MX2008008741A - Hydrogen-generating fuel cell cartridges - Google Patents

Abstract

The present application is directed to a gas-generating apparatus and various pressure regulators or pressure-regulating valves. Hydrogen is generated within the gas-generating apparatus and is transported to a fuel cell. The transportation of a first fuel component to a second fuel component to generate of hydrogen occurs automatically depending on the pressure of a reaction chamber within the gas-generating apparatus. The pressure regulators and flow orifices are provided to regulate the hydrogen pressure and to minimize the fluctuation in pressure of the hydrogen received by the fuel cell. Connecting valves to connect the gas-generating apparatus to the fuel cell are also provided.

Description

CARTRIDGES THAT GENERATE HYDROGEN FOR CELLS OF FUEL CROSS REFERENCE TO RELATED REQUESTS This application is a continuation-in-part of United States Application No. 10 / 629,006, filed July 29, 2003, Application of the United States No. 11 / 067,167, filed on February 25, 2005, Application Provisional Application No. 60 / 689,538, filed June 13, 2005, and United States Provisional Application No. 60 / 689,539, filed June 13, 2005, all of which are incorporated herein by reference in their wholes.

BACKGROUND OF THE INVENTION Fuel cells are devices that directly convert chemical energy from reagents, ie fuel and oxidant, into direct current (DC) electricity. For a growing number of applications, fuel cells are more efficient than conventional power generation, such as the combustion of a fossil fuel as well as for portable energy storage, such as lithium-ion batteries.

In general, fuel cell technologies include a variety of different fuel cells, such as alkaline fuel cells, polymer electrolyte fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, fuel cells of solid oxide and enzyme fuel cells. The most important fuel cells today can be divided into several general categories, namely: (i) fuel cells that use compressed hydrogen (H2) as fuel; (ii) proton exchange membrane fuel (PEM) fuel cells using alcohols, for example, methanol (CH3OH), metal hydrides, for example, sodium borohydride (NaBH4), hydrocarbons, or other fuel reformed in hydrogen; (iii) PEM fuel cells that can consume non-hydrogen fuel directly or direct oxidation fuel cells; and (iv) solid oxide fuel cells (SOFCs) that directly convert hydrocarbon fuels into high temperature electricity.

The compressed hydrogen is generally maintained under high pressure and is therefore difficult to handle. Moreover, large storage tanks are typically required, and can not be manufactured small enough for consumer electronic devices. Conventional reformed fuel cells require reformers and other vaporization and auxiliary systems to convert fuels to hydrogen to react with the oxidant in the fuel cell. Recent advances make promising the refurbishing or reforming fuel cells for electronic devices for the consumer. The most common direct oxidation fuel cells are the direct methanol or DMFC fuel cells. Other direct oxidation fuel cells include direct ethanol fuel cells and direct tetramethyl orthocarbonate fuel cells. The DMFC, where methanol reacts directly with the oxidant in the fuel cell, is the simplest and potentially smallest fuel cell and also has a promising application of energy for electronic devices for the consumer. SOFC converts hydrocarbon fuels, such as butane, to high heat to produce electricity. The SOFC requires relatively high temperature in the range of 1000 ° C for the fuel cell reaction to occur.

The chemical reactions that produce electricity are different for each type of fuel cell. For the DMFC, the electrochemical reaction at each electrode and the overall reaction for a direct methanol fuel cell are described as follows: Hemirreaction at the anode: CH3OH + H20? C02 + 6H + + 6e ~ Hemirreaction at the cathode: 1, 502 + 6H + + 6e "? 3H20 The global reaction of the fuel cell: CH3OH + 1, 502? C02 + 2H20 Due to the migration of the hydrogen ions (H +) through the PEM from the anode to the cathode and due to the inability of the free electrons (e ~) to cross the PEM, the electrons flow through an external circuit, thus producing an electric current through the external circuit. The external circuit can be used to power many useful consumer electronic devices, such as mobile or cell phones, calculators, personal digital assistants, laptop computers, and power tools, among others.

The DMFC is discussed in U.S. Pat. Nros. 5,992,008 and 5,945,231, which are incorporated herein by reference in their entirety. Generally, the PEM is made of a polymer, such as Nafion available from DuPont, which is a perfluorinated sulfonic acid polymer having a thickness in the range of about 0.05 mm to about 0.50 mm, or other suitable membranes. The anode is typically made of a Teflonized carbon paper backing with a thin layer of catalyst, such as platinum-ruthenium, deposited thereon. The cathode is typically a gas diffusion electrode in which platinum particles are attached to one side of the membrane.

In another direct oxidation fuel cell, the borohydride fuel cell (DBFC) reacts as follows: Hemirreaction at the anode: BH4 ~ + 80H "? B02 ~ + 6H20 + 8e ~ Hemirreaction at the cathode: 202 + 4H20 + 8e "? 80H" In a metal hydride chemical fuel cell, sodium borohydride is reformed and reacts as follows: NaBH4 + 2H20? (heat or catalyst)? 4 (H2) + (NaB02) Hemirreaction at the anode: H2? 2H + + 2e ~ Hemirreaction at the cathode: 2 (2H + + 2e ") + 02? 2H20 Suitable catalysts for this reaction include platinum and ruthenium, and other metals. The hydrogen fuel produced from reforming sodium borohydride reacts in the fuel cell with an oxidant, such as 02, to create electricity (or a flow of electrons) and water as a byproduct. The secondary product sodium borate (NaB02) is also produced by the reforming process. A sodium borohydride fuel cell is discussed in U.S. Pat. No. 4,261,956, which is incorporated herein by reference in its entirety.

One of the most important characteristics for the application of fuel cells is the storage of fuel. Another important feature is to regulate the transportation of fuel out of the fuel cartridge to the fuel cell. To be commercially useful, fuel cells such as DMFC or PEM systems should have the ability to store enough fuel to meet the normal use of consumers. For example, for mobile or cell phones, for laptops, and for personal digital assistants (PDAs), fuel cells need to power these devices for at least as long as current batteries and, preferably, much more. Additionally, fuel cells should have easily replaceable or rechargeable fuel tanks to minimize or obviate the need for long recharges required by today's rechargeable batteries.

A disadvantage of known hydrogen gas generators is that once the reaction begins the gas generating cartridge can not control the reaction. Thus, the reaction will continue until the supply of reagents is exhausted or the source of the reagents is turned off manually.

Accordingly, there is a desire to obtain a hydrogen gas generating apparatus that is capable of self-regulating the flow of at least one reagent within the reaction chamber and another device to regulate the flow of fuel.

SUMMARY OF THE INVENTION The present application is directed to an apparatus that generates gas and various pressure regulators or valves that regulate the pressure. Hydrogen is generated inside the apparatus that generates gas and is transported to a fuel cell. The transport of a first fuel component to a second fuel component to generate hydrogen occurs automatically depending on the pressure of a reaction chamber within the gas generating apparatus. Pressure regulators are provided, which include flow orifices, to regulate the hydrogen pressure and to minimize the fluctuation in the pressure of the hydrogen received by the fuel cell. Connection valves are also provided to connect the gas generating apparatus to the fuel cell.

BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings, which form a part of the specification and should be read in conjunction therewith and in which similar reference numbers are used to indicate similar parts in the various views: FIG. 1 is a schematic cross-sectional view of an apparatus that generates gas in accordance with the present invention; FIG. IA is a partial enlarged cross-sectional view of a solid fuel container for use in the gas generating apparatus of FIG. 1; FIG. IB is a partial enlarged cross-sectional view of an alternative solid fuel container for use in the gas generating apparatus of FIG. 1; FIG. 1C is an alternative embodiment of FIG. IB; FIG. ID is a cross-sectional view of an alternative embodiment of a fluid conduit; FIG. 2A is a cross-sectional view of a shut-off valve or connection for use in the gas generating apparatus of FIG. 1 shown in the disconnected and closed position; FIG. 2B is a cross-sectional view of the shut-off valve shown in FIG. 2A shown in the connected and open position; FIG. 3 is a cross-sectional view of a pressure regulated fluid nozzle or valve for use in the gas generating apparatus of FIG. 1; FIG. 4A is a cross-sectional view of a valve that regulates the pressure for use in the gas generating apparatus of FIG. 1; FIG. 4B is an exploded perspective view of the valve regulating the pressure of FIG. 4A; FIG. 4C is a cross-sectional view of an alternative valve that regulates the pressure; FIG. 4D is an exploded perspective view of the valve regulating the pressure of FIG. 4C; FIG. 5A is a cross-sectional view of another valve that regulates the pressure connected to a first valve component of the shut-off valve of FIG. 2; FIGS. 5B-D are cross-sectional views showing the valve regulating the pressure and the first valve component with a second valve component of the shut-off valve in the disconnected, connected / closed and connected / open positions; FIG. 6A is a cross-sectional view of a valve that regulates the pressure for use in the gas generating apparatus of FIG. 1; FIG. 6B is an exploded view of the valve regulating the pressure of FIG. 6A; Y FIGS. 7A and 7B are cross-sectional views of an orifice of variable diameter for use with the valves that regulate the pressure of the present invention.

