EP3735393A1 - Portable device for producing hydrogen, and use thereof - Google Patents

Portable device for producing hydrogen, and use thereof

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Publication number
EP3735393A1
EP3735393A1 EP19710741.0A EP19710741A EP3735393A1 EP 3735393 A1 EP3735393 A1 EP 3735393A1 EP 19710741 A EP19710741 A EP 19710741A EP 3735393 A1 EP3735393 A1 EP 3735393A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
portable
fuel cell
chamber
heat exchange
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.)
Withdrawn
Application number
EP19710741.0A
Other languages
German (de)
French (fr)
Inventor
Oleksiy NICHIPORUK
Jed Kraiem
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.)
Yxens SAS
Original Assignee
Apollon Solar SAS
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 Apollon Solar SAS filed Critical Apollon Solar SAS
Publication of EP3735393A1 publication Critical patent/EP3735393A1/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701—Temperature
    • H01M8/04708—Temperature of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0687—Reactant purification by the use of membranes or filters
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/30—Fuel cells in portable systems, e.g. mobile phone, laptop
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to the fields of chemistry and energy production, and more particularly the field of reactors used in chemical engineering to produce hydrogen. More specifically, the invention relates to a small hydrogen generator, capable of generating hydrogen by the reaction between a chemical compound introduced in the solid state and an aqueous liquid. This hydrogen generator can be used to supply hydrogen to a portable fuel cell.
  • Portable fuel cells can power small electrical systems; such systems exist in commerce. If they operate on hydrogen, they need to be supplied with hydrogen by a hydrogen source, such as a hydrogen generator. It would be convenient if this hydrogen generator is also portable. Numerous portable hydrogen generators are known by electrolysis of water, described for example in GB 2 549 369 (O'Neill). However, it would also be convenient for this portable hydrogen generator to operate autonomously, i.e. without the need for a power supply. To have an autonomous hydrogen generator, hydrogen must therefore be generated not electrochemically but chemically, most often by decomposing a solid precursor of hydrogen in a liquid.
  • WO 2010/035250 discloses a hydrogen generator using a solid compound capable of releasing hydrogen gas in a liquid medium; this solid compound is a borohydride, such as NaBH 4 .
  • the system comprises a reaction chamber, wherein said solid compound is contacted with water and a catalyst based on noble and expensive (ruthenium) or hazardous (cobalt) metals, to decompose into borate and hydrogen gas.
  • the latter is evacuated through a hydrophobic membrane impervious to water but permeable to hydrogen.
  • the disadvantage of this generator is that the resulting borate solution is toxic and must not be discharged into the sewage pipe.
  • Other hydrogen generators based on the decomposition of NaBH 4 in water are described in US 3,459,510 (US Pat. Carbide), US 6,939,529 (Millenium Cell, Inc.), US 2005/0158595 (Integrated Fuel Cell Technologies), US 2007/003671 (Ardica Technologies Inc.), WO 2010/075410 (BIC).
  • the invention aims to remedy at least some of the disadvantages of the prior art.
  • the invention aims in particular to provide a device which, while being small in size and low mass, ensures a reliable production of hydrogen.
  • the invention also aims at providing such a device, which ensures effective separation between the initial products of the reaction and the hydrogen thus produced.
  • the invention also aims at providing such a device which makes it possible to regulate the temperature prevailing in the reaction zone.
  • the invention also aims at providing such a device, whose structure is simple and the implementation intuitive for the operator.
  • the invention relates to a portable device for producing hydrogen from a hydrogen precursor and a liquid, this device comprising
  • thermal exchange means provided on at least a part of the periphery of said main enclosure,
  • auxiliary chamber intended for collecting the hydrogen thus produced, a separation membrane delimiting said main enclosure with respect to said auxiliary chamber,
  • Said hydrogen precursor may be a solid precursor, for example a powder of a suitable metal; the pH value of the liquid phase is adjusted according to the metal.
  • active cooling means such as ventilation means
  • Servo-control means for controlling the active cooling means (in particular the ventilation means) to the temperature measuring means.
  • this device further comprises means for detachably fixing the auxiliary chamber with respect to the main enclosure,
  • the removable fastening means comprise a quick coupling, in particular of quarter-turn type,
  • the means for evacuating the hydrogen comprise a quick coupling, capable of being connected to a feed pipe of a fuel cell,
  • the means for evacuating the hydrogen comprise a safety valve calibrated at a predetermined pressure
  • the ventilation means comprise an electric fan, which is powered by supply means adapted to be connected to a fuel cell,
  • the bottom of the auxiliary chamber turned towards the main enclosure, comprises a lattice against which the separation membrane is pressed, this lattice defining openings for the passage of hydrogen,
  • the heat exchange means comprise a plurality of fins extending outwards (preferably radially) from the periphery of the main enclosure,
  • this device further comprises a duct for confining the ventilation air, extending at the periphery of the heat exchange means, an auxiliary chamber comprises means for trapping the residual moisture present in the hydrogen,
  • the separation membrane is permeable to hydrogen gas while being impermeable to polar liquids
  • the separation membrane is made of metallic or non-metallic material, and in the latter case preferably ceramic material or polymer material; mm
  • the largest dimension of the device is less than 800 mm, especially less than 250 mm.
  • the total mass of the device, unladen, is less than 5.0 kg, and especially less than 1.0 kg.
  • the invention also relates to a use of the above device for supplying a fuel cell.
  • FIGS 1 to 13 illustrate an embodiment of the invention, but do not limit the scope of the invention.
  • Figure 1 is a longitudinal sectional view of a portable device for producing hydrogen according to the invention, which is associated with a fuel cell.
  • Figures 2 and 3 are perspective views, illustrating from two different angles the portable device for producing hydrogen according to the invention.
  • Figures 4 to 6 are views respectively in perspective, partially cut away front and end, illustrating the main chamber of the device according to the invention, and fins provided at the periphery of the enclosure.
  • Figures 7 to 9 are views respectively in perspective, front and end, illustrating the annex chamber of the device according to the invention.
  • Figures 10 and 1 1 are views respectively in longitudinal section and in perspective, illustrating a closure cap of the auxiliary chamber of the device according to the invention.
  • Figures 12 and 13 are views respectively in longitudinal section and in perspective, illustrating a closure cap of the main enclosure of the device according to the invention.
  • the following numerical references are used in the figures and in the description:
  • the attached figures describe a device for producing hydrogen according to the invention, which is portable type.
  • the term "portable” means that this device can be transported and manipulated by an operator, without significant physical effort.
  • the largest dimension of the device is advantageously less than 330 mm, especially less than 280.
  • its empty weight is advantageously less than 1200 g, especially less than 1000 g.
  • This device designated as a whole by the reference 1, firstly comprises a main chamber 2 for receiving a solid hydrogen precursor and a liquid so as to form hydrogen.
  • This chamber comprises a main shaft 20 which is typically cylindrical, whose A20 is noted the longitudinal axis, which corresponds to the main axis of the device.
  • a plurality of fins 21, extending longitudinally, are fixed by any appropriate means to the outer periphery of the barrel.
  • a soldering or soldering attachment is preferred, if the cylindrical main barrel 20 and the fins 21 are made of metal, for example extruded aluminum alloy.
  • main enclosure 2 and the main shaft 20 may have a shape other than cylindrical, such as: oval, prismatic or otherwise flattened, with heat exchange means (including fins 21) which can cover the whole or only part of the periphery of the main enclosure 2.
  • a plug 3 At its first end, the internal volume of the barrel 20 is closed by a plug 3.
  • the latter comprises a closed web 30, axially extended by a flange 31.
  • the diameter of the plug is close to that of the barrel, but lower than that of the fins . Therefore, as will be seen in what follows, this cap does not prevent the progression of air in the vicinity of these fins.
  • This plug 3 supports a fan 4, of any suitable type, including electrical.
  • This attachment is advantageously removable type, for example by means of a screw 40.
  • the fan 4 is fed by a cable 102, shown schematically, which is connected to a fuel cell 100, also shown schematically.
  • the electrical energy generated by the fuel cell is capable of supplying the fan 4.
  • the energy consumption of this fan 4 is low, for example 2 W, which corresponds to at most a few percent of the energy consumption of the fan. electrical energy generated by the fuel cell.
