WO2006113463A2 - Appareil et procede permettant une production controlable d'hydrogene a une vitesse acceleree - Google Patents

Appareil et procede permettant une production controlable d'hydrogene a une vitesse acceleree Download PDF

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WO2006113463A2
WO2006113463A2 PCT/US2006/014122 US2006014122W WO2006113463A2 WO 2006113463 A2 WO2006113463 A2 WO 2006113463A2 US 2006014122 W US2006014122 W US 2006014122W WO 2006113463 A2 WO2006113463 A2 WO 2006113463A2
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reaction
metal
reaction medium
colloidal
cathode
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WO2006113463A3 (fr
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Linnard Griffin
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Linnard Griffin
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • 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
    • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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 is directed to a method and apparatus for the production of hydrogen gas from water.
  • Dihydrogen gas, H 2 also referred to as hydrogen gas, diatomic hydrogen, or elemental hydrogen is a valuable commodity with many current and potential uses.
  • Hydrogen gas may be produced by a chemical reaction between water and a metal or metallic compound. Very reactive metals react with mineral acids to produce a salt plus hydrogen gas. Equations 1 through 5 are examples of this process, where HX represents any mineral acid. HX can represent, for example HCl, HBr, HI, H 2 SO 4 , HNO 3 , but includes all acids .
  • Equations 6 and 7 are examples, again where HX represents all mineral acids.
  • Reactions of this type provide a better method for the production of hydrogen gas due to their relatively slower and therefore more controllable reaction rate.
  • Metals like these have not, however, been used in prior art production of diatomic hydrogen because of the expense of these metals.
  • Equations 13 - 16 are examples of this process.
  • An apparatus for the production of hydrogen generally comprising a reaction medium; an anode in contact with the reaction medium; a cathode in contact with the reaction medium, wherein the cathode is capable of being in conductive contact with the anode; and a catalyst suspended in the reaction medium, wherein the catalyst has a high surface-area-to-volume ratio.
  • the catalyst is a colloidal metal.
  • the catalyst has a surface-area-to-volume ratio of at least 298,000,000 m 2 per cubic meter.
  • a salt is dissolved in the reaction medium.
  • a cation of the salt is less reactive than a metal composing the anode.
  • a cation of the salt comprises zinc or cobalt.
  • the apparatus further comprises a second catalyst suspended in the reaction medium, wherein the second catalyst is a colloidal metal or has a surface-area-to-volume ratio of at least 298,000,000 m 2 per cubic meter.
  • anode and cathode are connected via a conductive path.
  • the conductive path is hardwired to the cathode and the anode.
  • the apparatus further comprises a controller in the conductive path between the cathode and the anode, wherein the controller is configured to selectively allow or hinder the flow of electrical current between the cathode and the anode through the conductive path.
  • reaction medium is an aqueous solution. In a further additional embodiment, the reaction medium comprises an acid or a base.
  • the cathode comprises tungsten carbide or carbonized nickel.
  • the anode comprises aluminum.
  • the cathode comprises surface-area-increasing features.
  • the surface area of the cathode is greater than the surface area of the anode.
  • the apparatus further comprises an energy source configured to provide energy to the reaction medium.
  • a reaction vessel containing the reaction medium is configured to maintain an internal pressure above atmospheric pressure.
  • the apparatus further comprises an electrical power source configured to provide an electrical potential between the cathode and the anode.
  • Also disclosed is a method of producing hydrogen gas comprising the steps of: suspending a colloidal metal in a reaction medium; contacting the reaction medium with a cathode; contacting the reaction medium with an anode; and electrically connecting the cathode and the anode.
  • the method further comprises the step of dissolving a salt in the reaction medium.
  • the method further comprises the steps of: interrupting the conductive path between the anode and cathode; and providing an electrical potential between the anode and cathode.
  • the method further comprises the step of adding energy to the reaction medium.
  • Also disclosed is a method of controlling the production of hydrogen generally comprising the steps of: suspending a colloidal metal in a reaction medium; contacting the reaction medium with a cathode; contacting the reaction medium with an anode; connecting the cathode and the anode via a conductive path; and varying the resistance along the conductive path.
  • an electrical power generator generally comprising: a reaction vessel; a reaction medium contained within the reaction vessel; an anode in contact with the reaction medium; a cathode in contact with the reaction medium, wherein the cathode is in conductive contact with the anode; a catalyst metal in contact with the reaction medium, wherein the catalyst metal is in colloidal form or has a surface-area-to- volume ratio of at least 298,000,000 m 2 per cubic meter; an outlet in the reaction vessel configured to allow hydrogen gas to escape from the reaction vessel; and a fuel cell configured to accept hydrogen has from the outlet and use the gas to produce an electric potential.
  • FIGURE 1 is a diagram of a reactor for the production of hydrogen.
  • a colloid is a material composed of very small particles of one substance that are dispersed
  • colloidal particles do not settle out of solution, even though they exist in the solid state.
  • a colloid of any particular metal is then a very small particle of that metal suspended in a solution.
  • These suspended particles of metal may exist in the solid (metallic) form or in the ionic form, or as a mixture of the two.
  • the very small size of the particles of these metals results in a very large effective surface area for the metal. This very large effective surface area for the metal can cause the surface reactions of the metal to increase dramatically when it comes into contact with other atoms or molecules.
  • the catalysts used in the experiments described below are colloidal metals obtained using a colloidal silver machine, model: Hvac-Ultra, serial number: U-03- 98-198, sold by CS Prosystems of San Antonio, Texas.
  • the website of CS Prosystems is www. csprosystems . com.
  • Colloidal solutions of metals that are produced using this apparatus result from an electrolytic process and are thought to contain colloidal particles, some of which are electrically neutral and some of which are positively charged. Other methods can be employed in the production of colloidal metal solutions. It is believed that the positive charge on the colloidal metal particles used in the experiments described below provides additional rate enhancement effects.
  • the particles of a metal in the colloidal solutions used in the experiments described below are believed to range in size between 0.001 and 0.01 microns. In such a solution of colloidal metals, the concentration of the metals is believed to be between about 5 to 20 parts per million.
  • a catalyst in colloidal form it may be possible to use a catalyst in another form that offers a high surface-area-to-volume ratio, such as a porous solid, nanometals, colloid-polymer nanocomposites and the like.