DETAILED DESCRIPTION OF THE INVENTION As illustrated in the accompanying drawings and discussed in detail below, the present invention is directed to a fuel supplier, which stores fuels for fuel cells, such as methanol and water, methanol / water mixture, methanol / water mixtures. varying concentrations, pure methanol, and / or methyl clathrates described in U.S. Patent Nos. 5,364,977 and 6,512,005 B2, which are incorporated herein by reference in their entirety. Methanol and other alcohols are usable in many types of fuel cells, for example, DMFC, enzyme fuel cells and reforming fuel cells, among others. The fuel supplier may contain other types of fuel cell fuels, such as ethanol or alcohols; metal hydrides, such as sodium borohydride; other chemical agents that can be reformed to hydrogen; and other chemical agents that can improve the performance or efficiency of fuel cells. Fuels also include electrolyte potassium hydroxide (KOH), which is usable with metal fuel cells or alkali fuel cells, and can be stored in fuel suppliers. For metal fuel cells, the fuel is in the form of zinc particles rising in fluid immersed in an electrolytic KOH solution, and the anodes within the cavities of the cell are particulate anodes formed by the zinc particles. The KOH electrolyte solution is disclosed in U.S. Published Patent Application No. 2003/0077493, entitled "Method of Using Fuel Cell System Configured to Provide Power to One or More Loads," published April 24, 2003. , which is incorporated here as a reference in its entirety. The fuels can also include a mixture of methanol, hydrogen peroxide and sulfuric acid, which flows through a catalyst formed on silicon chips to create a fuel cell reaction. Moreover, the fuels include a combination or mixture of methanol, sodium borohydride, an electrolyte, and other compounds, such as those described in U.S. Patent Nos. 6,554,877, 6,562,497 and 6,758,871, which are incorporated here as a reference in their totalities. Additionally, fuels include those compositions that are partially dissolved in a solvent and partially suspended in a solvent, described in U.S. Patent No. 6,773,470 and those compositions that include both liquid fuels and solid fuels, described in the Application of US Patent No. US 2002/0076602. Suitable fuels are also disclosed in co-pending U.S. Patent Application Serial No. 60 / 689,572, entitled "Fuels for Hydrogen-Generating Cartridges," filed June 13, 2005. These references also they are incorporated here as a reference in their totalities.

The fuels may also include a metal hydride such as sodium borohydride (NaBH4) and water, discussed above. The fuels may further include hydrocarbon fuels, including, but not limited to, butane, kerosene, alcohol, and natural gas, as set forth in U.S. Published Patent Application No.US 2003/0096150, entitled " Liquid Hereto-Interface Fuel Cell Device ", published on May 22, 2003, which is incorporated here as a reference in its entirety. Fuels can also include liquid oxidants that react with fuels. The present invention is therefore not limited to any type of fuel, electrolyte solutions, oxidant solutions or liquids or solids contained in the supplier or otherwise used by the fuel cell system. As used herein, the term "fuel" includes all fuels that can be reacted in fuel cells or in the fuel supplier, and include, but are not limited to, all of the above-mentioned suitable fuels, electrolyte solutions, solutions oxidizers, gases, liquids, solids, and / or chemical agents including additives and catalysts and mixtures thereof.

As used herein, the term "fuel supplier" includes, but is not limited to, disposable cartridges, rechargeable / reusable cartridges, containers, cartridges residing within the electronic device, removable cartridges, cartridges that are outside the electronic device, fuel tanks, refillable fuel tanks, other containers that store fuel and pipes connected to fuel tanks and containers. While describing a cartridge below in conjunction with the exemplary embodiments of the present invention, it is noted that these embodiments are also applicable to other fuel suppliers and the present invention is not limited to any particular type of fuel supplier.

The fuel supplier of the present invention can also be used to store fuels that are not used in fuel cells. These applications may include, but are not limited to, storing hydrocarbon and hydrogen fuels for gas turbine micro motors built on silicon chips, discussed in "Here Come the Microengines," published in The Industrial Physicist (Dec. 2001 / Jan. 2002) on pages 20-25. As used in the present application, the term "fuel cell" may also include micromotors. Other applications may include storing traditional fuels for internal combustion engines and hydrocarbons, such as butane for pocket or utility lighters and liquid propane.

Suitable known hydrogen generating apparatuses are disclosed in the co-pending US Patent Application of this same applicant, US No. 2005-0074643 Al and United States Patent Application Laid-Open No. 2005-0266281. and co-pending United States Patent Application Serial No. 11 / 066,573 filed February 25, 2005. The descriptive memories of these references are incorporated herein by reference in their totalities.

The gas generating apparatus of the present invention may include a reaction chamber, which may include a first optional reagent, and a reservoir having a second reagent. The first and second reagents can be a metal hydride, for example, sodium borohydride, and water. The reagents can be in gaseous, liquid, aqueous or solid form. Preferably, the first reagent stored in the reaction chamber is a metal hydride or solid metal borohydride with selected additives and catalysts such as ruthenium, and the second reagent is water optionally mixed with selected additives and catalysts. The water and the metal hydride of the present invention react to produce hydrogen gas, which can be consumed by a fuel cell to produce electricity. Other suitable reagents are disclosed in the parent application, previously incorporated previously.

Additionally, the gas generating apparatus may include a device or system that is capable of controlling the transport of a second reagent from the reservoir to the reaction chamber. The operating conditions within the reaction chamber and / or the reservoir, preferably a pressure within the reaction chamber, are capable of controlling the transport of the second reagent into the reservoir into the reaction chamber. For example, the second reagent in the reservoir can be introduced into the reaction chamber when the pressure within the reaction chamber is less than a predetermined value, preferably less than the pressure in the reservoir, and, more preferably less than the pressure in the reservoir. reservoir pressure by a predetermined amount. It is preferable that the flow of the second reagent from the reservoir to the reaction chamber is self-regulated. Thus, when the reaction chamber reaches a predetermined pressure, preferably a predetermined pressure above the pressure in the reservoir, the flow of the second reagent from the reservoir to the reaction chamber can be stopped to stop the production of hydrogen gas. Similarly, when the pressure of the reaction chamber is reduced below the reservoir pressure, preferably below the pressure in the reservoir by a predetermined amount, the second reagent can flow from the reservoir to the reaction chamber. The second reagent in the reservoir can be introduced into the reaction chamber by any known method including, but not limited to, pumping, osmosis, capillary action, differential pressure valves, other valve (s), or combinations thereof. The second reagent can also be pressurized with springs or pressurized gases and liquids. Preferably, the second reagent is pressurized with liquefied hydrocarbons, such as liquefied butane.

With reference to FIG. 1, an inventive fuel supply system is shown. The system includes an apparatus that generates gas 12 contained within a housing 13 and is configured to be connected to a fuel cell (not shown) by a fuel conduit 16 and a valve 34. Preferably, the fuel conduit 16 is started within the gas generating apparatus 12, and a valve 34 is in fluid communication with the conduit 16. The fuel conduit 16 may be a flexible tube, such as a plastic or rubber tube, or it may be a substantially rigid part connected to accommodation 13.

Within the housing 13, the gas generating apparatus 12 preferably includes two main compartments: a reservoir 44 of fluid fuel component containing a fluid fuel component 22 and a reaction chamber 18 containing a solid fuel component 24. The reservoir 44 and the reaction chamber 18 are insulated from each other until the production of a combustible gas, such as hydrogen, is desired by the reaction of the fluid fuel component 22 with the solid fuel component 24. The housing 13 is preferably divided. by an inner wall 19 to form the fluid reservoir 44 and the reaction chamber 18.

However, the reservoir 44 may preferably contain a coating, sac or similar fluid container 21 for containing the fluid or liquid fuel component 22 as shown. The fluid fuel component 22 preferably includes water and / or an additive / catalyst or other liquid reagents. Further fluid fuel components and additional suitable additives are discussed herein. Suitable additives / catalysts include, but are not limited to, anti-freeze agents (e.g., methanol, ethanol, propanol and other alcohols), catalysts (e.g., cobalt chloride and other known catalysts), pH regulating agents (eg. example, acids such as sulfuric acid and other common acids). Preferably, the fluid fuel component 22 is pressurized, such as by springs or by a pressurized / liquefied gas (butane or propane), although it may also be depressurized. When a liquefied hydrocarbon is used, it is injected into the reservoir 44 and is contained in the space between the liner 21 and the housing 13.

