WO2008094840A2 - Procédés de génération d'hydrogène utilisant des composés de silicium - Google Patents
Procédés de génération d'hydrogène utilisant des composés de silicium Download PDFInfo
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- WO2008094840A2 WO2008094840A2 PCT/US2008/052127 US2008052127W WO2008094840A2 WO 2008094840 A2 WO2008094840 A2 WO 2008094840A2 US 2008052127 W US2008052127 W US 2008052127W WO 2008094840 A2 WO2008094840 A2 WO 2008094840A2
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present invention generally relates to improved compositions and methods for generation of hydrogen using silicon-based compounds. More particularly, the invention is concerned with methods for generating hydrogen using organosilanes, polysilanes, and suicides and catalyst(s) under particular and specific reaction conditions.
- organosilicon compounds e.g., organosilanes
- hydrolysis of organosilicon compounds was used to generate hydrogen safely and on as needed basis, eliminating the need for storage of large amounts of hydrogen in pressure vessels. It was theorized that the dilute strong base provided hydroxyl ions throughout the aqueous mixture while the amine floated to the surface of the water as did the organosilanes.
- compositions and process(s) for use in generation of hydrogen as it is needed, in a safe and controlled manner, for use as a fuel in a fuel cell, in an engine as a NOx reducing agent or as a supplementary fuel or for any other hydrogen consuming device, using silicon-containing compounds as a starting material, resulting in improved efficiency and allowing to avoid generating airborne pollutants.
- silicon-containing compounds that have been shown to be an effective fuel for generating hydrogen as needed.
- silicon based compounds that can be used for this purpose, including but not limited to, powdered siloxene, layered polysilane Si 6 H 6 , and various silanes and oligosilanes, including a silane oligomer with at least three repeating groups.
- viable catalysts for the continuing replenishment for hydroxyl ions into the liquid phase of the reaction.
- such a catalyst is calcium oxide.
- the invention also provides for the use of combinations of catalysts that include alkali, such as potassium hydroxide (KOH) or sodium hydroxide (NaOH), and an organic amine catalyst, to produce hydrogen (H 2 ) on an as needed basis by altering the reaction conditions.
- alkali such as potassium hydroxide (KOH) or sodium hydroxide (NaOH)
- NaOH sodium hydroxide
- organic amine catalyst to produce hydrogen (H 2 ) on an as needed basis by altering the reaction conditions.
- An exemplary combination is two or more of octylamine, aniline, ethanolamine (EtOHNH 2 ), NaOH, and KOH.
- Functionalized octylamine catalysts are also within the scope of the invention.
- the processes of silane hydrolysis described in the present application allow to obtain hydrogen yields that may be two to three times higher than those obtainable using other fuel cell technologies, due to the fact the co-reactant is water, which can be collected in situ, precluding the need to carry the extra weight. Also, unlike methanol or hydrocarbon fueled fuel cell technologies, the processes of the present invention allow to avoid formation of carbon dioxide which is a harmful green house gas.
- the precipitate formed in the processes of the present invention is non-hazardous and non-valuable and need not be recovered, as opposed to sodium borohydride, lithium hydride or other by-products which are formed when other technologies are used, thus providing significant advantage to the consumer.
- Figure 1 illustrates schematically the overall hydrogen generation process.
- Figure 2 illustrates schematically a cartridge-type hydrogen generator for portable power applications.
- Figure 3 illustrates schematically a hydrogen generator for use with light duty automotives.
- Figure 4 illustrates schematically a hydrogen generator for heavy duty applications.
- Figure 5 illustrates schematically a system using powder siloxene or layered polysilane prepared from calcium suicide.
- 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 weight or mass of a particular element or component in a composition denotes the weight or mass relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed.
- X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
- a weight or mass percent (wt. % or mass %) of a component is based on the total weight of the formulation or composition in which the component is included.
- gravimetric efficiency means the yield of hydrogen per unit weight of starting material. A high gravimetric efficiency is achieved by optimization of starting materials, catalysts, and processes.
- 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, the order of mixing of reagents, and 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.
- alkane as used herein is a branched or unbranched saturated hydrocarbon group having the general formula of C n H 2n+2 and can have from 1 to 40 carbon atoms, such as methyl, ethyl, w-propyl, isopropyl, «-butyl, ⁇ -butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like.
