WO2009023535A2 - Dispositifs et procédés de génération améliorée d'hydrogène - Google Patents

Dispositifs et procédés de génération améliorée d'hydrogène Download PDF

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Publication number
WO2009023535A2
WO2009023535A2 PCT/US2008/072523 US2008072523W WO2009023535A2 WO 2009023535 A2 WO2009023535 A2 WO 2009023535A2 US 2008072523 W US2008072523 W US 2008072523W WO 2009023535 A2 WO2009023535 A2 WO 2009023535A2
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Prior art keywords
hydrogen
siloxene
catalyst
water
article
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PCT/US2008/072523
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English (en)
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WO2009023535A3 (fr
Inventor
Raymond E. Paggi
Michael D. Redemer
Robert S. Hirsch
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Hydrogen Solutions International
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Publication of WO2009023535A2 publication Critical patent/WO2009023535A2/fr
Publication of WO2009023535A3 publication Critical patent/WO2009023535A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention generally relates to compositions and methods for generation of hydrogen using silicon based compounds. More particularly, the invention discloses a composition of matter, processes and devices for generating hydrogen using such compounds as siloxene, organosilanes or polysilanes, and catalysts which result in generating hydrogen as needed safely and efficiently.
  • This invention disclosure describes compositions and processes for use in generation of hydrogen using silicon-based compounds as a starting material. This disclosure also describes devices that can be used to generate hydrogen as needed from silicon-based compounds.
  • This invention provides a method for generating hydrogen on an as needed basis in a controlled manner, by contacting an article, such as a tablet, a bar or a sphere comprising siloxene with water and a catalyst.
  • the catalyst may be an organic amine or a strong base such as sodium hydroxide, potassium hydroxide or calcium hydroxide which may be incorporated into the tablet, bar or sphere.
  • the tablet may further include a high molecular mass polymer such as carbopol which acts as a binder.
  • the invention also provides methods and devices for generating hydrogen on an as needed basis in a safe and controlled manner, by contacting the siloxene powder or tablet or an organosilane or polysilane gel with an organic amine catalyst or a strong base and the condensate from the exhaust stream of an internal combustion engine, thus providing a highly efficient NO x reducing agent .
  • the invention also provides methods for generating hydrogen directly by contacting water and a starting material comprising a metal suicide (e.g., calcium suicide), with a catalyst, such as KOH or NaOH, wherein hydrogen is produced as needed by altering the reaction conditions, such as conducting the reaction at a temperature of greater than 13O 0 F to enhance gravimetric efficiency.
  • a metal suicide e.g., calcium suicide
  • a catalyst such as KOH or NaOH
  • Figure 1 is a flow diagram of the overall hydrogen generation process where a siloxene tablet or organosilane or polysilane gel is used as a fuel.
  • Figure 2 is a schematic representation of a cartridge-type hydrogen generator for light duty diesel applications using siloxene tablets applications.
  • Figure 3 is a schematic representation of an exhaust gas condensate unit for use with internal combustion engines.
  • the present invention describes that the silicon-based compounds in the above referenced patent applications can be made into an article (such as a tablet, a bar, or a sphere) or a gel, providing higher levels of efficiency, control and safety.
  • the tablet format increases the volumetric density of the materials, eliminates the need for space-occupying and energy- consuming pumps required to move powders.
  • the tablet also provides the option of incorporating a catalyst for certain applications, for example, where a separate catalyst storage vessel would have functional or cost limitations.
  • the tablet format also eliminates the need for a powder cartridge and facilitates the re-fueling process.
  • the longest dimension of a tablet can range in size from less than one quarter inch to more than two inches.
  • a larger bar or sphere with a size of greater than five inches may be used in place of a tablet, further minimizing the need to move materials and further improving the economics based on volumetrics of an integrated unit.
  • tablets or bars having high aspect ratios of may be used, because the higher the surface area, the quicker and more complete the reaction.
  • a catalyst may be incorporated directly within the article eliminating the need for separate mixing devices while providing an increase in the rate of reaction.