  • the second end of the barrel 20, opposite the stopper 3, comprises a terminal neck 22 cut by means of notches 23, the function of which will be described hereinafter.
  • This second end is closed by a membrane 5 of hydrophobic type, which is permeable to gas while being impermeable to polar liquids. In other words, this membrane allows the passage of hydrogen produced, while preventing the flow of polar liquid.
  • This membrane 5 is preferably made of any material suitable for the above function. As such, it can be made of a ceramic material, polymer or metal permeable to hydrogen. Insofar as the sheets of hydrogen-permeable metal materials (especially palladium) are very expensive, a non-metallic material is preferred. Thus, membranes of polymer material are preferred. According to advantageous embodiments, the membrane is made in particular of PTFE (poly tetrafluoroethylene), PVDF (polyvinylidene fluoride), polyethylene, or polypropylene; advantageously it has pores with a size of between about 0.1 ⁇ m to about 0.5 ⁇ m.
  • PTFE poly tetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • This chamber 6 comprises a cylindrical cartridge 60, whose first end, facing the enclosure 2, is closed by means of a bottom 61.
  • the latter is made in the form of a lattice, or spider web, which is composed of concentric strips of material 62, which delimit intermediate passages 63.
  • This mesh 61 allows the reliable retention of the membrane by plating, while the passages 63 allow the flow of hydrogen, from the chamber 2 to the chamber .
  • This bottom 61 is extended by a neck 64, which is provided with ribs 65 intended to cooperate with the aforementioned notches 23.
  • This cooperation ensures a removable fastening type quarter quick connection between the main chamber 2 and the chamber
  • This chamber 6 is furthermore equipped with means for trapping any residual moisture present in the hydrogen circulating in this chamber.
  • the chamber 6 has in particular forms ensuring changes in its section, with a shoulder 66. It can provide any other type of forms, providing this trapping function, for example baffles or the like.
  • the adjoining chamber 6 is closed by means of a plug 7.
  • the latter comprises firstly a web 70, which is provided with a tip 71 called stitching, allowing the evacuation of the hydrogen out of the chamber 6.
  • the web 70 is extended axially by a threaded rim 72, allowing the cap to be screwed onto a threaded portion of the cartridge 60.
  • the plug 7 cooperates with a member ensuring the evacuation of hydrogen in the direction of the fuel cell 100, which is designated as a whole by the reference 8.
  • This discharge member comprises a pin 80, allowing the fixing on the stopper 7 by any suitable means.
  • This stud is dug a channel 81, which opens into a fitting 82, of a type known per se.
  • This coupling 82 is able to be connected, in a removable manner, to a pipe 104 placed in communication with the inlet of the fuel cell 100.
  • the evacuation member 8 is equipped with a safety valve 83, which is calibrated at a predetermined pressure, typically close to 0.5 bar.
  • the device 1 of the invention is furthermore equipped with a temperature sensor 9 of any suitable type.
  • This sensor 9 is fixed in the vicinity of the barrel 20, between two adjacent fins 21, so that it can measure the temperature inside the main chamber 2.
  • This sensor is connected, via a line 90, to a control module 91, of a type known per se, which is itself connected to the fan 4 via an additional line 92.
  • This control-command module 91 can be integrated into the device 1 or can be located at the outside, for example in a module comprising the fuel cell 100 powered by the device.
  • Said control-command module 91 can advantageously implement a PID type algorithm (proportional, integral, derivative), which is known as such.
  • the device according to the invention advantageously comprises a sheath 24, extending at the outer periphery of the fins.
  • This sheath is made of a material known in itself, including plastic shrinkable type.
  • the walls opposite this sheath and the barrel 20 delimit a path 25 for confining the air, in the vicinity of the fins 21. This improves the cooling efficiency by the forced air flow generated by the fan 4 between the fins. 21 and the sheath 24.
  • the presence of this sheath 24 is advantageous in terms of safety, since it allows the user to grip without risk, protecting the user on the one hand against the edges of the fins 21 and on the other hand against the heat.
  • the internal volume of the main chamber 2 is accessed by unlocking the cartridge 60 with respect to the barrel 20.
  • the hydrogen precursor and the polar liquid are then placed in this chamber, intended to produce the desired hydrogen.
  • the cartridge is locked again on the drum.
  • the hydrogen precursor may be a solid precursor, for example a metal, which is advantageously introduced in any appropriate finely divided form.
  • a metal powder which must be chosen so as to avoid the formation of toxic byproducts.
  • It may comprise a suitable catalyst.
  • This metal powder may be contained in a tablet or in a flexible package and permeable to the appropriate polar liquid to prevent its dispersion.
  • the said polar liquid may be water, the pH of which is adjusted according to the metal.
  • a powder based on aluminum, silicon, magnesium or other metal can be used.
  • the hydrogen generation reaction from a metal is significantly more exothermic than the hydrogen generation reaction from NaBH 4 . This requires providing means to dissipate the heat of reaction if it is desired to exploit the reaction under controlled conditions.
  • the production of hydrogen is initiated.
  • This hydrogen penetrates through the membrane 5, while the latter holds the liquid inside the main enclosure 2.
  • This hydrogen then passes through the annex chamber 6, being released from its residual moisture, then is directed towards of the fuel cell 100 through the discharge member 8.
  • the reaction of the metal powder with said polar liquid being highly exothermic, the temperature of the liquid increases rapidly, which accelerates said reaction.
  • the increase in temperature is limited by the effect of the heat exchange means provided on at least a portion of the periphery of the main enclosure; these heat exchange means may be said fins 21.
  • the temperature is controlled and regulated.
  • the senor 9 measures the temperature prevailing inside the main enclosure or on the surface of the enclosure.
  • the module 91 slaves the speed of the fan 4, so as to regulate the above-mentioned temperature around a predetermined reference value, typically between 40 ° C. and 70 ° C., and preferably between 50 ° C. C and 65 ' ⁇ , and even more preferably between 60 ° C and 65 ° C.
  • the system is regulated so that the temperature advantageously does not exceed 70 ° C, and preferably does not exceed 65 ' ⁇ , to prevent the user of the device does not burn when touched.
  • the inventors have found that this device can operate in a wide range of ambient temperatures, and in particular between 0 ° C and 45 q C.
  • the hydrogen production reaction continues continuously, for a period of time typically close to one hour.
  • the cartridge is unlocked again so as to access the interior volume of the chamber. It is thus possible, if necessary, to extract the package which contained the solid hydrogen precursor powder and replace it with a new packaging, or to put a new tablet containing the powder of said solid hydrogen precursor, and / or replace the polar fluid that contains the soluble byproducts of the reaction, in order to restart the hydrogen generation.
  • the invention has many advantages.
  • this membrane allows operation of the device in all spatial configurations, in particular vertically or vertically. horizontal.
  • the annex chamber 6 advantageously provides a triple function. First, it ensures the closure of the main enclosure. Furthermore, it forms a phase separator, trapping the residual moisture contained in the generated hydrogen, whether in the form of droplets or in the form of water vapor. This improves the purity of the hydrogen at the outlet of the evacuation member 8; for this reason the hydrogen generator according to the invention is particularly suitable for supplying a fuel cell. Finally, the annex chamber 6 integrates an additional safety function, thanks to the advantageous presence of the valve 83.
  • the fan 4 draws air through the fins 21.
  • Such a configuration has an improved efficiency, compared with a blowing in these fins.
  • the invention also allows efficient regulation of the device for producing hydrogen, at the thermal level. Indeed, the presence of the measuring and servo means makes it possible to operate the fan at the desired power, so as to adjust the temperature inside the enclosure to the desired value. Thus, the reaction takes place under constant temperature conditions, except for the starting phase at room temperature, which allows a constant production of hydrogen.
  • the device according to the invention is compact and portable, and particularly convenient handling.
  • the presence of the removable locking means is particularly advantageous. The operator can thus quickly and intuitively lock and unlock the auxiliary chamber vis-à-vis the main speaker.
  • the inside of the device is easy to clean.
  • An aluminum alloy apparatus having a dimension of approximately 90 mm ⁇ 240 mm, with an internal volume of 360 cm 3, was thus produced .