  • the catalysts may be in any form with an effective surface area that preferably on the order of 298,000,000 m 2 per cubic meter of catalyst, although smaller surface area ratios may also work.
  • Equations 22 - 24 are thus general equations that are believed to occur for any metals in spite of their normal reactivity, where M represents any metal in colloidal form.
  • M can represent, but is not limited to, silver, copper, tin, zinc, lead, and cadmium. In fact, it has been found that the reactions shown in equations 22 - 24 occur at a significant reaction rate even in solutions of 1% aqueous acid.
  • equations 22 - 24 represent largely endothermic processes for many metals, particularly those of low reactivity (for example, but not limited to, silver, gold, copper, tin, lead, and zinc)
  • the rate of the reactions depicted in equations 22 - 24 is in fact very high due to the surface effects caused by the use of the colloidal metal. While the reactions portrayed in equations 22 - 24 take place at a highly accelerated reaction rate, these reactions do not result in a useful production of elemental hydrogen since the colloidal metal by definition is present in very low concentrations.
  • a useful preparation of hydrogen results, however, by the inclusion of a metal more reactive than the colloidal metal such as, but not limited to, metallic iron, metallic aluminum, or metallic nickel.
  • a metal more reactive than the colloidal metal such as, but not limited to, metallic iron, metallic aluminum, or metallic nickel.
  • any colloidal metal in its ionic form, M + would be expected to react with the metal M e as indicated in equation 25, where those metals M + below M e on the electromotive or activity series of metals would react best.
  • equation 25 takes place quite readily due to the large effective surface area of the colloidal ion, M + , and also due to the greater reactivity of the metal M e compared to M + , which is preferably of lower reactivity.
  • equation 25 would result in a highly exothermic reaction.
  • the metal, M resulting from reduction of the colloidal ion, M + , would be present in colloidal quantities and thus, it is believed, undergoes a facile reaction with any mineral acid including, but not limited to, sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, hydroiodic acid, perchloric acid, and chloric acid.
  • the mineral acid is preferably sulfuric acid, H 2 SO 4 , or hydrochloric acid, HCl. Equation 26 describes this reaction where the formula HX (or H + + X ⁇ in its ionic form) is a general representation for any mineral acid.
  • equation 26 represents an endothermic reaction, it is believed the exothermicity of the reactions in equation 25 compensates for this, making the combination of the two reactions energetically obtainable using the thermal energy supplied by ambient conditions.
  • the metal M e reacts with the colloidal metal ion in equation 27 to produce a colloidal metal and the ionic form of M e .
  • the colloidal metal will then react with a mineral acid in equation 28 to produce elemental hydrogen and regenerate the colloidal metal ion.
  • the colloidal metal ion will then react again by equation 27, followed again by equation 28, and so on in a chain process to provide an efficient source of elemental hydrogen.
  • Equation 29 has as its result the production of elemental hydrogen from the reaction of the metal M e and a mineral acid.
  • Equation 29 summarizes a process that provides for very efficient production of elemental hydrogen where the metal M e and acid are consumed. It is believed, however, that both the elemental metal M e and the acid are regenerated as a result of a voltaic electrochemical process or thermal process that follows. It is believed that a colloidal metal M r (which can be the same one used in equation 27 or a different metal) can undergo a voltaic oxidation - reduction reaction indicated by equations 30 and 31.
  • the colloidal metal M r can in principle be any metal, but reaction 30 progresses most efficiently when the metal has a higher (more positive) reduction potential.
  • the reduction of the colloidal metal ion, as indicated in equation 30, takes place most efficiently when the colloidal metal is lower than the metal M e on the electromotive series of metals. Consequently, any colloidal metal will be successful, but reaction 30 works best with colloidal metals such as colloidal silver or lead, due to the high reduction potential of these metals.
  • lead for example, is employed as the colloidal metal ion in equations 30 and 31, the pair of reactions is found to take place quite readily.
  • the voltaic reaction produces a positive voltage as the oxidation and reduction reactions take place.
  • This positive voltage can be used to supply the energy required for other chemical processes.
  • the voltage produced can even be used to supply an over potential for reactions employing equations 30 and 31 taking place in another reaction vessel.
  • this electrochemical process can be made to take place more quickly without the supply of an external source of energy.
  • the resulting colloidal metal, M r can then react with oxidized ionic metal, M e + , as indicated in equation 32, which would result in the regeneration of the metal, M e , and the regeneration of the colloidal metal in its oxidized form.
  • Equation 32 could in fact occur using as starting material any colloidal metal, but will take place most effectively when the colloidal metal, M r , appears above the metal, M e , on the electromotive series.
  • equation 33 represents the regeneration of the elemental metal, M e , the regeneration of the acid, and the formation of elemental oxygen.
  • reaction shown in equations 30 and 31 occur best when the colloidal metal, M r , is as low as possible on the electromotive series of metals; however, it is believed that the reaction depicted by equation 32 takes place most efficiently when the colloidal metal, M r , is as high as possible on the electromotive series of metals.
  • the net reaction illustrated by equation 33 which is merely the sum of equations 30, 31, and 32, could in fact be maximally facilitated by either colloidal metals of higher activity or by colloidal metals of lower activity.
  • the relative importance of the reaction illustrated by equations 30 and 31 compared to the reaction shown in equation 32 would determine the characteristics of the colloidal metal that would best assist the net reaction in equation 33.
  • equation 34 results in a net process indicated in equation 34.
  • the reaction depicted in equation 30 proceeds most efficiently when the colloidal metal is found below the metal, M e , on the electromotive series.
  • the reaction represented by equation 32 is most favorable when the colloidal metal is found above the metal, M e , on the electromotive series. Accordingly, it has been observed that the concurrent use of two colloidal metals, one above the metal, M e , and one below it in the electromotive series—for example, but not limited to, colloidal lead and colloidal aluminum—produces optimum results in terms of the efficiency of the net process.
  • equation 34 merely depicts the decomposition of water into elemental hydrogen and elemental oxygen, the complete process for the production of elemental hydrogen now has only water as an expendable substance, and the only necessary energy source is supplied by ambient thermal conditions.
  • the additional energy supplied is in the form of thermal energy
  • the colloidal metallic ion catalysts M + and/or M r + , as well as the metal M e and the acid are regenerated in the process, leaving only water as a consumable material. Elemental Nonmetal
  • a further means by which the rate of hydrogen production could be increased involves the inclusion of a nonmetal in the reaction such as, but not limited to, carbon or sulfur.
