WO2013089669A1 - Production d'hydrogène au moyen d'une brosse mécanique sur de l'aluminium dans un milieu aqueux - Google Patents

Production d'hydrogène au moyen d'une brosse mécanique sur de l'aluminium dans un milieu aqueux Download PDF

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Publication number
WO2013089669A1
WO2013089669A1 PCT/US2011/064503 US2011064503W WO2013089669A1 WO 2013089669 A1 WO2013089669 A1 WO 2013089669A1 US 2011064503 W US2011064503 W US 2011064503W WO 2013089669 A1 WO2013089669 A1 WO 2013089669A1
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WO
WIPO (PCT)
Prior art keywords
aluminum
working surface
brush
contact
brushing
Prior art date
Application number
PCT/US2011/064503
Other languages
English (en)
Inventor
Robert Hirsch
Gregory Scott Hirsch
Original Assignee
Robert Hirsch
Gregory Scott Hirsch
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 Robert Hirsch, Gregory Scott Hirsch filed Critical Robert Hirsch
Priority to PCT/US2011/064503 priority Critical patent/WO2013089669A1/fr
Publication of WO2013089669A1 publication Critical patent/WO2013089669A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J7/00—Apparatus for generating gases
    • B01J7/02—Apparatus for generating gases by wet methods
    • 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

Definitions

  • the present invention relates to hydrogen production by reaction of aluminum metal with water, and more particularly, to a system and method of producing hydrogen gas by mechanical scraping of aluminum-containing surface in the presence of an aqueous medium.
  • Aluminum metal is known to react intensely with water. Production of hydrogen by means of the aluminum - water reaction is typically represented as:
  • European Patent No. 0055134 Bl discloses a method for the production of hydrogen by inducing an electrical discharge between aluminum wire and an aluminum drum, both of which are immersed in water. When a voltage is applied between the wire and drum, an arching discharge takes place between them, inducing an electro-plasmic reaction. The reaction produces hydrogen and oxygen gas and aluminum oxide. The arcing between the wire and drum helps remove the oxide layer formed on the wire tip, exposing fresh aluminum to the water, whereby a continuous generation of hydrogen gas may be achieved.
  • Japanese Patent Document No. JP2001-31401A discloses a method for producing hydrogen gas, by a cutting processing or a grinding processing of aluminum or an aluminum alloy in water.
  • a method of producing hydrogen gas by mechanical brushing of a working surface of an aluminum-containing material, in the presence of an aqueous medium including the steps of: (a) providing an apparatus including: (i) a reaction chamber having a discharge port, and adapted to sealably contain the aqueous medium, the chamber adapted to be substantially sealed with respect to an external environment; (ii) the aluminum-containing workpiece; (iii) a scraping mechanism having at least one brush having a brushing surface adapted to contact the working surface; (iv) a load mechanism adapted to apply a load between the brush and the working surface, and (v) an aqueous medium, disposed within the reaction chamber, the aluminum-containing workpiece and the brush disposed within the chamber, the working surface and the brush adapted to move in a relative motion, whereby, in an operating condition, the brushing surface scrapes against the working surface to effect a liberation of aluminum-containing
  • the brushing surface has a contact area, whereby, in this operating condition, the brushing surface contact area is adapted to contact at least 10%, but less than 95 %, of the working surface.
  • the contact area is adapted to contact at least 20%, at least 30%, or at least 40% of the working surface.
  • the contact area is adapted to contact less than 90% or less than 85% of the working surface.
  • the aqueous medium includes ethylene glycol.
  • the brushing of the working surface is effected whereby, in the operating condition, or even when operating in air or under a substantially pure nitrogen environment, at least 30% of the particles liberated from the aluminum-containing workpiece are elongated particles having orthogonal dimensions x, y, and z, the elongated particles characterized by a dimensionless shape parameter S defined by
  • S is at least 20, at least 30, at least 40, at least 50, at least 60, or at least 80.
  • the brushing of the working surface is effected whereby, in the operating condition, or even when operating in air or under a substantially pure nitrogen environment, the particles liberated from the aluminum-containing workpiece are, on a statistical weight basis, elongated particles having orthogonal dimensions x, y, and z, the elongated particles characterized by a dimensionless shape parameter S defined by
  • S is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, or at least 80.
  • the brushing of the working surface is effected whereby, in the operating condition, the particles liberated from the aluminum-containing workpiece, after an average residence time of 5 to 10 minutes within the aqueous medium, and after dewatering under a substantially pure nitrogen environment, have, on an average weight basis, an average oxygen to aluminum weight ratio of at least 0.15, at least 0.20, at least 0.25, at least 0.30, or at least 0.35.
  • the scraping mechanism and the load mechanism are adapted whereby the brushing largely or primarily removes, an oxidized aluminum layer of the working surface.
  • the working surface is a curved working surface such as a curved, generally conical or generally cylindrical working surface, and wherein the brushing surface is adapted to contact the curved conical or cylindrical working surface, and to flexibly conform thereto.
  • the scraping mechanism adapted whereby, in the operating condition, the brush is fully engaged against the curved, generally conical or cylindrical surface.
  • filaments of the brush have a cross-sectional area of less than 80 mm 2 , less than 55 mm , less than 45 mm , less than 30 mm , less than 25 mm , less than 20 mm , less than 11 mm 2 , less than 7 mm 2 , less than 5 mm 2 , less than 3 mm 2 , less than 2.1 mm 2 , or less than 1 mm 2 .
  • filaments of the brush have a length of at least 3 mm, at least 5 mm, at least 7 mm, at least 10 mm, at least 13 mm, or at least 18 mm.
  • filaments of the brush have a length to diameter ratio of at least 10: 1, at least 20: 1 , at least 30: 1, at least 40: 1, at least 55 : 1 , or at least 75 : 1.
  • the brush has a plurality of filaments providing the contact area.
  • the filaments include crimped filaments.
  • the brush has a plurality of filaments adapted to contact the working surface, the brush having a brush density (PB) or footprint contact fraction defined by: A amentAAfiiaments + A V oid), wherein: A a ments is a total contact surface area of the filaments, when the brush is in an unloaded rest condition; and A VO id is a total surface area of void areas disposed between the filaments, and wherein the brush density is at least 0.15 , at least 0.25 , at least 0.4, at least 0.6, or at least 0.75.
