• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    gas generator apparatus. The present application is directed to a hydrophobic membrane assembly (28) within a gas generating apparatus. hydrogen is separated from the reaction solution by traversing a hydrophobic membrane assembly (28) having a hydrophobic truss-like member (36) disposed within a hydrogen exit composite (32) further increasing the capacity of the exit composite hydrogen to separate the hydrogen gas and extending its useful life.
    公开号:BR112012033384B1
    申请号:R112012033384-4
    申请日:2011-06-21
    公开日:2018-12-26
    发明作者:Andrew J. Curello；Michael Curello；Constance R. Stepan
    申请人:Societe Bic；Commissariat A L'energie Atomique Et Aux Énergies Alternatives；
    IPC主号:
    专利说明:

    GAS GENERATOR APPLIANCE. CROSS REFERENCE WITH RELATED PATENT APPLICATION
    The present patent application is a partial continuation of the international patent application no. serial PCT / US2009 / 063108 filed on November 3, 2009 designating the United States. This order is incorporated here by reference in its entirety.
    FIELD OF THE INVENTION
    The invention generally relates to fuel supplies for fuel cells. In particular, the invention relates to hydrophobic membrane assemblies for separating hydrogen gas from reaction fluids.
    BACKGROUND OF THE INVENTION
    Fuel cells are devices that directly convert chemical energy from reagents, that is, fuel and oxidizer, into direct current (DC) electricity. A common fuel for fuel cells is hydrogen gas, which can be stored in compressed form or stored in a hydrogen-absorbent material, for example, nickel and lanthanum alloy, LaNisHe, or other hydride-absorbing metal hydrides. Hydrogen can also be produced on demand by the chemical reaction between a chemical metal hydride, such as sodium borohydride, NaBH4, and water or methanol.
    In a metal hydride reaction, a metal hydride, such as NaBH4, reacts as follows to produce hydrogen:
    NaBH 4 + 2H 2 O —► (heat or catalyst) 4 (H 2 ) + (NaBO 2 )
    Semi-reaction at the anode: H 2 -> 2H + + 2e
    Semi-reaction at the cathode: 2 (2H + + 2e) + O 2 2H 2 O
    Suitable catalysts for this reaction include cobalt, platinum and ruthenium and other metals. The fuel hydrogen produced from the sodium borohydride reform is reacted in the fuel cell with an oxidizer, such as O 2 , to create electricity (or a flow of electrons) and a water by-product. The sodium borate by-product (NaBO 2 ) is also produced by the reform process. A sodium borohydride fuel cell is discussed in United States Patent No. 4,261,956, which is incorporated herein by reference in its entirety. Hydrogen produced by chemical metal hydrides can be compressed or stored in a metal hydride hydrogen absorbent material for later consumption via a fuel cell.
    2/24
    A disadvantage of known hydrogen gas generators using chemical hydride as a fuel is that the separation of the hydrogen gas resulting from the reaction is not always complete. Over time, water, water vapor, reaction agents and reaction by-products can pass from the gas generator to the fuel cell, reducing fuel cell efficiency and operational life. j
    Consequently, there is a desire to obtain a hydrogen gas generating apparatus with a membrane assembly that efficiently separates the hydrogen gas resulting from the reaction solutions. í
    SUMMARY OF THE INVENTION
    The present invention is directed to a hydrophobic membrane assembly for use within a gas generating apparatus within the fuel supply to a fuel cell. The present invention is also directed to reaction chambers, gas generating devices, and / or fuel supplies incorporating the hydrophobic membrane assemblies of the current invention. i
    One aspect of the invention is directed to a gas generating apparatus with a reaction chamber; a mixture of fuels, which reacts to produce a gas in the presence of a catalyst, inside the reaction chamber. The reaction chamber contains a hydrogen outlet composite of a hydrophobic lattice structure disposed between two substantially liquid-impermeable and gas-permeable membranes, and the gas produced by the fuel mixture reaction flows through one or both membranes and in of the truss structure. The hydrophobic truss structure can have a static contact angle with water greater than about 120 °, and possibly even greater than about 150 °. Also, the hydrophobic truss structure can have a surface energy less than about 40 mJ / m 2 , and that the surface energy can have a dispersive energy component less than about 40 mJ / m 2 and a smaller polar energy component than about 2.0 mJ / m 2 . The surface energy of the hydrophobic truss structure may also be less than about 20 mJ / m 2 , and that the surface energy may have a dispersive energy component less than about 20 mJ / m 2 and a polar energy component less than about 1.0 mJ / m 2 . In addition, the surface energy of the hydrophobic truss structure can be less than about 10 mJ / m 2 , and that the surface energy can have a dispersive energy component less than about 10 mJ / m 2 and a polar energy component less than about 0.5
    3/24 mj / m 2 . The hydrophobic truss structure may also have a hysteresis measurement of the contact angle less than about 40 s , possibly even less than about 20 s , or additionally even less than about 10 9 .
    In that aspect of the invention, the hydrophobic lattice structure can be a polymer, and the polymer can be poly (tetrafluorethene), polypropylene, polyamides, polyvinylidene, polyethylene, polysiloxanes, lyophilized polyvinylidene fluoride, polyglactin, dura mater, silicone, rubber, and / or mixtures thereof. Preferably, the polymer can be polyvinylidene fluoride. Alternatively, the hydrophobic truss structure can be covered with a hydrophobic cover. The hydrophobic coating can be polyethylene, paraffin, oils, gelatins, pastes, greases, waxes, polydimethylsiloxane, poly (tetrafluorethene), polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether, propylene-ethylene fluoro, poly (polyfluoro), poly (fluoro) , polysiloxanes, silica, carbon black, alumina, titania, hydrated silanes, silicone, and / or mixtures thereof. Preferably, the hydrophobic coating can be poly (tetrafluoroethene), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, fluorinated propylene-ethylene, poly (perfluorooctylethylacrylate) or polyphosphazene. In addition, the hydrophobic trellis structure can be covered with a surfactant, and the surfactant can be perfluorooctanoate, perfluorooctane sulfonate, ammonium lauryl sulfate, sodium laureth sulfate, alkyl benzene sulfonate, a sulfated or sulfonated fatty material, aryloxyoxol alcohol alcohols. sulfated, alkylbenzene sulfonates, sodium dodecylbenzene sulfonate, fluorosurfactants, sodium lauryl sulfate, mixture of sulfosuccinate, sodium dioctyl sulfosuccinate, sodium sulfosuccinate, sodium 2-ethylhexyl sulfate, ethoxylated acetylenic alcohols, high oxide ethylene oxides high ethylene oxide phenols, secondary and linear ethylene oxide alcohols, ethoxylated amines of any length of ethylene oxide, ethoxylated sorbitan ester, random EO / PO polymer in butyl alcohol, water-soluble block EO / PO copolymers , sodium lauryl ether sulfate, and / or mixtures thereof. The surfactant can optionally include a cross-linking agent as well.
    In addition, the hydrophobic truss structure may have a roughened surface. Preferably, the hydrophobic truss structure exhibits the behavior of Cassie-Baxter.
    The gas generating apparatus may have a second hydrophobic lattice structure between the reaction chamber and the hydrogen outlet composite.
    Petition 870180124266, of 08/31/2018, p. 12/18
    4/24
    Also, the gas generating apparatus may also have a coarse filter between the catalyst and the hydrogen outlet composite, and preferably this coarse filter may be hydrophobic.
    Another aspect of the present invention is directed to a gas generating apparatus having a reaction chamber, a mixture of fuels, which reacts to produce a gas in the presence of a catalyst, within the reaction chamber. The reaction chamber comprises a hydrogen outlet composite having a lattice structure disposed between two substantially liquid-impermeable and gas-permeable membranes, at least of which had its hydrophobicity increased, and the gas produced by the fuel mixture reaction flows through of one or both membranes and around the truss structure. Preferably, both the hydrophobicities of the substantially liquid-impermeable and gas-permeable membranes may have been increased. The hydrophobicity of the substantially liquid-impermeable and gas-permeable membrane can be increased by covering the substantially liquid-impermeable and gas-permeable membrane with a hydrophobic covering. The hydrophobic coating can be polyethylene, paraffin, oils, gelatins, pastes, greases, waxes, polydimethylsiloxane, poly (tetrafluorethene), polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether, propylene-ethylene fluoro, poly (polyfluoro), poly (fluoro) , polysiloxanes, silica, carbon black, alumina, titania, hydrated silanes, silicone, and / or mixtures thereof. Preferably, the hydrophobic coating can be poly (tetrafluoroethene), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, fluorinated propylene ethylene, poly (perfluorooctyl acrylate) or polyphosphazene. Alternatively, the hydrophobicity of the substantially liquid-impermeable and gas-permeable membrane can be increased by covering the substantially liquid-impermeable and gas-permeable membrane with a surfactant. The surfactant can be perfluorooctanoate, perfluorooctane sulfonate, ammonium lauryl sulfate, sodium laureth sulfate, alkyl benzene sulfonate, a sulfated or sulfonated fatty material, alkyl sulfated aryloxypolialoxy alcohol salts, alkyl benzene sulfonates, sodium dodecyl sulfate, fluoride sulfates, dodecyl sulfate , mixture of sulfosuccinate, sodium dioctyl sulfosuccinate, sodium sulfosuccinate, sodium 2-ethylhexyl sulfate, ethoxylated acetylenic alcohols, high ethylene oxide octyl phenols, high ethylene oxide nonyl phenol, secondary ethylene oxide linear alcohols , ethoxylated amines of any length of ethylene oxide, ethoxylated sorbitan ester, polymer
    Petition 870180124266, of 08/31/2018, p. 13/18
    5/24
    Random EO / PO in butyl alcohol, water soluble block EO / PO copolymers, sodium lauryl ether sulfate, and / or mixtures thereof. Optionally, the surfactant can include a cross-linking agent.