- the alkane can also be cyclic, substituted, or unsubstituted, which are included within the meaning of the term "alkane.”
- a cyclic alkane can specifically be referred to as a cycloalkane, but these structures are included within the meaning of the term "alkane.”
- a radical of an alkane can be specifically referred to as an "alkyl,” but throughout the disclosure alkyls are also intended to be included within the meaning of alkanes.
- a "cycloalkyl” is a type of alkyl group and is included within the meaning of the word "alkyl.”
- a cycloalkyl group is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
- heterocycloalkyl is a type of cycloalkyl group, and is included within the meaning of “alkyl” and “cycloalkyl,” where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
- the cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted.
- the cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.
- alkoxy as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group can be defined as — OA 1 where A 1 is alkyl as defined above.
- alkene as used herein is a hydrocarbon group of from 2 to 40 carbon atoms with a structural formula containing at least one carbon-carbon double bond.
- alkene can also be cyclic, substituted, or unsubstituted, which are included within the meaning of the term "alkene.”
- a cyclic alkene can specifically be referred to as a cycloalkene, but these structures are included within the meaning of the term "alkene.”
- a radical of an alkene can be specifically referred to as an "alkenyl,” but throughout the disclosure alkenyls are also intended to be included within the meaning of alkenes.
- a "cycloalkenyl” is a type of alkenyl group and is included within the meaning of the word "alkenyl.”
- Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like.
- heterocycloalkenyl is a type of cycloalkenyl group, and is included within the meaning of the terms “alkenyl” and “cycloalkenyl,” where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
- the cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted.
- the cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.
- alkyne is a hydrocarbon group of 2 to 40 carbon atoms with a structural formula containing at least one carbon-carbon triple bond.
- the alkyne can also be cyclic, substituted, or unsubstituted, which are included within the meaning of the term "alkyne.”
- a radical of an alkyne can be specifically referred to as an "alkynyl,” but throughout the disclosure alkynyls are also intended to be included within the meaning of alkynes.
- 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.
- aryl also includes “heteroaryl,” which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
- non-heteroaryl which is also included in the term “aryl,” defines a group that contains an aromatic group that does not contain a heteroatom.
- aryl can also be substituted or unsubstituted, which are included within the meaning of the term “aryl.”
- the term “biaryl” is a specific type of aryl group and is included in the definition of “aryl.” "Biaryl” refers to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.
- 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.
- 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 hydroxy 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 teft-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.
- halide refers to the halogens fluorine, chlorine, bromine, and iodine.
- hydroxyl as used herein is represented by the formula -OH.
- 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, or appearing as part of the product. Catalysts typically act by lowering the activation energy of reactions, but they do not change the relative potential energy of the reactants and products.
- nucleation is defined as
- nucleation is defined as the beginning of chemical or physical changes at discrete points in a system.
- the present invention is directed to generation of hydrogen as needed from non-toxic, energy-dense liquids and solids for use in fuel cells, internal combustion engines, engine exhaust after-treatment systems for reducing oxides of nitrogen and any other device that consumes hydrogen.
- the invention provides an overall lower weight than other systems, requires no expensive precious metal catalysts, emits no carbon dioxide or other pollutants.
- the starting material for this chemistry is very plentiful silicon dioxide which could also be harvested from rice straw or rice husks.
- compositions, methods, and devices that address issues related to the perceived hazardous character, low hydrogen density, and poor regeneration capability of silanes as fuel.
- the compositions, methods, and devices disclosed herein can reduce or eliminate the need to provide separation or clean-up of the hydrogen from gaseous by-products.
- the disclosed compositions and processes also mitigate/eliminate the hazardous nature of the starting materials and the precipitate, eliminating special handling and recovery logistics.
- the disclosed compositions, methods, and devices can provide pressure to eliminate or reduce the need for mechanical pumping and assist the fuel cell with its own pumping needs.
- the disclosed compositions, methods, and devices do not result in the release of carbon dioxide (or any other gaseous pollutants) to the atmosphere.
- a residual by-product is formed, but it is environmentally benign (i.e., a silicate).