  • PB brush density
  • the brush density in the unloaded rest condition is below 0.98, below 0.95 , below 0.9, or below 0.85.
  • the total surface area of the void areas is measured in a normal fashion with respect to a longitudinal dimension of the filaments.
  • each of the filaments has an end adapted to contact the working surface.
  • the brush has a plurality of filaments adapted to contact the working surface, the brush having a brush density (p B ) defined by: A mam ents (Afii am ents + A void ), wherein: A mame nts is a total instantaneous contact surface area of the filaments, when the brush is in the operating condition; and A VO id is a total surface area of void areas disposed between the filaments, and wherein the brush density is at least 0.15, at least 0.25, at least 0.4, at least 0.6, or at least 0.75.
  • p B brush density defined by: A mam ents (Afii am ents + A void ), wherein: A mame nts is a total instantaneous contact surface area of the filaments, when the brush is in the operating condition; and A VO id is a total surface area of void areas disposed between the filaments, and wherein the brush density is at least 0.15, at least 0.25, at
  • the brush density in the operating condition, is below 0.98, below 0.95, below 0.9, or below 0.85.
  • the total surface area of the void areas is measured in a normal fashion with respect to contact ends of the filaments.
  • the brush includes steel filaments.
  • an apparatus for producing hydrogen gas by mechanical brushing of a working surface of an aluminum-containing workpiece, in the presence of an aqueous medium including: (a) a reaction chamber having a discharge port, and adapted to sealably contain the aqueous medium, the chamber adapted to be substantially sealed with respect to an external environment; (b) a holding arrangement or mounting assembly adapted to secure the aluminum-containing workpiece within the chamber; (c) a scraping mechanism having at least one brush having a brushing surface adapted to contact the working surface, and to flexibly conform thereto; and (d) a load mechanism adapted to apply a load between the brush and the working surface; the scraping mechanism and the holding arrangement adapted whereby, in an operating condition, the working surface and the brushing surface move in a relative motion, and whereby, in the operating condition, the brushing surface brushes against the working surface to effect a liberation of aluminum-containing particles from the aluminum-containing workpiece.
  • the brush surface including a contact area, whereby, in the operating condition, the contact area is adapted to contact at least 10%, but less than 95%, of the working surface.
  • the brushing surface is adapted to contact a first curved working surface, and to flexibly conform thereto.
  • the brushing surface is adapted to contact a curved, generally cylindrical or generally conical working surface, and to flexibly conform thereto.
  • the at least one brush is a plurality of brushes set in spaced condition around the first curved surface.
  • the scraping mechanism and load mechanism have a spring assembly having at least one spring, the assembly and the spring adapted to exert a substantially radial force on the first curved surface or the curved cylindrical surface.
  • the spring assembly is adapted to continuously exert the radial force on the first curved surface or the curved cylindrical surface as a diameter of the workpiece is gradually reduced by at least a factor of 1.1, at least 1.25, or at least 1.5.
  • the scraping mechanism includes a mechanically driven rotating shaft assembly that is at least partially enveloped by the brush.
  • an apparatus for producing hydrogen gas by mechanical scraping of a surface of an aluminum-containing material, in the presence of an aqueous medium including: (a) a reaction chamber having a discharge port, and adapted to sealably contain the aqueous medium; (b) an aluminum-containing workpiece having a working surface; (c) a scraping mechanism having at least one scraping element adapted to contact the working surface, and (d) an aqueous medium, the aluminum-containing workpiece, the scraping element, and the aqueous medium disposed within the chamber, the chamber adapted to be substantially sealed with respect to an external environment, the chamber further adapted whereby, during contacting of the aqueous medium and the particles within the chamber, the hydrogen gas evolved is discharged through the discharge port, the surface and the scraping element adapted to move in a relative motion, the chamber including a flexible external wall, adapted to be flexed by a force external to the chamber, to achieve the relative motion, whereby, in a
  • the surface and the mechanism are adapted whereby the force is of a magnitude whereby the relative motion is manually effected by human fingers, hand or foot.
  • the apparatus further includes a second membrane adapted to provide a substantially hermetical seal to the reaction chamber, and a protruding element, disposed and adapted to puncture, on demand, the second membrane, to enable the hydrogen gas to flow out of the reaction chamber.
  • the reaction chamber dimensioned whereby the apparatus is a hand-held apparatus that is portable by means of the fingers, hand or foot.
  • the apparatus further includes a mechanical arrangement adapted to provide the force.
  • the mechanical arrangement includes a cam.
  • the apparatus is a portable, hand-held disposable apparatus.
  • the apparatus may advantageously produce the hydrogen gas by mechanical scraping of an aluminum surface
  • other reactive metals such as magnesium, a magnesium alloy, or magnesium-containing materials may also be scraped and reacted with water or an aqueous solution to produce the hydrogen gas.
  • the apparatus further includes a mounting or holding assembly adapted to receive the workpiece, and a rotating drive mechanism adapted to rotate the workpiece to effect the relative motion.
  • the working surface of the workpiece is disposed in a slotted aluminum-containing block, wherein at least one slot is adapted to receive a brush having a scraping surface.
  • the mounting assembly includes a locking arrangement adapted to fix the workpiece with respect to the mounting assembly.
  • the surface and the mechanism are further adapted whereby the relative motion is manually effected.
  • the apparatus further includes a membrane adapted and disposed to inhibit water from exiting the reaction chamber via the discharge port, the membrane further adapted and disposed whereby, under operating conditions, the hydrogen gas flows through the membrane and out of the chamber.
  • the apparatus further includes a second membrane adapted to provide a substantially hermetical seal to the reaction chamber, and a protruding element, disposed and adapted to puncture, on demand, the second membrane, to enable the hydrogen gas to flow out of the reaction chamber.
  • the apparatus further includes a cooling system associated with the reaction chamber.
  • the cooling system includes a coolant circulation system adapted to circulate a coolant past a wall of the reaction chamber.
  • the cooling system includes a coolant circulation system adapted to effect a circulation of water within the reaction chamber to effect direct cooling of the chamber.
  • the circulation of water within the reaction chamber is adapted to remove spent particles from the chamber.
  • the apparatus further includes a filter or particle collection chamber adapted to collect spent particles from the reaction chamber.
  • the aluminum-containing material is an aluminum alloy typically containing at least 30%, at least 50%, at least 60%, at least 75%, at least 85%, or at least 90% aluminum, by weight.