The reservoir 44 and the reaction chamber 18 are fluidly connected by a fluid transfer conduit 88. The fluid transfer conduit 88 is connected to a conduit 15, which is in fluid communication with the liquid fuel component 22 within the liner 21, and one or more ducts 17, which contact the liquid fuel component 22 with the solid fuel component 24. The hole 15 may be directly connected to the duct 88, or as shown in FIG. 1, can be connected to a channel 84 defined on the outer surface of a plug 86 that defines the conduit 88 therein. A hole 87 connects the surface channel 84 to the conduit 88. The function of the plug 86 is further defined below. The fluid transfer conduit 88 can also be a similar channel or vacuum formed in the housing 13, or an external pipe located outside the housing 13. Other configurations are also suitable.

The reaction chamber 18 is contained within the housing 13 and separated from the reservoir of the fluid fuel component 44 by the inner wall 19 and is preferably made of a fluid impenetrable material, such as metal, for example, stainless steel, or a material of resin or plastic. While mixing the liquid fuel component 22 and the solid fuel component 24 within the reaction chamber 18 to produce a fuel gas, such as hydrogen, the reaction chamber 18 also preferably includes a localized pressure relief valve 52. in the housing 13. The pressure release valve 52 is preferably a pressure operated valve, such as a safety valve or a flat-mouth valve, which automatically vents the produced fuel gas if the pressure inside the reaction chamber , P18, reaches a specified drive pressure. Another pressure relief valve may be installed on the fuel component fluid reservoir 44.

The solid fuel component 24, which may be powders, granules, or other solid forms, is disposed within a solid fuel container 23, which, in this embodiment, is a gas permeable bag, liner or bag. Fillers and other additives and chemical agents can be added to the solid fuel component 24 to improve its reaction with the liquid reagent. Preferably, additives that may be corrosive to the valves and other elements within the fluid transfer conduit 88, conduits 15 and 17 should be included with the solid fuel 24. The solid fuel component 24 is packaged within a solid fuel container. 23, which is preferably cinched or wrapped tightly around one or more fluid dispersing elements 89; for example with rubber or elastic bands, such as rubber or metal bands, with heat-shrunk wrappings, pressure-sensitive adhesive tapes or the like. The solid fuel component 23 can also be formed by thermoforming. In one example, the solid fuel container 23 comprises a plurality of films that are selectively perforated to control the flow of liquid reagent, gas and / or byproducts therethrough. Each fluid dispersing element 89 is in fluid communication with the conduits 17, within which the liquid fuel is transported to the solid fuel. The dispersion element 89 is preferably a hollow rigid tube-like structure made of a non-reactive material having openings 91 along its extension and its end to assist in the maximum dispersion of the fluid fuel component 22 to come into contact with the solid fuel component 24. Preferably, at least some of the openings 91 in the fluid dispersing element 89 include capillary fluid conduits 90, which are relatively small tubular extensions to disperse the fluid even more effectively through the solid fuel component 24. Capillary conduits 90 can be fillers, fibers, fibrils or other capillary conduits. Each fluid dispersing element 89 is supported within the reaction chamber 18 by a support 85, which is also the tip at which the fluid dispersing element 89 is connected to the conduits 17 and the fluid transfer conduit 88 .

The internal diameter of the fluid dispersing element 89 is shaped and sized to control the volume and speed at which the liquid fuel component 22 is transported therethrough. In certain instances, the effective internal diameter of the element 89 needs to be sufficiently small, so that the manufacture of such a small tube can be difficult and costly. In such instances, a larger tube 89a may be used with a smaller rod 89b disposed within the longer tube 89a to reduce the effective internal diameter of the longer tube.89a. The liquid fuel component is transported through the annular space 89c between the tube and the internal rod, as shown in FIG. ID.

In another embodiment, to increase the permeability of the liquid fuel component 22 through the solid fuel component 24, hydrophilic materials, such as fibers, ground fiber fibers or other wicking materials can be intermixed with the solid fuel component 24. The hydrophilic materials can form an interconnected network within the solid fuel component 24, but the hydrophilic materials do not need to be connected to each other within the solid fuel component to improve permeability.

The solid fuel container 23 can be made of many materials and can be flexible or substantially rigid. In the embodiment shown in FIG. ÍA, the solid fuel container 23 is preferably made of a single layer 54 of a liquid-permeable, gas-permeable material such as CELGARD0 and GORE-TEX®. Other gas-permeable, liquid impervious materials usable in the present invention include, but are not limited to, SURBENT® Polyvinylidene Fluoride (PVDF) having a pore size of from about 0.1 μm to about 0.45 μm, available from Millipore Corporation. The pore size of SURBENT® PVDF regulates the amount of liquid fuel component 22 or water leaving the system. Materials such as vent-type electronic material having 0.2 μm hydro, available from W. L. Gore & Associates, Inc., may also be used in the present invention. Additionally, sintered and / or ceramic porous materials having a pore size of less than about 10 μm, available from Applied Porous Technologies Inc., are also usable in the present invention. Additionally, or alternatively, gas-permeable materials, impervious to liquid disclosed in U.S. Patent Application of this same applicant, co-pending No. 10 / 356,793, are also usable in the present invention, all of which are incorporated herein by reference in their entireties. Using such materials allows the fuel gas, produced by mixing the fluid fuel component 22 and the solid fuel component 24, to vent through the solid fuel container 23 and into the reaction chamber 18 to transfer to the cell of fuel (not shown), while restricting the liquid and / or paste-like by-products of the chemical reaction to the interior of the solid fuel container 23.

FIG. IB shows an alternative construction for the solid fuel container 23. In this embodiment, the walls of the solid fuel container 23 are made of multiple layers: an outer layer 57 and an inner layer 56 separated by an absorbent layer 58. Both inner layer 56 and outer layer 57 may be made of any material known in the art capable of having at least one groove 55 formed therein. The slots 55 are openings in the inner layer 56 and outer layer 57 to allow the produced fuel gas to vented from the solid fuel container 23. To minimize the amount of fluid fuel component 22 and / or paste-like by-products that may come out through the slots 55, the absorbent layer 58 is positioned between the inner layer 56 and the outer layer 57 to form a barrier. The absorbent layer 58 can be made of any absorbent material known in the art, but is preferably capable of absorbing liquid while allowing gas to pass through the material. An example of such a material is cellulose paste containing sodium polyacrylate crystals; Such a material is commonly used in diapers. Other examples include, but are not limited to, fillers, nonwovens, papers and foams. As will be recognized by those in the art, the solid fuel container 23 may include any number of layers, which alternate between layers containing slots 55 and absorbent layers.

In an example shown in FIG. 1C, the solid fuel component 24 is enclosed in four layers 54a, 54b, 54c and 54d. These layers are preferably gas permeable and liquid impervious. Alternatively, each layer can be made of any material with a plurality of holes or slots 55, as shown, to allow the gas produced to pass through. Adsorbed layers 58 are disposed between adjacent layers 54a-d. In this embodiment, the flow path for the gas and byproducts produced, if present, is torturous to encourage more liquid fuel component 22 to remain in more contact. time with the solid fuel component 24 to produce more gas. As shown, while the innermost layer 54 is perforated on both sides, the next layer 54b is perforated on only one side. The next layer 54c is also perforated on one side, but opposite the perforated side of the layer 54b. The layer 54d is perforated on one side, but opposite the perforated side of the layer 54c and so on. Alternatively, instead of using partially perforated layers 54a-b that surround the solid fuel component 24, coatings or pouches made with a permeable portion and a non-permeable portion, with the permeable portion of a localized coating, may be used instead. opposite to the permeable portion of the next outer layer.

A fluid transfer valve 33 is preferably disposed within the fluid transfer conduit 88 to control the flow of the fluid fuel component 22 within the reaction chamber 18. The fluid transfer valve 33 can be any type of open valve One-way pressure, known in the art, such as a safety valve (as shown in FIG.1), a solenoid valve, a flat-mouth valve, a valve having a diaphragm that responds to pressure , which opens when a pressure threshold is reached. The fluid transfer valve 33 can be opened by user intervention and / or automatically actuated by the pressurized fluid fuel component 22. In other words, the fluid transfer valve 33 acts as an "on / off" switch to drive the transfer of the fluid fuel component 22 to the reaction chamber 18. In this embodiment, a fluid transfer valve 33 is a safety valve that includes a thrust spring 35 that pushes a ball 36 against a sealing surface 37. Preferably, a deformable sealing member 39 such as an O-ring is also included to secure a seal. The valve portions 33 that will be compressed to form a seal are shown as overlapping areas in FIG. 1. The plug 86, discussed above, is used in an exemplary method as an assembly valve 33. A channel is formed in the lower end of the housing 13 for the fluid transfer conduit 88. First, the spring 35 is inserted in this channel, followed by the ball 36 and the sealing member 39. The plug 86 is finally inserted in this channel to compress the spring 35 and press against the ball 36 and the sealing member 39 to form a seal with the valve 33 Parts of the plug 86, ie, the hole 87 and the peripheral channel 86, connect the fluid transfer conduit 88 to the conduit 15 to reach the liquid fuel component 22.