  • the generator weighs about 800 g empty and has about thirty fins of a thickness of 1.5 mm with a size of about 16 mm x 160 mm. It can be loaded with about 45 g of metal powder and about 200 ml of water, and it then produces for about 80 minutes about 45 liters of hydrogen, with a constant flow (after a start-up phase) of the order of 0.5 liters per minute.
  • the maximum power of the fan is 2.2 W for a maximum rotation speed of 5,000 rpm, a maximum flow rate of 1.3 m 3 of air per minute and a static air pressure of 156 Pa.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Fuel Cell (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

Portable device (1 ) for producing hydrogen from a hydrogen precursor and a liquid, this device comprising - a main chamber (2), intended for receiving said hydrogen precursor and said liquid, - an additional chamber (6), intended for collecting the hydrogen thus produced, - a separation membrane (5), defining said main chamber relative to said additional chamber, - means (8) for discharging the hydrogen out of the additional chamber, and characterized in that it comprises heat exchange means (21), provided on at least one portion of the periphery of said main chamber. This device produces pure hydrogen which may supply a fuel cell.

Description

DISPOSITIF PORTABLE DE PRODUCTION D’HYDROGENE, ET SON UTILISATION Domaine technique de l’invention  PORTABLE DEVICE FOR PRODUCING HYDROGEN AND USE THEREOF Technical Field of the Invention
L’invention concerne les domaines de la chimie et de la production d’énergie, et plus particulièrement le domaine des réacteurs utilisés en génie chimique pour produire de l’hydrogène. Plus précisément l’invention concerne un générateur d’hydrogène de petite taille, capable de générer de l’hydrogène par la réaction entre un composé chimique introduit à l’état solide et un liquide aqueux. Ce générateur d’hydrogène peut être utilisé pour alimenter en hydrogène une pile à combustible portable. The invention relates to the fields of chemistry and energy production, and more particularly the field of reactors used in chemical engineering to produce hydrogen. More specifically, the invention relates to a small hydrogen generator, capable of generating hydrogen by the reaction between a chemical compound introduced in the solid state and an aqueous liquid. This hydrogen generator can be used to supply hydrogen to a portable fuel cell.
Etat de la technique State of the art
Les piles à combustibles portables peuvent alimenter de petits systèmes électriques ; de tels systèmes existent dans le commerce. Si elles fonctionnent à l’hydrogène, elles ont besoin d’être alimentées en hydrogène par une source d’hydrogène, tel qu’un générateur d’hydrogène. Il serait pratique que ce générateur d’hydrogène soit également portable. On connaît de nombreux générateurs portables d’hydrogène par électrolyse d’eau, décrits par exemple dans GB 2 549 369 (O’Neill). Cependant, il serait également pratique que ce générateur portable d’hydrogène fonctionne de manière autonome, c’est-à-dire sans avoir besoin d’une alimentation en énergie électrique. Pour disposer d’un générateur d’hydrogène autonome on doit donc générer l’hydrogène non pas par voie électrochimique mais par voie chimique, le plus souvent en décomposant un précurseur solide d’hydrogène dans un liquide. US 9,705,145 (Intelligent Energy Inc.) décrit un générateur d’hydrogène par décomposition thermique d’un composé approprié tel que AIH3 OU d’autres hydrures ; ce système nécessite un système de chauffage électrique intégré. On connaît également de systèmes qui décomposent un hydrure de métal en phase aqueuse ; dans ces cas la réaction est pilotée par la quantité de catalyseur. Portable fuel cells can power small electrical systems; such systems exist in commerce. If they operate on hydrogen, they need to be supplied with hydrogen by a hydrogen source, such as a hydrogen generator. It would be convenient if this hydrogen generator is also portable. Numerous portable hydrogen generators are known by electrolysis of water, described for example in GB 2 549 369 (O'Neill). However, it would also be convenient for this portable hydrogen generator to operate autonomously, i.e. without the need for a power supply. To have an autonomous hydrogen generator, hydrogen must therefore be generated not electrochemically but chemically, most often by decomposing a solid precursor of hydrogen in a liquid. US 9,705,145 (Intelligent Energy Inc.) describes a hydrogen generator by thermal decomposition of a suitable compound such as AIH 3 OR other hydrides; this system requires an integrated electric heating system. Also known are systems that break down a metal hydride in the aqueous phase; in these cases the reaction is controlled by the amount of catalyst.
WO 2010/035250 (Société BIC) décrit un générateur d’hydrogène utilisant un composé solide capable de libérer de l’hydrogène gazeux en milieu liquide ; ce composé solide est un borohydrure, tel que le NaBH4. Ce système comprend une chambre de réaction, dans laquelle ledit composé solide est mis en contact avec de l’eau et un catalyseur à base de métaux nobles et chers (ruthénium) ou dangereux (cobalt), pour se décomposer en borate et hydrogène gazeux. Ce dernier est évacué à travers une membrane hydrophobe, imperméable pour l’eau mais perméable pour l’hydrogène. L’inconvénient de ce générateur est que la solution de borate qui en résulte est toxique et ne doit pas être déchargée dans la canalisation des eaux usées. D’autres générateurs d’hydrogène basés sur la décomposition du NaBH4 dans l’eau sont décrits dans US 3,459,510 (Union Carbide), US 6,939,529 (Millenium Cell, Inc.), US 2005/0158595 (Integrated Fuel Cell Technologies), US 2007/003671 1 (Ardica Technologies Inc.), WO 2010/075410 (BIC). WO 2010/035250 (BIC Company) discloses a hydrogen generator using a solid compound capable of releasing hydrogen gas in a liquid medium; this solid compound is a borohydride, such as NaBH 4 . The system comprises a reaction chamber, wherein said solid compound is contacted with water and a catalyst based on noble and expensive (ruthenium) or hazardous (cobalt) metals, to decompose into borate and hydrogen gas. The latter is evacuated through a hydrophobic membrane impervious to water but permeable to hydrogen. The disadvantage of this generator is that the resulting borate solution is toxic and must not be discharged into the sewage pipe. Other hydrogen generators based on the decomposition of NaBH 4 in water are described in US 3,459,510 (US Pat. Carbide), US 6,939,529 (Millenium Cell, Inc.), US 2005/0158595 (Integrated Fuel Cell Technologies), US 2007/003671 (Ardica Technologies Inc.), WO 2010/075410 (BIC).
D’une manière générale l’état de la technique enseigne qu’un des problèmes que posent les générateurs d’hydrogène autonomes est le contrôle des conditions réactionnelles, dans la mesure où la cinétique des réactions chimiques susceptibles de générer de l’hydrogène, qu’elles soient endothermiques ou exothermiques, dépend fortement de la température du milieu réactionnel. Un autre problème est qu’il n’est pas souhaitable que le générateur utilise des produits dangereux, toxiques et/ou difficiles à stocker et/ou à manipuler en tant que composé capable de libérer de l’hydrogène. Il n’est pas non plus souhaitable que le générateur d’hydrogène génère des produits secondaires toxiques ou de manière plus générale des produits (tel qu’une phase aqueuse ou solide) qui nécessitent une attention particulière pour être déchargés. Et enfin, il est souhaitable que l’hydrogène gazeux qui est produit par le générateur portable soit aussi pur que possible, pour ne pas dégrader le fonctionnement de la pile à combustible qu’il alimente. In a general way, the state of the art teaches that one of the problems posed by autonomous hydrogen generators is the control of the reaction conditions, insofar as the kinetics of the chemical reactions capable of generating hydrogen, which they are endothermic or exothermic, strongly depends on the temperature of the reaction medium. Another problem is that it is undesirable for the generator to use products which are dangerous, toxic and / or difficult to store and / or handle as a compound capable of releasing hydrogen. Nor is it desirable that the hydrogen generator generates toxic byproducts or more generally products (such as an aqueous or solid phase) that require special attention to be discharged. And finally, it is desirable that the hydrogen gas that is produced by the portable generator is as pure as possible, not to degrade the operation of the fuel cell that it feeds.
Compte tenu de ce qui précède, l’invention vise à remédier à au moins certains des inconvénients de l’art antérieur. In view of the above, the invention aims to remedy at least some of the disadvantages of the prior art.
L’invention vise en particulier à proposer un dispositif qui, tout en étant de dimensions réduites et de masse faible, assure une production fiable d’hydrogène. The invention aims in particular to provide a device which, while being small in size and low mass, ensures a reliable production of hydrogen.