  • a nonmetal such as, but not limited to, carbon or sulfur.
  • equation 31 would be replaced by equation 35 which portrays a more facile reaction due to the thermodynamic stability of the oxide of the nonmetal.
  • Equation 33 would then be replaced by equation 36, and equation 34 would be replaced by equation 37.
  • the reaction would produce an oxide such as CO 2 or SO 2 of a nonmetal, where the thermodynamic stability of the nonmetal oxide would provide an additional driving force for the reaction and thus result in an even faster rate of hydrogen production.
  • the colloidal metal, M r can, in principle, be any metal but works most efficiently when the metal has a high (more positive) reduction potential.
  • the regeneration process takes place most efficiently when the colloidal metal is as low as possible on the electromotive series of metals. Consequently, any colloidal metal will be successful, but the reaction works well with colloidal silver ion, for example, due to the high reduction potential of silver.
  • silver is employed as the colloidal metal ion in equations 41 and
  • the pair of reactions is found to take place readily.
  • the voltaic reaction produces a positive voltage as the oxidation and reduction reactions indicated take place.
  • This positive voltage can be used to supply the energy required for other chemical processes.
  • the voltage produced can even be used to supply an over- potential for reactions employing equations 41 and 42 taking place in another reaction vessel.
  • this electrochemical process can be made to take place more quickly without the supply of an external source of energy.
  • the resulting colloidal metal, M r will then react to regenerate the metal, M e (equation 43) .
  • Equation 43 The reaction illustrated by equation 43 will take place most efficiently when the colloidal metal, M r , is more reactive than the metal, M e . That is, the reaction in equation 43 will proceed most efficiently when the colloidal metal, M r , is above the metal, M e , on the electromotive series of metals.
  • equation 44 represents the regeneration of the elemental metal, M e , the regeneration of the acid, and the formation of elemental oxygen.
  • Equation 41 and 42 seem to occur best when the colloidal metal, M r , is as low as possible on the electromotive series of metals; however, the reaction depicted by equation 43 takes place most efficiently when the colloidal metal, M r , is as high as possible on the electromotive series of metals.
  • the net reaction illustrated by equation 44 which is merely the sum of equations 41, 42, and 43, could in fact be facilitated by either colloidal metals of higher activity or lower activity than M e .
  • the relative importance of the reaction illustrated by equations 41 and 42 compared to the reaction shown in equation 43 would determine the characteristics of the colloidal metal that would best assist the net reaction in equation 44.
  • equation 45 merely depicts the decomposition of hydrogen peroxide into elemental hydrogen and elemental oxygen, the complete process for the production of elemental hydrogen now has only hydrogen peroxide as an expendable substance, and the only necessary energy source is supplied by ambient thermal conditions.
  • a further means by which the rate of hydrogen production could be increased would involve the inclusion of a nonmetal in the reaction such as, but not limited to, carbon or sulfur.
  • a nonmetal such as, but not limited to, carbon or sulfur.
  • equation 42 would be replaced by equation 46 which portrays a more facile reaction due to the thermodynamic stability of the oxide of the nonmetal.
  • Equation 44 would then be replaced by equation 47, and equation 45 would be replaced by equation 48.
  • a further alternative to this process involves the introduction of other reducing agents, such as formic acid, to react in the place of water or hydrogen peroxide.
  • other reducing agents such as formic acid
  • the reactions illustrated in equations 31 and 32 would be replaced by similar reactions illustrated by equations 38 and 39.
  • the net result of these two reactions would be the reaction represented in equation 40, the production of elemental hydrogen using an elemental metal, M e , and a mineral acid as reactants.
  • the colloidal metal, M r can in principle be any metal but works most efficiently when the metal has a high (more positive) reduction potential.
  • the regeneration process takes place most efficiently when the colloidal metal is as low as possible on the electromotive series of metals. Consequently, any colloidal metal will be successful, but the reaction works well with colloidal silver ion, for example, due to the high reduction potential of silver.
  • silver is employed as the colloidal metal ion in equations 41 and 49, the pair of reactions is found to take place quite readily.
  • the voltaic reaction produces a positive voltage as the oxidation and reduction reactions indicated take place. This positive voltage can be used to supply the energy required for other chemical processes.
  • the voltage produced can even be used to supply an over-potential for reactions employing equations 41 and 49 taking place in another reaction vessel.
  • this electrochemical process can be made to take place more quickly without the supply of an external source of energy.
  • the resulting colloidal metal, M r will then react to regenerate the metal, M e (equation 43) .
  • Equation 43 The reaction illustrated by equation 43 will take place most efficiently when the colloidal metal, M r , is more reactive than the metal, M e - That is, the reaction in equation 43 will proceed most efficiently when the colloidal metal, M r , is above the metal, M e , on the electromotive series of metals.
  • the combining of equations .41, 49 and 43 produces the net reaction shown by equation 50.
  • the net reaction represented by equation 50 results in the regeneration of the elemental metal, M e , the regeneration of the acid, and the formation of carbon dioxide.
  • Equation 41 and 49 seem to occur best when the colloidal metal, M r , is as low as possible on the electromotive series of metals. However, the reaction depicted by equation 43 takes place most efficiently when the colloidal metal, M r , is as high as possible on the electromotive series of metals.
  • the net reaction illustrated by equation 50 which is merely the sum of equations 41, 49, and 43, could, in fact, be maximally facilitated by either colloidal metals of higher activity or by colloidal metals of lower activity.
  • the relative importance of the reaction illustrated by equations 41 and 49 compared to the reaction shown in equation 43 would determine the characteristics of the colloidal metal that would best assist the net reaction in equation 50.
  • equation 51 merely depicts the decomposition of formic acid into elemental hydrogen and carbon dioxide, the complete process for the production of elemental hydrogen now has only formic acid as an expendable substance, and the only necessary energy source is supplied by ambient thermal conditions. Although the providing of additional energy would result in an enhanced rate of hydrogen formation, the reaction proceeds efficiently when the only energy supplied is ambient thermal energy.
  • Equations 52 - 54 are general equations that can be made to occur for any metals in spite of their normal reactivity, where M f represents any metal in colloidal form.