    In addition, the substantially liquid-impermeable membrane may have an outer surface that has been roughened to increase its hydrophobicity. Preferably, this surface exhibits Cassie-Baxter's behavior.
    The hydrophobicity of the substantially liquid-impermeable membrane can be increased by around 10%.
    A further aspect of the current invention is directed to a gas generating apparatus having a reaction chamber, a mixture of fuels, which reacts to produce a gas in the presence of a catalyst, within the reaction chamber. The reaction chamber has a hydrogen outlet composite with a lattice structure disposed between two substantially liquid-impermeable and gas-permeable membranes, and the gas produced by the fuel mixture reaction flows through one or both membranes and into of the truss structure. The surface tension of the fuel mixture in this aspect of the current invention is greater than the surface energy of the substantially liquid-impermeable and gas-permeable membranes. The surface tension of the fuel mixture is greater than 73 dynes / cm.
    Alternatively, the surface tension of the fuel mixture may be at least twice that of the surface energy of the membrane substantially impermeable to liquid and permeable to gas.
    A further aspect of the present invention is directed to a gas generating apparatus having a reaction chamber, a mixture of fuels, which reacts to produce gas in the presence of a catalyst, within the reaction chamber. The reaction chamber has a hydrogen outlet composite having a lattice structure disposed between two substantially liquid-impermeable and gas-permeable membranes, and the gas produced by the fuel mixture reaction flows through one or both membranes and into of the truss structure. In that aspect of the invention, a super acid filter is located downstream of the truss structure to substantially remove basic contaminants from the gas produced. The superacid filter may be a polymer of perfluorinated sulfonic acid. Also, the super acid filter can remove more than 90% of the basic contaminants in the gas produced.
    BRIEF DESCRIPTION OF THE FIGURES
    6/24
    In the attached figures, which form a part of the specification and must be read in conjunction with it:
    FIG. 1 is an exploded view of an inventive hydrogen generation device;
    FIG. 2 is a partial cross-sectional view of the inventive hydrogen generating apparatus shown in FIG. 1; and
    FIG. 3 is a partial cross-sectional view of the inventive hydrogen outlet composite of the present invention.
    DETAILED DESCRIPTION OF THE INVENTION
    As illustrated in the attached figures and discussed in detail below, the present invention is directed to the assembly of a hydrophobic membrane for a fuel supply or gas generator that produces hydrogen for use in fuel cells.
    The fuel supplies used with the membrane assembly contain a mixture of fuels and a catalyst. This fuel mixture is usually the solution formed by dissolving a solid fuel component into a liquid fuel component.
    The term "solid fuel" as used here includes all solid fuels that can be reacted to produce hydrogen gas, and includes, but is not limited to, all suitable chemical hydrides described here and in WO2010-051557 A1, including lithium hydride , lithium borohydride, sodium hydride, potassium hydride, potassium borohydride, aluminum and lithium hydride, combinations, salts and derivatives thereof. WO2010-051557 A1 is hereby incorporated by reference in its entirety. Preferably the solid fuel component is a chemical metal hydride, such as sodium borohydride. The solid fuel component can include other chemicals, such as solubility-enhancing chemicals or stabilizers, such as soluble metal hydroxides, and preferably include sodium hydroxide. Other usable stabilizers include potassium hydroxide or lithium hydroxide, among others.
    The term "liquid fuel" as used here includes all liquid fuels that can be reacted to produce hydrogen gas, and includes, but is not limited to, suitable fuels described here and in WO2010051557 A1, including water, alcohols and additives, catalysts and mixtures thereof. Preferably, liquid fuel, such as water or methanol, reacts with solid fuel in the presence of catalyst to produce
    I í i
    I
    7/24 hydrogen. Liquid fuel can also include additives, stabilizers or other elements that enhance the reaction, such as sodium hydroxide with a stabilizer, a polyglycol as a surfactant, or many others.
    The catalyst can be platinum, ruthenium, nickel, cobalt and other metals including those described in W02010-051557 A1 and derivatives thereof. Preferred catalysts include cobalt chloride or ruthenium chloride, or both. Another preferred catalyst is a compound containing cobalt and boron. In the presence of the catalyst, the fuel mixture reacts to produce hydrogen. A preferred catalyst system is discussed in International Application No. PCT / US2009 / 0069239, which is incorporated herein by reference in its entirety.
    As used herein, the term “fuel supply” includes, but is not limited to, disposable cartridges, reusable / refillable cartridges, containers, cartridges that reside within the electronic device, removable cartridges, cartridges that are outside the electronic device, tanks of fuel, refillable fuel tanks, other containers that hold fuel, and the pipes connected to the fuel tanks and containers. While a cartridge is described in conjunction with the exemplary embodiments of the present invention, it is noted that these embodiments are also applicable to other fuel supplies and the present invention is not limited to any particular type of fuel supply.
    The fuel supply used with the membrane assembly of the present invention can also be used to produce fuels that are not used in fuel cells. These applications may include, but are not limited to, hydrogen production for gas turbine micro-engines built on silicone chips, discussed in “Here Come the Microengines,” published in The Industrial Physicist (Dec. 2001 / Jan. 2002 ) on pp. 20-25. As used in the present application, the term "fuel cell" can also include micro-engines.
    The hydrophobic membrane can be used with any known hydrogen generators. Suitable known hydrogen generation devices are described in United States Patent Nos. 7,674,540 and 7,481,858, United States Patent Application Publication No. US2006-0174952 A1, International Publication No. WO2010051557 A1 and International Application No. PCT / US2009 / 0069239 with which
    8/24 inventive hydrophobic membrane assembly can be used. The descriptions of these references are incorporated here by reference in their entirety. «
    FIGS. 1-3 illustrates a representative hydrogen generating apparatus according to the present invention. Hydrogen generating apparatus 10, as illustrated, is operated by pressing the locking button 12 inwards or1 towards the outlet valve 14, which is located at the opposite end of the hydrogen generating unit 10. As shown, the locking button 12 It's!
    attached to seal piston 16, which moves seal 18 towards an open position when locking button 12 is pressed. Does that release the
    solid fuel contained within the inner shell 22 of chamber 20. The solid fuel then dissolves within the liquid fuel present within the interior of container 24 to form an aqueous fuel mixture, discussed above. This aqueous fuel mixture comes in contact with a catalyst inside the reactor buoy 26 and irrigates to produce hydrogen. As described in detail in WO2010-051557 A1, reactor buoy 26 opens and closes depending on the internal pressure of the hydrogen generator 10 and a reference pressure to control access to the catalyst to control hydrogen production. The hydrogen gas produced permeates the membrane assembly 28 and is transported out of the container 12 and the hydrogen generator 10, discussed below.
    As illustrated, the membrane assembly 28 comprises the outer truss 30 and the hydrogen outlet composite 32. The hydrogen outlet composite 32 comprises, in this preferred embodiment, two layers of hydrogen-permeable membranes 34 positioned on either side of the inner truss. 36. Hydrogen-permeable membranes allow hydrogen to pass through, but substantially exclude liquids. Suitable hydrogen-permeable membranes include any substantially liquid-impermeable and gas-permeable material known to those skilled in the art. Such materials can include, but are not limited to, hydrophobic materials having an alkane group. More specific examples include, but are not limited to: polyethylene, polytetrafluoroethylene, polypropylene, polyglactin (VICRY®), lyophilized dura mater or combinations thereof. Suitable commercially available hydrogen permeable membranes include GORE-TEX® polyvinylidene fluoride (PVDF), CELGARD® and SURBENT®. Additionally, or alternatively, the hydrogen-permeable membrane may include any substantially liquid-impermeable materials and
    Gas permeable 9/24 described in United States Patent No. 7,147,955, incorporated herein by reference.