  • Methods and devices described in the present invention may also provide hydrogen as needed by mixing the water condensate from the exhaust of an internal combustion engine with the siloxene, organosilane or polysilane-based tablets and a catalyst.
  • This method reduces the volume, mass and cost of materials required and also provides the opportunity to improve engine combustion efficiency by lowering the temperature of the exhaust gases returned to the combustion chamber and also providing the opportunity for the addition of a small amount of hydrogen which has been shown to be effective in improving combustion and lowering harmful exhaust emissions.
  • calcium suicide may be utilized (optionally, in combination with a catalyst such as KOH or NaOH) as a direct hydrogen source, in particular at higher temperatures, to generate hydrogen as shown in the general reaction scheme
  • Ranges can be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10" is also disclosed.
  • references in the specification and concluding claims to parts by mass of a particular element or component in a composition denotes the mass relationship between the element or component and any other elements or components in the composition or article for which a part by mass is expressed.
  • X and Y are present at a mass ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • a mass percent (mass %) of a component is based on the total mass of the formulation or composition in which the component is included.
  • gravimetric efficiency means the yield of hydrogen per unit mass of starting material. A high gravimetric efficiency is achieved by optimization of starting materials, catalysts, and processes.
  • the term "aspect ratio” refers to a ratio between the longest and the shortest dimension of an article; for example, for tablets it means the ratio between the diameter and the thickness of the tablet, and for bars - a ratio between the length and the thickness.
  • the term "as needed basis” used interchangeably with the term “on demand” refers to the ability to control the reaction conditions wherein the amount of hydrogen produced is controlled.
  • the term “in a controlled manner” means the amount of hydrogen produced can be varied in a predictable manner by alteration of the reaction conditions.
  • reaction conditions includes, but is not limited to, temperature, feed rate, stoichiometry and back pressure.
  • the term "substituted" is contemplated to include all permissible substituents of organic or inorganic compounds.
  • the permissible substituents can include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of compounds.
  • Illustrative substituents include, for example, those described below.
  • the permissible substituents can be one or more and the same or different for appropriate compounds.
  • the heteroatoms, such as nitrogen can have hydrogen substituents and/or any permissible substituents . of organic or inorganic compounds described herein which satisfy the valences of the heteroatoms. This disclosure is not intended to be limited in any manner by the permissible substituents of compounds.
  • a 1 ,” “A 2 ,” “A 3 ,” and “A 4 " are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents.
  • alkyl refers to substituted and unsubstituted C 1 -C 30 straight chain or branched saturated aliphatic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, tert-buty ⁇ , sec-butyl, and the like.
  • aryl as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like.
  • silane as used herein is represented by the formula H-SiA 1 A 2 A 3 , where A 1 , A 2 , and A 3 can be, independently, hydrogen, or a substituted or unsubstituted alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, or cycloalkenyl.
  • silane means a silicon analogue of an alkane, alkoxyl, alkene, alkyne, or aryl where one, more than one, or all carbon atoms in those structures are replaced by a silicon atom and at least one of the silicon atoms is covalently bonded to a hydrogen atom.
  • organosilane refers to the same basic structure and is generally used interchangeably with the term “silane,” with the proviso that in an organosilane at least one of A 1 , A 2 , and A 3 is not hydrogen.
  • a silane can be analog of an unsubstituted alkane and have the general formula of Si n H 2n + 2 .
  • Such structures are typically named according to regular nomenclature where the word "silane" is preceded by a numerical prefix (di, tri, tetra, etc.) for the number of silicon atoms in the molecule.
  • Si 2 H 6 is disilane
  • Si 3 H 8 is trisilane, and so forth.
  • SiH 4 is referred to as simply "silane.”
  • Silanes can also be named like any other inorganic compound; for example, silane can be named silicon tetrahydride, disilane can be named disilicon hexahydride, and so forth. Silanes that are substituted with a hydroxyl group are called silanols.
  • a silane can be substituted with one or more organic groups such as an alkane, alkene, alkyne, or aryl.