  • M f can represent but is not limited to Ag, Cu, Sn, Zn, Pb, Mg, Fe, Al and Cd. In fact, it has been found that the reactions shown in equations 52 - 54 occur at a significant rate.
  • equations 52 - 54 would represent largely endothermic processes for a great many metals, particularly those of traditional low reactivity (for example but not limited to silver, gold, copper, tin, lead, nickel, and zinc) , the rates of the reactions depicted in equations 52 - 54 could in fact be very large due to the surface effects caused by the use of the colloidal metal. While reactions represented by equations 52 - 54 would take place at a highly accelerated rate, they would not result in a useful production of elemental hydrogen since the colloidal metal by definition is present in very low concentrations, and would therefore yield insignificant amounts of hydrogen upon reaction.
  • a useful preparation of hydrogen can result by the inclusion of a solid metal, M 3 , more reactive than the colloidal metal, M f , such as but not limited to elemental aluminum, iron, lead, nickel, tin, tungsten, or zinc.
  • a solid metal M 3
  • M f colloidal metal
  • any colloidal metal in its ionic form would be expected to react with the solid metal, M 3 , as indicated in equation 55, where those metals below M 3 on the electromotive or activity series of metals would react best.
  • Equation 55 would in fact take place quite readily due to the large effective surface area of the colloidal ion, M f + , and also perhaps due to the greater reactivity of the solid metal M 5 , compared to any metal of lower reactivity. In fact, for colloidal metals normally lower in reactivity than M 3 , equation 55 would be an exothermic reaction.
  • the resulting metal, M f would be theorized to be present in colloidal form and thus would undergo a facile reaction with water to produce elemental hydrogen and a base, either by equation 52, 53, or 54 depending upon the oxidation state of the resulting colloidal metal ion.
  • equations 52, 53, or 54 would most likely be endothermic, it is believed that the exothermicity of the reaction shown in equation 55 compensates for this. Therefore, the combination of the two reactions yields a process that is thermally obtainable.
  • Equation 56 reacts with the colloidal metal ion (equation 56) to produce a product theorized to be a colloidal metal. It is believed the colloidal metal will then react with water in equation 57 to produce elemental hydrogen and regenerate the colloidal metal ion. The colloidal metal ion will then react again by equation 56, followed again by equation 57, and so on in a chain reaction process to provide an efficient source of elemental hydrogen. In principle, any colloidal metal ion should undergo this process successfully. It is found that the reaction works most efficiently when the colloidal metal ion is lower in reactivity than the metal, M 3 , on the electromotive series table. Equations 56 and 57 can be combined, and this would result in the net reaction that is illustrated by equation 58. Equation 58 has as its result the production of elemental hydrogen from the reaction of a metal, M 3 , and water.
  • Equation 58 summarizes a process that can provide an efficient production of elemental hydrogen where an elemental metal, M 3 , and water are consumed. It is believed, however, that the elemental metal can be regenerated as a result of a voltaic electrochemical process and a thermal process that- follows.
  • a colloidal metal which can be the same or different from the one represented in equation 56 referred to as M rs in equation
  • the colloidal metal, M rs can in principle be any metal but works most efficiently when the metal has a higher (more positive) reduction potential.
  • the regeneration process takes place most efficiently when the colloidal metal is as low as possible on the electromotive series of metals. Consequently, any colloidal metal will be successful, but the reaction works best with colloidal silver ion, due to the high reduction potential of silver.
  • silver is employed as the colloidal metal ion, for example, the reactions portrayed in equations 59 and 60 take place readily.
  • the voltaic reaction produces a positive voltage, as the indicated oxidation and reduction reactions occur. This positive voltage can be used to supply the energy required for other chemical processes.
  • the voltage produced can even be used to supply an over- potential for reactions employing the conversions portrayed by equations 59 and 60 but taking place in another reaction vessel.
  • this electrochemical process can be made to take place more quickly without the supply of an external source of energy. It is believed that the resulting colloidal metal, M rs , may then react to regenerate the elemental metal, M s (equation 61) .
  • Equation 61 The reaction illustrated by equation 61 will take place most efficiently when the colloidal metal, M rs , is more reactive than the metal, M 3 . That is, the reaction in equation 61 will proceed most readily when the colloidal metal, M rs , is above the metal, M s , on the electromotive series of metals. Combining equations 59 - 61 results in the chemical reaction represented by equation 62, which results in the regeneration of the elemental metal M 3 , and the formation of elemental oxygen.
  • Equation 59 and 60 seem to occur best when the colloidal metal, M rs , is as low as possible on the electromotive series of metals; however, the reaction depicted by equation 61 takes place most efficiently when the colloidal metal, M rs , is as high as possible on the electromotive series of metals.
  • the net reaction illustrated by equation 62 is merely the sum of equations 59, 60, and 61 and could be maximally facilitated by either colloidal metals of higher activity or by colloidal metals of lower activity.
  • the relative importance of the reaction illustrated by equations 59 and 60 compared to the reaction shown in equation 61 would determine the characteristics of the colloidal metal that would best assist the net reaction in equation 62.
  • the net reaction indicated in equation 62 proceeds at a maximal rate when the colloidal metal is of maximum activity, that is, when the colloidal metal is as high as possible on the electromotive series of metals. It has been found that the more reactive colloidal metal ions such as, but not limited to colloidal magnesium ion or colloidal aluminum ion produce the most facile processes for the reduction of cationic metals. In fact, it has been found that the overall reaction proceeds most efficiently when at least two colloidal metals are present, preferably where at least one of the colloidal metal ions is higher than the solid metal M e on the electromotive series, and at least one of the colloidal metal ions is lower than the solid metal M e on the electromotive series.
  • equation 34 merely depicts the decomposition of water into elemental hydrogen and elemental oxygen, the complete process for the production of elemental hydrogen now has only water as an expendable substance.
  • any two metals of different reactivity can be employed along with any colloidal metal catalysts at any level of pH, the process will be illustrated in the form of reactions performed at ambient temperature, under basic conditions using the metal-like material tungsten carbide as the cathode, the metal zinc as the anode, and colloidal silver and colloidal magnesium. Similar results were obtained for reactions carried out in acidic media as described in experiments 19 - 21.
  • Zinc is known to undergo reaction under basic conditions with water according to the reaction represented by equation 19.