    Hydrogen-permeable membranes 34 are preferably α sealed together around the inner truss 36 to form the composite of>
    multi-layered hydrogen outlet 32. The internal truss 36 minimizes the possibility that the two hydrogen-permeable membranes 34 come into contact with each other or seal together to minimize the flow of hydrogen. The outer truss 30 is used to minimize contact between the hydrogen outlet composite 32 with the container 24, which would reduce the hydrogen flow rate into the hydrogen outlet composite 32. The outer truss 30 and the inner truss 36 are preferably flexible. In a preferred embodiment, the multilayer hydrogen outlet composite 32 is constructed as a flat structure, as best shown in FIG. 3, with the hydrogen conduit 38 attached to one side of the hydrogen outlet composite 32. A coarse filter 37, such as a wrinkled or non-woven paper or fabric on the side of the membrane reactor, can be placed on top of the flat structure to minimize the contact between the hydrogen outlet composite 32 and any solids that may precipitate from the fuel '<
    solution. The entire flat structure can simply be rolled up and inserted into container 24. Hydrogen conduit 38 is in fluid communication with the interior of the hydrogen outlet composite 32 and the hydrogen chamber 40.
    The hydrogen gas is separated from the reaction solution when it crosses the hydrogen-permeable membranes 34 into the hydrogen outlet composite 32, where the hydrogen crosses and / or passes along the internal lattice 36 to the hydrogen conduit 38 to flow the hydrogen outlet composite 32 out. The hydrogen conduit 38 is connected to the hydrogen chamber 40, and the hydrogen collects in chamber 40. The hydrogen chamber 40 may contain a superacid to filter out unwanted alkalis. The outlet valve 14 is connected to the hydrogen chamber 40 and is also connected to a fuel cell (not shown). The first relief valve 42 is provided for the hydrogen chamber 40 to vent the hydrogen when the pressure within the chamber 40 is above a predetermined limit level. THE!
    second relief valve 44 is provided for chamber 24 for ventilation when the pressure in that chamber is above the predetermined limit level.
    Buoy 26 is connected by tube 46 to the external atmosphere, so that atmospheric pressure can serve as the reference pressure, as
    10/24 best shown in FIG. 2. Tube 46 may be rigid and hold buoy 26 vertically or at an angle of about 45 °, preferably between about 35 ° and about 55 °. These angles preferably allow the trapped gas to move away from the float 26 when the float opens or closes. Tube 46 is preferably connected to surface channels 48, which are;
    depressions formed on an outer surface of the chamber 24. Multiple surface channels 48 ensure that tube 46 remains open to the atmosphere even when the user's finger or debris blocks or partially blocks tube 46. Channels 48 may be arranged in the bottom part of chamber 24, as shown, or on the side of chamber 24.í
    The outlet valve 14 can be any valve capable of controlling the flow of hydrogen, and preferably they are valves described in international patent application publication nos. W02009-026441 and W02009-026439, which are incorporated here by reference in their entirety. Preferably, the outlet valve 14 comprises central stop 48, which is substantially immobile in relation to the chamber 24, and can be fixedly attached to the lower part of the chamber 24, as best illustrated in FIG. 2. Seal 50, which can be a
    O-ring or a flat washer around the central stop 48 and provides a seal i for the hydrogen chamber 40. Retainer 52 holds or locks seal 50 in;
    its appropriate location. Other suitable outlet valves include, but are not limited to, valves described in United States Patent nos. 7,537,024, 7,059,582, 7,617,842 and published United States patent applications nos. US2006-0174952 and US2010-0099009. These references are also incorporated here by reference in their entirety.
    To make outlet valve 14 more difficult to operate by unintended users or to reduce the possibility of connecting the hydrogen generator 10 to incompatible machinery, an equivalent pre-pilot blind hole 54 is provided around outlet valve 14. For opening the valve 14, a valve of I coupling or equivalent must have a cylindrical member that fits around the central stop 48 and internal retainer 52 to open the seal 50 and an annular / concentric member that fits inside the pre-hole pilot 54. Other mechanisms to ensure difficult operation by unintended users and / or incompatible machinery are described in the United States published patent application nos. US 2005-0074643, US2008-0145739, US2008-0233457 and US2010-0099009, which are incorporated herein by reference in their entirety.
    11/24
    Generally, trusses 30, 36 can be of any material similar * to truss and can be rigid or flexible. The trellis material can be a solid hydrophobic trellis *, a farm material, textile, nylon mesh, felt, weft <
    metal, canvas, wrinkled shape, or other gas-permeable structure that can # serve as a base for lamination and prevent the membranes 34 from collapsing with each other. Suitable trellis materials including those positioned or inserted into a fuel balloon described in United States Patent No. 7,172,825, which is incorporated herein by reference in its entirety. The hydrogen outlet composite 32 filters the hydrogen gas produced out of the fuel mixture and transmits the produced gas to the hydrogen outlet 38 and the outlet valve 14. The construction of the hydrogen separator in this way, which is also discussed in WO2010-051557 A1, the membrane assembly 28 is inserted in the middle of the solution allowing the pressure to be equal on both sides with a pressure differential resulting in compression.
    The inventors of the present invention have observed that, after a period of time, liquid fuel and / or liquid by-product, which contains water, entered the hydrogen outlet composite. The water appeared to contain additives, such as potassium hydride, KOH, or sodium hydride, NaOH, and reaction by-products, such as potassium borates, KBO2, and sodium borates, NaBO 2 . These contaminants can adversely affect the polymer electrolyte or 0 MEA of the fuel cell when they pass through the outlet valve 14 with hydrogen gas. After considerable effort, without being bound by any particular theory, it was determined that the truss 36 may be responsible for the entry of liquid fuel into the hydrogen outlet composite 32. The inventors found that the inner truss 36 was hydrophilic in nature in comparison with the substantially liquid-impermeable and hydrogen-permeable membranes 34. When the inner truss 36 was in contact with the substantially liquid-impermeable and hydrogen-permeable membrane 34, it may have caused or encouraged through the osmotic entrainment process that water >
    or liquid fuel with contaminants through the membrane pores substantially impermeable to liquid and permeable to hydrogen 34. It has also been found that the internal pressure of chamber 24, especially when hydrogen is being produced, also encourages liquid fuel to pass through the membranes 34. Liquid fuel with contaminants can accumulate inside the hydrogen outlet composite 32.
    12/24
    The current invention relates to a hydrophobic hydrogen outlet composite.4 32, and preferably a hydrophobic membrane assembly 28. |
    The hydrophobicity of a solid (or wettability) depends on the forces of interaction between water, the surface and the surrounding air. See J. C. Berg, Wettabílity, í
    Marcei Dekker, New York, 1993 and A. W. Adamson, Physical Chemistry ofI
    Surfaces, Wiley. The interaction forces between water and air are surface tension, γι_ν. Similarly, surface energy, ysv. defined θ | as the forces between a solid and the surrounding air and the interface voltage, Yls, θ 'defined as the forces between the solid and the water. For a drop of liquid in | equilibrium on a surface, Young's equation states that y S v - Yls = Ylv cosr
    Θ, where Θ is the contact angle of the water drop in relation to the surface. Young's equation also shows that, if the surface tension of the liquid is less than the surface energy, the contact angle is zero and the water moistens the surface. In addition, water can partially moisten the surface (contact angle more than 0 o ). If the contact angle is between 0 o and 90 °, the surface is considered hydrophilic; and if the contact angle is greater than 90 °, the surface is considered hydrophobic. And in certain cases, hydrophobic supermaterials, such as lotus leaves, have been noted to have a greater contact angle with static water than 150 °. In particular, the static contact angle of a substrate can be measured using a contact angle goniometer and can be measured using methods of those skilled in the art including the sessile drop method (static or dynamic),
    Wihelmy (dynamic and single fiber), and powder contact angle method.
    The surface energy of a solid, the excess energy available on the surface of a solid compared to its volume, is determinant of the hydrophilic or hydrophobic state of the solids. The material seeks to be in a low energy state and chemical bonds reduce energy. Thus, surfaces, which have high surface energies tend to be hydrophilic, since | those surfaces will initiate the bond with the hydrogen molecules in there water. Hydrophobic materials have lower surface energies and are | unable to form hydrogen bonds with water, and water repels the | hydrophobic in favor of connecting with oneself. Young's equation illustrates this »point. (
    The surface energy of a solid depends on several factors (J. P. Renaud!
    and P. Dinichert, 1956, Etats de surface et etalement des huiles d’horlogerie,
    Bulletin SSC III page 681): the chemical composition and crystallographic structure of the
    13/24 solid, and in particular of its surface, the geometric characteristics of the surface and its roughness (and, therefore, the defects and / or the polishing state), and the presence of molecules physically adsorbed or chemically linked to the surface, the which can easily mask the solid and significantly modify its surface energy.i
    Owens Wendt's Theory, also known as the medium method;
    harmonic, can be used to measure the surface energy of a solid.