  • the aluminum-containing material is an aluminum-based material.
  • the aluminum-containing material consists essentially of aluminum.
  • the apparatus further includes a fuel cell adapted to receive the hydrogen gas and to produce water and energy from the hydrogen gas.
  • the cylinder is a replaceable cylinder adapted to be reversibly and detachably inserted and removed from the mounting assembly.
  • the apparatus further includes a second membrane adapted to provide a complete or hermetical seal to the reaction chamber, until the second membrane is punctured by a protruding or pin-like device associated with, or integral with, the connector to a device into which the hydrogen is to flow.
  • the flexible wall includes a bellows or accordion-type arrangement.
  • the apparatus further includes a stop or limiter, disposed within the reaction chamber, to keep a spring-loaded device from expanding beyond a particular or pre-determined limit.
  • the space above an initial water charge within the chamber is filled with a gas, preferably hydrogen, to provide flexibility during initial operation of the apparatus.
  • a gas preferably hydrogen
  • the apparatus further includes an arrangement for recycling water, produced in a connected fuel cell, back into the reaction chamber.
  • the method further includes recycling the oxidized aluminum produced, and/or the unreacted aluminum, to produce fresh aluminum.
  • the method further includes reacting the hydrogen gas to produce water and energy, for example, in a fuel cell.
  • the aqueous medium includes a material selected to lower a freezing point of the medium.
  • Figure 1 provides a schematic, partly cross-sectional view of a portion of a sub- arrangement of a hydrogen generating system of the present invention
  • Figure 2a provides a schematic, partly cross-sectional view of a portion of another sub-arrangement of the inventive hydrogen generating system
  • Figure 2b provides a schematic, side cross-sectional view of a portion of the sub-arrangement provided in Figure 2a, wherein:
  • Figure 2b(i) shows the aluminum cylinder in an initial, unconsumed state
  • Figure 2b(ii) shows the cylinder in a partially consumed state
  • Figure 3 is a schematic block diagram of a hydrogen generating system attached to a hydrogen-consuming fuel cell arrangement, according to another embodiment of the present invention.
  • Figure 4 is a schematic block diagram of an inventive hydrogen generating system, attached to a hydrogen-consuming combustion system such as an internal combustion engine;
  • Figure 5a provides a schematic, side cross-sectional view of a portable, manually-driven hydrogen generating apparatus, according to another aspect of the present invention
  • Figure 5b provides a schematic, cutaway top view of the portable, hydrogen generating apparatus of Figure 5a;
  • Figure 6a provides a schematic, side cross-sectional view of a portion of a brush and sleeve arrangement according to another embodiment of the present invention
  • Figure 6b shows a schematic cross-section of a hydrogen generating apparatus having an abrading assembly working against a surface of a generally conical aluminum sleeve
  • Figure 7a provides a schematic perspective view of a hydrogen generating sub- arrangement integrated with, and driven by, a pulley and belt arrangement;
  • Figure 7b provides a side view of the arrangement of Figure 7a
  • Figures 8a and 8b provide schematic perspective views of a hydrogen generating apparatus having a mechanical cam arrangement, with Figure 8a showing a relaxed configuration of the hydrogen generating apparatus, and Figure 8b showing a compressed configuration thereof;
  • Figure 9 a provides a schematic block diagram of a connecting arrangement adapted to connect between a hydrogen generating system and a power generating system such as a fuel cell;
  • Figure 9b provides a schematic cross-sectional view of one embodiment of a first tube assembly, connecting arrangement, and second tube assembly, according to another embodiment of the present invention.
  • FIG. 1 provides a schematic, partly cross-sectional view of a portion of a sub- arrangement 180 of a hydrogen generating system, according to a first embodiment of the present invention.
  • An aluminum metal based workpiece such as hollow cylinder 10 is disposed around a scraping assembly 20 having at least one brush or scraping element 22 having a brushing surface adapted to contact a working surface 12 of cylinder 10.
  • Scraping element 22 may typically include a large plurality of bristles or wires, usually made of a metal such as a stainless steel or carbon steel.
  • Scraping element 22 may be attached to a drive arrangement 50 by means of a frame 24.
  • Scraping assembly 20 may include a spring assembly 26 having at least one spring 28, assembly 26 and spring 28 adapted to exert a substantially radial force on scraping element 22, whereby scraping element 22 is urged against working surface 12.
  • Drive arrangement 50 may include a motor or other drive means (shown in
  • a drive or rotating shaft 52 which may have a bearing and a shaft holder 54 connected, at an end distal to drive shaft 52, to a rotating shaft 55 disposed substantially parallel to a longitudinal axis of cylinder 10.
  • a shaft bearing and anchor 56 At the end of rotating shaft 55 proximal to drive shaft 52, may be disposed a shaft bearing and anchor 56.
  • Cylinder 10 may be held in place with respect to scraping assembly 20 by means of a holder or clamp 14.
  • cylinder 10 and scraping assembly 20 are adapted to move in a relative motion, whereby, scraping element 22 brushes against working surface 12 to effect a liberation of fine aluminum-containing particles from working surface 12.
  • Cylinder 10 may typically be sealed by means of a conventional sealing arrangement that will be apparent to those of ordinary skill in the art. However, such a sealing arrangement may be obviated by the use of a magnet arrangement in which a changing external magnetic field may induce a relative motion between a scraping assembly such as assembly 20 and a workpiece such as cylinder 10.
  • U.S. Patent No. 3,443,742 directs the invention to pumping devices, and more particularly, to pumping devices which may be used to eliminate gases in a high- vacuum system.
  • pumping devices typically employ a vacuum of 10 ⁇ 2 torr to 10 ⁇ 8 torr.
  • the pumping device is not intended for use in pressures exceeding 10 ⁇ 2 torr.
  • the present invention relates to hydrogen production systems in which hydrogen is produced by reaction of aluminum metal with water.
  • the reaction is between water and aluminum, in a reactor immersed in an aqueous medium, and is not in any way a metal-gas reaction.
  • Patent No. 3,443,742 is to eliminate gas from the vessel by reacting the gas with the metal surface.
  • the present invention is directed towards the production of hydrogen gas.