  • the reaction requires the input of significant thermal energy in order to proceed at a reasonable rate. In fact, if this reaction is performed at room temperature, the observed reaction rate is virtually zero. In theory, the rate of this reaction could be enhanced by the inclusion of a colloidal metal catalyst. If colloidal silver in its ionic form, Ag c + , is introduced, the colloidal silver ion will react efficiently with the zinc, due to the large effective surface area of the colloidal silver ion, and also perhaps due to the enhanced reactivity of zinc compared to silver, a result of the fact that zinc is above silver in the electromotive series. Thus, the colloidal silver ion will undergo reaction with zinc at an impressive rate according to equation 63. 2 Ag 0 + + Zn ⁇ Zn +2 + 2 Ag c (63)
  • the reduced silver, Ag c/ would be theorized to be present in a colloidal form and would thus undergo a facile reaction with water to produce elemental hydrogen and a base, as illustrated in equation 64.
  • Equation 65 the solid zinc metal reacts with the colloidal silver ion in equation 65 to produce a product theorized to be elemental colloidal silver. It is believed the elemental colloidal silver will then react with water in equation 66 to produce elemental hydrogen and regenerate the colloidal-silver ion. The colloidal- silver ion will then react again by equation 65, followed again by equation 66, and so on in a chain reaction process to provide an efficient source of elemental hydrogen. Equations 65 and 66 can be combined, and this would result in the net reaction that is illustrated by equation 67. Equation 67 has as its result the production of elemental hydrogen from the reaction of zinc and water.
  • Equation 67 summarizes a process that can provide an efficient production of elemental hydrogen where elemental zinc and water are consumed. It is believed, however, that the elemental zinc can be regenerated as a result of a voltaic electrochemical process and a thermal process that follows. Thus, colloidal magnesium ion Mg c +2 can undergo a voltaic oxidation - reduction reaction indicated by equations 68 and 60.
  • Equation 69 The reaction illustrated by equation 69 will take place quite efficiently due to the fact that magnesium is above zinc on the electromotive series of metals. Combining equations 68, 60, and 69 results in the reaction illustrated in equation 70, which represents the regeneration of the elemental zinc, and the formation of elemental oxygen.
  • equation 34 merely depicts the decomposition of water into elemental hydrogen and elemental oxygen, the complete process for the production of elemental hydrogen now has only water as an expendable substance.
  • reaction rate is still found to be extremely slow at ambient temperatures presumably due to the low reactivity of zinc in the absence of additional thermal energy.
  • the reaction rate can be significantly enhanced by the introduction of a second material that is inert but highly conductive, such as, but not limited to, tungsten carbide, which will be employed for this discussion.
  • tungsten carbide must be conductively connected to the metallic zinc. The required connection can be achieved by having the two materials directly in contact, or they can be connected by a conductive medium, preferably made of a material low in reactivity such as copper.
  • reaction represented by equation 65 is followed by an electrochemical voltaic process transpiring as illustrated in equations 71 and 60.
  • the oxidation reaction represented by equation 71 takes place at the surface of the zinc electrode and the reduction reaction represented by equation 60 occurs at the surface of the tungsten carbide electrode.
  • Equation 66 results in the generation of elemental hydrogen; however equation 66 also produces a measurable electrical potential that will produce a potentially useful electrical current. Therefore the chemical system described here can provide a voltaic cell that produces energy. Concurrently, there is the production of hydrogen gas which can be used to provide additional energy when employed in a hydrogen cell or engine.
  • equation 66 The favorable potential produced by equation 66 allows the entire process to proceed without the requirement of an outside energy source. It is the favorable energetics of equation 66 that provide the driving force for the entire process. If the connection between the zinc electrode and the tungsten carbide electrode is broken, however, the reaction of equation 66 will not occur, resulting in a decrease or a virtual cessation in the rate of production of hydrogen. Thus one can generate hydrogen gas in a completely controllable manner simply by completing and disconnecting the circuit created by connecting the tungsten carbide and zinc electrodes. Combining equations 65, 71 and 60 again yields a net reaction that is illustrated by equation 67 as shown below.
  • Equation 67 Although elemental zinc is consumed (equation 67), it is believed the zinc can be regenerated as a result of a voltaic electrochemical process and a subsequent thermal process similar to that shown for the regeneration of elemental metal, U s , in equation 61.
  • colloidal magnesium ion, Mg c +2 can take part in a voltaic oxidation - reduction reaction indicated by equations 68 and 60.
  • equation 70 represents the regeneration of the elemental zinc, and the formation of elemental oxygen.
  • equation 34 merely depicts the decomposition of water into elemental hydrogen and elemental oxygen, the complete process for the production of elemental hydrogen now has only water as an expendable substance.
  • the rate of hydrogen production can also be increased by using as the anode a metal of higher reactivity, such as aluminum, and as the cathode a material that is inert but highly conductive, such as tungsten carbide, in a highly acidic solution that contains one or more dissolved acids, such as, but not limited to, sulfuric acid or hydrochloric acid. Additionally, there are preferably one or more salts or metal oxides (where, in acidic media, a metal oxide is the precursor to a salt) dissolved in the acidic solution, where each salt or metal oxide contains a cation of intermediate reactivity.
  • the salts or metal oxides may be, but are not limited to, zinc sulfide, zinc chloride, cobalt (II) sulfate, cobalt (II) chloride, zinc oxide, or cobalt (II) oxide.
  • the solution preferably also contains one or more colloidal-metal ions.
  • reaction medium is a solution of sulfuric acid that contains colloidal silver ion, colloidal magnesium ion and zinc sulfate.
  • Aluminum will be discussed as the metal of high reactivity, and tungsten carbide will be employed as the highly conductive, inert material.
  • Equation 74 summarizes a process that can provide an extremely efficient production of elemental hydrogen where elemental aluminum and sulfuric acid are consumed. It is believed, however, that the elemental aluminum and the sulfuric acid can both be regenerated as a result of a voltaic electrochemical process and a thermal process described below:
  • Colloidal magnesium ion Mg c +2 can undergo a voltaic oxidation - reduction reaction indicated by equations 77 and 78.
  • Equation 79 The reaction illustrated by equation 79 will take place quite efficiently due to the fact that magnesium is above aluminum on the electromotive series of metals. Combining equations 77, 78 and 79 results in the reaction illustrated in equation 80, which represents the regeneration of the elemental aluminum, the regeneration of the sulfuric acid, and the formation of elemental oxygen. 6 Mg c +2 + 12 e " ⁇ 6 Mg c (77)
  • equation 81 merely depicts the decomposition of water into elemental hydrogen and elemental oxygen, the complete process for the production of elemental hydrogen now has only water as an expendable starting material.