    Owens, D. K .; Wendt, R. G. Estimation of the surface force energy of polymers, l
    J. Appl. Polym. Know. 1969, 51, 1741-1747. This theory postulates that the surface energetic surface is the sum of its polar and dispersive components. The polar component accounts for dipole-dipole, induced dipole, hydrogen bonding and other site-specific interactions between a solid and a liquid. The dispersive component accounts for surface interactions based on non-site-specific and Van der Waals interactions between a solid and a liquid.
    The model is based on two fundamental equations that describe the surface interactions between solids and liquids: Good equation (osl = Os + to L 2 (to L D as D ) 1/2 -2 (ol p os p ) 1 / 2 ) and Young's equation (os = o S l + o l cos θ). The dispersive component of the surface tension of the wetting liquid is L D ; the polar component of the surface tension of the wetting liquid is L p ; the dispersive component of the solid's surface energy is Os D ; and the polar component of the solid's surface energy is Os P. The combination of the Good and Young equations produces the following equation: oL (cos 9 + 1) / 2 (oL D ) 1/2 = (as p ) 1/2 ((aL p ) 1/2 / (aL D )) + (as D ) 1/2 . The equation has the linear form of y = mx + b, thus y = oL (cos 9 + 1) / 2 (o L D ) 1/2 ; m = (os p ) 1,2 ; x = (aL p ) 1/2 / (oL D ); b = (os D ) 1/2 .
    The dispersive and polar components of wetting liquids are known in the literature. A series of replicated contact angles are measured for each of at least two wetting liquids that include, ( but are not limited to, diiodomethane, benzyl alcohol, ethylene glycol, formamide and water. Y's are plotted as a function of x's it's the;
    polar component of surface energy, the P , is equivalent to the square root of the * slope, m, and the dispersive component of the surface energy, Os D , is equivalent to the square root of the y-intercept, b.í
    In addition, the surface energy of a solid can be measured using contact angle hysteresis. To make this measurement, a pipette injects a liquid into a solid, and the liquid forms an angle of contact. The pipette then injects more liquid, the droplet will increase in volume and its angle of
    14/24 contact will increase, but your three-phase limit will remain stationary until it advances out suddenly. The contact angle that the droplet has advanced outward just before is called the forward contact angle. The recoil contact angle is now measured by pumping the liquid back out of the droplet. The droplet will decrease in volume, the contact angle will decrease, but its limit of three phases will remain stationary until it recedes downward suddenly. The contact angle that the droplet retreated inward just before is referred to as the indentation contact angle. The difference »between the forward and backward contact angles is called contact angle hysteresis and can be used to characterize the heterogeneity of the surface, roughness, mobility and wettability. Preferably, the contact angle hysteresis should be relatively small for a hydrophobic surface; and for a super-hydrophobic surface it must be less than 5 o .
    The hydrophobic membrane assembly 28 of the current invention preferably comprises a hydrophobic inner trellis 36 and optionally the hydrophobic outer trellis 30. Additionally, the hydrophobicity of membrane 34 can be increased, and / or the surface tension of the reaction solution in relation to the surface of the reaction. membrane 34 can be increased. I
    According to an embodiment of the invention, the lattice-like material is made of hydrophobic materials. A hydrophobic material suitable for the current invention can be determined by at least one, or more, of the following measures: static water contact angle, surface energy, and contact angle hysteresis. If the contact angle of static water is used, the contact angle of static water must be greater than 90 °, preferably greater than 120 °, and most preferably greater than 150 °. If surface energy is used, the surface energy of truss materials 30, 36 should be less than 40 mJ / m 2 , more preferably less than 20 mJ / m 2 , and most preferably less than 10 mJ / m 2 . The surface energies can be further evaluated in their polar and dispersive energy components. In particular, the polar energy component of surface energy can be less than about 5%, less than about 2.5%, less than about 1%, preferably less than 0.4%, and most preferably less than 0.1%. For example, in the case where the surface energy is less than 40 mJ / m 2 , preferably the dispersive energy component is less than 40 mJ / m 2 and the polar energy component is less than 2.0 mJ / m 2 . Similarly, where the surface energy of the truss 36, 30 is less than 20 mJ / m 2 ,
    15/24 preferably the dispersive energy component is less than 20 mj / m 2 and the polar energy component is less than 1 mj / m 2 . Properties of Polymers by DW Van Krevelen (Elsevier 1990) describes various polymers, their surface energies, and the polar and dispersive components of their surface energies and are incorporated here by reference. Also, where the truss surface energy 36, 30 is less than 10 mj / m 2 , preferably the dispersive energy component is less than 10 mj / m 2 and the polar energy component is less than 0.5 mj / m 2 . Where the measure is the contact angle hysteresis, the measurement should be less than about 40 s , more preferably less than about 20 s , more preferably less than about 10 s . Since the hydrophobic membrane assembly 28 is submerged in an aqueous solution, surface energy and the hysteresis measurement of the contact angle are preferred determinants of whether a material can be considered hydrophobic.
    Preferably, truss 36, 30 is as hydrophobic as membrane 34. As noted above, Cellgard ™ is an example of a material suitable for use as membrane 34 and has a contact angle of about 120 s , a surface energy of about of 22.04 (± 0.16) mj / m 2 with a dispersive energy component of about 22.00 (± 0.15) mj / m 2 and a polar energy component of about 0.04 (± 0.01) mj / m 2 , and a hysteresis measurement of the contact angle of about 30 s . More preferably, truss 36, 30 is more hydrophobic than membrane 34, that is, truss 36, 30 has a greater static contact angle measurement, a surface energy that is less than the surface energy of membrane 34, and / or a measure of hysteresis of the contact angle that is less than the measure of hysteresis of the contact angle for the membrane 34.
    Hydrophobic materials suitable for the manufacture of the trellis include hydrophobic substrates such as ceramics, plastics, polymers, glass, fibers, nonwovens, fabrics, textiles, farms, carbon and carbon fibers, ion exchange resins, metals, alloys, yarns , and meshes. It is preferred that the hydrophobic materials are compatible with the reaction solution and do not inhibit the ability of the hydrogen outlet composite 32 to allow the hydrogen gas to pass through. Suitable hydrophobic materials include, but are not limited to, hydrophobic polymeric materials, such as poly (tetrafluorethene) (PTFE), polypropylene (PP), polyamides, polyvinylidene, polyethylene, polysiloxanes, silicone, rubber, polyglactin (VICRY®), durability lyophilized material, or combinations thereof. Preferably, the hydrophobic material is PTFE, better known
    Petition 870180124266, of 08/31/2018, p. 14/18
    16/24 as TEFLON® marketed by Dupont. More preferably, materials suitable for membrane 34, such as GORETEX®, CELGARD® and SURBENT® can be used as well as provided so that the inner truss 36 and membrane 34 do not together block an impediment of hydrogen flow if they are made from the same material. In addition, superhydrophobic polymeric materials including, but not limited to, superhydrophobic linear low density polyethylene as described in Yuan et al. Preparation and characterization of self-cleaning stable superhydrophobic linear low-density poly ethylene. Know. Technol. Adv. Mater. 9 (2008), can be used as well.
    In an alternative embodiment, the lattice-like materials can be additionally hydrophobic or alternatively a hydrophilic-based material can be made hydrophobic by coating it with a hydrophobic or super-hydrophobic coating. Solutions used to coat the lattice-like material may include, but are not limited to, polyethylene, paraffin, oils, gelatins, pastes (TEFLON® and carbon paste), greases, waxes, polydimethylsiloxane, PTFE, polyvinylidene fluoride, copolymer of tetrafluoroethylene-perfluoroalkyl vinyl ether, fluorinated propylene ethylene (FEP), poly (perfluorooctylethylene acrylate) (FMA), polyphosphazene, polysiloxanes, silica, carbon black, alumina, titania, hydrated silanes, silicone, and / or mixtures thereof. Preferably, highly water-repellent material, such as PTFE, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), fluorinated propylene ethylene (FEP), poly (perfluorooctyl acrylate) (FMA), polyphosphazene, and / or mixtures thereof, is used to coat trellis-like material 36, 30. Methods of forming hydrophobic overcoats, and applying hydrophobic overcoats, such as those described in International Publication Nos. WO 98/42452 and WO 01/14497, incorporated herein by reference, are also contemplated.