- a method for generating hydrogen comprising hydrolyzing a silicon-containing compound in the presence of an organic amine catalyst and/or a hydroxide, i.e., reacting such a silicon-containing compound with water and a hydroxide.
- the use of the amine lowers the pH of the system and enhances the overall safety of the unit. Hydrogen is a product of this reaction.
- the method of the invention may be practiced using a variety of starting silicon-containing compound(s), organic amine catalysts, and hydroxides under various specific conditions, as discussed below in more detail. By varying and altering the specific conditions of the reacting we provide for substantially and unexpectedly improved gravimetric and volumetric efficiency, and for other advantages, as discussed below.
- the organic amine catalyst has to be matched to the specific silicon- containing compound to minimize the concentration of catalyst needed, to improve the rate of reaction or to optimize the hydrogen yield.
- propylamine works well with siloxene but poorly with 1 ,4 disilabutane.
- the order in which the materials are mixed significantly impacts the yield.
- the catalyst and water therefore, should be mixed prior to the contact with the silane material to gain the optimum performance.
- the water and catalyst mixture may then either be added to the silicon-based compound or the silicon-based compound may be added to the water/catalyst mixture.
- a slight excess of stoichiometric water has to be maintained locally for the organosilanes and a significant excess of water is needed for siloxene.
- Silicon-containing compounds that can be employed as starting products to generate hydrogen as needed include silanes, poly- or oligosilanes organosilanes, and siloxenes derived from suicides. All of the silicon-containing products that can be used are capable of being hydrolyzed or alcoholized under various conditions to produce hydrogen gas. The reaction is typically carried out in a basic solution, and in a presence of a catalyst, as discussed below in greater detail.
- One example of the process of generating hydrogen may be illustrated by the net reaction scheme I (hydrolysis of phenylsilane):
- Reaction I (which omits showing the intermediate products) proceeds via a nucleophilic attack of the hydroxyl anion on the silane bond Si-H.
- reaction I employs an amine, e.g., octyl amine catalyst
- the reaction may proceed via formation of an ammonium cation, e.g., CH 3 (CH 2 ) 7 NH 3 + and hydroxyl, which form as a result of interaction of water with octyl amine.
- the hydroxyl then attacks the Si-H bond of phenylsilane leading to the formation of S-OH fragment and to the release of a proton, followed by generation of hydrogen gas and regeneration of octyl amine.
- the reaction may be carried out at temperatures ranging between about -I 0 C and about 43 0 C and can utilize various kinds of water, including seawater, brackish water, distilled water, tap water, and water contained in urine. It is worth mentioning that water may be supplied from the effluent of the fuel cell or from the engine exhaust which may, therefore, help to lower the weight and volume of the system in these applications. In addition, the water recovered from the engine exhaust contains acids that are neutralized by the catalyst, thereby preventing harm to the vehicle components and lowering the amount ofNO x required to be converted by the catalyst.
- compositions comprising silanes can be used to generate hydrogen, which in turn can be supplied, for example, to a fuel cell or an internal combustion engine or catalyst.
- Silanes or organosilanes that may be used include silane oligomers with at least three repeating groups, such as pentasilane, cyclopentasilane, substituted cyclopentasilane, hexasilane, cyclohexasilane and substituted cyclohexasilane all of which do have low vapor pressure, high boiling point and high energy density with respect to hydrogen evolution capability.
- silanes or organolsilanes that may be used include short chain hydrocarbons with at least one terminal silane group(s), disilabutane, disilapropane, layered polysilane Si 6 H 6 (i.e., a product of reaction between calcium suicide and hydrochloric acid under cold conditions), and aromatic silanes such as phenylsilane, disilylbenzene, trisilylbenzene, and hexasilylbenzene.
- Very dry powdered siloxenes may be also used as starting silicon-containing products for generating hydrogen by hydrolysis in the presence of a hydroxide and an amino catalyst.
- Powdered siloxenes having the net structure Si 6 H 6 O 3 are synthetic products that may be obtained from suicides using methods and techniques known to those skilled in the art, for example, by an exemplary reaction II:
- layered polysilane Si 6 H 6 which may be also generated from the low temperature reaction of calcium suicide with hydrochloric acid has a higher gravimetric efficiency than siloxene because there are no oxygen atoms in the molecule. The presence of oxygen atoms reduces the amount of available silicon sites to be oxidized and also adds to the weight of the overall fuel.