In this embodiment, the fluid transfer valve 33 is opened when the fluid pressure inside the reservoir 44 exceeds the pressure of the reaction chamber 18 by a predetermined amount. Since the reservoir 44 is preferably pressurized, this actuating pressure is immediately exceeded under the pressurization of the reservoir 44. To prevent the fluid transfer valve 33 from opening before the fuel gas is desired to be produced, a mechanism may be included. stop (not shown), such as a latch or pull tab, so that the first user of the fuel supplier can begin the transfer of the fluid fuel component 22 by releasing the stop mechanism. Alternatively, the chamber 18 is pressurized with an inert gas or hydrogen to equalize the pressure on the other side of the valve 33 within said predetermined amount.

The fuel conduit 16 is attached to the housing 13 as shown by any method known in the art. Optionally, a gas-permeable membrane, impermeable to liquid 32, can be fixed on the side of the duct 16 facing the reaction chamber. The membrane 32 limits the amount of liquids or by-products being transferred out of the gas generating apparatus 12 to the fuel cell via the fuel conduit 16. The filling materials or the foam can be used in combination with the membrane 32 to retain liquids or byproducts and to reduce obstructions. The membrane 32 may be formed of any liquid-permeable, gas-permeable material known to one skilled in the art. Such materials may 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) compositions, lyophilized hard material, or combinations thereof. The gas permeable member 32 may also comprise a gas permeable / liquid impermeable membrane that covers a porous membrane. Such a membrane 32 can be used in any of the embodiments discussed herein. The valve 34 can be any valve, such as a pressure operated valve (a safety valve or a flat-mouth valve) or a pressure regulating valve or pressure regulator described above. When valve 34 is a pressure operated valve (such as valve 33), fuel can not be transferred until P18 reaches a threshold pressure. The valve 34 can be positioned in the fuel conduit 16 as shown in FIG. 1, or it may be located away from the device that generates gas 12.

A shut-off valve or shut-off valve 27 may also be included, preferably in fluid communication with the valve 34. As shown in FIG. 2A, the connecting valve 27 is preferably a separable valve having a first valve component 60 and a second valve component 62. Each valve component 60, 62 has an internal seal. In addition, the first valve component 60 and the second valve component 62 are configured to form an intercomponent seal between them before they are opened. Is the connection valve 27 similar to the shut-off valves described in the parent application? 006 The connecting valve 27 is formed and sized to transport gas.

The first valve component 60 includes a housing 61 and the housing 61 defines a first flow path 79 through its interior. A first slidable body 64 is disposed within the first flow path 79. The slidable body 64 is configured to seal the first flow path 79 by pressing a sealing surface 69 against a deformable sealing member 70, such as an O-ring. , disposed in the first flow path 79 near a shoulder 82 formed by the configuration of the first flow path 79. The slidable body 64 is urged against the shoulder 82 formed on a second end of the first valve component 60 to secure the seal formed in the sealing surface 69. The sliding body 64 will remain in this pushing position until the first valve component 60 and the second valve component 62 are engaged. Alternatively, the slidable body 64 is made from an elastomeric material to form a seal and the sealing member 70 can be omitted.

An elongated member 65 extends from one end of the slidable body 64, as shown. The elongate member 65 is a needle-like extension projecting from the housing 61. The elongate member 65 is preferably covered with a tubular sealing surface 67. A void space or void is formed in the annular space between the elongate member 65 and the tubular sealing surface 67 for extending the first flow path 79 out of the housing 61. The tubular sealing surface 67 is connected to the elongate member 65 with optional spacers or ribs (not shown) so as not to close the first flow path 79. The elongated member 65 and the tubular sealing surface 67 are configured to be inserted into the second valve component 62.

The second valve component 62 is similar to the first valve component 60 and includes a housing 63 made of a substantially rigid material. The housing 63 defines a second flow path 80 through its interior. A second slidable body 74 is disposed within the second flow path 80. The slidable body 74 is configured to seal the second flow path 80 by pressing a sealing surface 75 against a deformable sealing member 73 near a shoulder 83. The Sliding body 74 is biased against the sealing position by a spring 76. The second valve component 62 is thus kept sealed until the first valve component 60 and the second valve component 62 are properly connected. Alternatively, the slidable body 74 is made of an elastomeric material to form a seal and the sealing member 73 can be omitted.

A lug 81 extends from the other end of the slidable body 74. The lug 81 is a needle-shaped extension and is held within the housing 63, and does not seal the second flow path 80. The lug 81 is also shaped and sized to engage with the elongated member 65 when the first valve component 60 and the second valve component 62 are engaged. A sealing member 71, such as an O-ring, may be positioned between the tab 81 and the interface end of the second valve component 62 so that a seal is formed around the tubular sealing surface 67 before and during the period when the first valve component 60 and the second valve component 62 are engaged.

To open the first valve component 60 and the second valve component 62 to form a single flow path through them, the first valve component 60 is inserted into the second valve component 62 or vice versa. While the two valve components 60, 62 are pushed against each other, the elongate member 65 engages with the pin 81, which press against each other to move the first slidable body 64 off the shoulder 82 and the second slidable body. 74 outside the shoulder 83. As such, the sealing members 70 and 73 are disengaged to allow fluid to flow through the first flow path 79 and the second flow path 80, as shown in FIG. 2B.

The first valve component 60 and the second valve component 62 are configured such that an inter-component seal is formed between the tubular sealing surface 67 and the sealing member 71, preferably before both the sealing surface 69 of the first body Sliding member 64 or sealing surface 75 of second slidable body 74 disengage from sealing members 70 and 73, respectively.

A first end of the housing 61 and a second end of the housing 63 preferably include tabs 92 and 87, respectively, for easy and secure insertion into the fuel conduit 16. Alternatively, the tabs 92, 87 can be any known safety connector in the art, such as threaded connectors or snap connectors. Additional configurations for connecting valves are more fully described in the parent application '006, also published as United States Patent Application US 2005/0022883 A1, previously incorporated by reference.

A stop ring 77 is positioned on the interface end of the second valve component 62. The stop ring 77 can also be a sealing member, such as an O-ring, a weatherstrip, a viscous gel, or the like. The stop ring / sealing member 77 is configured to engage a front sealing surface 78 on the first valve component 60 to provide another inter-component seal.

One of the valve components 60 and 62 may be integrated with a fuel supply, and the other valve component may be connected to a fuel cell or a device energized by the fuel cell. Any valve component 60 and / or 62 may also be integrated with a flow or pressure regulator or pressure regulating valve, discussed below.

Before the first use, the fluid transfer valve 33, as shown in FIG. 1, is opened both by removing a tab or latch for pulling or removing the initial pressurized gas in chamber 18. The pressurized fluid fuel component 22 is transferred into the reaction chamber 18 via the fluid transfer conduit 88 to react with the solid fuel component 24. The pressurized fluid fuel component 22 passes through an orifice 15 and into the fluid transfer conduit 88. While the fluid transfer valve is open, the fluid fuel component 22 is continuously fed into the reaction chamber 18 to create the fuel gas which is then transferred to the fuel cell or device through the fuel conduit 16. In one embodiment, to stop the production of additional gas, the transfer valve fluid 33 can be closed manually.

In another embodiment, one of several pressure regulating devices may be employed within the gas generating apparatus 12 to allow automatic and dynamic control of gas generation. This is generally achieved by allowing the pressure in the reaction chamber P18 to control the incoming flow of the fluid fuel component 22 using the fluid transfer valve 33 and / or one or more valves that regulate the pressure 26, as described in FIG. continuation .

In one embodiment, as shown in FIG. 3, the valve regulating the pressure 26 is positioned in the support 85 or conduits 17 and generally acts as an inlet port between the fluid transfer conduit 88 and the fluid dispersion element 89. The valve that regulates the pressure 26 it can also be positioned in the conduit 88 or conduit 15. One end of the fluid dispersion element 89 is connected to a carrier 99, which is slidably disposed within the support 85. Near where the fluid transfer conduit 17 ends, a end of the carrier 99 is in contact with a balloon seal 93 surrounding an injector 94. The injector 94 is fluidly connected to the conduit 17, and the balloon seal 93 is configured to control the fluid connection between them. As shown in FIG. 3, the valve 26 is in an open configuration, so that the fluid will be able to flow from the fluid transfer conduit 88 into the injector 94.

The other end of the carrier 99 is connected to a pressure operated system which includes a diaphragm 96 exposed to the reaction chamber 18 and the pressure of the reaction chamber P? 8, an elastic 95 which pushes the diaphragm 96 towards the chamber reaction 18, and a support plate 98. The carrier 99 is engaged with the support plate 98. The diaphragm 96 can be any type of pressure sensitive diaphragm known in the art, such as a thin sheet of rubber, metal or elastomeric When the pressure of the reaction chamber P18 increases due to the production of fuel gas, the diaphragm 96 tends to deform and expand towards the base of the support 85, but is held in place by the force F95 of the elastic 95. When the pressure of the reaction chamber P18 exceeds the thrust force F95 provided by the elastic 95, the diaphragm 96 pushes the support plate 98 towards the base of the support 85. While the carrier 99 engages with the support plate 98, the carrier 99 it also moves towards the base of the support 85. This movement deforms the balloon seal 93 to seal the connection between the fluid transfer conduit 88 and the injector 94, thereby cutting the flow of fluid fuel component 22 towards the chamber of reaction 18.