L’invention vise également à proposer un tel dispositif, qui assure une séparation efficace entre les produits initiaux de la réaction et l’hydrogène ainsi produit. The invention also aims at providing such a device, which ensures effective separation between the initial products of the reaction and the hydrogen thus produced.
L’invention vise également à proposer un tel dispositif, qui permet de réguler la température régnant dans la zone réactionnelle. The invention also aims at providing such a device which makes it possible to regulate the temperature prevailing in the reaction zone.
L’invention vise également à proposer un tel dispositif, dont la structure est simple et la mise en œuvre intuitive pour l’opérateur. The invention also aims at providing such a device, whose structure is simple and the implementation intuitive for the operator.
Objets de l’invention Objects of the invention
A cet effet l’invention a pour objet un dispositif portable de production d’hydrogène à partir d’un précurseur d’hydrogène et d’un liquide, ce dispositif comprenant For this purpose the invention relates to a portable device for producing hydrogen from a hydrogen precursor and a liquid, this device comprising
- une enceinte principale, destiné à la réception dudit précurseur d’hydrogène et dudit liquide, a main enclosure for receiving said hydrogen precursor and said liquid,
- des moyens d’échange thermique, prévus sur au moins une partie de la périphérie de ladite enceinte principale,  thermal exchange means, provided on at least a part of the periphery of said main enclosure,
- une chambre annexe, destiné à la collecte de l’hydrogène ainsi produit, - une membrane de séparation, délimitant ladite enceinte principale par rapport à ladite chambre annexe, an auxiliary chamber, intended for collecting the hydrogen thus produced, a separation membrane delimiting said main enclosure with respect to said auxiliary chamber,
- des moyens d’évacuation de l’hydrogène, hors de la chambre annexe,  means for evacuating the hydrogen, out of the auxiliary chamber,
Ledit précurseur d’hydrogène peut être un précurseur solide, par exemple une poudre d’un métal approprié ; la valeur pH de la phase liquide est ajustée en fonction du métal. Said hydrogen precursor may be a solid precursor, for example a powder of a suitable metal; the pH value of the liquid phase is adjusted according to the metal.
Selon d’autres caractéristiques du dispositif conforme à l’invention le dispositif peut comprendre : According to other characteristics of the device according to the invention the device can comprise:
- des moyens de refroidissement actif (tels que des moyens de ventilation), qui coopèrent avec les moyens d’échange thermique, active cooling means (such as ventilation means), which cooperate with the heat exchange means,
- des moyens de mesure de la température au niveau de la paroi de l’enceinte principale,  means for measuring the temperature at the wall of the main enclosure,
- des moyens d’asservissement, permettant d’asservir les moyens de refroidissement actif (en particulier les moyens de ventilation) aux moyens de mesure de la température.  - Servo-control means for controlling the active cooling means (in particular the ventilation means) to the temperature measuring means.
Selon encore d’autres caractéristiques du dispositif selon l’invention : According to still other characteristics of the device according to the invention:
- ce dispositif comprend en outre des moyens de fixation amovible de la chambre annexe par rapport à l’enceinte principale,  this device further comprises means for detachably fixing the auxiliary chamber with respect to the main enclosure,
les moyens de fixation amovible comprennent un raccord rapide, notamment de type quart de tour,  the removable fastening means comprise a quick coupling, in particular of quarter-turn type,
- les moyens d’évacuation de l’hydrogène comprennent un raccord rapide, propre à être connecté à une conduite d’alimentation d’une pile à combustible,  the means for evacuating the hydrogen comprise a quick coupling, capable of being connected to a feed pipe of a fuel cell,
- les moyens d’évacuation de l’hydrogène comprennent une soupape de sécurité tarée à une pression prédéterminée,  the means for evacuating the hydrogen comprise a safety valve calibrated at a predetermined pressure,
- les moyens de ventilation comprennent un ventilateur électrique, lequel est alimenté par des moyens d’alimentation aptes à être reliés à une pile à combustible,  - The ventilation means comprise an electric fan, which is powered by supply means adapted to be connected to a fuel cell,
- le fond de la chambre annexe, tourné vers l’enceinte principale, comprend un treillis contre lequel est plaquée la membrane de séparation, ce treillis définissant des ouvertures de passage de l’hydrogène,  the bottom of the auxiliary chamber, turned towards the main enclosure, comprises a lattice against which the separation membrane is pressed, this lattice defining openings for the passage of hydrogen,
- les moyens d’échange thermique comprennent une pluralité d’ailettes s’étendant vers l’extérieur (de préférence radialement), à partir de la périphérie de l’enceinte principale,  the heat exchange means comprise a plurality of fins extending outwards (preferably radially) from the periphery of the main enclosure,
- ce dispositif comprend en outre une gaine de confinement de l’air de ventilation, s’étendant à la périphérie des moyens d’échange thermique, une chambre annexe comprend des moyens de piégeage de l’humidité résiduelle présente dans l’hydrogène, this device further comprises a duct for confining the ventilation air, extending at the periphery of the heat exchange means, an auxiliary chamber comprises means for trapping the residual moisture present in the hydrogen,
la membrane de séparation est perméable à l’hydrogène gazeux tout en étant imperméable aux liquides polaires,  the separation membrane is permeable to hydrogen gas while being impermeable to polar liquids,
la membrane de séparation est réalisée en matériau métallique ou non métallique, et dans ce dernier cas de préférence en matériau céramique ou en matériau polymère ; mm  the separation membrane is made of metallic or non-metallic material, and in the latter case preferably ceramic material or polymer material; mm
la plus grande dimension du dispositif est inférieure à 800 mm, notamment inférieure à 250mm.  the largest dimension of the device is less than 800 mm, especially less than 250 mm.
la masse totale du dispositif, à vide, est inférieure à 5,0 kg, et notamment inférieure à 1 ,0 kg.  the total mass of the device, unladen, is less than 5.0 kg, and especially less than 1.0 kg.
L’invention a également pour objet une utilisation du dispositif ci-dessus, pour alimenter une pile à combustible. The invention also relates to a use of the above device for supplying a fuel cell.
Description des figures Description of figures
Les figures 1 à 13 illustrent un mode de réalisation de l’invention, mais ne limitent pas la portée de l’invention. Figures 1 to 13 illustrate an embodiment of the invention, but do not limit the scope of the invention.
La figure 1 est une vue en coupe longitudinale d’un dispositif portable de production d’hydrogène conforme à l’invention, lequel est associé à une pile à combustible. Figure 1 is a longitudinal sectional view of a portable device for producing hydrogen according to the invention, which is associated with a fuel cell.
Les figures 2 et 3 sont des vues en perspective, illustrant sous deux angles différents le dispositif portable de production d’hydrogène conforme à l’invention. Figures 2 and 3 are perspective views, illustrating from two different angles the portable device for producing hydrogen according to the invention.
Les figures 4 à 6 sont des vues respectivement en perspective, de face avec arrachements partiels et en bout, illustrant l’enceinte principale du dispositif conforme à l’invention, ainsi que des ailettes prévues à la périphérie de cette enceinte. Figures 4 to 6 are views respectively in perspective, partially cut away front and end, illustrating the main chamber of the device according to the invention, and fins provided at the periphery of the enclosure.
Les figures 7 à 9 sont des vues respectivement en perspective, de face et en bout, illustrant la chambre annexe du dispositif conforme à l’invention. Figures 7 to 9 are views respectively in perspective, front and end, illustrating the annex chamber of the device according to the invention.
Les figures 10 et 1 1 sont des vues respectivement en coupe longitudinale et en perspective, illustrant un bouchon de fermeture de la chambre annexe du dispositif conforme à l’invention. Figures 10 and 1 1 are views respectively in longitudinal section and in perspective, illustrating a closure cap of the auxiliary chamber of the device according to the invention.