- silicon-containing products that can be employed as starting products to generate hydrogen as needed include the pyrolized ash of rice husks or the pyrolized ash of rice straw.
- the pyrolized ash of rice husks or the pyrolized ash of rice straw have been identified as renewable and environmentally favorable source of hydrogen generating fuels.
- rice straw contains up to twelve percent silicon, has no current value and has a cost for disposal.
- the silicon in rice husk and rice straw exists as silicon dioxide intermingled closely with cellulosic chains. It is well known that bulk silicon does not react with water because of a layer of silicon dioxide that builds up on the surface. However, under proper conditions, silicon may react rapidly with water, similar to the behavior of lithium, magnesium, sodium, aluminum and other metals.
- rice husk and rice straw can be pyrolized in a steam atmosphere to form a reduced silicic acid, or can be combined with magnesium to form amorphous silicon.
- the theoretical gravimetric efficiency in grams of hydrogen that could be produced per hundred grams of rice husk ash ranges from 14 to 17% according to the schematic equations III and IV:
- the hydrogen-generating process of hydrolysis of silicon- containing compounds is conducted in the presence of a catalyst.
- Strong acids, strong bases, and transition or precious metals may be used as catalysts.
- Typical catalysts that may be used include hydroxides, such as potassium or sodium hydroxide (KOH or NaOH), calcium oxide (CaO), or calcium hydroxide (Ca(OH) 2 ), and nitrogen-containing compounds, such as a soluble or insoluble amines.
- solid CaO can be an effective catalyst for the reaction of the silicon- based compounds with water to generate hydrogen.
- the limited solubility of Ca(OH) 2 in water provides the advantage of maintaining a continuous supply of hydroxyl ions as they are consumed in the reaction.
- CaO generates two hydroxyl ions per mole as opposed to NaOH and KOH which generate one hydroxyl ion per mole.
- the density and the effectiveness of this solid catalyst significantly reduces the volume and weight of the hydrogen generating system.
- the pH of the calcium hydroxide solution generated by the calcium oxide is also significantly less alkaline than a strong base catalyst improving the safe handling and disposal of commercial products using this technology.
- Suitable catalysts include, but are not limited to, 10% Pd-C, Pd-Cu, Raney nickel, 5% Ru-C, H 2 PtCl 6 , PdCl 2 , PdOAc 2 , CuOAc 2 , superacid membranes, phosphonic acid containing membranes, sulfonic acid containing membranes, and polymers, along with alkaline membrane and polymers.
- amines include, but are not limited to, substituted or unsubstituted mono-, di-, and tri-alkyl amines, hydroxyalkylamines, substituted or unsubstituted mono-, di-, and tri- alkenylamines, and jeffamines, including combinations thereof.
- TAA triethylamine
- DMEDA tributylamine
- DMEA dimethylaminoethanol
- TEDTA ethylenediamine tetraacetic acid
- TMEDA ethylenediamine tetraacetic acid
- PMDETA pyridine, dimethylaminopyridine, benzyldimethylamine, tris-(dimethylaminomethyl) phenol, alkyl- substituted imidazoles (e.g., 1,2- dimethylimidazole), phenyl-substituted imidazoles, or bis(2- dimethylamino
- the catalyst is an alkyl amine, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamin, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, henicosylamine, doicosylamine, triicosylamine, tetraicosylamine, and the like.
- Some exemplary amine catalysts that may be used include propylamine and octylamine.
- specific combinations of particular starting silicon-containing compounds paired with particular catalysts may lead to enhanced gravimetric efficiency and/or can increase the rate of the hydrogen generation reaction.
- particularly beneficial specific combinations include propylamine paired with siloxene and 1,4-disilabutane paired with octylamine.
- the efficiency of such special pairs may be illustrated by the fact that closely related to 1,4-disilabutane is 1,3-disilabutane which in combination with octylamine provided only 6.8 % efficiency. Yet, 1,4-disilabutane/octylamine combination gave 13.3% efficiency.
- Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art.
- the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co., (Milwaukee, Wis.), Acros Organics (Morris Plains, ⁇ .J.), Fisher Scientific (Pittsburgh, Pa.), or Sigma (St.