While the valve 33 (shown in FIG.1) is open, the operation of the gas generating apparatus 12 can therefore occur in a dynamic and cyclic manner to provide fuel on demand to the fuel cell. When the valve 33 is initially opened, the pressure of the reaction chamber P18 is low, then the valve that regulates the pressure 26 is completely open. The valves 33 and 26 can have substantially similar pressure differentials for opening and closing, and in the preferred embodiment one valve can act as a backup for the other. Alternatively, the opening pressure differentials may be different, that is, the differential pressure for opening or closing the valve 33 may be higher or lower than that of the valve 26, to provide additional ways to control the flow through the conduit 88. .

While the fluid fuel component 22 is fed into the reaction chamber via valve 26 and / or valve 33 and fluid dispersion elements 89, the reaction between the fluid fuel component 22 and the solid fuel component 24 starts generating combustible gas. The pressure in the reaction chamber P18 increases gradually with the accumulation of the fuel gas until a threshold pressure P34 is reached and the valve 34 is opened to allow gas flow through the fuel conduit 16. The fuel gas is then transferred outside the reaction chamber 18. While this process can reach a steady state, the gas production can exceed the gas transfer through the valve 34, or, alternatively, the valve 34 or another downstream valve can be closed manually by a user or electronically closed by the fuel cell or the host device. In such a situation, the pressure of the reaction chamber Pi8 can continue to grow until the pressure of the reaction chamber P18 exceeds the force F95 supplied by the elastic 95. At this point, the diaphragm 96 deforms towards the base of the support 85, thus leading the carrier 99 towards the base of the support 85. As described above, this action causes the balloon seal 93 to seal the connection between the fluid transfer conduit 88 and the injector 94. As it can not be introduced component of additional fluid fuel 22"inside the reaction chamber 18, the production of fuel gas decreases and eventually stops. The valve 33 can also be closed by P? 8, that is, when P? 8 exceeds P44 or when the difference between Pie and P44 is less than a predetermined amount, for example, the amount of force exerted by the elastic 35.

If the valve 34 is still open, or if it is re-opened, the fuel gas is then transferred out of the reaction chamber 18, so that the pressure of the reaction chamber P? 8 decreases. Eventually, the pressure of the reaction chamber P18 decreases below the force F95 provided by the elastic 95, which pushes the support 98 towards the reaction chamber 18. While the support 98 engages with the carrier 99, the carrier 99 also it slides into the reaction chamber 18, which allows the balloon seal 93 to return to its unsealed configuration. Consequently, additional fluid fuel component 22 begins to flow through the injector 94 and into the reaction chamber via the fluid dispersion element 89. New fuel gas is produced, and the pressure of the reaction chamber P18 increases once plus. Similarly, when P18 is less than P4, or is less than P4 by a predetermined amount, then valve 33 is opened to allow the fluid fuel component 22 to flow.

This dynamic operation is summarized below in Table 1, when the valve 33 is manually opened, or when the valve 33 and the valve 26 have substantially the same differential pressure of operation so that one valve backs the other valve.

Table 1: Pressure Cycle of the Apparatus that Generates Gas with the Valve 33 Open or Omitted Condition Balance of the State of Production of Pressure Valve that regulates gas, pressure in the Chamber of Table 2: Pressure Cycle of the Apparatus that Generates Gas with the Valve 26 Open or Omitted With reference to FIGS. 4A and 4B, another regulator or valve that regulates the appropriate pressure 126 is shown. The pressure regulating valve 126 may be positioned within the fluid transfer conduit 88, similar to the position of the fluid transfer valve 33 as shown in FIG. 1. The pressure regulating valve 126 is preferably located in series with the fluid transfer valve 33, or the pressure regulating valve 126 can replace the fluid transfer valve 33. The valve 126 can be used with other cartridges or hydrogen generators and can act as a pressure regulator. In another embodiment, the regulating valve 126 can replace the valve 34. The regulating valve 126 may be connected or be a part of the fuel cell or the device that houses the fuel cell. The regulating valve 126 can be located both upstream and downstream of the valve components 60 and 62 of the connecting or closing valve 27.

Similar to the pressure regulating valve 26, discussed above, the pressure regulating valve 126 includes a pressure sensitive diaphragm 140. The diaphragm 140 is similar to the diaphragm 96 described above. In this embodiment, however, the diaphragm 140 is encased between two housing elements, a valve housing 146 and a valve cover 148, and has a hole 149 formed through its center, as best seen in FIG. 4A. Additionally, a vacuum 129 is formed in the interface of the valve housing 146 and the valve cover 148 to allow the diaphragm 140 to move or flex due to the pressure difference between the inlet pressure in the channel 143, the pressure outlet on channel 145, and a reference pressure, Pref- Valve housing 146 has an internal configuration defining a flow path through regulator valve 126. Specifically, channels 143 and 145 are formed in the housing valve 146, where the channel 143 is exposed to the inlet pressure and the channel 145 is exposed to the outlet pressure. In addition, a vent channel 141 is formed in the valve cover 148 so that the diaphragm 140 is exposed to the reference pressure that can be atmospheric pressure.

The channel 143 of the valve housing is configured to slidably receive a valve rod 142. The channel 143 of the valve housing is configured to narrow to or close to the interface of the valve housing 146 and the valve cover 148 to form a shoulder 137. The valve rod 142 is preferably a unitary element having a thin rod portion 138 and a cap 131. This configuration allows the thin rod portion 138 to extend through the narrow portion of the valve housing channel 143 while the cover 131 comes to rest against the shoulder 137. As such, the cover 131 and the shoulder 137 both include sealing surfaces for closing the flow path through the valve 126 in the shoulder 137 when the cover 131 is accommodated against it . Additionally, a washer 147 secures the valve stem 142 within the hole 149 in the diaphragm 140, thereby creating a seal and a secure connection between the diaphragm 140 and the valve stem 142. Therefore, as the diaphragm 140 moves, the valve stem 142 also moves so that the cap 131 is supported and disengaged against the shoulder 137 thus opening and closing the valve 126.

When the pressure regulating valve 126 is positioned in the conduit 88 of the gas generating apparatus 12, the pressure of the reaction chamber P18 supplies the outlet pressure in the channel 145 and the pressure of the reservoir P44 provides the inlet pressure in the reservoir. channel 143. When the pressure of reaction chamber Pi8 is low, valve 126 is in an open configuration as shown in FIG. 4A, where the diaphragm is un-flexed and the cap 131 of the valve stem 142 is not supported on the shoulder 137. In this manner, the fluid fuel component 22 (shown in FIG. 1) flows through the valve. 126 and within the fluid dispersion element 89 (shown in FIG.1), assuming that the fluid transfer valve is also open. The introduction of the fluid fuel component 22 into the solid fuel component 24 initiates the production of fuel gas, which is filtered through the container 23 of the solid fuel (shown in FIG. 1) and into the reaction chamber 18, as described above. The pressure of the reaction chamber P18 starts to grow. The pressure within the conduit 145 grows with P18 and moves into the vacuum 129. The pressure in the reaction chamber P18 increases gradually with the formation of fuel gas until the threshold pressure P34 and the valve 34 (shown in FIG. 1) opens to allow gas flow through the fuel conduit 16 (shown in FIG 1). The fuel gas is then transferred outside the reaction chamber 18. While this process can reach a steady state, the gas production can exceed the gas transfer through the valve 34, or, alternatively, the valve 34 or the valve 27 can be closed manually or electronically. In such a situation, the pressure of the reaction chamber Pi8 can continue to grow until the pressure of the reaction chamber P18 exceeds Pref, P44 or (P44 less than Pref) and to <3 that no more gas is transferred from the reaction chamber 18 with the valve 34 (or valves 34, 37) closed. As a result of the increase in pressure of the reaction chamber P? 8, the diaphragm 140 deforms towards the valve cover 148. If the pressure of the reaction chamber P18 continues to increase, the diaphragm 140 deforms towards the cover of the diaphragm. valve 148 to an extent such that the cap 131 of the valve stem 142 fits against the shoulder 137 to seal the valve 126. In this way, the flow of the additional fluid fuel component is stopped, which decreases and eventually stops the production of combustible gas in the reaction chamber 18.

If the valve 34 is kept open, the fuel gas is transferred out of the reaction chamber 18, which reduces the pressure of the reaction chamber Pi8. This reduction in the pressure of the reaction chamber P18 is transferred to the vacuum 129 via the conduit 145, and the diaphragm 140 begins to return to its original configuration as the pressure difference across it starts to equalize, ie P18 , P44 and ref begin to swing. As the diaphragm 140 moves back into position, the valve stem 142 also moves, thus disengaging the cover 131 of the shoulder 137 to re-open the valve 126. Thus, the fluid fuel component 22 is free to flow once more into the reaction chamber 18. This cycle, which is similar to the cycle described in Table 1, is repeated until the fluid transfer valve 33, the fluid transfer valve 34, or another Downstream valve is closed by the operator or controller.