  • organic groups such as an alkane, alkene, alkyne, or aryl.
  • organosilanes Such structures, which contain a silicon-carbon bond, are typically referred to as organosilanes. Examples of some well known organosilanes include te/t-butyldimethylsilane, trimethylsilane, phenylsilane, and the like. Silanes with more than one silicon atom can also be referred to as polysilanes.
  • silane is intended to include organosilanes, polysilanes, branched silanes, cyclic silanes, substituted silanes (e.g., silanols), and unsubstituted silanes, though in some instances these structures can be referred to specifically herein.
  • a radical of such a silane can be specifically referred to as a "silyl,” but throughout the disclosure silyls are also intended to be included within the meaning of silanes.
  • amine or "amino” as used herein are represented by the formula NA 1 A 2 A 3 , where A 1 , A 2 , and A 3 can be, independently, hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
  • a catalyst is defined as substance that changes the speed or yield of a chemical reaction without being itself substantially consumed or otherwise chemically changed in the process.
  • polymer is defined as being inclusive of homopolymers and copolymers.
  • homopolymer is defined as a polymer derived from a single species of monomer.
  • copolymer is defined as a polymer derived from more than one species of monomer, and includes terpolymers, and quaterpolymers.
  • compositions, methods, and devices that improve the overall system efficiency and hydrogen yield when using organosilanes, polysilanes and siloxene as fuel.
  • hydrogen generating articles are provided.
  • shape of articles that can be used include cuboidal or discal (i.e., shaped as tablets), spherical, elliptical or lenticular.
  • the shape of the hydrogen generating articles there are no limitations on the shape of the hydrogen generating articles, and additional shapes into which the hydrogen generating articles can be shaped include also oblate spherical, prolate spherical, cylindrical (including right circular cylindrical), convex (including plano-convex), pyramidal (including truncated pyramidal), conical (including frustoconical), and ogival shape.
  • oblate spherical prolate spherical
  • cylindrical including right circular cylindrical
  • convex including plano-convex
  • pyramidal including truncated pyramidal
  • conical including frustoconical
  • ogival shape Those having ordinary skill in the art can determine the required shape and can devise a method of shaping the hydrogen generating articles in any other desired way.
  • the hydrogen generating articles are shaped as tablets or bars having the ranges of dimensions as discussed above.
  • tablets or bars having high aspect ratios such as between about 3: 1 and about 20: 1 .
  • Tablet compositions comprising siloxene can be used to generate hydrogen, which in turn can be used in (e.g., supplied to) a fuel cell or an internal combustion engine or exhaust after treatment catalyst.
  • the siloxene is produced from suicides or from rice straw and has the basic formula SIeH 3 ⁇ O 3-O (such as Si 6 H 6 Os) with a varying amount of repeating units and layers.
  • the size of the siloxene aggregates can range from under one micron to over sixty microns in addition to higher amounts of oxygen.
  • the siloxene powder is typically mixed with an organic solvent, such as methanol or isopropanol, a polymer which acts as the binder, and an amine activator, i.e., a base which acts to crosslink active sites on the polymer.
  • a catalyst can be also optionally incorporated to facilitate the hydrogen liberation reactions when contacted with water.
  • the polymer is a high molecular mass hydrocarbon that unfolds at temperatures higher than ambient.
  • the polymer comprises carbonyl functionalities along the length of the chain.
  • one or more synthetic polymeric thickeners from a family known under the trade name Carbopol ® may find particular utility in this composition.
  • An amino activator that is used to crosslink with the active sites on the polymer can be at least one organic amine that ranges from a C 3 amines to an amine with 50 or more carbons (C50), such as C3 to Ci 6 amines.
  • the amino activator used to crosslink the polymer may also serve as a catalyst.
  • the amino activator used to crosslink the polymer may also serve as a catalyst.
  • propylamine may be utilized as such a catalyst.
  • suitable catalysts include NaOH, KOH, Ca(OH) 2 and CaH 2 .
  • the quantity of propylamine catalyst may be between about 0.1 % and about 5 % by mass.