- compositions are disclosed and a number of modifications that can be made to a number of components of the composition are discussed, each and every combination and permutation that are possible are specifically contemplated unless specifically indicated to the contrary.
- each of the combinations of A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed just from the disclosure of A, B, and C; D, E, and F; and the example combination A-D.
- any subset or combination of these is also specifically contemplated and disclosed.
- the conditions of the process of generating hydrogen may be selected to optimize of the yield of hydrogen, mitigate potential safety risks and obtain other benefits.
- the optimal steps of the process include:
- step (c) selectively isolating and directing the hydrogen obtained in step (b) through a delivery port to prevent contamination of the fuel cell or automotive catalyst or combustion chamber with unreacted, partially reacted or products of the complete reaction;
- the catalyst may be mixed with water to obtain the concentration of the catalyst in water that is between about 2 and about 5 mass %, for example, about mass 5%, in the water. Typically, the process is expected to be slower at a lower part of the range of concentrations.
- the feed rate of the silicon-containing compound may be selected to ensure acceptable supply pressure of the resulting hydrogen.
- the supply pressure of hydrogen that has to be maintained may be determined by those having ordinary skill in the art and for most fuel cells it may be in a range between about from 0.2 atmosphere (i.e., ⁇ 3 psi) and about 0.7 atmosphere (i.e., ⁇ 10 psi).
- the supply pressure needed for automotive after-treatment systems may be between about 0.14 atmosphere (i.e., ⁇ 2 psi) and about 0.35 atmosphere (i.e., ⁇ 5 psi).
- step (c) selective isolation of hydrogen may be needed since the gas obtained in some instances o f the process may not be 100% pure hydrogen, but include partially reacted silanes.
- step (b) those having ordinary skill in the art may put a size exclusion membrane or filter in the outlet since the silicon compounds will have much bigger size than hydrogen. A secondary benefit of that will be to reflux those partially reacted compounds back into the reaction, improving the yield.
- the intermediate product of the organosilane reaction is a silanol which may be present but is not shown on the reaction scheme I above.
- Silanol is known to react with some alkyl amines thus inactivating them. Therefore, having ordinary skill in the art may choose only those alkyl amines that do not interact with silanol. If silanol is formed, it quickly polymerizes via condensation reaction at its tails. This causes the formation of a cake that floats on the surface of the water. This cake may interrupt or even completely stop the reaction of hydrolysis. Therefore, a step of removing the precipitate may be performed to avoid the premature termination of the reaction.
- a process exemplifying the above-described processes may include, but is not limited to, the following steps:
- a silicon-containing compound e.g., a polysilane, organosilane, or siloxene
- a feed rate that would ensure the above-described hydrogen supply pressure, the feed rate being controlled by check valves and/or sensors, to satisfy but not exceed the needs of the fuel cell, engine or exhaust after-treatment system and to maintain a slightly excess of stoichiometric water-to-the silicon-containing compound ratio;
- the process of obtaining hydrogen may be speeded up and the yield of hydrogen may be improved by optionally using UV radiation.
- hexasilane may be used as a starting silane.
- the theoretical yield for the reaction of hexasilane with water and a catalyst is 15 kg of hydrogen for every 100 kg of hexasilane.
- the hydrogen yield may be increased from 15% to 21% if the Si-Si bonds could be broken to form six silyl radicals. Such cleavage of the Si-Si bonds may be facilitated by using UV radiation.
- reaction blend including hexasilane may be irradiated by UV light emitted from a mercury vapor lamp or from a UV light emitting diode potentially releasing all the hydrogen and forming amorphous SiO 2 as a by-product.
- UV light emitted from a mercury vapor lamp or from a UV light emitting diode potentially releasing all the hydrogen and forming amorphous SiO 2 as a by-product.
- UV light emitting diode potentially releasing all the hydrogen and forming amorphous SiO 2 as a by-product.
- the process of obtaining hydrogen may be further accelerated and the yield of hydrogen may be improved by optionally using an induced vortex.
- the vortex may be created, for example, by flutes in the supply line and reaction chamber. When vortex was used, the bubbles of hydrogen were coming almost exclusively from the very center of the vortex, and the yield of hydrogen was increased by about 20 %.