    Also, the processes that can be used to apply the hydrophobic coatings noted above are also known in the art and include chemical and physical coating processes. For example, the compositions can be used with solvents, such as N-methyl-2-pyrrolidone and dimethyl acetamide, or as an emulsion. Coating processes can be performed by any method including brush application, spray application, submersion, and screen printing. Coatings can also be made using Sol-Gel processes. In a Sol-Gel process, the surface is coated with hydrophobic nanoparticles that are included within a network
    Petition 870180124266, of 08/31/2018, p. 15/18
    17/24 polymer. Coatings are composite materials (nanocomposites) with organic and inorganic components that are produced using Sol-Gel processes. The coating is applied by using simple submersion or spray processes followed by a hardening process.
    In addition, a hydrophobic coating can be introduced into the;
    surface of trellis-like material 36, 30 by plasma treatment. Thereby, the hydrophobic layer can be formed to a desired thickness.
    With the application, for example, of CF4 plasma treatment to the surface, water repeating is applied to the surface of the base material.
    In addition to the hydrophobic coatings noted above, surfactants, including, but not limited to, soaps, detergents, and wetting agents can be applied to the surface of trellis-like material 36, 30. Surfactants are amphiphilic: the surfactant particles contain a hydrophobic tail and hydrophilic head. Without being bound by any particular theory, it is believed that a surfactant coating on the surface of the lattice-like material 36, 30 will form an additional barrier. Specifically, the surfactant particles will orient themselves so that the hydrophobic tails are in contact with the surface of the lattice-like material and their hydrophilic heads are in contact with the liquid, thus isolating the surface of the lattice-like material 36, 30 of liquid fuel. Surfactants for use as a coating include, but are not limited to, tonic (anionic, cationic or zwitterionic) or nonionic surfactants. Surfactants include, but are not limited to, perfluorooctanoate, perfluorooctane sulfonate, ammonium lauryl sulfate, sodium laureth sulfate, alkylbenzene sulfonate, a sulfated or sulfonated fatty material, alkyl sulfated aryloxypolialoxyalkyl sulfate, alkylbenzene sulfonates (d Rhodacal LDS-10 surfactant from Rhone Poulenc), fluorosurfactants (Fluorad FC-170C surfactant available from 3M), sodium lauryl sulfate (commercially available as Sipon UB), sulfosuccinate mixture (commercially available as Aerosol OTNV), sodium dioctyl sulfosuccinate ( commercially available as Aerosol TO by Cytec Industries), sodium sulfosuccinate, or 2-ethylhexyl <
    sodium sulfate (commercially available as Rhodapon BOS); ethoxylated acetylenic alcohols, such as Surfynol CT-111, high EO (ethylene oxide) octylphenols, such as Iconol OP-10 and Triton CF-87; high EO nonylphenols, such as Igepal CO-730 (NP-15); secondary and linear EO alcohols, such as Tergitol 15-S-12 (secondary), Tergitol TMN 10 (90%) (linear), Neodol 118/24
    9 (linear), Neodol 25-12 (linear), and Mazawet 36 (random decyl EO / PO; ethoxylated amines of any length of EO, such as Chemeen T-10 (tallow, f
    10EÓ), Chemeen T-15, Chemeen C-15 (Coco. 15 EO), Trymeen 6640A, Tomah
    E-18-15 (18C, 15EO), Tomah E-18 10, and Tomah E-S-15 (Soya); ethoxylated sorbitan ester, for example, POE 20 Sorbitan Monoleate (BASF T-Maz 80); polymer |
    Random EO / PO in butyl alcohol, such as Tergitol XJ, Tergitol XD, Tergitol XH, | and Tergitol XH; other water-soluble block EO / PO copolymers, such as |
    Pluronic L61LF, Pluronic L101, Pluronic L121, and Plurafac LF131, and Norfox LF-30 e |
    LF-21, sodium lauryl ether sulfate and / or mixtures thereof. In addition, surfactant coating solutions can include crosslinking agents to increase the longevity and strength of the surfactant coating. Trellis-like material 36, 30 can be coated using the methods described above.
    Furthermore, it is known that microstructuring of a surfaceii amplifies the natural tendency of a surface (Wenzel equation), and in certain cases, if the roughened surface can trap vapor (such as air or other gases) the hydrophobicity of the surface it can be additionally increased beyond that obtained in the state of Wenzel (Cassie-Baxter equation).
    Thus, a hydrophobic surface becomes more hydrophobic when it is;
    microstructured or roughened. A critical roughness factor, rc = -1 / cos8, 'provides the perception as to when a roughened surface will exhibit the behavior of Wenzel or Gassie-Baxter. Preferably, the roughened material similar to the truss 36, 30 exhibits the behavior of CassieBaxter. Additionally, it may be useful to provide trellis-like material 36, 30 with a dual / hierarchical multi-scale surface structure as described in Naik, V., Mukherjee, R., Majumdar, A., Sharma, A., Super functional materials: Creation and control of wettability, adhesion, and optical j effects by meso-structuring of surfaces, Current Trends in Science, Bangalore, I
    Indian Academy of Sciences, pp. 129-148, 2009, incorporated herein by reference.
    In addition to the means noted above of making the material similar to the truss 36, | hydrophobic, it is also contemplated that the surface of lattice-like material 36, 30 can be microstructured using methods known in the art, including, but not limited to, top down approaches, such as direct replication of natural repellent surfaces through which molding and modeling including nanofusion, replica molding using moldable polymers, and / or creating patterns or textures on surfaces}
    19/24 using micro-machining, lithography (photolithography, smooth lithography (nano printing lithography, capillary force lithography, capillary micro-molding, microtransfer molding), electron beam lithography), and plasma indentation; as well as botíom up approaches (from bottom to top), such as chemical bath deposition, chemical vapor deposition, electrochemical deposition, layer by layer deposition through electrostatic assembly, colloidal assembly, sol-gel methods, nanosphere lithography, formation of t · pattern induced by water droplet condensation, and / or microabrasion.>
    Preferably, the microstructuring is done before coating with a hydrophobic material, but can be done following the coating depending on the thickness of the coating.
    The above described refers to the lattice-like material 36, 30, but it will be appreciated that the same principles and processes can be applied to other hydrogen generator parts 10, such as coarse filter 37.
    In an alternative embodiment, the hydrophobicity of membrane 34 is increased. This can be achieved by coating membrane 34 with one;
    hydrophobic coating, micro-coating / roughening the surface of membrane 34, and / or coating membrane 34 with a surfactant, as noted above. In addition, it was noted that super-hydrophobic surfaces are resistant to attachment by water-soluble electrolytes, such as acids and alkalis, and thus, preferably, the surface of membrane 34 is coated with super-hydrophobic compounds or microstructured according to the described above. It is preferred that, after the treatments noted above, the hydrophobicity of the membrane 34 is increased by at least 10%. In particular, the surface energy of membrane 34 decreases by at least about 10%, more preferably after modification the membrane 34 has a surface energy of less than about 20 mJ / m 2 with a dispersive energy component of less than about 20 mJ / m 2 and a polar energy component i less than about 1 mJ / m 2 , and / or a hysteresis measure of the contact angle less than 30 °. Most preferably, membrane 34 has a surface energy less than about 10 mJ / m 2 with a dispersive energy component less than about 10 mJ / m 2 and a polar energy component less than about 0.5 mJ / m 2. m 2 , and / or a measure of contact hysteresis less than about 10 °. The membrane can be coated with a hydrophobic or surfactant coating, and / or micro-coated in addition to or alternatively to the hydrophobic 36, 30 lattice-like material, as noted above.
    20/24
    One of ordinary skill in the art will appreciate that the hydrophobic membrane assembly 28 of the current invention may include three or more layers. There
    FIG. 3 provides a hydrogen output composite diagram 32 consisting of two membranes 34 and a trellis-like material 36. However, a>
    Hydrophobic membrane assembly 28 may have one or more hydrogen outlet composites 32 with one or more lattice-like materials separating the various membrane layers from the hydrogen outlet composites.
    Preferably, the membrane assembly may be multilayered (to maintain the hydrophobic nature of the membrane assembly for the life of the gas generating cartridge, so that if an outer layer may lose its hydrophobicity, one of the inner layers will continue to prevent contaminants from being transported to the fuel cell.
    Additionally, the lattice-like materials in the hydrogen outlet composites can be cut as a slope (at an angle so that the individual lattice grids resemble diamonds instead of boxes) so that any water or water vapor enters on the hydrogen outlet composite it is guided away from the outlet valve 14. The hydrophobic membrane mounting form 28 can be additionally adapted for a similar use in other fuel supply devices. For example, membrane 34 can be sandwiched between two or more trellis-like materials 36, 30 to provide rigidity in arrangements where the membrane is not under compressive forces and there is a risk that expansion forces may break the membrane 34.