  • the present invention operates at superatmospheric pressure, often at pressures of at least 2 or 3 atmospheres (absolute). Under such conditions, the specific hydrogen production rate (liters per unit surface area of aluminum surface) may be quite high, and the dissipation of the hydrogen gas away from the metal surface, past the brush, and through the aqueous medium, represent technical criteria that were not relevant to the solution provided by U.S. Patent No. 3,443,742.
  • FIG. 2a provides a schematic, partly cross-sectional view of a portion of a sub-arrangement 280 of a hydrogen generating system, according to another embodiment of the present invention.
  • An aluminum based (or aluminum containing) workpiece such as cylinder 210, is disposed radially within a scraping assembly 220 having at least one brush or scraping element 222 having a surface adapted to contact a working surface 212 (in this case, an outer working surface) of cylinder 210.
  • Scraping element 222 may typically include a large plurality of bristles, filaments, or wires, substantially as described hereinabove.
  • Scraping assembly 220 may include a load mechanism such as spring assembly 226 having at least one spring 228, and a frame, backing or support 224, which may be adapted to hold in place scraping element 222.
  • Spring assembly 226 may be braced, in an outward or outwardly radial direction by an internal wall 242 of a housing 240 at least partially enveloping scraping assembly 220 and cylinder 210. Consequently, spring assembly 226 and spring 228 may be adapted to exert a substantially inward or inwardly radial force on scraping element 222, typically via frame, backing or support 224, whereby a brushing surface of scraping element 222 is urged against working surface 212.
  • Cylinder 210 may be connected to a drive arrangement 250 by means of a holding arrangement such as a cylinder seating or receptacle 215. Holding arrangement may be adapted to secure the aluminum-containing workpiece (such as cylinder 210) within a reaction chamber (such as chamber 390 shown in Figure 3).
  • Drive arrangement 250 may include a motor or other drive means (shown in Figure 3), a drive or rotating shaft 252, which may have a shaft bearing and anchor 256.
  • cylinder 210 rotates with respect to scraping assembly 220, which is typically fixed.
  • the relative motion between cylinder 210 and scraping assembly 220 causes scraping element 222 to scrape against working surface 212 to effect a liberation of fine aluminum-containing particles from working surface 212.
  • a pressuring arrangement may be used to juxtapose the scraping mechanism to the receding surface of the aluminum.
  • the magnitude of the pressure may be adapted to the brush assembly.
  • the angle of the bristles and the density of the bristles may also be adapted to achieve superior performance.
  • the pressure on the brush assembly may also be adapted to the particular metallurgical characteristics of the aluminum.
  • the aluminum workpiece may be of various thicknesses, depending on the nature of the application.
  • the thickness may vary from less than one centimeter to tens of centimeters, but thinner or thicker walls are possible.
  • the wall of the aluminum cylinder gradually and substantially uniformly recedes. Indeed, the uniform reduction of aluminum is one of the key advantages of the cylindrical embodiment of this invention.
  • the pressuring arrangement maintains optimum contact between the aluminum surface of the workpiece and the scraper as the aluminum face recedes by at least the thickness of the alumina layer, and more preferably, by at least the thickness of the alumina layer plus an additional atomic layer of aluminum.
  • the scraping mechanism is preferably adapted to remove primarily the alumina or oxidized aluminum layer, along with a thin layer of pure aluminum disposed thereunder. Such an arrangement uses significantly less energy to run, and maximizes the lifespan and utilization of the aluminum workpiece.
  • a single spring may be positioned above the brush assembly, pushing down on a lever assembly attached to the brushes, whereby the ends of the brush or wires are urged against the surface of the aluminum workpiece.
  • leaf springs may be mounted on each brush assembly between the shaft and the brush, pushing the brush out one leaf spring per brush.
  • the embodiment provided in Figure 1 may produce a vortex, which represents wasted mechanical energy, and reduces the net energy produced by the system.
  • the embodiment provided in Figure 2 has reduced drag forces, producing a reduced vortex (or substantially no vortex), thereby appreciably improving the net energy produced by the system.
  • the improved energy efficiency may be achieved without reducing the production rate of hydrogen gas, and without reducing the aluminum utilization.
  • the prior art generally teaches that the production or use of extremely fine aluminum particles is highly advantageous. If the particles have a characteristically high average particle size, the aluminum in the particles does not quickly and completely react with the water to form hydrogen. Thus, large particles are underutilized, and may result in low production rates of hydrogen per unit surface area of the aluminum workpiece.
  • Milling may not be suitable to in-situ production of hydrogen gas, particularly for applications requiring compact and/or portable apparatus.
  • the liberation of elongated particles from the aluminum workpiece surface may provide the requisite surface area for elevated production rates of hydrogen, coupled with high utilization of the aluminum material and relatively low energy input per energy value (or unit of hydrogen) produced.
  • the scraping element, spring assembly and aluminum workpiece are disposed and adapted, whereby, under operating conditions, the particles liberated from the aluminum-containing workpiece include elongated particles having orthogonal dimensions x, y, and z, the elongated particles characterized by a dimensionless shape parameter S defined by
  • S is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, or at least 80.
  • a cubic particle having a characteristic length of 3 micrometers ( ⁇ ) has a dimensionless shape parameter (S) equal to 1.
  • a particle produced by the system and method of the present invention may have dimensions of 25 ⁇ 25 ⁇ 3 ⁇ has a dimensionless shape parameter (S) equal to about 69.
  • At least 30% of the particles liberated from the aluminum-containing workpiece, and more preferably, at least 50% of the particles, are characterized by an S of at least 20.
  • the elongated particles are preferably characterized by an S of at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, or at least 80.
  • the smallest of the three characteristic (orthogonal) dimensions may advantageously be less than 10 ⁇ , less than 7 ⁇ , less than 5 ⁇ , less than 4 ⁇ , or less than 3 ⁇ , in order to achieve extremely high utilization of the aluminum metal.
  • the utilization of the cubic aluminum particles is calculated to be 38.6%; the utilization of the elongated aluminum particles is calculated to be 78.8%. If we assume the reaction depth of the water with the aluminum metal surface to be 2 ⁇ , the utilization of the cubic aluminum particles is calculated to be 48.8%; the utilization of the elongated aluminum particles of the present invention is calculated to be 100%.
  • An advantage of the invention compared to various other mechanical abrasion techniques is that the system ultimately converts a large fraction of the aluminum to reacted aluminum in a controlled, safe manner, thereby maximizing the hydrogen output potential of the aluminum.