- the process of obtaining hydrogen may be further accelerated and the yield of hydrogen may be improved by optionally using a material capable of causing the increase in nucleation sites, e.g., a fiber glass material, such as an absorbed glass mat.
- a material capable of causing the increase in nucleation sites e.g., a fiber glass material, such as an absorbed glass mat.
- the use of materials increasing nucleation may help to pull the precipitate out of the reaction zone and prevent the formation of a cake or lid on the reaction. Hydrogen bubbled quickly from many sites on the fiberglass material and improved the yield by about 20%.
- Devices or cartridges that can be used to generate hydrogen according to the methods of the present invention can be designed to be specific to each application, whether it be portable or stationary, and whether weight or volume is more important.
- the devices or cartridges connect 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.
- 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.
- 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.
- the reaction zone may also contain a source of UV light to catalyze the reaction.
- FIG. 3 Another example of a device that may be used, i.e., a device for automobiles or light duty trucks, is shown in Figure 3.
- the device comprises a metal housing with separated storage for the organosilane, polysilane or silicide-based fuel, and a reaction chamber. Water 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 hydrogen liberated 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 onboard fuel cell. The precipitate is collected in the cartridge.
- FIG. 4 Yet another example of a device that may be used, i.e., a device that can produce large amounts of hydrogen, is shown in Figure 4.
- This device can use water condensed from engine exhaust or from any other source.
- the organosilane, polysilane or silicide-based fuel, water and catalyst are mixed in a reaction chamber and both the hydrogen and the precipitate is removed.
- This device has a hydrogen permeable membrane on the hydrogen outlet.
- a device to mix a powder silicide-based fuel is shown in Figure 5.
- the device incorporates a feed system for the powder. Water and catalyst is mixed with the fuel in the auger and hydrogen is collected using a hydrogen permeable membrane. The auger discharges the precipitate from the unit.
- Table 1 shows some of the data collected employing nucleation methods to enhance the production of hydrogen.
- a small piece of absorbed glass mat and 2 ml of water was added to a 50 ml reaction vial.
- KOH was then added to make a 0.25 M solution.
- 0.050 ml of n-octylamine was added.
- a septum was then used to cover the neck of the flask.
- the side neck of the flask was then connected by tubing to a 250 ml graduated cylinder that was filled with water and then inverted and placed in a reservoir of water.
- 0.20 ml of phenylsilane was injected using a 1 ml 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 amount of gas collected in this reaction was twenty five percent higher than reactions described in U.S. Patent Application Serial No. 60/705,331, without the absorbed glass mat.
- Table 1 Also shown in Table 1 are the results of an experiment utilizing 1,4-disilabutane.
- 1000 ml of water was added to a 1 liter Erlenmeyer flaks along with sufficient NaOH to make a solution of 0.5 molarity. This mixture was stirred rapidly to generate a vortex to enhance nucleation of the reaction. 0.25 ml of 1, 4 disilabutane was injected into the flask. The amount of gas collected in this reaction was thirteen percent higher than reactions described in patent application 60/705,331 without an induced vortex.
- the calculated gravimetric efficiency which is the weight of the hydrogen generated divided by the weight of the phenylsilane is shown in the table.
- Table 2 shows some of the data collected utilizing mixtures of catalysts to enhance the rate of production of hydrogen.
- a 4 ml of water was added to a 50 ml reaction vial.
- KOH was then added to make a 0.5 M solution.
- N-octylamine was added in the separate tests in the amount indicated in the table.
- a septum was then used to cover the neck of the flask.
- the side neck of the flask was then connected by tubing to a 250 ml graduated cylinder that was filled with water and then inverted and placed in a reservoir of water.
- ImI of phenylsilane was injected using a 1 ml 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 amount of gas collected in fifteen minutes in these reactions improves significantly with the addition of increasing amounts of n-octylamine to the KOH solution.
- Example 3 shows some of the data collected to utilizing « -propylamine as a catalyst to enhance the rate of production of hydrogen and to lower the alkalinity of the starting material and by-products.
- siloxene approximately 0.25 g was added to a 50 ml reaction vial.
- a septum was then used to cover the neck of the flask.
- the side neck of the flask was then connected by tubing to a 1000 ml graduated cylinder that was filled with water and then inverted and placed in a reservoir of water.