    In addition, as indicated above, a liquid moistens a surface when the surface tension of the liquid is less than the surface energy of the solid. Therefore, in order to improve the hydrophobic nature of the membrane assembly 28, it may be desirable to increase the surface tension of the reaction solution. Surface tension is a property of the surface of a liquid, and what does it do
    with that the surface portion of the liquid is attracted to another surface, such as that of the other portion of liquid. Surface tension is caused by cohesion (the attraction of molecules to similar molecules). Since the molecules on the surface of the liquid are not surrounded by similar molecules on all sides, they are more attracted to their neighbors on the surface. Thus, if the surface tension of the reaction solution is increased, the solution will be less likely to break the surface tension and cross the hydrogen outlet composite 32.
    21/24
    This can be achieved in two ways. First, certain surfactants added to the reaction solution, such as alcohol-based compositions,
    used as antifreeze agents, or glycols used as antifoaming agents should be used sparingly or substituted as the surfactants reduce the surface tension of a solution. Alternatively, inorganic salts, such as sodium chloride, can be used to increase the surface tension of the solution. However, care must be taken that inorganic salt does not interfere with the ongoing reaction between sodium borohydride and water.í
    The surface tension of the reaction solution should be more than 73 dyne / cm, preferably more than 100 dyne / cm. Alternatively, the surface tension of the fuel reaction / mixture solution must be at least twice the surface energy of the membrane 34, and more preferably the surface tension of the fuel reaction / mixture solution must be at least
    2.5 times greater than the surface energy of the membrane 34.
    As noted above, contaminants can clog the membrane | fuel cell polymer electrolyte. In particular, basic contaminants (alkali) are known to permeate and reduce the effectiveness of the membrane;
    of polymer electrolyte through neutralization of highly acidic perfluorinated sulfonic acid polymer (NAFION® available from Dupont) used as the polymer electrolyte membrane. As an additional precaution against contaminants, especially alkali contaminants, such as sodium or potassium borate or sodium hydroxide, the outlet of the fuel system 10 and the obstruction of the fuel cell, it is preferable to locate a super acid filter 25 downstream of the composite. hydrogen outlet 32. Preferably, this filter may be located inside the hydrogen conduit 38, hydrogen chamber 40, valve 14, inside the pipeline or conduit from the fuel supply 10 to the fuel cell (not shown) , and / or ξ inside a separate housing located between 10í fuel supply and the fuel cell. If the filter is intended to be replaceable, it is preferable that it be incorporated in a separate housing or within detachable elements of the fuel supply or the <
    fuel.
    The super acid filter is made of an acidic material that, in one embodiment, is;
    substantially the same material as the polymer electrolyte membrane, ie NAFION®. Once the super acid filter of the current invention is located »
    22/24 upstream of the MEA, basic contaminants would be attracted to the filter and would be removed from the hydrogen gas before the hydrogen gas reaches the MEA.
    The filter material can also be made of sulfonated ion exchange and cation exchange resins that are strongly acidic, such as Amberlyst® by Rohm &, j
    Haas. Similar acid filters are described in state patents;
    United numbers 7,329,348 and 7,655,147, which are incorporated here by reference · in their entirety .:
    In the present embodiment, the polymer can be present as a continuous sheet (woven or non-woven), web, fabric, matrix, foam and / or gel; oui alternatively may be present as discrete pieces, such as nanoparticles, microcounts and / or powders, provided so that they do not impede the flow of hydrogen gas from the fuel supply 10 to the fuel cell. Filters formed of discrete pieces may be preferred given the increased surface area provided by such filter assemblies. The discrete pieces of the filter can be linked together using suitable binders that are resistant to hydrogen gas and potential contaminants. Alternatively, instead of a binder, the filter material may be contained within an open mesh fuel resistant grid, such as the matrix described in United States patent number 7,172,825, which is incorporated herein by reference in its entirety. In addition, as noted above, the acid filter material may be contained within a separate housing, preferably made of materials resistant to hydrogen gas and potential contaminants, the separate housing may contain screens on an inlet and an outlet port for prevent the filter material from escaping from the housing and act as a diffuser to slow the flow for ion exchange to occur. In addition, the density and permeability of the acid filter material determines the flow characteristics of the hydrogen gas through the superacid filter. <
    The basic contaminants contained within the hydrogen gas are;
    absorbed or attached to the acid filter material downstream of the hydrogen outlet composite 32 so that the hydrogen gas exiting the acid filter has less basic contaminants than the hydrogen gas entering the acid filter. The acidic filter must remove substantially all basic contaminants from the hydrogen gas. About 90% of basic contaminants can be removed, more preferably about 95% of basic contaminants can be removed.
    23/24 w
    ο removed, and most preferably about 99% of basic contaminants4 can be removed.
    A means of monitoring the removal of basic contaminants' known to those skilled in the art includes, but is not limited to, i monitoring the pH level of the hydrogen gas. Although pH is a measure of the acidic / basic nature of a solution, it can be adapted for gases by;
    exposing a moistened material, such as a cloth or paper, to the gas and then testing the pH of the exposed moistened material. The pH of the hydrogen gas can * act as an additional indicator of the removal of basic contaminants, the pH of the hydrogen gas leaving the acid filter should be 7, neutral, indicating the removal of all basic contaminants.
    In accordance with another aspect of the present invention, a sensor can be provided to ensure the effectiveness of the acid filter and to determine when the acid filter must be replaced. The sensor can be arranged as described in the '348 and' 147 patents discussed above. A pH sensor can preferably be located downstream of the acid filter and upstream of the MEA both I inside the fuel supply 10 (hydrogen chamber 40 and / or valve I
    14), a conduit, pipe or passage, from the fuel supply
    10, inside a separate housing that can contain the acid filter, or inside the fuel cell. The pH sensor can simply consist of moist litmus paper that changes color in response to the presence of a base placed within the fluid flow of the hydrogen gas that can be viewed from a transparent window in the fuel cell, separate housing and / or conduit for the fuel cell. A transformation in the color of litmus paper would be indicative of the need to replace the acid filter, or fuel supply 10, where the acid filter is integral to the fuel supply 10. In addition, the pH sensor can be electric in nature and connected to a controller, and is readable by the controller. The controller periodically reads the pH sensor, the controller displays a message or other signal, such as a visual or audible signal, for the user to change the acid filter, possibly on the next fuel supply fill. United States co-owned and concurrently deposited entitled “Gas generating with Starter Mechanism and Catalyst Shield” and having the power of attorney document number BIC-129 is incorporated here by reference in its entirety.
    24/24 <
    Someone commonly versed in the technique will appreciate that the assembly of>
    hydrophobic membrane of the present invention can be applied to gas generation fuel supplies in addition to the hydride system | chemical described above provided that the hydrogen gas needs to be separated from | an aqueous solution. Other embodiments of the present invention will be evident | those skilled in the art from considering the present specification and the practice of the present invention described here. It is intended that this | specification and examples are considered to be exemplary only with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof.
    权利要求:
    Claims (16)
    [1]
    1. Gas generating apparatus (10), characterized by the fact that it comprises:
    a reaction chamber (24);
    a fuel mixture inside the reaction chamber (24), where the fuel mixture reacts to produce a gas in the presence of a catalyst (58); and wherein the reaction chamber (24) contains a hydrogen outlet composite (32) comprising a hydrophobic lattice structure (36) disposed between two liquid-impermeable and gas-permeable membranes (34) and the gas produced flows through one or both membranes (34) and around the truss structure (36).
    [2]
    2. Gas generating apparatus, according to claim 1, characterized by the fact that the hydrophobic truss structure (36) has a static contact angle with water greater than 120 s .
    [3]
    3. Gas generating apparatus according to claim 1, characterized by the fact that the hydrophobic truss structure (36) has a surface energy of less than 40 mJ / m 2 .
    [4]
    4. Gas generating apparatus according to claim 3, characterized by the fact that the surface energy has a dispersive energy component less than 40 mJ / m 2 and a polar energy component less than 2.0 mJ / m 2 .
    [5]
    5. Gas generating apparatus according to claim 1, characterized by the fact that the hydrophobic truss structure (36) has a hysteresis measurement of the contact angle less than 40 s .
    [6]
    6. Gas generating apparatus according to claim 1, characterized by the fact that the hydrophobic truss structure (36) is a polymer.
    [7]
    Gas generating apparatus according to claim 6, characterized by the fact that the polymer comprises poly (tetrafluoroethene), polypropylene, polyamides, polyvinylidene, polyethylene, polysiloxanes, polyvinylidene fluoride, polyglactin, lyophilized dura, silicone, and / or rubber.
    [8]
    8. Gas generating apparatus according to claim 6, characterized by the fact that the polymer comprises polyvinylidene fluoride.