  • compositions are compressed at high pressures (500 to 20,000 psi) (i.e., approximately 3.4 MPa to 137.9 MPa) to form an article in the desired shape described above, e.g., a tablet, a bar or a sphere.
  • the materials are then dried to remove the organic solvent.
  • the so formed tablet, bar or sphere can liberate hydrogen when combined with water, in the mass ratio of water to siloxene that is between about 1 : 1 and about 10: 1 , in the presence of a catalyst at temperatures ranging from 3O 0 F to 212 0 F (i.e., approximately from -I 0 C to 100 0 C), as long as the water is a liquid.
  • the embodiments of the present invention provide for the ratio of the binder polymer to siloxene that may be between about 0.1 % and about 1.0 % by mass of the siloxene, and for the ratio of the amine activator to siloxene that is between about 0.1 % and about 1.0 % by mass of the siloxene.
  • An amount of the amine greater than about 0.5 % may cause the release of hydrogen prematurely, due to the initiation of the reaction generating hydrogen using only trace amount of water that is contained in the solvents used, i.e., methanol or isopropanol.
  • An amount of either the amine or the binder lower than 0.1% may not be sufficient to ensure effective binding of the siloxene tablet.
  • a gel may also be utilized when a liquid organosilane or polysilane is selected for a given application.
  • Carbopol or similar compounds may be used as a cross-linking agent to thicken the organosilane or polysilane. No additional organic solvent is required. A small amount of water may be useful in initiating the thickening reaction. The gel lowers the volatility of the organosilane and polysilane thus improving its safety and efficiency through reduced evaporative losses.
  • organosilane may be any of trisilane, tetrasilane, hexasilane, pentasilane, cyclopentasilane, substituted cyclopentasilane, cyclohexasilane, substituted cyclohexasilane; a short chain hydrocarbon with at least one terminal silane group(s), disilabutane, disilapropane, phenylsilane, disilylbenzene, trisilylbenzene, hexasilylbenzene , or combinations thereof.
  • a strong base catalyst may be incorporated in the above-described organosilane or polysilane gel, such as organosilane or polysilane.
  • the gel may be shaped in any of the above-described forms, including a tablet, a bar, or a sphere.
  • the so formed gel-based article may be combined with water, wherein the quantity of the catalyst is between about 0.1 % and about 5 % by mass of the water, and the mass ratio of water to the starting material is between about 1 : 1 and about 1 :4.
  • the devices may include an exhaust gas cooler for condensing out water vapor; a mixing chamber for mixing the exhaust gas condensate and a catalyst; a mixing chamber for mixing an organosilane, polysilane or a siloxene starting material, the exhaust gas condensate, and a catalyst; a reaction chamber comprising a hydrogen outlet; a hydrogen outlet comprising a hydrogen permeable membrane; and a silicate by-product precipitate collector.
  • the devices or cartridges may be connected to a fuel cell, to the intake air of an engine, to a vehicle exhaust after-treatment system or to any other device that needs hydrogen as a fuel.
  • Fig. 1 generally devices feed the reactants and catalyst as needed to a reaction zone.
  • the call for the reactants to the reaction chamber can be controlled simply by a check valve responding to a pressure increase in the reaction zone or can be controlled by electronic activation of valves and pumps.
  • the devices blend the reactants in the desired concentrations, segregate the resulting hydrogen gas, and deliver the gas to the fuel cell, engine, engine exhaust after-treatment system or other hydrogen consuming device.
  • the devices can also contain a means for segregating and collecting the silicate precipitate, refluxing clean water, and preventing backflow of reaction products into the reactant streams.
  • An example of a particularly useful device is a system that functions in the exhaust stream of an internal combustion engine.
  • the device/system first cools the exhaust stream to collect a water vapor condensate.
  • the exhaust gas cooler also solubulizes nitrogen dioxide in the condensed water to form nitric acid, particularly after an oxidation catalyst which converts nitrogen oxide which is non-soluble in water, to nitrogen dioxide which is highly soluble in water. Condensing the nitrogen dioxide out of the exhaust stream reduces the amount OfNO x that must be treated by the exhaust after treatment system.