- 0.1 ml of propylamine in solution with between 2.0 and 2.5 ml of water was injected using a 3 ml 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 amount of gas collected in less than ten seconds in these reactions improves significantly when propylamine replaces KOH or NaOH in the solution.
- the largest quantity of hydrogen gas collected with 0.5 M KOH as the catalyst was 160 ml.
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Abstract
L'invention concerne des compositions qui comprennent divers composés à base de silicium tels que les polysilanes, les polysilanes en couches, les organosilanes ou les siloxènes, qui sont utilisés pour générer de l'hydrogène. Des procédés et des dispositifs permettant la génération d'hydrogène sont également décrits, y compris ceux qui concernent les procédés de génération d'hydrogène pour des piles à combustible ou comme carburant supplémentaire pour des moteurs à combustion interne.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010070001A1 (fr) * | 2008-12-16 | 2010-06-24 | Universite De La Mediterranee Aix-Marseille Ii | Nouveau procédé de production d'hydrogène à partir de dérivés silylés servant de porteur d'hydrogène |
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 |
WO2011098614A1 (fr) | 2010-02-15 | 2011-08-18 | Universite De La Mediterranee Aix-Marseille Ii | Procédé catalysé par oxyde de phosphine pour obtention d'hydrogène de dérivés de silyles comme porteurs d'hydrogène |
US9751759B2 (en) | 2012-10-01 | 2017-09-05 | Oxford University Innovation Limited | Composition for hydrogen generation |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3673115A (en) * | 1968-12-30 | 1972-06-27 | Lever Brothers Ltd | Catalysts |
US4637867A (en) * | 1981-10-14 | 1987-01-20 | Herbst Jr Ralph L | Process for producing hydrogen from short wavelength electromagnetic radiation |
US5650132A (en) * | 1994-12-14 | 1997-07-22 | Director-General Of Agency Of Industrial Science And Technology | Process for producing hydrogen from hydrocarbon |
US5840270A (en) * | 1993-04-23 | 1998-11-24 | H Power Corporation | Catalytic method of generating hydrogen |
US5858541A (en) * | 1994-09-19 | 1999-01-12 | Kabushiki Kaisha Toshiba | Glass composite material, precursor thereof, nitrogen-containing composite material and optical device |
US6336430B2 (en) * | 1998-06-29 | 2002-01-08 | Fatpower Inc. | Hydrogen generating apparatus |
US6544400B2 (en) * | 2000-03-30 | 2003-04-08 | Manhattan Scientifics, Inc. | Portable chemical hydrogen hydride system |
WO2005037421A2 (fr) * | 2003-10-14 | 2005-04-28 | Advanced Technology Materials, Inc. | Production d'hydrogene |
US20060013753A1 (en) * | 2004-03-26 | 2006-01-19 | Vajo John J | Reversible hydrogen storage systems |
US7037484B1 (en) * | 2002-06-21 | 2006-05-02 | University Of Central Florida Research Foundation, Inc. | Plasma reactor for cracking ammonia and hydrogen-rich gases to hydrogen |
-
2008
- 2008-01-25 WO PCT/US2008/052127 patent/WO2008094840A2/fr unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3673115A (en) * | 1968-12-30 | 1972-06-27 | Lever Brothers Ltd | Catalysts |
US4637867A (en) * | 1981-10-14 | 1987-01-20 | Herbst Jr Ralph L | Process for producing hydrogen from short wavelength electromagnetic radiation |
US5840270A (en) * | 1993-04-23 | 1998-11-24 | H Power Corporation | Catalytic method of generating hydrogen |
US5858541A (en) * | 1994-09-19 | 1999-01-12 | Kabushiki Kaisha Toshiba | Glass composite material, precursor thereof, nitrogen-containing composite material and optical device |