The pressure at which the regulator / valve 126 opens or closes can be adjusted by adjusting the length of the valve stem or the space that the cover 131 travels between the open and closed position and / or by adjusting Pref • The rod 138 is shaped and dimensioned to be movable relative to the washer 147 to adjust the length of the rod 138. The longer the length of the rod 138 between the washer 147 and the lid 131, the higher the pressure needed to close the valve 126.

In the embodiment where the pressure regulating valve 126 is located downstream of the reaction chamber 18, for example, when the valve 126 replaces the valve 34 or when the valve 126 is connected to the fuel cell or to the device that houses the fuel cell, P18 becomes the inlet pressure in channel 143 and the outlet pressure in channel 145 is the pressure of the hydrogen fuel gas that would be received by the fuel cell. Preferably, the outlet pressure is substantially constant or is maintained within an acceptable range, and the reference pressure, Pref, is selected or adjusted to provide such an outlet pressure. In other words, Pref is adjusted so that when the inlet pressure exceeds a predetermined amount, the diaphragm 140 closes to minimize a high or fluctuating outlet pressure in the channel 145.

In FIGS. 4C and 4D, another embodiment of a pressure regulating valve 226 is shown. The pressure regulating valve 226 is similar to the pressure regulating valve 126 discussed above, in which a valve housing 248 is attached to a pressure relief valve 226. valve 247. An inlet 243 is formed in the valve cover 247, while a pressure regulated outlet 245 is formed in the valve housing 248. A hole 251 is formed in a lower portion of the valve cover 247. Preferably, the hole 251 is slightly offset from the longitudinal axis of the valve that regulates pressure 226.

A deformable cap cylinder 250 is encased and retained between the valve cap 247 and the valve housing 248. The capped cylinder 250 includes an upper end 259, a lower end 287, and a hole or channel 201 formed therethrough. The capped cylinder 250 is made of any deformable, elastomeric material known in the art, such as rubber, urethane, or silicone. The capped cylinder 250 functions similar to the pressure sensitive diaphragm.

The upper end 259 is positioned adjacent the valve cover 247 so that, when no fluid flows through the pressure regulating valve 226, the upper end 259 is ramping against a lower surface of the valve cover 247. The edges of the upper end 259 are fixed in position so that even if the remainder of the upper cover 259 flexes, the edges remain stationary and sealed.

The lower end 287 is positioned adjacent the valve housing 248. A vacuum 202 is formed in the valve housing 248 and is positioned directly below the lower end 287 to allow the lower end 287 to flex freely. Preferably, the lower end 287 has a different diameter than the upper end 259, as explained below.

A stop ring 253 made of a substantially rigid material surrounds the capped cylinder 250. The stop ring 253 defines a hole 241 for connecting to a second vacuum 203 • formed circumferentially between the capped cylinder 250 and the stop ring 253 with a pressure Reference Pref • The portion 205 of the second vacuum 203 is configured to extend partially along and over the lower cover 287.

To regulate the pressure, the gas or inlet liquid enters the valve which regulates the pressure through the inlet 243 and passes inside the hole 251. The hole 251 can be a channel or circular ring defined on the lid 247. The end upper 259 seals the hole 251 until the pressure exerted by the gas or inlet liquid from the inlet 243 reaches a threshold to deform the upper end 259. When the gas deforms the upper end 259, the deformation travels through the body of the cylinder 250 to also deform lower end 287. Once the upper end 259 is deformed, the gas is able to pass through hole 251, through capped cylinder 250 and regulated outlet outlet 245.

Since the forces applied to the capped cylinder 250 are the products of the pressure applied by the area exposed to that pressure, the forces acting on the capped cylinder 250 can be summarized as follows: Input Force + Reference Force «? Output Force (P at entry 243 • Top end area 259) + (Pref • Port area 205) «? (P to exit 245 • Lower end area 287) When the output force is greater than the input and reference forces, then the valve that regulates the pressure is closed, and when the output force is less than the input and reference forces, valve 226 is opened. that, in this embodiment, the output force has to counter-balance both input and reference forces, the area of the lower end 287 is advantageously made larger than the area of the upper end 259, as shown, so that the Output force can be larger without increasing the outlet pressure. By varying the areas of the ends 259 and 287 and the portion 205, the balance of forces on the capped cylinder 250 can be controlled and the pressure differential required to open and close the valve 226 can be determined.

Since the reference pressure Pref tends to press down on the lower end 287, this additional pressure can lower the threshold pressure to start the flow, i.e., the reference pressure Pref is relatively high to assist the gas in deforming the cylinder capped 250. The reference pressure Pref can be adjusted higher or lower to regulate .more the pressure of the gas leaving outlet 245.

FIGS. 5A-D show a combination of a pressure regulating valve 326 that is used with a connecting or cutting valve 27. FIG. 5A shows a pressure regulating valve 326 being coupled to be in fluid communication with the valve component 60 of the connecting valve 27. The pressure regulating valve 326 is similar to the pressure regulating valves 126 and 226 described above, and has a diaphragm 340 subjected to thrust by a spring. The diaphragm 340 is supported by a first piston 305, which is being urged by a spring 306 against a second piston 307. The first piston 305 is opposite the second piston 307 being urged by the spring 309, which pushes the piston 307 against the piston 305. A ball 311 is disposed between the spring 309 and the second piston 307.

The springs 306 and 309 oppose each other, and, by balancing the forces exerted by the two springs, the outlet pressure of the channel 313 can be determined. The spring 309 does not act on or have any effect on the spring 66 of the spring component. valve 60. When the valve component 60 is open to mate with the valve component 62, shown in FIGS. 5B-5D, hydrogen fuel gas or other fluids flow through valve component 60 and into inlet 315. If the fluid is hydrogen gas, then hydrogen is transported to the fuel cell. A flow path through the valve 326 is established from the inlet 315 through the spring 309, around the ball 311, through the space between the piston 307 and the shoulder 337 of the housing 346, through the orifice 337 of the housing 346, and through hole 348 and outlet 313. In this embodiment, the space between piston 307 and shoulder 337 is normally open to allow fluid to pass therethrough.

The pressure of the incoming fluid through the inlet 315 or the pressure at the outlet 313, if they are high enough, can exceed the resultant force between the springs 306 and 309 and move the diaphragm 340 and the pistons 305 and 307 to the left as shown in FIG. 5A. The spring 309 then pushes the ball 311 to the sealing member 319 to seal the valve 326. To ensure that the fuel flow follows the preferred path, a sealing member 317 can be provided.

In one embodiment, the force applied on the diaphragm 340 and the pistons 305 and 307 can be adjusted. The spring 306 is adjustable by a rotational adjustment member 320, which is secured by a threaded locknut 321. The rotational adjustment member 321 further compresses, in one direction, the spring 306 to increase the force applied to the diaphragm and the pistons, and, rotating in the opposite direction, expands the spring 306 to decrease the force applied on the diaphragm and the pistons. Additionally, a reference pressure, Pref, can be applied to the channel 323 behind the piston 305 to apply another force on the piston 305.

FIG. 5B shows the pressure regulator / valve 326 connected to the valve component 60 with the valve component 62 not connected to the valve component 60. FIG. 5C shows the regulator / valve 326 with the valve components 60 and 62 partially engaged, but without flow path established through the valve components 60 and 62. FIG. 5D shows the regulator / valve 326 with the valve components 60 and 62 fully engaged with a flow path established through the valve components 60 and 62. In one embodiment, the valve component 62 can be connected to the conduit 16 of the valve. gas generating apparatus 12, shown in FIG. 1, and the regulator 326 replaces the valve 34 and is connected to the fuel cell or the device. On the other hand, the valve component 62 can be connected to the fuel cell or the device and the regulator 326 and the valve component 60 are connected to the gas generating apparatus or the fuel supplier. If a high pressure suddenly emerges through the valve 326, the diaphragm 340 limits the amount of fuel that can be transported through the conduit 313.

In FIGS. 6A and B shows another embodiment of a valve that regulates the pressure 426. The valve that regulates the pressure 426 is similar to the valve that regulates the pressure 226, discussed above, except that the valve 426 has a slide piston 450 in place of the flexible capped cylinder 350. The valve 426 has a valve housing 448 coupled to a valve cover 447. An inlet 443 is formed in the valve cover. 447, while a regulated pressure outlet 445 is formed in a valve housing 448. A hole 451 is formed in a lower portion of the valve cover 447. Preferably, the hole 451 is slightly offset from the longitudinal axis of the valve that regulates the pressure 426. The hole 451 may comprise a plurality of holes formed as a ring such that the inlet pressure is applied , uniformly on the slide piston 450.