  • reaction illustrated in equation 76 is replaced by the reaction shown in equation 83.
  • reaction of colloidal silver and zinc cation occurs preferentially to the reaction of colloidal silver and sulfuric acid, it has been found that the reaction proceeds at a rather low rate.
  • combining equations 75 and 84 results in the net equation 85.
  • the reaction illustrated in equation 85 results in the consumption of aluminum; however, it is found to proceed at a rather low rate, and, thus, will not result in a large consumption of aluminum.
  • the reaction shown in equation 85 will still, however, take place preferentially when in competition with the net reaction that is depicted in equation 74.
  • the tungsten carbide in place of tungsten carbide, significant rate enhancement has also been achieved using nickel which has been melted with an acetylene torch with a carbonizing flame and then resolidified.
  • the tungsten carbide must be conductively connected to the metallic aluminum.
  • the required connection can be achieved by having the two materials directly in contact, or they can be attached by a conductive medium, preferably made of a material low in reactivity such as copper.
  • the reaction represented by equation 75 is followed by an electrochemical voltaic process transpiring as illustrated in equations 86 and 87.
  • the oxidation reaction represented by equation 86 is believed to take place at the surface of the aluminum electrode and the reduction reaction represented by equation 87 is believed to occur at the surface of the tungsten carbide electrode.
  • Equation 88 results in the generation of elemental hydrogen. Additionally, equation 88 produces a measurable electrical potential that could produce a potentially useful electrical current. Therefore, the chemical system described here can provide a voltaic cell that produces useful electrical energy. Concurrently, there is the production of hydrogen gas, which can be used to provide additional energy when employed in a hydrogen cell or an engine.
  • the favorable potential produced by equation 88 is believed to allow the entire process to proceed without the requirement of an outside energy source. It is the favorable energetics of equation 88 that is believed provides the driving force for the entire process.
  • reaction that is represented by equation 89 occurs at an impressive reaction rate due to the high reactivity of aluminum. With the inclusion of the tungsten carbide electrode, however, the net reaction shown by equation 89 will now progress at an even faster rate. It is believed that this is due at least in part to the increased surface area of the tungsten carbide compared to that of the colloidal elemental silver. It has been found that the generation of elemental hydrogen takes place at a considerable rate even at usual ambient temperatures. Since the rate of hydrogen production is believed to be at least partially dependent upon the surface area of the tungsten carbide cathode, the reaction rate can be further enhanced using any means that increases the surface area of the cathode.
  • the cathode is present as a thin foil or as a mesh in order to increase its surface area, there is an increase in the rate of hydrogen formation.
  • the use of multiple cathodes, each in electrical contact with the metallic aluminum anode produces an increase in the rate of hydrogen production, presumably resulting from the increase in the surface area of the cathode.
  • the combination of these two effects that is, the use of multiple cathodes consisting of a tungsten carbide mesh or foil, results in a large surface area of the cathode and a corresponding increase in the rate of hydrogen produced.
  • FIGURE 1 shows a mixture and apparatus that may be used for the production of hydrogen.
  • a reaction vessel 100 contains a reaction medium 102.
  • the reaction medium preferably comprises water and, most preferably, further comprises either a base or an acid, although the reaction can exist at virtually any level of pH. Alternatively, it is believed that other reaction media may be used, including other solvents, or non-liquid media, such as gelatinous or gaseous media.
  • the base is preferably sodium hydroxide with a concentration of about 2.5 Molar, although other bases and other concentrations may be used.
  • acid is preferably sulfuric acid or hydrochloric acid with a pH of about 1.0, although other acids and other concentrations may be used.
  • the reaction vessel 100 is preferably inert to the reaction medium 102.
  • the reaction medium 102 preferably contains a first colloidal metal (not shown) suspended in the solution. Although some of the reactions described above may proceed without a colloidal metal in the reaction medium 102, the colloidal metal significantly enhances the reaction rate.
  • the first colloidal metal is preferably a metal with low activity, such as silver, gold, platinum, tin, lead, copper, zinc, or cadmium, although other metals may be used. Alternatively, as discussed above, other high-surface-area catalysts may be used in place of the colloidal metal.
  • the cathode 104 may be in any form, but is preferably in the form of a solid with a relatively large surface area.
  • the cathode 104 comprises a plurality of surface-area-enhancing features 105, which increase the surface area of the cathode.
  • the surface-area-enhancing features 105 are preferably arranged to allow the reaction medium 102 or its constituents to move between them and to allow bubbles of produced gas to easily escape from the surface of the cathode 104.
  • the surface- area-enhancing features 105 are preferably vertically- oriented rods projecting upwardly from a base of the cathode 104.
  • the surface-area-enhancing features may be any feature, in electrical contact with the cathode 104, which effectively increases the surface area of the cathode 104.
  • the cathode 104 may be in another relatively high-surface-area form, such as a coil, film, wool, nanomaterial, nanocoating, or the like. Further alternatively, a plurality of cathodes 104 may be used which combine to provide a larger surface area. The total surface area of the cathode (s) 104 is preferably greater than the surface area of the anode.
  • the cathode 104 preferably comprises a material that is highly conductive but virtually inert to the reaction medium 102, such as nickel, carbonized nickel, tungsten, or tungsten carbide.
  • the cathode 104 most preferably comprises tungsten carbide.
  • the reaction vessel 100 also preferably comprises an anode 106 in contact with the reaction medium.
  • the anode 106 preferably comprises a metal of high-range activity, and thus of a higher activity than the cathode.
  • the anode 106 comprises aluminum, or a mixture of aluminum and other, less reactive, metals.
  • the reaction medium 102 also contains a second colloidal metal (not shown) .
  • the second colloidal metal preferably has a higher activity than the metals comprising the cathode 104 and the anode 106, such as aluminum, magnesium, beryllium, and lithium.
  • other high-surface- area catalysts may be used in place of the second colloidal metal.
  • the reaction medium 102 also contains an ionic salt (not shown) comprising a metal cation that is less reactive than the metal composing the anode 106, and an anion that is largely inert to other constituents in the reaction medium, such as, but not limited to, zinc sulfate, zinc chloride, cobalt (II) sulfate, and cobalt (II) chloride.