    Petition 870180124266, of 08/31/2018, p. 16/18
    2/3
    [9]
    9. Gas generating apparatus according to claim 1, characterized by the fact that the hydrophobic truss structure (36) is covered with a hydrophobic covering.
    [10]
    10. Gas generating apparatus according to claim 9, characterized by the fact that the hydrophobic coating comprises polyethylene, paraffin, oils, gelatins, pastes, greases, waxes, polydimethylsiloxane, poly (tetrafluorethene), polyvinylidene fluoride, copolymer of tetrafluoroethylenoperfluoroalkyl vinyl ether, fluorinated propylene ethylene, poly (perfluorooctylethylene acrylate), polyphosphazene, polysiloxanes, silica, carbon black, alumina, titania, hydrated silanes, and / or silicone.
    [11]
    11. Gas generating apparatus according to claim 9, characterized in that the hydrophobic coating comprises poly (tetrafluoroethene), copolymer of tetrafluoroethylene-perfluoroalkyl vinyl ether, fluorinated propylene ethylene, poly (perfluorooctyl acrylate), or polyphosphazene.
    [12]
    12. Gas generating apparatus, according to claim 1, characterized by the fact that the hydrophobic truss structure (36) is covered with a surfactant, in which the surfactant comprises perfluorooctanoate, perfluorooctane sulfonate, ammonium lauryl sulfate, laureth sulfate sodium, alkylbenzene sulfonate, a sulfated or sulfonated fatty material, alkyl sulfated aryloxypolialoxy alcohol salts, alkylbenzene sulfonates, sodium dodecylbenzene sulfonate, fluorosurfactants, sodium lauryl sulfate, sulfosuccinate mixture, sodium dioctyl sulfosuccinate, sodium sulfosuccinate sodium ethylhexyl sulfate, ethoxylated acetylenic alcohols, octyl high ethylene oxide phenols, nonyl phenyl high ethylene oxide, secondary and linear alcohols of high ethylene oxide, ethoxylated amines of any length of ethylene oxide, ethoxylated sorbitan ester, random EO / PO polymer in butyl alcohol, soluble block EO / PO copolymers water, and / or sodium lauryl ether sulfate.
    [13]
    13. Gas generating apparatus according to claim 12, characterized in that the surfactant includes a crosslinking agent.
    [14]
    14. Gas generating apparatus according to claim 1, characterized in that it additionally comprises a second hydrophobic lattice structure (30) between the reaction chamber and the hydrogen outlet composite.
    [15]
    15. Gas generating apparatus according to claim 1, characterized in that it is additionally comprised of a coarse filter (37) between the catalyst (58) and the hydrogen outlet composite (32).
    Petition 870180124266, of 08/31/2018, p. 17/18
    3/3
    [16]
    16. Gas generating apparatus according to claim 15, characterized by the fact that the coarse filter (37) is hydrophobic.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012033384B1|2018-12-26|gas generator apparatus.
    CA2695979C|2013-04-23|Reinforced solid polymer electrolyte composite membrane, membrane electrode assembly for solid polymer fuel cell, and solid polymer fuel cell
    JP6320754B2|2018-05-09|Method and device for restoring and maintaining superhydrophobicity under liquid
    JP2008270146A|2008-11-06|Fuel cell
    MXPA06001186A|2006-05-12|Fuel cartridge with flexible liner.
    KR20180095845A|2018-08-28|Gas diffusion electrode
    WO2014111053A1|2014-07-24|Diaphragm cloth for water electrolyzer and manufacturing method therefor
    WO2018139616A1|2018-08-02|Electrolytic bath, electrolysis device, electrolysis method, and method for producing hydrogen
    KR20210038648A|2021-04-07|Integrated composite membrane with continuous ionomer phase
    JP2011134600A|2011-07-07|Membrane electrode assembly and fuel cell
    JP5665631B2|2015-02-04|Fuel cell
    JP2019183252A|2019-10-24|Diaphragm, electrolytic bath, and hydrogen manufacturing method
    JP2009080964A|2009-04-16|Fuel cell
    JP2006294323A|2006-10-26|Proton conductive electrolyte membrane, manufacturing method of proton conductive electrolyte membrane, and polymer electrolyte fuel cell
    WO2021229963A1|2021-11-18|Electrolysis system and method for using same
    JP2011070991A|2011-04-07|Polymer electrolyte fuel cell single cell, production method thereof, and fuel cell stack having same
    RU2522617C2|2014-07-20|Composite nanomodified perfluorosulphocationite membrane and method of obtaining thereof
    JP5141365B2|2013-02-13|Method for producing membrane-electrode assembly
    JP6837130B2|2021-03-03|Anode, multi-pole electrolytic cell, hydrogen production method
    JP2022036814A|2022-03-08|How to operate the electrolyzer and the electrolyzer system
    JP2021172867A|2021-11-01|Water-electrolysis bipolar electrolytic cell
    WO2018139609A1|2018-08-02|Bipolar electrolytic cell, bipolar electrolytic vessel, and method for manufacturing hydrogen
    KR20180090298A|2018-08-10|Gas diffusion electrode and fuel cell
    Afra et al.2020|Experimental Investigation and Visualization of Water Transport in Gas-Diffusion Layer of Polymer Electrolyte Membrane Fuel Cell
    TW201711263A|2017-03-16|Solid electrolyte reinforcement member and solid electrolyte film including reinforcement member
    同族专利:
    公开号 | 公开日
    CA2804045A1|2012-01-05|
    JP2014159366A|2014-09-04|
    US20140120006A1|2014-05-01|
    EP2588228B1|2016-11-09|
    US9539558B2|2017-01-10|
    JP5507011B2|2014-05-28|
    JP2013537477A|2013-10-03|
    ZA201300244B|2014-06-25|
    US20150047506A1|2015-02-19|
    KR20130087000A|2013-08-05|
    EP2588228A2|2013-05-08|
    BR112012033384A2|2016-11-22|
    EP2588228A4|2014-04-16|
    US20110104021A1|2011-05-05|
    US8636826B2|2014-01-28|
    US9005344B2|2015-04-14|
    CA2804045C|2017-03-14|
    CN103068479A|2013-04-24|
    WO2012003111A3|2012-03-22|
    KR101375591B1|2014-03-18|
    WO2012003111A2|2012-01-05|
    CN103068479B|2015-07-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3416985A|1967-06-30|1968-12-17|Gen Electric|Method for making a gas transfer device|
    US3447286A|1967-08-02|1969-06-03|Gen Electric|Totally enclosed liquid permselective membrane|
    CA959628A|1970-11-06|1974-12-24|Glen C. Smith|Production of polysulfide|
    US4024229A|1970-11-06|1977-05-17|The Mead Corporation|Production of polysulfide with PTFE coated catalyst|
    US4261956A|1979-06-13|1981-04-14|Engelhard Minerals & Chemicals Corporation|Cartridge for gas generator|
    DE3332348C2|1983-09-08|1989-06-22|Kernforschungsanlage Juelich Gmbh, 5170 Juelich, De|
    US4797259A|1986-12-15|1989-01-10|Pall Corporation|Well-type diagnostic plate device|
    US5131927A|1991-04-22|1992-07-21|Union Carbide Industrial Gases Technology Corporation|Reactive treatment of composite gas separation membranes|
    US5997594A|1996-10-30|1999-12-07|Northwest Power Systems, Llc|Steam reformer with internal hydrogen purification|
    AUPO578997A0|1997-03-20|1997-04-17|Unisearch Limited|Hydrophobic film|
    EP0924162A3|1997-12-16|1999-10-20|dbb fuel cell engines GmbH|Membrane for the separation of hydrogen, methanol reformer using this membrane and process for its operation|
    JP3927318B2|1998-06-17|2007-06-06|伸幸 西宮|Method for producing composite hydrogen storage|
    AUPQ234599A0|1999-08-20|1999-09-16|Lamb, Robert Norman|Hydrophobic material|
    US6319306B1|2000-03-23|2001-11-20|Idatech, Llc|Hydrogen-selective metal membrane modules and method of forming the same|
    US6569227B2|2001-09-27|2003-05-27|Idatech, Llc|Hydrogen purification devices, components and fuel processing systems containing the same|
    US20030194368A1|2002-04-16|2003-10-16|Devos John A.|Hydrogen production system|
    US20030198862A1|2002-04-19|2003-10-23|Enernext|Liquid gallium alkaline electrolyte fuel cell|
    US7147955B2|2003-01-31|2006-12-12|Societe Bic|Fuel cartridge for fuel cells|