A slide piston 450 is slidably disposed between the valve cover 447 and the valve housing 448. The slide piston 450 includes an upper portion 459 having a first diameter, a lower portion 487 having a second diameter that is preferably larger than the diameter of the upper portion 459, and a hole 401 formed therethrough. The slide piston 450 is made of any rigid material known in the art, such as plastic, elastomer, aluminum, a combination of elastomer and a rigid material or the like.

A space 402 is formed in the valve housing 448 to allow the piston 450 to slide between the cover 447 and the housing 448. A second vacuum 403 is formed between the slide piston 450 and the valve housing 448. The vacuum 403 is connected with a reference pressure Pref • A vacuum portion 405 is positioned opposite the lower end 487, so that a reference force can be applied to the piston 450.

An upper portion 459 is positioned adjacent the valve cover 447 so that, when the output force exceeds the input force and the reference force, as discussed above, the upper portion 459 is raking against a lower surface of the Valve cap 447 for closing valve 426, as shown in FIG. 6A. When the output force is less than the input and reference forces, the piston 450 is urged into the housing 448 to allow fluids, such as hydrogen gas, to flow from the inlet 443 through the hole (s) (FIG. s) 451 and hole 401 to outlet 445. Again, as discussed above with reference to valve 226, the surface areas of ends 459 and 487, and space 405 can be varied to control opening and closing of the valve 426.

As will be recognized by those in the art, any of these valves can be used, either alone or in combination, to provide regulation based on the pressure of the gas generating apparatus 12. For example, the valve 126, 226, 326 or 426 it can be used instead of valve 26, 33 or 34.

In accordance with another aspect of the present invention, a pre-selected orifice is provided in conjunction with valve 126, 226, 326 and / or 426 to regulate the pressure or volume, of the fluid, eg, hydrogen gas, which exits from the outlet of these valves. For example, with reference to valve 326, shown in FIG. 5A, the hole 348 is positioned upstream of the outlet 313. In one aspect, the orifice 326 acts as a flow restrictor to ensure that when the inlet pressure at the inlet 315 or inside the pressure regulating valve 326 is high, the orifice 348 sufficiently limits the outflow at 313 so that the high pressure can act on the diaphragm 340, moving it to the left, to close the valve 326. An advantage of using the flow reducer / orifice 348 is when the outlet 313 is open at a low pressure, for example, atmospheric pressure, or open to a chamber that can not contain the pressure, the orifice 348 helps ensure that the diaphragm 340 senses the inlet pressure.

The orifice 348 can also control the flow of fluid out of the outlet 313. When the input pressure range at the inlet 315 or internal pressure of the valve regulating the pressure 326 is known and the desirable flow rate is also known, applying equations of flow for compressible fluid flow, such as Bernoulli's equations (or using non-compressible fluid flow equations as a close approximation thereof), the diameter (s) of hole 348 can be determined.

Additionally, the diameter of the effective diameter of the hole 348 may vary according to the inlet pressure at the inlet 315 or the internal pressure of the valve 326. Such a variable orifice is described in the United States Published Application of this same applicant. , co-pending No. US 2005/0118468, which is incorporated herein by reference in its entirety. The reference x 468 discloses the valve (252) shown in FIGS. 6 (a) - (d) and 7 (a) - (k) and the corresponding texts of that reference. The various embodiments of this valve (252) have a reduced effective diameter when the flow pressure is high and have an increased effective diameter when the flow pressure is lower.

In FIGS. 7A and 7B, another variable orifice 348 is shown. In this embodiment, the orifice 348 or other fluid conduit has a flat mouth valve 350 disposed therein with a nozzle 352 facing the direction of fluid flow, as shown. The pressure of the fluid acts on the neck 354 and when the pressure is relatively low, the diameter of the nozzle 352 is relatively large, and when the pressure is relatively high, the diameter of the nozzle 352 is relatively small to further restrict flow.

When the pressure is sufficiently high, the nozzle 352 can be closed.

Some examples of fuels that are used in the present invention, include, but are not limited to, hydrides of elements of Groups IA-IVA of the Periodic Table of the Elements and mixtures thereof, such as alkali metal hydrides or alkaline, or mixtures thereof. Other compounds, such as alkali metal aluminum hydrides (alanatos) and alkali metal borohydrides can also be employed. More specific examples of metal hydrides include, but are not limited to, lithium hydride, lithium aluminum hydride, lithium borohydride, sodium hydride, sodium borohydride, potassium hydride, potassium borohydride, magnesium hydride, hydride calcium, and salts and / or derivatives thereof. Preferred hydrides are sodium borohydride, magnesium borohydride, lithium borohydride, and potassium borohydride. Preferably, the hydrogen-containing fuel comprises the solid form of NaBH 4, Mg (BH 4) 2, or clathrate methanol compound (MCC) which is a solid and includes methanol. In solid form, NaBH4 does not hydrolyze in the absence of water and therefore improves the life of the cartridge. However, the aqueous form of the hydrogen-containing fuel, such as aqueous NaBH, can also be used in the present invention. When an aqueous form of NaBH 4 is used, the chamber containing the aqueous NaBH 4 also includes a stabilizer. Exemplary stabilizers may include, but are not limited to, metals and metal hydrides, such as alkali metal hydrides. Examples of such stabilizers are described in U.S. Patent No. 6,683,025, which is incorporated herein by reference in its entirety. Preferably, the stabilizer is NaOH.

The solid form of the hydrogen-containing fuel is preferred over the liquid form. In general, solid fuels are more advantageous than liquid fuels because liquid fuels contain proportionally less energy than solid fuels and liquid fuels are less stable than solid counterpart fuels. Accordingly, the most preferred fuel for the present invention is sodium borohydride powder or agglomerated powder.

In accordance with the present invention, the fluid fuel component is preferably capable of reacting with a solid fuel containing hydrogen in the presence of an optional catalyst to generate hydrogen. Preferably, the fluid fuel component includes, but is not limited to, water, alcohols, and / or diluted acids. The most common source of fluid fuel component is water. As indicated above and in the formulation that follows, the water can react with the hydrogen-containing fuel, such as NaBH 4 in the presence of an optional catalyst to generate hydrogen.

X (BH4) and + 2H20 - > X (BO) 2 + 4H2 Where X includes, but is not limited to, Na, Mg, Li and all alkali metals, and y is an integer.

The fluid fuel component also includes optional additives that reduce or increase the pH of the solution. The pH of the fluid fuel component can be used to determine the rate at which hydrogen is produced. For example, additives that reduce the pH of the fluid fuel component result in a higher rate of hydrogen generation. Such additives include, but are not limited to, acids, such as acetic acid and sulfuric acid. Conversely, additives that increase the pH can decrease the rate of reaction to the point where hydrogen is almost not developed. The solution of the present invention can have any pH value less than 7, such as a pH of from 1 to about 6 and, preferably, from about 3 to about 5.

In some exemplary embodiments, the fluid fuel component includes a catalyst that can initiate and / or facilitate the production of hydrogen gas by increasing the rate at which the fluid fuel component reacts with the fuel component. The catalyst of these example embodiments includes any shape or size that is capable of promoting the desired reaction. For example, the catalyst may be small enough to form a powder or it may be as large as the reaction chamber, depending on the desired surface area of the catalyst. In some exemplary embodiments, the catalyst is a catalytic bed. The catalyst may be located within the reaction chamber or next to the reaction chamber, as long as at least one of either the fluid fuel component or the solid fuel component is contacted with the catalyst.

The catalyst of the present invention may include one or more transition metals of Group VIIIB of the Periodic Table of the Elements. For example, the catalyst may include transition metals such as iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), osmium (Os ) and iridium (Go). Additionally, in the catalyst of the present invention, transition metals of Group IB, ie copper (Cu), silver (Ag) and gold (Au), and of Group IIB, ie zinc (Zn), can also be used. ), cadmium (Cd) and mercury (Hg). The catalyst may also include other transition metals including, but not limited to, scandium (Se), titanium (Ti), vanadium (V), chromium (Cr) and manganese (Mn). The transition metal catalysts useful in the present invention are described in U.S. Patent No. 5,804,329, which is incorporated herein by reference in its entirety. The preferred catalyst of the present invention is CoCl2.

Some of the catalysts of the present invention can be defined generically with the following formula: MaXb where M is the cation of the transition metal, X is the anion, and "a" and "b" are integers from 1 to 6 as needed to balance the charges of the transition metal complex.