  • the cathode 104 and the anode 106 are preferably conductively connected through conductive paths 107 and 109, respectively, to a controller 108 which may be manipulated to allow or restrict the flow of electricity between the cathode 104 and the anode 106.
  • the controller 108 may be a switch, a variable resistor, or other device for allowing or resisting electric currents.
  • electrical current flows freely between the cathode 104 and the anode 106, it is found that the production of hydrogen will be maximized.
  • hydrogen production will be minimal or zero. It is believed that a variable resistor between the anode 106 and the cathode 104 would allow a user to select from a wide range of hydrogen production rates.
  • the electrical energy produced by the reaction which flows from the anode 104 to the cathode 106 through the conductive paths 107 and 109 may be used to provide electrical energy for a similar reaction occurring in a similar apparatus, or the system may be used as a battery, and the electrical energy created by the reaction can be used for other purposes.
  • the cathode 104 and anode 105 may be placed in direct contact with one another.
  • the reaction vessel 100 preferably comprises an outlet 110 to allow hydrogen gas (not shown) and/or other products to escape.
  • the reaction vessel may also have an inlet 112 for adding water or other constituents to maintain desired concentrations.
  • an electrical power source 114 may be used to intermittedly provide an electrical current through the reaction medium 102.
  • the electrical power source 114 may be a battery, power outlet, generator, transformer, or the like.
  • the electrical power source 114 preferably provides DC electrical power at a potential of at least 12 volts.
  • a first terminal 115 of the electrical power source 114 is electrically connected through conductive paths 116 and 109 to the anode 106.
  • a second terminal 117 of the electrical power source 114 is electrically connected through conductive paths 118 and 107 to the cathode 104.
  • the first terminal 115 has a higher electrical potential than the second terminal 117 so that when the controller 108 is configured in an open position (restricting current flow between the anode 106 and cathode 108), the electrical potential source 114 will cause a flow of electrical current in the opposite direction from when the controller 108 is closed and no external potential is applied. Power is applied from the electrical power soure 114 as needed to regenerate the anode and increase the hydrogen production rate. For most of the reaction duration, however, current is not applied.
  • the anode 106 may be replaced by a new anode 106.
  • the apparatus preferably comprises an energy source 122.
  • an energy source 122 is an electric heating coil, however, any form of thermal energy may be used including solar heating, combustion heating, hot plates, or the like. Generally, any energy source capable of heating the reaction medium above ambient temperatures may be used, and the particular source will preferably be chosen based on cost considerations. Additionally, it is believed that other energy types may be used, including, without limitation, electric energy, nuclear energy or electromagnetic radiation.
  • the hydrogen gas produced may be used in many known ways. Particularly, without limitation, the produced gas may be fed to a fuel cell to produce electric energy. Thus, the hydrogen production apparatus shown in Figure 1 may be combined with a fuel cell (not shown) to form a compact and efficient source of electrical energy, which could be used to power a wide variety of devices.
  • Experimental Results Experiment #1 Summary:
  • the maximum yield is 0.23 liters of H 2 per gram of H 2 SO 4 .
  • the starting solution had a total volume of 250 mL, including water, about 50 mL of colloidal magnesium and 80 mL of colloidal lead, each at a concentration believed to be about 20 ppm, 10 mL of 93% concentration H 2 SO 4 , and 30 mL of 35% concentration HCl as in experiment #1 above.
  • Ten grams of aluminum metal was added to the solution, which was heated and maintained at 90 0 C.
  • the reaction ran for 1.5 hours and yielded 12 liters of gas.
  • the pH was found to have a value under 2.0 at the end of 1.5 hours.
  • the reaction was stopped after 1.5 hours by removing the unused metal and weighing it.
  • the non- consumed aluminum weighed 4.5 grams, indicating a consumption of 5.5 grams of aluminum.
  • the maximum amount of hydrogen gas normally expected by the net consumption of 5.5 grains of aluminum is 6.8 liters, as indicated in the table below.
  • the starting solution included a total volume of 250 mL, including water, about 50 mL of colloidal magnesium and 80 mL of colloidal lead, each at a concentration believed to be about 20 ppm, 10 mL of 93% concentration H 2 SO 4 and 30 mL of 35% concentration HCl, as in experiment #1 above.
  • One hundred grams of iron pellets (sponge iron) was added to the solution, which was heated and maintained at 90 0 C.
  • the reaction ran for 30 hours and yielded 15 liters of gas.
  • the pH was found to have a value of about 5.0 at the end of 30 hours.
  • the reaction was stopped after 30 hours by removing the unused metal and weighing it.
  • the non-consumed iron weighed 94 grams, indicating a consumption of 6 grams of iron.
  • the maximum amount of hydrogen gas normally expected by the net consumption of 6 grams of iron, without the regeneration reaction described above, is 2.41 liters, as indicated in the table below.
  • the maximum amount of hydrogen gas expected solely from the reaction of acid with metal would be 8.06 liters.
  • the metal recovered was 100% Al, a maximum of 13.75 liters of hydrogen gas would be expected from the consumption of 11 grams of aluminum; and b) alternatively, assuming the metal recovered was 100% Fe, a maximum of 21.25 liters of hydrogen gas would be expected from the consumption of 17 grams of aluminum (20 grams supplied minus three grams used in the production of iron) .
  • the initial reaction rate was similar to that found in experiment #1, where 9 liters of gas was produced in slightly less than one hour. At this point, however, the reaction rate was found to decrease by a factor of approximately one-half. The addition of 20 grams of iron caused an immediate increase in reaction rate to the value that was initially observed at the onset of the experiment.
  • the initial reaction rate was similar to that found in experiment #1, where 9 liters of gas was produced in slightly less than one hour. At this point, however, the reaction rate was found to decrease by a factor of approximately one-half. The addition of 20 grams of iron caused an immediate increase in reaction rate to the value that was observed at the onset of the experiment.
  • An initial solution comprising 10 g of sodium hydroxide, 20 mL of colloidal silver, and 10 mL of colloidal magnesium, where each colloidal solution had a concentration believed to be about 20 ppm, was diluted with 70 mL of distilled water. There was then added to the solution a small piece of metallic zinc, and a small piece of a tungsten carbide, each connected to a piece of copper wire that extended outside of the solution. When the ends, of the copper wire were not in direct contact, virtually no reaction and no gas evolution were observed. When the two ends of the copper wire were placed into contact a vigorous evolution of gas was observed emanating from the surface of the tungsten carbide electrode.