Les figures 12 et 13 sont des vues respectivement en coupe longitudinale et en perspective, illustrant un bouchon de fermeture de l’enceinte principale du dispositif conforme à l’invention. Les repères numériques suivants sont utilisés sur les figures et dans la description : Figures 12 and 13 are views respectively in longitudinal section and in perspective, illustrating a closure cap of the main enclosure of the device according to the invention. The following numerical references are used in the figures and in the description:
Description détaillée detailed description
Les figures annexées décrivent un dispositif de production d’hydrogène conforme à l’invention, lequel est de type portable. Au sens de l’invention, le terme « portable » signifie que ce dispositif peut être transporté et manipulé par un opérateur, sans effort physique important. À cet effet, la plus grande dimension du dispositif est avantageusement inférieure à 330 mm, notamment inférieure à 280. Par ailleurs, son poids à vide est avantageusement inférieur à 1 200 g, notamment inférieur à 1 000 g. Ce dispositif, désigné dans son ensemble par la référence 1 , comprend tout d’abord une enceinte principale 2 destinée à la réception d’un précurseur solide d’hydrogène et d’un liquide de manière à former de l’hydrogène. Cette enceinte comporte un fût principal 20 qui est typiquement cylindrique, dont on note A20 l’axe longitudinal, lequel correspond à l’axe principal du dispositif. Une pluralité d’ailettes 21 , s’étendant longitudinalement, sont fixées par tout moyen approprié à la périphérie extérieure du fût. À titre d’exemple, une fixation par soudage ou brasage est préférée, si le fût principal cylindrique 20 et les ailettes 21 sont fabriqués en métal, par exemple en alliage d’aluminium extrudé.  The attached figures describe a device for producing hydrogen according to the invention, which is portable type. For the purposes of the invention, the term "portable" means that this device can be transported and manipulated by an operator, without significant physical effort. For this purpose, the largest dimension of the device is advantageously less than 330 mm, especially less than 280. Furthermore, its empty weight is advantageously less than 1200 g, especially less than 1000 g. This device, designated as a whole by the reference 1, firstly comprises a main chamber 2 for receiving a solid hydrogen precursor and a liquid so as to form hydrogen. This chamber comprises a main shaft 20 which is typically cylindrical, whose A20 is noted the longitudinal axis, which corresponds to the main axis of the device. A plurality of fins 21, extending longitudinally, are fixed by any appropriate means to the outer periphery of the barrel. For example, a soldering or soldering attachment is preferred, if the cylindrical main barrel 20 and the fins 21 are made of metal, for example extruded aluminum alloy.
On note que l’enceinte principale 2 et le fût principal 20 peuvent avoir une forme autre que cylindrique, tel que : ovale, prismatique ou autrement aplatie, avec des moyens d’échange thermique (notamment des ailettes 21 ) qui peuvent couvrir la totalité ou une partie seulement de la périphérie de l’enceinte principale 2. À sa première extrémité, le volume intérieur du fût 20 est obturé par un bouchon 3. Ce dernier comprend un voile fermé 30, prolongé axialement par un rebord 31. Le diamètre du bouchon est voisin de celui du fût, mais inférieur à celui des ailettes. Par conséquent, comme on le verra dans ce qui suit, ce bouchon n’empêche pas la progression d’air au voisinage de ces ailettes. Note that the main enclosure 2 and the main shaft 20 may have a shape other than cylindrical, such as: oval, prismatic or otherwise flattened, with heat exchange means (including fins 21) which can cover the whole or only part of the periphery of the main enclosure 2. At its first end, the internal volume of the barrel 20 is closed by a plug 3. The latter comprises a closed web 30, axially extended by a flange 31. The diameter of the plug is close to that of the barrel, but lower than that of the fins . Therefore, as will be seen in what follows, this cap does not prevent the progression of air in the vicinity of these fins.
Ce bouchon 3 supporte un ventilateur 4, de tout type approprié, notamment électrique. Cette fixation est avantageusement de type amovible, par exemple au moyen d’une vis 40. Le ventilateur 4 est alimenté par un câble 102, représenté de manière schématique, lequel est relié à une pile à combustible 100, également illustrée de manière schématique. En d’autres termes, l’énergie électrique générée par la pile à combustible est susceptible d’alimenter le ventilateur 4. La consommation énergétique de ce ventilateur 4 est faible, par exemple 2 W, ce qui correspond au plus à quelques pourcents de l’énergie électrique générée par la pile à combustible. This plug 3 supports a fan 4, of any suitable type, including electrical. This attachment is advantageously removable type, for example by means of a screw 40. The fan 4 is fed by a cable 102, shown schematically, which is connected to a fuel cell 100, also shown schematically. In other words, the electrical energy generated by the fuel cell is capable of supplying the fan 4. The energy consumption of this fan 4 is low, for example 2 W, which corresponds to at most a few percent of the energy consumption of the fan. electrical energy generated by the fuel cell.
La deuxième extrémité du fût 20, opposée au bouchon 3, comprend un col terminal 22 creusé au moyen d’encoches 23, dont la fonction va être décrite ci-après. Cette deuxième extrémité est obturée par une membrane 5 de type hydrophobe, qui est perméable aux gaz tout en étant imperméable aux liquides polaires. En d’autres termes, cette membrane autorise le passage de l’hydrogène produit, tout en empêchant l’écoulement du liquide polaire. The second end of the barrel 20, opposite the stopper 3, comprises a terminal neck 22 cut by means of notches 23, the function of which will be described hereinafter. This second end is closed by a membrane 5 of hydrophobic type, which is permeable to gas while being impermeable to polar liquids. In other words, this membrane allows the passage of hydrogen produced, while preventing the flow of polar liquid.
De manière préférée cette membrane 5 est réalisée en tout matériau approprié à la fonction ci-dessus. A ce titre, elle peut être réalisée en un matériau céramique, polymère ou métallique perméable à l’hydrogène. Dans la mesure où les feuilles en matériaux métalliques perméables à l’hydrogène (surtout le palladium) sont très chères, on préfère un matériau non métallique. Ainsi, on préfère les membranes en matériau polymère. Selon des modes de réalisation avantageux, la membrane est réalisée notamment en PTFE (poly tétra fluoro éthylène), en PVDF (poly fluorure de vinylidène), en polyéthylène, ou en polypropylène ; avantageusement elle présente des pores d’une taille comprise entre environ 0,1 pm jusqu’à environ 0,5 pm. This membrane 5 is preferably made of any material suitable for the above function. As such, it can be made of a ceramic material, polymer or metal permeable to hydrogen. Insofar as the sheets of hydrogen-permeable metal materials (especially palladium) are very expensive, a non-metallic material is preferred. Thus, membranes of polymer material are preferred. According to advantageous embodiments, the membrane is made in particular of PTFE (poly tetrafluoroethylene), PVDF (polyvinylidene fluoride), polyethylene, or polypropylene; advantageously it has pores with a size of between about 0.1 μm to about 0.5 μm.
La membrane 5 décrite ci-dessus sépare l’enceinte principale, vis-à-vis d’une chambre 6 dite annexe ou auxiliaire. Cette chambre 6 comprend une cartouche cylindrique 60, dont la première extrémité, tournée vers l’enceinte 2, est fermée au moyen d’un fond 61. Ce dernier est réalisé sous forme d’un treillis, ou toile d’araignée, qui est composé de bandes de matière 62 concentriques, lesquelles délimitent des passages intermédiaires 63. Ce treillis 61 permet le maintien fiable de la membrane par plaquage, alors que les passages 63 autorisent l’écoulement de l’hydrogène, depuis l’enceinte 2 vers la chambre. Ce fond 61 est prolongé par un col 64, qui est pourvu de nervures 65 destinées à coopérer avec les encoches précitées 23. Cette coopération assure une fixation amovible, de type raccord rapide par quart de tour, entre l’enceinte principale 2 et la chambre annexe 6. Cette chambre 6 est en outre équipée de moyens, permettant de piéger l’humidité résiduelle éventuellement présente dans l’hydrogène circulant dans cette chambre. À cet effet, la chambre 6 présente notamment des formes assurant des changements de sa section, grâce à un épaulement 66. On peut prévoir tout autre type de formes, assurant cette fonction de piégeage, par exemple des chicanes ou analogues. The membrane 5 described above separates the main enclosure, vis-à-vis a room 6 said annex or auxiliary. This chamber 6 comprises a cylindrical cartridge 60, whose first end, facing the enclosure 2, is closed by means of a bottom 61. The latter is made in the form of a lattice, or spider web, which is composed of concentric strips of material 62, which delimit intermediate passages 63. This mesh 61 allows the reliable retention of the membrane by plating, while the passages 63 allow the flow of hydrogen, from the chamber 2 to the chamber . This bottom 61 is extended by a neck 64, which is provided with ribs 65 intended to cooperate with the aforementioned notches 23. This cooperation ensures a removable fastening type quarter quick connection between the main chamber 2 and the chamber This chamber 6 is furthermore equipped with means for trapping any residual moisture present in the hydrogen circulating in this chamber. For this purpose, the chamber 6 has in particular forms ensuring changes in its section, with a shoulder 66. It can provide any other type of forms, providing this trapping function, for example baffles or the like.