Suitable cations of the transition metals include, but are not limited to, iron (II) (Fe2 +), iron (III) (Fe3 +), cobalt (Co2 +), nickel (II) (Ni2 +), nickel (III) (Ni3 + ), ruthenium (III) (Ru3 +), ruthenium (IV) (Ru4 +), ruthenium (V) (Ru5 +), ruthenium (VI) (Ru6 +), ruthenium (VIII) (Ru8 +), rhodium (III) (Rh3 +), rhodium (IV) (Rh4 +), rhodium (VI) (Rh6 +), palladium (Pd2 +), osmium (III) (0s3 +), osmium (IV) (0s4 +), osmium (V) (0s5 +), osmium (VI) ( 0s6 +), osmium (VIII) (0s8 +), iridium (III) (Ir3 +), iridium (IV) (Ir +), iridium (VI) (Ir6 +), platinum (II) (Pt2 +), platinum (III) (Pt3 +) , platinum (IV) (Pt4 +), platinum (VI) (Pt6 +), copper (I) (Cu +), copper (II) (Cu2 +), silver (I) (Ag +), silver (II) (Ag2 +), gold (I) (Au +), gold (III) (Au3 +), zinc '(Zn2 +), cadmium (Cd2 +), mercury (I) (Hg +), mercury (II) (Hg +), and the like.

Suitable anions include, but are not limited to, hydride (H ~), fluoride (F "), chloride (Cl"), bromide (Br "), iodide (I"), oxide (O2-), sulfide (S2") ), nitride (N3"), phosphide (P4"), hypochlorite (CIO "), chlorite (C102"), chlorate (C103"), perchlorate (C104"), sulfite (S032"), sulfate (S042"), hydrogen sulfate (HS04"), hydroxide (OH"), cyanide (CN "), thiocyanate (SCN "), cyanate (OCN"), peroxide (022"), manganate (Mn042"), permanganate (Mn0 ~), dichromate (Cr2072"), carbonate (C032"), hydrogen carbonate (HC03"), phosphate ( P042"), hydrogen phosphate (HP0"), dihydrogen phosphate (H2P04"), aluminate (Al2042"), arsenate (As043"), nitrate (N03"), acetate (CH3COO"), oxalate (C2042")., And the like. A preferred catalyst is cobalt chloride.

In some exemplary embodiments, the optional additive, which is in the fluid fuel component and / or in the reaction chamber, is any composition that is capable of substantially preventing the freezing of or reducing the freezing point of the fuel component. fluid and / or the solid fuel component. In some exemplary embodiments, the additive may be an alcohol-based composition, such as an anti-freeze agent. Preferably, the additive of the present invention is CH3OH. However, as stated above, any additive capable of reducing the freezing point of the fluid fuel component and / or the solid fuel component can be used.

Other embodiments of the present invention will become apparent to those skilled in the art, from consideration of the present specification and practice of the present invention disclosed herein. For example, any of the valves herein may be operated by an electronic controller such as a microprocessor. One component of a valve can be used with another valve. Also, a pump may be included for pumping the fluid fuel component into the reaction chamber. It is the intention that the present specification and examples are considered only as examples, the true scope and spirit of the invention being indicated by the following claims and equivalents thereof.

Claims (45)

CLAIMS We claim:

1. An apparatus that generates gas comprising: a reaction chamber containing a solid fuel component; a reservoir that contains a liquid fuel component; a fluid path for introducing the liquid fuel component into the reaction chamber to produce a gas; means for controlling the flow of the liquid fuel component within the reaction chamber; and means for controlling the flow of gas from the reaction chamber.

2. An apparatus that generates gas comprising: a gas permeable container containing a solid fuel component; a reservoir that contains a liquid fuel component; and a fluid path to introduce the liquid fuel component into the gas permeable container to produce a gas.

3. The gas generating apparatus of claim 2, wherein the gas permeable container is disposed in a reaction chamber.

4. The gas generating apparatus of claim 3, wherein the gas permeable container is impermeable to liquid.

5. The gas generating apparatus of claim 4, wherein the gas permeable container comprises an absorbent layer disposed between an inner layer and an outer layer, wherein at least one of the inner layer and outer layer comprises a liquid impermeable material that it has at least one opening formed therethrough.

6. The gas generating apparatus of claim 5, wherein the solid fuel component comprises hydrophilic material.

7. The gas generating apparatus of claim 4, wherein the gas permeable container comprises at least one fluid dispersing tube.

8. The gas generating apparatus of claim 7, wherein the fluid dispersing tube comprises at least one capillary or wick extension.

9. The gas generating apparatus of claim 3, wherein the reservoir is pressurized.

10. The gas generating apparatus of claim 9, wherein the fluid path comprises a valve that opens and closes relative to the pressures of the reaction chamber and the reservoir.

11. The gas generating apparatus of claim 2 further comprising a valve that regulates the pressure.

12. The gas generating apparatus of claim 11, wherein the valve regulating the pressure comprises a diaphragm responsive to the pressure.

13. The gas generating apparatus of claim 12, wherein the diaphragm is subjected to thrust by an energy storage element.

14. The gas generating apparatus of claim 13, wherein the energy storage element comprises a spring.

15. The gas generating apparatus of claim 13, wherein the energy storage element comprises a reference pressure.

16. The gas generating apparatus of claim 12, wherein the diaphragm is in communication with the reaction chamber.

17. The gas generating apparatus of claim 12, wherein the diaphragm is connected to a sealing member.

18. The gas generating apparatus of claim 17, wherein the sealing member is adjustable to vary the pressure sealing the valve that regulates the pressure.

19. A valve for connecting a fuel supplier to a device comprising: a first valve component connectable to one of either a fuel supplier or a fuel cell, and a second valve component connectable to the other of either a fuel supplier or a fuel cell, wherein each valve component comprises a housing and a slidable internal body subjected to thrust, wherein the sliding inner body is pushed against a sealing surface to form an internal seal on each valve component, in wherein during the connection the first valve component and the second valve component form an inter-component seal at least before the inner seal is opened to create a fluid flow path through the valve, and wherein at least one valve component comprises an extension member that extends out of the housing and is configured to be in sealed inside the other valve component.

20. The valve of claim 19, wherein the extension member comprises a rod and the fluid flow path includes the space between the extension member and the rod.

21. A valve that regulates the pressure comprising a movable member that responds to the pressure disposed in a housing member, wherein the movable member responsive to the pressure responds to an inlet pressure and an outlet pressure, wherein the valve that The pressure regulator is fluidly connected to an apparatus that generates gas and at least one of the inlet and outlet pressures is a pressure of the gas generating apparatus.

22. The valve regulating the pressure of claim 21, wherein the movable member responsive to the pressure is also exposed to a reference pressure.

23. The valve regulating the pressure of claim 21, wherein the movable member responsive to the pressure comprises a diaphragm wherein an outer edge of the diaphragm is fixed to the housing.

24. The valve regulating the pressure of claim 21, wherein the movable member responsive to the pressure comprises a slidable piston.

25. The valve regulating the pressure of claim 21, wherein the movable member responsive to pressure comprises pistons subjected to opposing thrust.

26. The valve that regulates the pressure of the claim 24, wherein the movable member responsive to the pressure further comprises a diaphragm wherein an outer edge of the diaphragm is fixed to the housing.

27. The valve regulating the pressure of claim 23, wherein the diaphragm is subjected to thrust by an energy storage device.

28. The valve regulating the pressure of claim 21, wherein the outlet pressure is the pressure of a reaction chamber within the gas generating apparatus.

29. The valve regulating the pressure of claim 21, wherein the inlet pressure is the pressure of a reservoir within the gas generating apparatus.

30. The valve regulating the pressure of claim 21, wherein the outlet pressure is the pressure in a fuel cell.

31, The valve that regulates the pressure of claim 21, wherein the inlet pressure is the pressure of a reaction chamber within the gas generating apparatus.

32, The valve regulating the pressure of claim 21, wherein the movable member responsive to pressure is connected to a sealing member.

33, The valve regulating the pressure of claim 32, wherein the sealing member is adjustable to vary the pressure sealing the valve that regulates the pressure.

34. The valve that regulates the pressure of claim 21, wherein a connecting valve connects the valve that regulates the pressure to the gas generating apparatus.

35. The valve that regulates the pressure of the claim 34, wherein the connecting valve comprises two valve components and wherein each valve component has an internal seal.

36. The valve that regulates the pressure of the claim 35, wherein the valve components form an inter-component seal before at least one of the internal seals is opened.

37. The valve that regulates the pressure of the claim 36, wherein the inter-component seal is formed between a rod extending from a valve component and a sealing member of the other valve component.

38. The valve that regulates the pressure of the claim 37, wherein the sealing member comprises an O-ring.

39. The pressure regulating valve of claim 37, wherein the gas from the gas generating apparatus is transported within the rod.

40. The valve that regulates the pressure of claim 39, wherein the gas is transported through an annular space within the rod.

41. The valve regulating the pressure of claim 21, wherein at least two springs act on the movable member that responds to pressure in opposite directions.

42. The valve that regulates the pressure of claim 21 further comprising a flow reducer in fluid communication with an outlet of the valve that regulates the pressure.

43. The valve that regulates the pressure of the claim 42, wherein the flow reducer comprises an orifice.

44. The valve that regulates the pressure of the claim 43, wherein the orifice has a variable effective diameter.

45. The valve that regulates the pressure of the claim 44, wherein the orifice comprises a flat mouth valve.