  • the efficiency of aluminum conversion to reacted product is very important.
  • Unreacted aluminum may be less than 50% by weight (of the initial weight of the aluminum), preferably less than 40%, more preferably, less than 30%. In some cases, more than 90% or even more than 95% of the original aluminum is reacted (corresponding to less than 10% or less than 5% unreacted aluminum), releasing near the maximum amount of hydrogen possible.
  • the oxidized aluminum is relatively easily scraped off so there is little or no attrition to the scraper.
  • the scraper may be made of a hard material, so its attenuation (wear) is minimized.
  • the filaments of the brush may have a cross-sectional area of less than 55 mm 2 , less than 45 mm 2 , less than 30 mm 2 , less than 25 mm 2 , less than 20 mm 2 , less than 11 mm 2 , less than 7 mm 2 , or less than 5 mm 2 .
  • the cross-sectional area may be less than 3 mm 2 , less than 2.1 mm 2 , or less than 1 mm 2 .
  • the length of the brush filaments may be at least 3 mm, at least 5 mm, or at least 7 mm, and in some cases, at least 10 mm, at least 13 mm, or at least 18 mm.
  • the brush filaments may advantageously have a length to diameter ratio of at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 55 :1 , or at least 75:1. These parameters may be particularly important in providing the scraping mechanism with sufficient flexibility to advantageously contact the working surface and flexibly conform thereto, and in providing sufficient stiffness whereby the brushing action efficaciously flakes off the oxidized alumina on the workpiece surface, but does not disadvantageously gouge or cut deeply into the workpiece surface.
  • Figure 2b provides a schematic, side cross-sectional view of a portion of the sub-arrangement provided in Figure 2a, wherein Figure 2b(i) shows aluminum-based workpiece or cylinder 210 in an initial, unconsumed state, having a radius Ro, and Figure 2b(ii) shows cylinder 210 in a partially consumed state, having a radius Ri.
  • Cylinder 210 is radially enveloped or surrounded by scraping assembly 220.
  • Scraping assembly 220 includes a plurality of spring assemblies, spring assembly 226 having at least one spring 228, and a frame, backing or support 224, which may be adapted to hold in place scraping element 222 against working surface 212 of cylinder 210.
  • Spring assembly 226 may be braced, in an outward or outwardly radial direction by internal wall 242 of housing 240, which completely envelops or at least partially envelops scraping assembly 220 and cylinder 210. Consequently, spring assembly 226 and spring 228 may be adapted to exert a substantially inward or inwardly radial force on scraping element 222, typically via support 224, whereby scraping element 222 is urged against working surface 212.
  • the arrangement may be designed and adapted whereby, in the initial, unconsumed state, a distance Do is maintained between adjacent scraping elements 222, along working surface 212, as shown in Figure 2b(i), and whereby in the partially consumed state, a distance Di (Di > 0) still exists between these adjacent scraping elements 222, along working surface 212, as shown in Figure 2b(ii).
  • this arrangement in which distance Di remains non- negative, holds for a wide range of ratios of Ri to Ro, (Ri/ Ro) typically within a ratio of at least 0.6 to 1, at least 0.5 to 1, or at least 0.4 to 1 to 1 to 1.
  • FIG 3 provides a schematic block diagram of a hydrogen generating and power producing system 300, according to another embodiment of the present invention.
  • an assembly containing the aluminum energy source and the scraping assembly such as sub- arrangement 280 (shown in Figure 2a) is disposed within a substantially gas-tight chamber, reactor or hydrogen generating apparatus 390, which may be at least partially or fully filled with water or an aqueous medium.
  • a motor or drive means 358 for achieving the above-described relative motion is preferably disposed adjacent to chamber or reactor 390. Hydrogen gas evolving during the aluminum- water reaction is discharged from reactor 390, via a hydrogen outlet line 362.
  • the gas may be filtered by means of an on-line filter or membrane 364, whereby hydrogen gas passes through filter 364, but other species, such as water vapor, do not.
  • Hydrogen outlet line 362 may be further equipped with a pressure regulator 366, which may be adapted and set to enable a particular or pre-determined pressure to be built up within reactor 390.
  • the pressure set point may be fixed according to the downstream destination of the hydrogen gas, but may be within the range of 1.2 to 10 atmospheres (absolute) for a wide variety of applications.
  • the downstream destination of the hydrogen gas is an electricity-producing unit such as a fuel cell stack 325.
  • Pressure regulation and hydrogen flow may be controlled by means of pressure regulator 366, which may be solely mechanical (such as an orifice in hydrogen outlet line 362) or may be a control valve in the discharge line, the control valve responsive to a controller, such as controller 305 described in greater detail hereinbelow.
  • pressure regulator 366 may be solely mechanical (such as an orifice in hydrogen outlet line 362) or may be a control valve in the discharge line, the control valve responsive to a controller, such as controller 305 described in greater detail hereinbelow.
  • Motor or drive mechanism or means 358 may be powered by a power source external to hydrogen generating system 335.
  • a power or electricity-producing unit such as fuel cell stack 325
  • electric power may be provided to motor 358 from the electric power generated within system 300, in fuel cell stack 325.
  • an additional hydrogen accumulation tank 368 may be installed as part of the inventive apparatus.
  • Tank 368 may fluidly connect with hydrogen generation system 335 to receive hydrogen gas.
  • Hydrogen accumulation tank 368 may be adapted to discharge stored gas during peak consumption periods or in response to other particular needs.
  • Tank 368 may have one or more hydrogen sensors connected to the controller unit, and may be used as a direct feed into the desired hydrogen output use, such as a fuel cell stack 325.
  • a cooling system such as a circulating cooling system 370 may advantageously be associated with reactor 390.
  • Cooling system 370 may include a circulation line 371, circulation means such as a circulation pump 372, fluidly communicating with line 371, and a cooling unit 374, fluidly communicating with line 371, and adapted to discharge heat to the environment.
  • a makeup water reservoir 376 may advantageously be connected to circulation line 371.
  • a filtration unit such as filter 378 on line 371, for example, on the water outlet side, as shown.
  • the system or apparatus of the present invention may include an aluminum thickness sensor 391 associated with the aluminum cylinder for sensing the extent of the aluminum consumption, or when a cylinder requires replacement.