À l’opposé de l’enceinte 2, la chambre annexe 6 est fermée par l’intermédiaire d’un bouchon 7. Ce dernier comprend tout d’abord un voile 70, qui est pourvu d’un embout 71 dit de piquage, permettant l’évacuation de l’hydrogène hors de la chambre 6. Le voile 70 est prolongé axialement par un rebord taraudé 72, permettant le vissage du bouchon sur une portion filetée de la cartouche 60. Opposite the chamber 2, the adjoining chamber 6 is closed by means of a plug 7. The latter comprises firstly a web 70, which is provided with a tip 71 called stitching, allowing the evacuation of the hydrogen out of the chamber 6. The web 70 is extended axially by a threaded rim 72, allowing the cap to be screwed onto a threaded portion of the cartridge 60.
Le bouchon 7 coopère avec un organe assurant l’évacuation de l’hydrogène en direction de la pile à combustible 100, lequel est désigné dans son ensemble par la référence 8. Cet organe d’évacuation comprend un téton 80, permettant la fixation sur le bouchon 7 par tout moyen approprié. Ce téton est creusé d’un canal 81 , qui débouche dans un raccord 82, de type connu en soi. Ce raccord 82 est propre à être connecté, de manière amovible, à une conduite 104 mise en communication avec l’entrée de la pile à combustible 100. Par ailleurs l’organe d’évacuation 8 est équipé d’une soupape de sécurité 83, laquelle est tarée à une pression prédéterminée, typiquement voisine de 0,5 bar. The plug 7 cooperates with a member ensuring the evacuation of hydrogen in the direction of the fuel cell 100, which is designated as a whole by the reference 8. This discharge member comprises a pin 80, allowing the fixing on the stopper 7 by any suitable means. This stud is dug a channel 81, which opens into a fitting 82, of a type known per se. This coupling 82 is able to be connected, in a removable manner, to a pipe 104 placed in communication with the inlet of the fuel cell 100. Moreover, the evacuation member 8 is equipped with a safety valve 83, which is calibrated at a predetermined pressure, typically close to 0.5 bar.
Le dispositif 1 de l’invention est en outre équipé d’un capteur de température 9, de tout type approprié. Ce capteur 9 est fixé au voisinage du fût 20, entre deux ailettes 21 voisines, de sorte qu’il permet de mesurer la température régnant à l’intérieur de l’enceinte principale 2. Ce capteur est relié, via une ligne 90, à un module de contrôle- commande 91 , de type connu en soi, qui qui est lui-même relié au ventilateur 4 via une ligne supplémentaire 92. Ce module de contrôle-commande 91 peut être intégré dans le dispositif 1 ou peut se situer à l’extérieur, par exemple dans un module comportant la pile à combustible 100 alimentée par le dispositif. Ledit module de contrôle-commande 91 peut avantageusement mettre en oeuvre un algorithme de type PID (proportionnel, intégral, dérivé), qui est connu en tant que tel. The device 1 of the invention is furthermore equipped with a temperature sensor 9 of any suitable type. This sensor 9 is fixed in the vicinity of the barrel 20, between two adjacent fins 21, so that it can measure the temperature inside the main chamber 2. This sensor is connected, via a line 90, to a control module 91, of a type known per se, which is itself connected to the fan 4 via an additional line 92. This control-command module 91 can be integrated into the device 1 or can be located at the outside, for example in a module comprising the fuel cell 100 powered by the device. Said control-command module 91 can advantageously implement a PID type algorithm (proportional, integral, derivative), which is known as such.
Enfin, le dispositif conforme à l’invention comprend avantageusement une gaine 24, s’étendant à la périphérie extérieure des ailettes. Cette gaine est réalisée en un matériau connu en soi, notamment de type plastique thermo rétractable. Les parois en regard de cette gaine et du fût 20 délimitent un chemin 25 de confinement de l’air, au voisinage des ailettes 21. Cela améliore l’efficacité du refroidissement par le flux d’air forcé généré par le ventilateur 4 entre les ailettes 21 et la gaine 24. Par ailleurs, la présence de cette gaine 24 est avantageuse en termes de sécurité, puisqu’elle autorise une préhension sans risque par l’utilisateur, protégeant l’utilisateur d’une part contre les arêtes des ailettes 21 et d’autre part contre la chaleur. Finally, the device according to the invention advantageously comprises a sheath 24, extending at the outer periphery of the fins. This sheath is made of a material known in itself, including plastic shrinkable type. The walls opposite this sheath and the barrel 20 delimit a path 25 for confining the air, in the vicinity of the fins 21. This improves the cooling efficiency by the forced air flow generated by the fan 4 between the fins. 21 and the sheath 24. Moreover, the presence of this sheath 24 is advantageous in terms of safety, since it allows the user to grip without risk, protecting the user on the one hand against the edges of the fins 21 and on the other hand against the heat.
La mise en œuvre du dispositif conforme à l’invention, décrit ci-dessus, va maintenant être explicitée. On accède au volume intérieur de l’enceinte principale 2, en déverrouillant la cartouche 60 par rapport au fût 20. On place alors, dans cette enceinte, le précurseur d’hydrogène et le liquide polaire destinés à produire l’hydrogène souhaité. Puis, on verrouille à nouveau la cartouche sur le fût. The implementation of the device according to the invention, described above, will now be explained. The internal volume of the main chamber 2 is accessed by unlocking the cartridge 60 with respect to the barrel 20. The hydrogen precursor and the polar liquid are then placed in this chamber, intended to produce the desired hydrogen. Then, the cartridge is locked again on the drum.
En particulier, le précurseur d’hydrogène peut être un précurseur solide, par exemple un métal, que l’on introduit avantageusement sous toute forme finement divisée appropriée. De manière préférée il s’agit d’une poudre métallique, qui doit être choisie de manière à éviter la formation de produits secondaires toxiques. Elle peut comporter un catalyseur approprié. Cette poudre métallique peut être contenue dans un comprimé ou dans un emballage souple et perméable au liquide polaire approprié pour éviter sa dispersion. Ledit liquide polaire peut être de l’eau dont on ajuste le pH en fonction du métal. On peut utiliser une poudre à base d’aluminium, de silicium, de magnésium ou autre métal. In particular, the hydrogen precursor may be a solid precursor, for example a metal, which is advantageously introduced in any appropriate finely divided form. Preferably it is a metal powder, which must be chosen so as to avoid the formation of toxic byproducts. It may comprise a suitable catalyst. This metal powder may be contained in a tablet or in a flexible package and permeable to the appropriate polar liquid to prevent its dispersion. The said polar liquid may be water, the pH of which is adjusted according to the metal. A powder based on aluminum, silicon, magnesium or other metal can be used.
On note que la réaction de génération d’hydrogène à partir d’un métal, tel que l’aluminium ou le silicium, est significativement plus exothermique que la réaction de génération d’hydrogène à partir du NaBH4. Cela nécessite de prévoir des moyens pour dissiper la chaleur de réaction si l’on souhaite exploiter la réaction dans des conditions contrôlées. It is noted that the hydrogen generation reaction from a metal, such as aluminum or silicon, is significantly more exothermic than the hydrogen generation reaction from NaBH 4 . This requires providing means to dissipate the heat of reaction if it is desired to exploit the reaction under controlled conditions.