US5650132A (en) * | 1994-12-14 | 1997-07-22 | Director-General Of Agency Of Industrial Science And Technology | Process for producing hydrogen from hydrocarbon |
US6336430B2 (en) * | 1998-06-29 | 2002-01-08 | Fatpower Inc. | Hydrogen generating apparatus |
US6544400B2 (en) * | 2000-03-30 | 2003-04-08 | Manhattan Scientifics, Inc. | Portable chemical hydrogen hydride system |
US7037484B1 (en) * | 2002-06-21 | 2006-05-02 | University Of Central Florida Research Foundation, Inc. | Plasma reactor for cracking ammonia and hydrogen-rich gases to hydrogen |
WO2005037421A2 (fr) * | 2003-10-14 | 2005-04-28 | Advanced Technology Materials, Inc. | Production d'hydrogene |
US20060013753A1 (en) * | 2004-03-26 | 2006-01-19 | Vajo John J | Reversible hydrogen storage systems |
Non-Patent Citations (5)
Title |
---|
BROWNING D.: 'DERA Research on H2 storage and Generation Methods for Fuel Cells', [Online] 24 September 2006, page 20 Retrieved from the Internet: <URL:http://www.h2net.org.uk/PDFs/Stor2000/H2nettalk_Nov00.pdf> * |
HAHN J.J.: 'Hydrogen Production from Biomass', [Online] December 2006, page 77 Retrieved from the Internet: <URL:http://www.edt.missouri.edu/Fall2006/Dissertation/HahnJ-120806-D5413/research.pdf > * |
NATH ET AL.: 'Hydrogen from Biomass' CURRENT SCIENCE vol. 85, no. 3, 10 August 2003, page 267 * |
NEAL ET AL.: 'Primary Reaction Channels and Kinetics of the Thermal Decomposition of Phenylsilane' JOURNAL OF PHYSICAL CHEMISTRY vol. 99, 1995, page 9397 * |
ZORBAS S.: 'Japan to Produce Hydrogen from Seawater' AUSTRALIAN HYDROGEN NEWS, [Online] 08 December 2006, page 7 Retrieved from the Internet: <URL:http://www.h2.net.org.uk/PDFs/Stor2000/H2nettalk_Nov00.pdf> * |
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US7879310B2 (en) | 2005-08-03 | 2011-02-01 | Board Of Trustees Of The University Of Alabama | Silanes as a source of hydrogen |
WO2010070001A1 (fr) * | 2008-12-16 | 2010-06-24 | Universite De La Mediterranee Aix-Marseille Ii | Nouveau procédé de production d'hydrogène à partir de dérivés silylés servant de porteur d'hydrogène |
EP2206679A1 (fr) | 2008-12-16 | 2010-07-14 | Université de la Méditerranée - Aix-Marseille II | Nouveau procédé de production d'hydrogène à partir de dérivés silylés en tant que transporteur d'hydrogène |
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 |
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 |
US8920769B2 (en) | 2009-02-20 | 2014-12-30 | Universite D'aix-Marseille | Amino catalyzed production of hydrogen from silylated derivatives as hydrogen carrier |
JP2013519615A (ja) * | 2010-02-15 | 2013-05-30 | ユニベルシテ デ―マルセイユ | ホスフィンオキシド触媒を用いた、水素キャリアとしてのシリル化誘導体からの水素の製造方法 |
US8642003B2 (en) | 2010-02-15 | 2014-02-04 | Universite D'aix-Marseille | Phosphine-oxide catalyzed process of production of hydrogen from silylated derivatives as hydrogen carrier |
CN103025650A (zh) * | 2010-02-15 | 2013-04-03 | 埃克斯-马赛大学 | 从作为氢载体的甲硅烷基化衍生物中制氢的氧化膦催化法 |
CN103025650B (zh) * | 2010-02-15 | 2015-09-09 | 埃克斯-马赛大学 | 从作为氢载体的甲硅烷基化衍生物中制氢的氧化膦催化法 |
WO2011098614A1 (fr) | 2010-02-15 | 2011-08-18 | Universite De La Mediterranee Aix-Marseille Ii | Procédé catalysé par oxyde de phosphine pour obtention d'hydrogène de dérivés de silyles comme porteurs d'hydrogène |
KR101830448B1 (ko) | 2010-02-15 | 2018-02-20 | 위니베르시떼 덱스-마르세이유 | 수소 캐리어로서 실릴화된 유도체로부터의 수소의 산화 포스핀 촉매된 제조 방법 |
US9751759B2 (en) | 2012-10-01 | 2017-09-05 | Oxford University Innovation Limited | Composition for hydrogen generation |
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