  • Sensor 391 may be a simple mechanical device or it may be electronic and be connected to a controller unit, such as controller 305.
  • Controller 305 may be configured to notify an operator that the aluminum source requires replenishing.
  • Controller 305 may contain a processor that processes input from one or more of the following: 1) one or more hydrogen pressure sensors 393 that may be located in one or all of the following: within reactor 390, in/near fuel cell 325, in hydrogen outlet line 362, and in the feeder and/or storage tank (not shown); 2) aluminum thickness sensor 391; 3) a water level sensor 397 associated with, or disposed in, reactor 390; 4) a controller adapted to control the rotational speed, e.g., for increasing or decreasing hydrogen output, and 5) an input to receive a user power increase or decrease request. Controller 305 may be configured to inform an operator to replace the aluminum cylinder, or of any fault condition. Controller 305 may be further configured to inform the operator of the need to replace the brush assembly based on hydrogen production levels calculated against the wear rate of the aluminum workpiece.
  • FIG. 4 provides a schematic block diagram of a hydrogen generating and power producing system 400, according to another embodiment of the present invention.
  • System 400 is largely similar to system 300 of Figure 3, but the hydrogen produced in hydrogen generating system 400, is combusted in a power-producing unit such as a combustor 425.
  • a power-producing unit such as a combustor 425.
  • motor or drive means 458 may be powered from electric power generated within the system surrounding combustor 425, or by rotational (mechanical) power from combustor 425.
  • hydrogen production systems like those of the present invention must be highly energy efficient to be economical, requiring a low energy input per energy value (hydrogen gas) produced.
  • Energy losses may include heat losses, mechanical losses including drag forces in the aqueous medium, and energy spent in exposing fresh aluminum surface and producing aluminum particles.
  • the brush may contain a dense array of bristles over a broad area, and the contact area is preferably at least 10%, 20%, 30%, 40%, or 50%, of the working surface, the contact area preferably should not exceed 95%, 90%, or 85% of the working surface.
  • the contact area (usually measured at the ends of the bristles) is preferably at least 10%
  • the contact area preferably should not exceed 95%, 90%, or 85% of that footprint.
  • the specific rate of hydrogen production i.e., the rate of hydrogen production per unit surface area of the aluminum workpiece, may be appreciably enhanced in a surface area having a characteristically low grain size.
  • the apparatus of the present invention may be operated in a pulsed mode by starting the scraping action in a vacuum or under an inert gas.
  • the accumulated aluminum particles may then be exposed to water, releasing hydrogen in a burst.
  • the hydrogen fuel produced by the apparatus of the present invention may be added to a system of a conventional combustion engine to improve efficiency and/or reduce harmful emissions.
  • the top of the permanent casing unit has a lid that is sealed to contain hydrogen pressure and can be opened with a latch or other locking device.
  • Brackets or another type of clamp hold the aluminum cylinder in place and prevent it from being moved by the scraper.
  • the brushes and springs fit over a spindle or spindle-like holder.
  • the casing lid is opened and the securing mechanism holding the aluminum is opened.
  • the brush and spring assembly is not expected to suffer significant wear compared to the aluminum, such that it would be replaced less often than the aluminum cylinder.
  • the assembly slides straight off the spindle. Water can be added directly into the cylinder unit and/or into a water-cooling unit and/or into a water reservoir unit.
  • a power unit may be connected to the controller unit that controls scraper and/or cylinder rotation.
  • the power unit may consist of a battery, capacitor, or other energy storage device. Since the system may produce the desired hydrogen output immediately after scratching begins, the resulting hydrogen might be used to power the scraper almost instantly via electric power from a hydrogen-powered fuel cell.
  • An external battery or capacitor can be used to start and operate the unit, depending on system design. The battery, capacitor, or other energy storage device can be recharged during normal operation.
  • aluminum alloy refers to any alloy in which aluminum has the highest content of any element present in the alloy, by weight.
  • alloy refers to any alloy in which that particular metal has the highest content, by weight, of any element present in the alloy.
  • the term "aluminum-containing material” refers to any alloy (or pure or substantially pure aluminum) in which the aluminum content exceeds 10%, and more typically, more than 20%, by weight.
  • metal-containing material with respect to a particular metal (e.g., “magnesium-containing material”), refers to any alloy (or pure or substantially pure metal) in which the content of that particular metal exceeds 10%, and more typically, at least 20%, by weight.
  • aluminum-based material refers to any material, including pure or substantially pure aluminum, in which the aluminum content exceeds 50% by weight.
  • metal-based material with respect to a particular metal (e.g., “magnesium-based material”), refers to any material in which the content of that particular metal exceeds 50%, by weight.
  • reactive metal refers to a metal such as aluminum, titanium, magnesium, or other metal, or an alloy including such metals, which, upon contact with water, undergoes an oxidation reaction whereby hydrogen gas is liberated.
  • the present invention may have a wide variety of applications in electric power generation at various scales, including both very small applications (e.g., cell phones or laptop computers) and large applications (e.g., motor vehicle propulsion, portable civilian or military power).
  • the present invention may be of particular value in applications in which either robust hydrogen and/or safe fuel delivery is particularly advantageous or required.
  • FIG. 5 a provides a schematic, side cross-sectional view of a typically portable, manually-driven hydrogen generating apparatus 590, according to another aspect of the present invention.
  • a housing 540 may have the general size and shape of two dimes (such as plates or faces 540a, 540b), disposed one on top of the other, in a spaced-apart fashion (whereby apparatus 590 typically has a thickness of at least 7 mm).
  • the space between faces 540a, 540b may be sealed, typically along a perimeter thereof, by means of a side wall 545 having a flexible element 542 such as a bellows (typically made of metal).
  • Flexible element 542 may be adapted to provide flexibility in a direction generally orthogonal to faces 540a, 540b.
  • a chamber 529 within, and typically formed by, housing 540 may be partially filled with an aqueous medium such as water. It may be advantageous to leaving a space to facilitate brush movement. It may be of further advantage to fill this space with hydrogen gas, e.g., at atmospheric pressure.
  • an aluminum or aluminum- containing surface 512 of a workpiece such as a slotted aluminum-containing block 510, and an abrasive surface such as a plurality of wires 522 (typically having short bristles) of suitable hardness and density, disposed within a scraping assembly 520.
  • Each slot 513 may be disposed and adapted to receive at least a portion of scraping assembly 520.