Au bout d’une période de démarrage, par exemple voisine de quelques dizaines de secondes, la production d’hydrogène est initiée. Cet hydrogène pénètre au travers de la membrane 5, alors que cette dernière retient le liquide à l’intérieur de l’enceinte principale 2. Cet hydrogène traverse ensuite la chambre annexe 6, en étant libéré de son humidité résiduelle, puis est dirigé en direction de la pile à combustible 100 par l’intermédiaire de l’organe d’évacuation 8. La réaction de la poudre métallique avec ledit liquide polaire étant fortement exothermique, la température du liquide augmente vite, ce qui accélère ladite réaction. L’augmentation de température est limitée par l’effet des moyens d’échange thermique prévus sur au moins une partie de la périphérie de l’enceinte principale ; ces moyens d’échange thermique peuvent être lesdites ailettes 21. Dans un mode de réalisation avantageux, la température est contrôlée et régulée. A cette fin, en parallèle, le capteur 9 mesure la température régnant à l’intérieur de l’enceinte principale ou à la surface de l’enceinte. En fonction des données de ce capteur, le module 91 asservit la vitesse du ventilateur 4, de manière à réguler la température précitée autour d’une valeur de consigne prédéterminée, typiquement comprise entre 40 °C et 70 'Ό, et préférentiellement entre 50‘C et 65 'Ό, et encore plus préférentiellement entre 60 °C et 65°C. Le système est régulé de manière à ce que la température ne dépasse avantageusement pas 70 °C, et préférentiellement ne dépasse pas 65 'Ό, afin d’éviter que l’utilisateur du dispositif ne se brûle pas lors qu’il le touche. Les inventeurs ont constaté que ce dispositif peut fonctionner dans une large gamme de températures extérieures, et notamment entre 0‘C et 45 qC. After a start-up period, for example close to a few tens of seconds, the production of hydrogen is initiated. This hydrogen penetrates through the membrane 5, while the latter holds the liquid inside the main enclosure 2. This hydrogen then passes through the annex chamber 6, being released from its residual moisture, then is directed towards of the fuel cell 100 through the discharge member 8. The reaction of the metal powder with said polar liquid being highly exothermic, the temperature of the liquid increases rapidly, which accelerates said reaction. The increase in temperature is limited by the effect of the heat exchange means provided on at least a portion of the periphery of the main enclosure; these heat exchange means may be said fins 21. In an advantageous embodiment, the temperature is controlled and regulated. To this end, in parallel, the sensor 9 measures the temperature prevailing inside the main enclosure or on the surface of the enclosure. According to the data of this sensor, the module 91 slaves the speed of the fan 4, so as to regulate the above-mentioned temperature around a predetermined reference value, typically between 40 ° C. and 70 ° C., and preferably between 50 ° C. C and 65 'Ό, and even more preferably between 60 ° C and 65 ° C. The system is regulated so that the temperature advantageously does not exceed 70 ° C, and preferably does not exceed 65 'Ό, to prevent the user of the device does not burn when touched. The inventors have found that this device can operate in a wide range of ambient temperatures, and in particular between 0 ° C and 45 q C.
La réaction de production d’hydrogène se poursuit de manière continue, pendant une durée typiquement voisine d’une heure. Au terme de cette réaction, on déverrouille à nouveau la cartouche, de manière à accéder au volume intérieur de l’enceinte. On peut ainsi, le cas échéant, extraire l’emballage qui contenait la poudre du précurseur solide d’hydrogène et le remplacer par un emballage neuf, ou poser un nouveau comprimé contenant la poudre dudit précurseur solide d’hydrogène, et/ou on peut remplacer le liquide polaire qui contient les sous-produits solubles de la réaction, afin de redémarrer la génération d’hydrogène. The hydrogen production reaction continues continuously, for a period of time typically close to one hour. At the end of this reaction, the cartridge is unlocked again so as to access the interior volume of the chamber. It is thus possible, if necessary, to extract the package which contained the solid hydrogen precursor powder and replace it with a new packaging, or to put a new tablet containing the powder of said solid hydrogen precursor, and / or replace the polar fluid that contains the soluble byproducts of the reaction, in order to restart the hydrogen generation.
L’invention présente de nombreux avantages. The invention has many advantages.
Ainsi, elle assure une séparation fiable entre l’hydrogène produit et le liquide, grâce à la présence de la membrane 5. On notera que cette membrane autorise un fonctionnement du dispositif dans toutes les configurations spatiales, en particulier à la verticale ou à l’horizontale. Thus, it ensures a reliable separation between the produced hydrogen and the liquid, thanks to the presence of the membrane 5. It will be noted that this membrane allows operation of the device in all spatial configurations, in particular vertically or vertically. horizontal.
Par ailleurs, la chambre annexe 6 assure avantageusement une triple fonction. Tout d’abord, elle assure la fermeture de l’enceinte principale. Par ailleurs, elle forme un séparateur de phases, en piégeant l’humidité résiduelle contenue dans l’hydrogène généré, que ce soit sous la forme de gouttelettes ou sous la forme de vapeur d’eau. Cela améliore la pureté de l’hydrogène en sortie de l’organe d’évacuation 8 ; pour cette raison le générateur d’hydrogène selon l’invention convient particulièrement bien pour alimenter une pile à combustible. Enfin, la chambre annexe 6 intègre une fonction supplémentaire de sécurité, grâce à la présence avantageuse de la soupape 83. Furthermore, the annex chamber 6 advantageously provides a triple function. First, it ensures the closure of the main enclosure. Furthermore, it forms a phase separator, trapping the residual moisture contained in the generated hydrogen, whether in the form of droplets or in the form of water vapor. This improves the purity of the hydrogen at the outlet of the evacuation member 8; for this reason the hydrogen generator according to the invention is particularly suitable for supplying a fuel cell. Finally, the annex chamber 6 integrates an additional safety function, thanks to the advantageous presence of the valve 83.
De manière avantageuse, le ventilateur 4 aspire l’air au travers des ailettes 21. Une telle configuration présente une efficacité améliorée, par rapport à un soufflage dans ces ailettes. L’invention autorise également une régulation efficace du dispositif de production d’hydrogène, au niveau thermique. En effet, la présence des moyens de mesure et d’asservissement permet de faire fonctionner le ventilateur à la puissance désirée, de manière à régler la température à l’intérieur de l’enceinte à la valeur voulue. Ainsi, la réaction se déroule dans des conditions constantes de température, hormis la phase de démarrage à température ambiante, ce qui permet une production constante d’hydrogène. Advantageously, the fan 4 draws air through the fins 21. Such a configuration has an improved efficiency, compared with a blowing in these fins. The invention also allows efficient regulation of the device for producing hydrogen, at the thermal level. Indeed, the presence of the measuring and servo means makes it possible to operate the fan at the desired power, so as to adjust the temperature inside the enclosure to the desired value. Thus, the reaction takes place under constant temperature conditions, except for the starting phase at room temperature, which allows a constant production of hydrogen.
Enfin, le dispositif conforme à l’invention est compact et portable, et d’une manipulation particulièrement commode. À cet égard, la présence des moyens de verrouillage amovible est tout particulièrement avantageuse. L’opérateur peut ainsi, de manière rapide et intuitive, verrouiller et déverrouiller la chambre annexe vis-à-vis de l’enceinte principale. L’intérieur du dispositif est facile à nettoyer. Finally, the device according to the invention is compact and portable, and particularly convenient handling. In this respect, the presence of the removable locking means is particularly advantageous. The operator can thus quickly and intuitively lock and unlock the auxiliary chamber vis-à-vis the main speaker. The inside of the device is easy to clean.
On a ainsi réalisé un appareil en alliage d’aluminium d’une dimension approximative de 90 mm x 240 mm, avec un volume interne de 360 cm3. Le générateur pèse à vide environ 800 g et présente une trentaine d’ailettes d’une épaisseur de 1 ,5 mm d’une dimension d’environ 16 mm x 160 mm. On peut le charger avec environ 45 g de poudre métallique et environ 200 ml d’eau, et il produit alors sur une durée de 80 minutes environ 45 litres d’hydrogène, avec un débit constant (après une phase de démarrage) de l’ordre de 0,5 litres par minute. La puissance maximale du ventilateur est de 2,2 W pour une vitesse de rotation maximale de 5 000 tours par minute, un débit maximal de 1 ,3 m3 d’air par minute et une pression statique d’air de 156 Pa. An aluminum alloy apparatus having a dimension of approximately 90 mm × 240 mm, with an internal volume of 360 cm 3, was thus produced . The generator weighs about 800 g empty and has about thirty fins of a thickness of 1.5 mm with a size of about 16 mm x 160 mm. It can be loaded with about 45 g of metal powder and about 200 ml of water, and it then produces for about 80 minutes about 45 liters of hydrogen, with a constant flow (after a start-up phase) of the order of 0.5 liters per minute. The maximum power of the fan is 2.2 W for a maximum rotation speed of 5,000 rpm, a maximum flow rate of 1.3 m 3 of air per minute and a static air pressure of 156 Pa.