    WO2004103891A1|2003-05-23|2004-12-02|Gyros Patent Ab|Fluidic functions based on non-wettable surfaces|
    US7648792B2|2004-06-25|2010-01-19|Ultracell Corporation|Disposable component on a fuel cartridge and for use with a portable fuel cell system|
    US7762278B2|2003-07-29|2010-07-27|Societe Bic|Valves for fuel cartridges|
    US7172825B2|2003-07-29|2007-02-06|Societe Bic|Fuel cartridge with flexible liner containing insert|
    US7537024B2|2003-07-29|2009-05-26|Societe Bic|Fuel cartridge with connecting valve|
    US8002853B2|2003-07-29|2011-08-23|Societe Bic|Hydrogen-generating fuel cell cartridges|
    US8613297B2|2003-07-29|2013-12-24|Societe Bic|Fuel supply systems having operational resistance|
    US7617842B2|2003-07-29|2009-11-17|SOCIéTé BIC|Valves for fuel cartridges|
    US7674540B2|2003-10-06|2010-03-09|Societe Bic|Fuel cartridges for fuel cells and methods for making same|
    US7059582B2|2003-12-01|2006-06-13|Societe Bic|Fuel cell supply having fuel compatible materials|
    US7329348B2|2003-12-01|2008-02-12|Societe Bic|Fuel cell system including an ion filter|
    JP2008511403A|2004-08-27|2008-04-17|ドナルドソンカンパニー，インコーポレイティド|Impregnated filter element and manufacturing method thereof|
    US20060042210A1|2004-08-27|2006-03-02|Dallas Andrew J|Acidic impregnated filter element, and methods|
    US7297183B2|2004-09-20|2007-11-20|Idatech, Llc|Hydrogen purification devices, components, and fuel processing systems containing the same|
    GB0502227D0|2005-02-03|2005-03-09|Thermal Energy Systems Ltd|Gas separation and compresssion device|
    US7481858B2|2005-02-25|2009-01-27|Societe Bic|Hydrogen generating fuel cell cartridges|
    JP4855467B2|2005-07-01|2012-01-18|コミサリアアレネルジーアトミックエオゼネルジーアルテルナティブ|Hydrophobic surface coating with low wetting hysteresis, its deposition method, fine elements and uses|
    TW200717906A|2005-07-18|2007-05-01|Bic Soc|Fuel supply with improved connecting valve|
    TW200733460A|2006-02-15|2007-09-01|Toagosei Co Ltd|Method for preparing functional film|
    JP4953278B2|2006-03-08|2012-06-13|三菱マテリアル株式会社|Hydrogen permeation separation thin film with excellent hydrogen permeation separation performance|
    JP2008086888A|2006-09-29|2008-04-17|Fujifilm Corp|Passage structure, micro-device equipped with this structure and bubble removing method using this micro-device|
    US7803499B2|2006-10-31|2010-09-28|Gm Global Technology Operations, Inc.|Super-hydrophobic composite bipolar plate|
    US7791815B2|2007-03-13|2010-09-07|Varioptic S.A.|Dielectric coatings for electrowetting applications|
    US8105721B2|2007-04-04|2012-01-31|GM Global Technology Operations LLC|Microtextured fuel cell elements for improved water management|
    US7896273B2|2007-07-09|2011-03-01|Grah Dolores H|Ergonomic portable pill crusher tool and system|
    US20090078568A1|2007-07-24|2009-03-26|Rovcal, Inc.|On-demand hydrogen gas generation device having gas management system|
    EP2183801B1|2007-08-22|2017-11-08|Intelligent Energy Limited|Pressurized fuel cell cartridges|
    CN101849004A|2007-09-06|2010-09-29|德克萨斯理工大学|Use of iridoptin to induce toxicity in insects|
    BRPI0921811A2|2008-11-03|2016-01-12|SOCIéTé BIC|gas generating apparatus.|
    US8636826B2|2009-11-03|2014-01-28|Societe Bic|Hydrogen membrane separator|
    KR101649386B1|2008-12-23|2016-08-19|인텔리전트 에너지 리미티드|Hydrogen generator with aerogel catalyst|US8986404B2|2009-11-03|2015-03-24|Societe Bic|Gas generator with starter mechanism and catalyst shield|
    US8636826B2|2009-11-03|2014-01-28|Societe Bic|Hydrogen membrane separator|
    BRPI0921811A2|2008-11-03|2016-01-12|SOCIéTé BIC|gas generating apparatus.|
    US9005333B1|2011-06-20|2015-04-14|The United States Of America, As Represented By The Secretary Of Agriculture|Systems and methods for reducing ammonia emissions from and for recovering the ammonia liquid effluents|
    DE102011121018A1|2011-12-13|2013-06-13|Sartorius Stedim Biotech Gmbh|Hydrophobic or oleophobic microporous polymer membrane with structurally induced Abperl effect|
    WO2013102243A1|2012-01-07|2013-07-11|Technigro Australia Pty Ltd|A liquid applicator device|
    CN102641830B|2012-05-08|2013-09-25|吉林大学|Method for preparing self-healing super-hydrophobic coating by means of spraying technology|
    US9586183B2|2012-06-26|2017-03-07|Fujifilm Manufacturing Europe Bv|Membranes|
    GB2505202A|2012-08-21|2014-02-26|Inova Power Ltd|A hydrogen generation unit|
    US9771656B2|2012-08-28|2017-09-26|Ut-Battelle, Llc|Superhydrophobic films and methods for making superhydrophobic films|
    US20140154171A1|2012-12-04|2014-06-05|Eveready Battery Company, Inc.|Hydrogen Generation from Stabilized Alane|
    US9352258B2|2013-01-10|2016-05-31|Massachusetts Institute Of Technology|Liquid collecting permeable structures|
    US9680171B2|2013-03-15|2017-06-13|Intelligent Energy Limited|Methods for operating a fuel cell system|
    US9577273B2|2013-03-15|2017-02-21|Intelligent Energy Limited|Fluidic interface module for a fuel cell system|
    EP2969154A4|2013-03-15|2017-04-19|PECOFacet , Inc.|Modified surface energy non-woven filter element|
    US10193169B2|2013-03-15|2019-01-29|Intelligent Energy Limited|Fluidic interface module for a fuel cell system|
    KR20140123218A|2013-04-12|2014-10-22|삼성전자주식회사|Hydrogen separation membrane and device including hydrogen separation membrane|
    JP6499164B2|2013-06-06|2019-04-10|コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ．|Use of barrier contact media for chemical-chemical-optical sensors in transdermal applications|
    CN104591088A|2013-10-30|2015-05-06|扬光绿能股份有限公司|Fuel treatment device and hydrogen purification device thereof|
    US20150239773A1|2014-02-21|2015-08-27|Ut-Battelle, Llc|Transparent omniphobic thin film articles|
    DE102014003314A1|2014-03-08|2015-09-10|Hydac Fluidcarecenter Gmbh|Method for adapting a filter medium to specifiable parameters and preferably a filter medium produced by this method|
    US9876240B2|2014-04-07|2018-01-23|Intelligent Energy Limited|Multi-functional fuel cable|
    US20170218895A1|2014-05-29|2017-08-03|Ufi Innovation Center S.R.L.|A filter structure for fuel, a cartridge and a filter group|
    CA2969317A1|2014-12-24|2016-06-30|Dic Corporation|Hollow-fiber degassing module and inkjet printer|
    US9926213B2|2015-06-01|2018-03-27|The United States Of America, As Represented By The Secretary Of Agriculture|Systems and methods for recovering ammonium and phosphorus from liquid effluents|
    DE102015014496A1|2015-11-10|2017-05-11|Hydac Technology Gmbh|degassing|
    WO2017122486A1|2016-01-12|2017-07-20|富士フイルム株式会社|Gas separation membrane, method for producing gas separation membrane, gas separation membrane module and gas separation device|
    FR3072304B1|2017-10-18|2019-11-01|Commissariat A L'energie Atomique Et Aux Energies Alternatives|DEVICE FOR GENERATING GAS|
    EP3733592A4|2017-12-29|2021-07-28|Huis Ten Bosch Co., Ltd.|Hydrogen gas generating body|
    CN109735822B|2018-11-14|2021-04-09|北京北方华创微电子装备有限公司|Reaction chamber and semiconductor device|
    WO2021231938A1|2020-05-15|2021-11-18|Meso Scale Technologies, Llc.|Automation compatible removable lids and methods of use|
    法律状态:
    2018-01-30| B25A| Requested transfer of rights approved|Owner name: SOCIETE BIC (FR) , COMMISSARIAT A L'ENERGIE ATOMIQ |
    2018-05-29| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2018-10-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-12-26| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/829,827|2010-07-02|
    US12/829,827|US8636826B2|2009-11-03|2010-07-02|Hydrogen membrane separator|
    PCT/US2011/041227|WO2012003111A2|2010-07-02|2011-06-21|Hydrogen membrane separator|
    [返回顶部]