  • One or more springs 528 disposed within manually-driven apparatus 590, and typically bridging between faces 540a, 540b, may be used to maintain the desired separation between the scraper and aluminum surface.
  • a stopping element or mechanism 547 may be employed to limit the distance between faces 540a, 540b resulting from the extension of spring 528.
  • manually-driven apparatus 590 may be adapted whereby a pressure exerted on at least one, and typically both of faces 540a, 540b draws together faces 540a, 540b, whereby scraping assembly 520 and wires 522 move with respect to, and against surface 512.
  • the newly exposed aluminum metal surfaces (on surface 512 and/or aluminum metal in particles liberated from surface 512) react with the water to produce a small quantity of hydrogen gas.
  • Apparatus 590 may be connected to a miniature fuel cell or another electricity producing unit, as described hereinabove with respect to Figure 3. This arrangement may be utilized to power portable electronic equipment such as cellular phones and the like.
  • An occasional squeezing or pressing of hydrogen generating apparatus 590 may produce instant micropower requisite for a hydrogen fuel cell of the cellular phone or other portable electronic equipment.
  • Figure 5b provides a schematic, cutaway top view of the portable, hydrogen- generating apparatus of Figure 5 a.
  • Hydrogen gas may be generated by one or more human fingers squeezing, sliding, or pushing the outside of the unit, causing the scraper to abrade an aluminum surface or surfaces. Any manual or automatic mechanical process could activate hydrogen production, including pressing the buttons of a cell phone, by way of example.
  • Apparatus 590 may be adapted to snap into a pre-provided opening in the fuel cell unit to be powered (which may be separated from, or integral with, a cellular phone or the like), by means of a fastening arrangement that may include clips or a perforated or slide-in casing design.
  • apparatus 590 may be adapted to fit inside a standalone power unit in the same manner. An advantage of this approach is the continued utilization of the same fuel cell assembly after a particular aluminum cartridge has been exhausted.
  • the pressure may be felt by the operator during the squeezing of housing 540. This pressure indicates to the operator that an adequate hydrogen pressure has been achieved, so the operator knows to stop the squeezing or pumping operation. If the hydrogen pressure builds up excessively, the fingers will have increasing difficulty to pump the unit or may simply become incapable of pumping the unit.
  • excess hydrogen gas could be released from the device into the air or into a release chamber.
  • a control lock mechanism to inhibit the operator from performing excessive squeezing or pumping.
  • Figure 6a provides a schematic, side cross-sectional view of a portion of a brush and sleeve arrangement 621 according to another embodiment of the present invention.
  • a manually-driven hydrogen generating apparatus such as manually-driven apparatus 590 (shown in Figure 5 a) is disposed an aluminum or aluminum-containing surface 612 of a workpiece such as a slotted aluminum-containing block 510 (shown in Figure 5a) having generally conical slots or sleeves such as a sleeve 610.
  • Brush and sleeve arrangement 621 may include an abrading assembly 620 including a base 624 surrounded by an abrasive surface such as a plurality of wires 622.
  • Each sleeve 610 may be disposed and adapted to receive at least a portion of abrading assembly 620.
  • the mechanical action of abrading assembly 620 against surface 612 may be substantially similar to that of manually-driven apparatus 590, and may be effected by various means, including fingers, a hand or foot, and a mechanical cam device or the like.
  • abrading assembly 620 against surface 612 of a generally conical slot or sleeve such as aluminum or aluminum-containing sleeve 610 may be effected in a hydrogen generating apparatus (typically manually-driven) such as apparatus 690, a schematic cross-section of which is provided in Figure 6b.
  • apparatus 690 typically manually-driven
  • Sleeve 610 may be supported by at least one support 614, which may be mounted to a bottom face 640b of apparatus 690.
  • One or more springs 628 disposed within apparatus 690, and typically bridging between faces 640a, 640b, may be used to maintain the desired separation between the scraper and aluminum surface.
  • a stopping element or mechanism 647 may be employed to limit the distance between faces 640a, 640b resulting from the extension of spring 628. Stopping element or mechanism 647 may be advantageously disposed within a slot 648, which determines the vertical travel limits of conical brush 624 or abrading assembly 620 with respect to surface 612 of sleeve 610.
  • the inventive apparatus may be powered by various powering arrangements.
  • motor or drive means 358 may be powered by a power source external to the hydrogen generating system. It may be of particular advantage to adapt the inventive apparatus to be powered by available, harnessable power sources.
  • an existing rotating arrangement such as a pulley and belt arrangement 758 may be used. Automobiles or other powered vehicles may have such pulley and belt arrangements.
  • Figure 7a provides a perspective view of an exemplary pulley and belt arrangement 758. The arrangement may include pulleys such as pulleys 759, and a moving or rotating belt 759a.
  • Various hydrogen generating apparatus and sub-arrangements may be adapted to be integrated with pulley and belt arrangement 758, whereby rotating belt 759a directly or indirectly engages a shaft such as drive shaft 52 of hydrogen generating sub-arrangement 180.
  • Figure 7b provides a side view of hydrogen generating sub-arrangement 180 integrated with, and driven by, pulley and belt arrangement 758.
  • FIG. 8a provides a perspective view of a hydrogen generating apparatus such as apparatus 890, which may be similar to apparatus 690 described hereinabove.
  • Apparatus 890 may include a support or platform 891, which may advantageously house, or at least partially house, the hydrogen outlet and cooling water connections (not shown).
  • a drive means such as a mechanical cam 858 having a rotating shaft or axis such as eccentrically positioned shaft 858a.
  • a short end of cam 858 faces, and may contact, end 892 of apparatus 890.
  • the relatively small distance between the short end of cam 858 and shaft 858a enables apparatus 890 to assume a relaxed or open position.
  • shaft 858a rotates, the long or pointed end of cam 858 is urged against end 892 of apparatus 890, as shown in Figure 8b. Consequently, side walls 845 of apparatus 890 are compressed, such that a scraping of the brush against the aluminum-containing surface (not shown), within apparatus 890, is effected.
  • An alternative manually-driven apparatus may have a small lever adapted to automatically move the brush assembly.
  • the lever may be powered by a small rechargeable battery or capacitor.
  • a hand-held unit resembling a nutcracker or grip exerciser may have a spring (or other activation element), allowing a squeezing action, between the handles, on manually-driven apparatus 590 or the like.