Claims

REVENDICATIONS
1. Dispositif portable (1 ) de production d’hydrogène à partir d’un précurseur d’hydrogène et d’un liquide, ce dispositif comprenant 1. Portable device (1) for producing hydrogen from a hydrogen precursor and a liquid, this device comprising
- une enceinte principale (2), destiné à la réception dudit précurseur d’hydrogène et dudit liquide, a main enclosure (2) intended for receiving said hydrogen precursor and said liquid,
- une chambre annexe (6), destinée à la collecte de l’hydrogène ainsi produit, an auxiliary chamber (6) for collecting the hydrogen thus produced,
- une membrane de séparation (5), délimitant ladite enceinte principale par rapport à ladite chambre annexe, a separation membrane (5) delimiting said main enclosure with respect to said auxiliary chamber,
- des moyens (8) d’évacuation de l’hydrogène, hors de la chambre annexe, et caractérisé en ce qu’il comporte des moyens d’échange thermique (21 ), prévus sur au moins une partie de la périphérie de ladite enceinte principale.  means (8) for evacuating the hydrogen, out of the auxiliary chamber, and characterized in that it comprises heat exchange means (21) provided on at least a part of the periphery of said enclosure main.
2. Dispositif selon la revendication 1 , caractérisé en ce qu’il comprend au moins un moyen de refroidissement actif qui coopère avec lesdits moyens d’échange thermique. 2. Device according to claim 1, characterized in that it comprises at least one active cooling means which cooperates with said heat exchange means.
3. Dispositif portable de production d’hydrogène selon la revendication 1 ou 2, caractérisé en ce qu’il comprend des moyens de ventilation (4), qui coopèrent avec les moyens d’échange thermique. 3. Portable device for producing hydrogen according to claim 1 or 2, characterized in that it comprises ventilation means (4), which cooperate with the heat exchange means.
4. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 1 à 3, caractérisé en ce qu’il comprend des moyens (9) de mesure de la température au niveau de la paroi de l’enceinte principale. 4. Portable device for producing hydrogen according to any one of claims 1 to 3, characterized in that it comprises means (9) for measuring the temperature at the wall of the main enclosure.
5. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 2 à 4, caractérisé en ce qu’il comprend des moyens d’asservissement (91 ), permettant d’asservir les moyens de refroidissement actif aux moyens de mesure de la température. 5. Portable device for producing hydrogen according to any one of claims 2 to 4, characterized in that it comprises servocontrol means (91), for controlling the active cooling means to the measuring means of temperature.
6. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 1 à 5, caractérisé en ce que ce dispositif comprend en outre des moyens (23, 65) de fixation amovible de la chambre annexe (6) par rapport à l’enceinte principale {2)1. Dispositif portable de production d’hydrogène selon la revendication 6, caractérisé en ce que les moyens de fixation amovible comprennent un raccord rapide, notamment de type quart de tour 6. Portable device for producing hydrogen according to any one of claims 1 to 5, characterized in that this device further comprises means (23, 65) for removably fixing the auxiliary chamber (6) relative to the main enclosure {2) 1. Portable hydrogen production device according to claim 6, characterized in that the removable fixing means comprise a quick coupling, in particular of the quarter turn type
8. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 1 à 7, caractérisé en ce que les moyens (8) d’évacuation de l’hydrogène comprennent un raccord rapide (82), propre à être connecté à une conduite (104) d’alimentation d’une pile à combustible (100). 8. Portable hydrogen production device according to any one of claims 1 to 7, characterized in that the means (8) for discharging the hydrogen comprise a quick connector (82), adapted to be connected to a conduit (104) for supplying a fuel cell (100).
9. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 1 à 8, caractérisé en ce que les moyens d’évacuation de l’hydrogène comprennent une soupape de sécurité (83) tarée à une pression prédéterminée. 9. portable device for producing hydrogen according to any one of claims 1 to 8, characterized in that the means for discharging the hydrogen comprise a safety valve (83) calibrated at a predetermined pressure.
10. Dispositif portable de production d’hydrogène l’une quelconque des revendications 2 à 9, caractérisé en ce que les moyens de ventilation (4) comprennent un ventilateur électrique, lequel est alimenté par des moyens d’alimentation (102) aptes à être reliés à une pile à combustible (100). Portable hydrogen production device according to one of Claims 2 to 9, characterized in that the ventilation means (4) comprise an electric fan, which is powered by supply means (102) capable of being connected to a fuel cell (100).
1 1. Dispositif portable de production d’hydrogène l’une quelconque des revendications 1 àPortable hydrogen production device according to one of claims 1 to
10, caractérisé en ce que le fond de la chambre annexe (6), tourné vers l’enceinte principale, comprend un treillis (61 ) contre lequel est plaquée la membrane de séparation10, characterized in that the bottom of the adjoining chamber (6), facing towards the main enclosure, comprises a lattice (61) against which the separation membrane is pressed.
(5), ce treillis définissant des ouvertures (63) de passage de l’hydrogène. (5), this lattice defining openings (63) for the passage of hydrogen.
12. Dispositif portable de production d’hydrogène l’une quelconque des revendications 1 àPortable hydrogen generating device according to one of claims 1 to
1 1 , caractérisé en ce que les moyens d’échange thermique comprennent une pluralité d’ailettes (21 ) s’étendant, de préférence radialement, vers l’extérieur, à partir de la périphérie de l’enceinte principale. 1 1, characterized in that the heat exchange means comprise a plurality of fins (21) extending, preferably radially outwardly, from the periphery of the main enclosure.
13. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 3 à 121 , caractérisé en ce que ce dispositif comprend en outre une gaine (24) de confinement de l’air de ventilation, s’étendant à la périphérie des moyens d’échange thermique. 14. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 1 à 13, caractérisé en ce que la chambre annexe comprend des moyens de piégeage de l’humidité résiduelle présente dans l’hydrogène. 13. Portable device for producing hydrogen according to any one of claims 3 to 121, characterized in that this device further comprises a sheath (24) for confining the ventilation air, extending at the periphery of the heat exchange means. 14. Portable device for producing hydrogen according to any one of claims 1 to 13, characterized in that the auxiliary chamber comprises means for trapping the residual moisture present in the hydrogen.
15. Dispositif portable de production d’hydrogène selon l’une quelconque des revendications 1 à 14, caractérisé en ce que la membrane de séparation (5) est perméable aux gaz tout en étant imperméable aux liquides. Portable hydrogen generating device according to one of claims 1 to 14, characterized in that the separation membrane (5) is gas-permeable while being impermeable to liquids.
16. Dispositif selon l’une quelconque des revendications 1 à 15, caractérisé en ce que ladite membrane de séparation (5) est réalisée en polytétrafluoroéthylène, en polyfluorure de vinylidène, en polyéthylène, ou en polypropylène. 16. Device according to any one of claims 1 to 15, characterized in that said separation membrane (5) is made of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or polypropylene.
17. Utilisation d’un dispositif portable de production d’hydrogène selon l’une quelconque des revendications 1 à 16, pour alimenter une pile à combustible. 17. Use of a portable hydrogen generating device according to any one of claims 1 to 16 for supplying a fuel cell.
18. Utilisation selon la revendication 17, dans laquelle lesdits moyens d’asservissement sont au moins en partie contenus dans un module comportant une pile à combustible. 18. Use according to claim 17, wherein said servo means are at least partly contained in a module comprising a fuel cell.
EP19710741.0A 2018-02-13 2019-02-13 Portable device for producing hydrogen, and use thereof Withdrawn EP3735393A1 (en)

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FR1851180A FR3077815B1 (en) 2018-02-13 2018-02-13 PORTABLE HYDROGEN PRODUCTION DEVICE, AND ITS USE
PCT/FR2019/050310 WO2019158853A1 (en) 2018-02-13 2019-02-13 Portable device for producing hydrogen, and use thereof

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CN111788149A (en) 2020-10-16

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