  • a siloxene or a calcium suicide starting material may be combined with the condensate from an internal combustion engine and a catalyst, thus generating hydrogen.
  • the solubulized NO 2 being present in the condensate may be further sequestered into a harmless nitrate precipitate, allowing to achieve the reduction of nitrogen oxides by between about 1 % and about 99 %.
  • the catalyst that may be used in such an embodiment may be a dilute strong base, e.g., NaOH, KOH, Ca(OH) 2 , an alkylamine, an arylamine, CaH 2 , UV light, or combinations thereof.
  • the alkylamine may include a substituted or unsubstituted mono-, di-, and tri-alkyl amine, hydroxyalkylamine, and a substituted or unsubstituted mono-, di-, tri-alkenylamine, for example, any of methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, henicosylamine,
  • the exhaust gas water condensate is then mixed with a catalyst as described in PCT US08/52127 and then mixed with the siloxene tablet to produce hydrogen.
  • the water condensate can be mixed directly with a tablet comprised of the siloxene and a catalyst, such as calcium hydride.
  • the hydrogen produced is directed to a Lean NO x Trap (LNT) as a reducing agent for nitrogen oxides not condensed out of the exhaust stream.
  • LNT Lean NO x Trap
  • the hydrogen can be routed directly to the combustion chamber through the exhaust gas recirculation (EGR) stream as a supplementary fuel and combustion enhancer.
  • EGR exhaust gas recirculation
  • the reduction OfNO x in the exhaust by trapping the NO 2 fraction in the condensed exhaust water vapor can range from 1 to 99 %.
  • the hydrogen then not needed by the LNT could be routed to the combustion chamber.
  • the exhaust gas cooler provides additional benefit by improving the volumetric efficiency of the engine through the reduction in temperature of the EGR stream.
  • the device can be as shown by Fig. 2.
  • the device comprises a mixing chamber for mixing a polysilane or organosilane, water and catalyst(s).
  • the mixing chamber can comprise an inlet for the polysilane or organosilane with check valve to regulate the amount of fuel introduced into the reaction zone to minimize pressure build up, and a water inlet also with a check valve.
  • the reaction chamber can also comprise a silicate collector such as absorbed glass mat, which can be used to contain and/or remove the silicate by-product of the reaction.
  • a silicate collector such as absorbed glass mat
  • the reaction zone may also contain a source of UV light to catalyze the reaction.
  • a device for automobiles or light duty vehicles can be as shown by Fig. 3.
  • the device comprises a metal housing with separated storage for the organosilane, polysilane or silicide-based fuel, and a reaction chamber.
  • Water vapor is condensed from the engine exhaust and directed to the device where it is first mixed with the catalyst and then mixed with the fuel.
  • the liberated hydrogen is directed to the intake air system of the engine, or is directed to the exhaust gas after-treatment system or is directed to an on-board fuel cell.
  • the precipitate is collected in the cartridge.
  • a siloxene tablet as described above was added to a reaction flask.
  • a rubber stopper was then used to seal the neck of the flask.
  • the flask was then connected by tubing to a graduated cylinder that was filled with water and then inverted and placed in a reservoir of water.
  • a solution of 0.5 M sodium hydroxide in water was then injected using a syringe into the reaction vial.
  • the gas generated during the reaction was collected in the top portion of the graduated cylinder displacing the water.
  • the calculated gravimetric efficiency which is the mass of the hydrogen generated divided by the mass of the siloxene is shown in the table.

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Abstract

La présente invention concerne des compositions, procédés et dispositifs qui peuvent être utilisés pour générer de l'hydrogène. La présente invention concerne également des procédés et dispositifs de génération d'hydrogène pour piles à combustible et d'autres applications telles qu'un combustible ou un combustible supplémentaire pour moteurs à combustion interne ainsi que des réducteurs pour améliorer l'efficacité des catalyseurs de contrôle des émissions.
