46 to enable the top 45 and bottom 46 clamping plates to be assembled together.
The clamping system 60 also includes clamping means 56, 57, 58 at each clamping orifice 54 of the top 45 and bottom 46 clamping plates cooperating with the clamping rods 55 to enable the top 45 and bottom 46 clamping plates to be assembled together.
More precisely, the clamping means include, at each clamping orifice 54 in the top clamping plate 45, a first clamping nut 56 cooperating with the corresponding clamping rod 55 inserted through the clamping orifice 54. In addition, the clamping means include, at each clamping orifice 54 in the bottom clamping plate 46, a second clamping nut 57 associated with a clamping washer 58, these cooperating with the corresponding clamping rod 55 inserted through the clamping orifice 54. The clamping washer 58 is located between the second clamping nut 57 and the bottom clamping plate 46.
In accordance with the invention, the assembly 80 includes at least one coupling system 90, gastight at high temperature, of the pack 20, for example such as the one described with reference to
A description will now be given of such an example of a coupling system 90 gastight at high temperature with reference to
In this example, the assembly 80 includes four coupling systems 90 gastight at high temperature mounted on the bottom clamping plate 46, in proximity to the four clamping nuts 57.
Thus, these four clamping systems 90 gastight at high temperature, for coupling to the furnace 10, are distributed regularly around a support stud 100, secured to the bottom clamping plate 46, intended to allow the support of the assembly 80 in the furnace 10.
As more particularly visible on
In addition, this clamping base 91 includes a first through internal pipe 91a, emerging on the first 91e and second 91f ends, which allows the passage of a tube 103 intended to provide the inlet and/or outlet of gas G.
Moreover, each gastight coupling system 90 also includes a support base 92. This support base 92 includes a first end 92a forming the head of the support base 92 and an opposite second end 92b. The support base 92 is located in the first internal pipe 91a of the clamping base 91. Its second end 92b is attached to the tube 103. For example, it may be attached welded, by TIG method or any other welding means, in line with the tube 103.
In addition, the support base 92 comprises a second through internal pipe 92i, emerging on the first 92a and second 92b ends, which allows the passage of gas G coming from the tube 103 and/or from the solid-oxide pack 20 of the SOEC/SOFC type.
When each gastight coupling system 90 is fitted, the clamping base 91 is preferentially slid onto the tube 103, while taking care to check the direction of introduction so that the thread cooperates with the threaded countersink 102b, described hereinafter, of the bottom clamping plate 46, before welding the support base 92 at the end of the tube 103.
Furthermore, each gastight coupling system 90 also includes a seal 93, preferentially metal, which has a C shape. This seal 93 is positioned against the first end 92a of the support base 92.
This seal 93 is distinguished from the normal static joints of the prior art, functioning rather as a flat joint between two flanges with very little or even no relative movement between them.
Advantageously, the seal 93 is formed by a flexible metal joint comprising: a core formed by a metal helical spring with contiguous turns closed on itself and, in the state of rest, having the form of a torus; a first envelope made from non-ductile metal in which the spring is embedded, this envelope having, in the state of rest, the form of a toric surface the generator circle of which does not close on itself; and a second envelope made from ductile metal in which the first envelope is embedded and also having, in the state of rest, the form of a toric surface the generator circle of which does not close on itself. Such an example of a seal is described in the French patent application FR 2 151 186 A1.
The seal 93 can be produced form a nickel-based superalloy, in particular of the Inconel 718 type. It may have an outside diameter of approximately 2.5 mm and an inside diameter of approximately 12.5 mm. It may be coated with gold and the clamping torque may be of the order of 12 N.m.
In order to be able to mount each gastight coupling system 90 on the bottom clamping plate 46, the latter includes a through pipe 102 for the passage of gas G, in fluid communication with the solid-oxide pack 20 of the SOEC/SOFC type and the inlet and/or outlet tube 103 for gas G.
As still visible in
In addition, the passage pipe 102 of the bottom clamping plate 46 also includes a threaded countersink 102b for receiving the thread Fi of the clamping base 91, and thus being able to mount each gastight coupling system 90 on the bottom clamping plate 46.
Thus each gastight coupling system 90 is assimilated to a system of the “screw/nut” type, the “screw” being formed by the clamping base 91 and the “nut” being formed by the threaded countersink 102b of the bottom clamping plate 46.
Advantageously, it should also be noted that the clamping base 91 includes a first support surface 91c, located in the first internal pipe 91a. Likewise, the support base 92 includes a second support surface 92c. Thus the first 91c and second 92c support surfaces are in contact with each other in accordance with a contact of the plane-on-plane CPP type, formed in the direction of flow of the gas G. It is therefore possible to have a plane-on-plane contact CPP when the threaded clamping base 91 is clamped in the threaded countersink 102b of the bottom clamping plate 46. This action will therefore compress the seal 93 on the countersink surface of the bottom clamping plate 46. It is then the clamping torque imparted by the clamping base 91 that provides the force necessary for the gastightness on the seal 93.
This join furthermore makes it possible to take up any defect in perpendicularity by means of the clearance that will be put between the support base 92 and the clamping base 91. The purpose is to be able to obtain an abutment distributed over the seal surface and the planar contact thereof with the bottom of the countersink.
Furthermore, the support base 92 includes a housing 92I, on its first end 92a, to house the seal 93.
Advantageously, the clamping base 91 and the support base 92 are produced from the same material as the bottom clamping plate 46, especially from austenitic stainless steel, in particular of the 310S type. In this way, the thermal expansions are identical.
Moreover, the nominal diameter of the threaded clamping base 91 and of the threaded countersink 102b of the bottom clamping plate 46 can be M36.
Before fitting and clamping, the clamping base 91 and the threaded countersink 102b can be covered with anti-binding paste resistant to high temperature to facilitate dismantling and to avoid the phenomenon of diffusion welding in the threads during thermal cycling. This anti-binding paste also makes it possible to lubricate the connection and to withstand corrosion. It makes it possible to avoid the jamming and excessive wear of parts exposed to extreme temperatures or a so-called aggressive atmosphere, for example in the case of threads on thermal machines, manifolds for hot gases, burners, valves, disc brakes, spark plugs, exhaust shackles, rollers, bolts, collars, etc. Its formulation based on copper, aluminium and graphite can protect the metal parts and ensure dismantling thereof.
Various tests for testing the gastightness level were implemented with mica joints and metal seals. It became clear that the use of metal seals 93 with a C shape makes it possible to obtain the best gastightness over time while greatly limiting the leakage rate. In addition, they can be replaced easily.
Naturally, the invention is not limited to the example embodiments that have just been described. Various modifications can be made thereto by a person skilled in the art.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1910287 | Sep 2019 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2020/051584 | 9/14/2020 | WO |