  • the use of this mechanism enables the user to pump harder than is possible with the fingers alone, such that a higher hydrogen output may be attained.
  • the fuel cell may be disposed directly on or in the handle, or may be disposed in an adjoining device.
  • Figure 9 a provides a schematic block diagram of a connecting arrangement 995 for connecting between a hydrogen generating system 935 and a power generating system such as a hydrogen-consuming fuel cell arrangement 925, according to another embodiment of the present invention.
  • Fluidly communicating between generating system 935 and connecting arrangement 995 is a tube assembly 986.
  • Fluidly communicating between connecting arrangement 995 downstream to fuel cell arrangement 925 is a second tube assembly 987.
  • FIG. 9b A cross-sectional view of one embodiment of tube assembly 986, connecting arrangement 995 and second tube assembly 987 is shown in Figure 9b.
  • An on-line filter or membrane 964 which selectively passes hydrogen gas (but not water or water vapor), is disposed in a first tube 988 of tube assembly 986.
  • Second tube assembly 987 may include a second tube 989 having an end 991 such as a flared end adapted to connect to first tube 988. Disposed near (and typically within) end 991 is a piercing unit such as a pin 967, which is adapted to pierce second membrane 985, when second tube assembly 987 is attached to tube assembly 986.
  • a piercing unit such as a pin 967, which is adapted to pierce second membrane 985, when second tube assembly 987 is attached to tube assembly 986.
  • Connecting arrangement 995 and second tube assembly 987 may be associated with, or integral to, fuel cell arrangement 925.
  • Connecting arrangement 995 may include a securing arrangement 996 such as a locking wing nut adapted to secure second tube assembly 987 to tube assembly 986. This may be achieved by complementary connecting surfaces 997, 984, on securing arrangement 996 and on an outer surface of first tube 988, respectively.
  • connecting surfaces 997, 984 are complementary threaded surfaces.
  • the above-described arrangement enables the generated hydrogen to safely and robustly reach the fuel cell housed in, or connected to, a computing device, toy, cellular phone or other portable electronic equipment.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

La présente invention concerne un appareil, un procédé et un système permettant de produire de l'hydrogène gazeux par grattage mécanique d'une surface d'un matériau contenant de l'aluminium, en présence d'un milieu aqueux, l'appareil comprenant : (a) une chambre de réaction ayant un orifice de refoulement, conçue pour contenir hermétiquement le milieu aqueux ; (b) une pièce contenant de l'aluminium ayant une surface de travail ; (c) un mécanisme de grattage ayant une brosse conçue pour entrer en contact avec la surface de travail, la pièce et l'élément de grattage disposés à l'intérieur de la chambre, la surface et l'élément de grattage étant conçus pour se déplacer dans un mouvement relatif l'un par rapport à l'autre, ce qui permet, en fonctionnement, le grattage de l'élément de grattage contre la surface de travail afin d'entraîner la libération de particules contenant de l'aluminium de la pièce, la chambre étant conçue pour être sensiblement étanche par rapport au milieu ambiant, jusqu'à un seuil de pression super-atmosphérique, et davantage adaptée pour que, pendant le contact entre le milieu aqueux et les particules à l'intérieur de la chambre, le gaz hydrogène soit dégagé et évacué par l'intermédiaire de l'orifice de refoulement, lorsqu'une pression dans la chambre dépasse le seuil.
PCT/US2011/064503 2011-12-12 2011-12-12 Production d'hydrogène au moyen d'une brosse mécanique sur de l'aluminium dans un milieu aqueux WO2013089669A1 (fr)

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FR3009297A1 (fr) * 2013-08-01 2015-02-06 Gerard Yves Francois Montel Generateur d'hydrogene par frottement d'aluminium
FR3014424A1 (fr) * 2013-12-06 2015-06-12 Gerard Yves Francois Montel Generateur d'hydrogene par contact d'eau et d'aluminium pur
CN115090056A (zh) * 2022-07-11 2022-09-23 上海交通大学 一种煤制氢的变压吸附式氢气净化器
EP4074412A1 (fr) * 2021-04-13 2022-10-19 Hysilabs, SAS Dispositif de production contrôlée de gaz à partir de deux réactifs de fluide déposés sur une surface

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US20040208820A1 (en) * 2002-09-11 2004-10-21 Dynax Corporation Method for producing hydrogen gas utilizing mechano-corrosive reaction
US20090041657A1 (en) * 2005-03-25 2009-02-12 Takeshi Miki Hydrogen generating material and method for producing the same, and method for producing hydrogen
US20090252671A1 (en) * 2008-04-02 2009-10-08 Cedar Ridge Research Llc Aluminum-alkali hydroxide recyclable hydrogen generator
US20090267023A1 (en) * 2005-07-20 2009-10-29 Takeshi Miki Hydrogen Generating Material and Method for Producing the Same

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US20040208820A1 (en) * 2002-09-11 2004-10-21 Dynax Corporation Method for producing hydrogen gas utilizing mechano-corrosive reaction
US20090041657A1 (en) * 2005-03-25 2009-02-12 Takeshi Miki Hydrogen generating material and method for producing the same, and method for producing hydrogen
US20090267023A1 (en) * 2005-07-20 2009-10-29 Takeshi Miki Hydrogen Generating Material and Method for Producing the Same
US20090252671A1 (en) * 2008-04-02 2009-10-08 Cedar Ridge Research Llc Aluminum-alkali hydroxide recyclable hydrogen generator

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3009297A1 (fr) * 2013-08-01 2015-02-06 Gerard Yves Francois Montel Generateur d'hydrogene par frottement d'aluminium
FR3014424A1 (fr) * 2013-12-06 2015-06-12 Gerard Yves Francois Montel Generateur d'hydrogene par contact d'eau et d'aluminium pur
EP4074412A1 (fr) * 2021-04-13 2022-10-19 Hysilabs, SAS Dispositif de production contrôlée de gaz à partir de deux réactifs de fluide déposés sur une surface
WO2022219027A1 (fr) * 2021-04-13 2022-10-20 Hysilabs, Sas Dispositif de production contrôlée d'un gaz à partir de deux réactifs fluides déposés sur une surface
CN115090056A (zh) * 2022-07-11 2022-09-23 上海交通大学 一种煤制氢的变压吸附式氢气净化器

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