PCT/US2008/072523 2007-08-10 2008-08-07 Dispositifs et procédés de génération améliorée d'hydrogène WO2009023535A2 (fr)

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WO2010094785A1 (fr) * 2009-02-20 2010-08-26 Universite De La Mediterranee Aix-Marseille Ii Production d'hydrogène catalysée par des composés amino à partir de dérivés silylés faisant office de transporteurs d'hydrogène
US7879310B2 (en) 2005-08-03 2011-02-01 Board Of Trustees Of The University Of Alabama Silanes as a source of hydrogen
WO2012010639A1 (fr) * 2010-07-23 2012-01-26 Eads Deutschland Gmbh Production d'hydrogène au moyen de polysilanes hydrogénés, pour le fonctionnement de piles à combustible
RU2545290C1 (ru) * 2013-11-15 2015-03-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский университет "МЭИ" (ФГБОУ ВПО "НИУ "МЭИ") Способ получения водорода за счет гидролиза твердого реагента-алюминия в реакционном сосуде
JP2020517577A (ja) * 2017-04-22 2020-06-18 ハイドロジェン テック センディリアン ベルハッド 水素ガス生成装置

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US6582676B2 (en) * 2000-08-14 2003-06-24 The University Of British Columbia Hydrogen generation from water split reaction
WO2006099716A1 (fr) * 2005-03-24 2006-09-28 University Of Regina Catalyseurs pour production d'hydrogène
WO2007054290A1 (fr) * 2005-11-09 2007-05-18 Rev Renewable Energy Ventures Inc. Procede et dispositif de production d’hydrogene

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US6582676B2 (en) * 2000-08-14 2003-06-24 The University Of British Columbia Hydrogen generation from water split reaction
WO2006099716A1 (fr) * 2005-03-24 2006-09-28 University Of Regina Catalyseurs pour production d'hydrogène
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WO2010094785A1 (fr) * 2009-02-20 2010-08-26 Universite De La Mediterranee Aix-Marseille Ii Production d'hydrogène catalysée par des composés amino à partir de dérivés silylés faisant office de transporteurs d'hydrogène
US8920769B2 (en) 2009-02-20 2014-12-30 Universite D'aix-Marseille Amino catalyzed production of hydrogen from silylated derivatives as hydrogen carrier
EP2962987A1 (fr) * 2009-02-20 2016-01-06 Universite d'Aix Marseille Procédé de production catalysée d'hydrogène à partir de dérivés silylés en tant que transporteurs d'hydrogène
WO2012010639A1 (fr) * 2010-07-23 2012-01-26 Eads Deutschland Gmbh Production d'hydrogène au moyen de polysilanes hydrogénés, pour le fonctionnement de piles à combustible
JP2013533597A (ja) * 2010-07-23 2013-08-22 シュパウント プライベート ソシエテ ア レスポンサビリテ リミテ 燃料電池を動作させるための水素添加ポリシランによる水素生成
CN103270634A (zh) * 2010-07-23 2013-08-28 斯帕恩特私人有限公司 用于运行燃料电池的通过氢化聚硅烷的氢生成
US20130266505A1 (en) * 2010-07-23 2013-10-10 Eads Deutschland Gmbh Hydrogen generation by hydrogenated polysilanes for operating fuel cells
JP2016189330A (ja) * 2010-07-23 2016-11-04 シュパウント プライベート ソシエテ ア レスポンサビリテ リミテＳｐａｗｎｔ Ｐｒｉｖａｔｅ Ｓ．ａ．ｒ．ｌ 燃料電池を動作させるための水素添加ポリシランによる水素生成
RU2545290C1 (ru) * 2013-11-15 2015-03-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский университет "МЭИ" (ФГБОУ ВПО "НИУ "МЭИ") Способ получения водорода за счет гидролиза твердого реагента-алюминия в реакционном сосуде
JP2020517577A (ja) * 2017-04-22 2020-06-18 ハイドロジェン テック センディリアン ベルハッド 水素ガス生成装置

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