  • the gas evolution could be stopped and restarted repeatedly simply by removing and then replacing the connection at the two ends of the copper wires.
  • a potential of about 0.3 volts was measured across the two ends of the copper wires.
  • the gaseous product produced at the surface of the tungsten carbide sample was captured in soap bubbles and was ignited. The explosion upon ignition strongly indicated the presence of elemental hydrogen in the product gas. After about 100 hours the rate of gas evolution and the measured potential were unchanged.
  • An initial solution comprising 10 g of sodium hydroxide, 20 mL of colloidal silver, and 10 mL of colloidal magnesium, where each colloidal solution had a concentration believed to be about 20 ppm, was diluted with 70 mL of distilled water. There was then added to the solution a small piece of metallic zinc and a small piece of a tungsten carbide, each connected to a piece of copper wire that extended outside of the solution. When the ends of the copper wire were not in direct contact, virtually no reaction and no gas evolution were observed. When the two ends of the copper wire placed into contact, a vigorous evolution of gas was observed emanating from the surface of the tungsten carbide electrode.
  • the gas evolution could be stopped and restarted repeatedly simply by removing and then replacing the connection at the two ends of the copper wires.
  • a potential of about 0.3 volts was measured across the two ends of the copper wires.
  • the gaseous product produced at the surface of the tungsten carbide sample was captured in soap bubbles and was ignited. The explosion upon ignition strongly indicated the presence of elemental hydrogen in the product gas.
  • An external 12-volt power source was then attached to the electrodes in order to cause a flow of electrical current in the direction opposite to what had been observed. Upon the application of this potential the zinc metal was observed to reform on the electrode with the concurrent production of a gas thought to be elemental oxygen.
  • An initial solution comprising 10 g of sodium hydroxide, 20 mL of colloidal silver, and 10 mL of colloidal magnesium, where each colloidal solution had a concentration believed to be about 20 ppm, was diluted with 70 mL of distilled water. There was then added to the solution a small piece of metallic zinc and a small piece of a tungsten carbide, each connected to a piece of copper wire that extended outside of the solution. When the ends of the copper wire were not in direct contact, virtually no reaction and no gas evolution were observed. When the two ends of the copper wire placed into contact a vigorous evolution of gas was observed emanating from the surface of the tungsten carbide electrode.
  • the gas evolution could be stopped and restarted repeatedly simply by removing and then replacing the connection at the two ends of the copper wires.
  • a potential of about 0.3 volts was measured across the two ends of the copper wires.
  • the gaseous product produced at the surface of the tungsten carbide sample was captured in soap bubbles and was ignited. The explosion upon ignition strongly- indicated the presence of elemental hydrogen in the product gas. After about 100 hours the rate of gas evolution and the measured potential were unchanged.
  • the zinc electrode was then removed and replaced by an electrode consisting of copper wire. There was no observable chemical reaction when the circuit was completed. An external 12-volt power source was then attached to the electrodes in order to cause a flow of electrical current in the direction opposite to what had been observed.
  • An initial solution was prepared by dissolving 10 g of sodium hydroxide in 100 mL of distilled water. There was then added to the solution a small piece of metallic zinc and a small piece of a tungsten carbide each connected to a piece of copper wire that extended outside of the solution. When the ends of the copper wire were not in direct contact, virtually no reaction and no gas evolution were observed. When the two ends of the copper wire were placed into contact, the evolution of gas was observed emanating from the surface of the tungsten carbide electrode. The rate of gas evolution was noticeably less than the rate observed with the inclusion of the colloidal catalysts. The gas evolution could be stopped and restarted repeatedly simply by removing and then replacing the connection at the two ends of the copper wires.
  • An initial solution comprising 10 g of sodium hydroxide, 20 mL of colloidal silver, and 10 mL of colloidal magnesium, where each colloidal solution had a concentration believed to be about 20 ppm, was diluted with 70 mL of distilled water. There was then added to the solution a small piece of metallic zinc, and a copper plate connected to four pieces of a tungsten carbide. The metallic zinc and the copper plate were each connected to a piece of copper wire that extended outside of the solution. When the ends of the copper wire were not in direct contact, virtually no reaction and no gas evolution were observed. When the two ends of the copper wire were placed into contact, a vigorous evolution of gas was observed emanating from the surface of each of the pieces of the tungsten carbide.
  • the total rate of gas evolution was approximately four times that obtained when a single piece of tungsten carbide was employed, indicating the relationship between the rate of hydrogen production and the surface area of the cathode.
  • the gas evolution could be stopped and restarted repeatedly simply by removing and then replacing the connection at the two ends of the copper wires. When the two copper wires were not in contact, a potential of about 0.3 volts was measured across the two ends of the copper wires.
  • the gaseous product produced at the surface of the tungsten carbide sample was captured in soap bubbles and was ignited. The explosion upon ignition strongly indicated the presence of elemental hydrogen in the product gas.
  • An initial solution comprising 5 mL of 93% concentration H 2 SO 4 , 10 mL of 35% concentration HCl, 25 mL of colloidal silver, and 10 mL of colloidal magnesium, where each colloidal solution had a concentration believed to be about 20 ppm, was diluted with 50 mL of distilled water. There was then added to the solution a small piece of a metal alloy consisting of metallic tin and metallic lead and a small piece of a tungsten carbide, each connected to a piece of copper wire that extended outside of the solution. When the ends of the copper wire were not in direct contact, virtually no reaction and no gas evolution were observed.
  • An initial solution comprising 5 mL of 93% concentration H 2 SO 4 , 10 mL of 35% concentration HCl, 25 mL of colloidal silver, and 10 mL of colloidal magnesium, where each colloidal solution had a concentration believed to be about 20 ppm, was diluted with 50 mL of distilled water. There was then added to the solution a small piece of a metal alloy consisting of metallic tin and metallic lead and a small piece of a tungsten carbide, each connected to a piece of copper wire that extended outside of the solution. When the ends of the copper wire were not in direct contact, virtually no reaction and no gas evolution were observed.

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Abstract

L'invention concerne un appareil de production d'hydrogène comprenant un certain nombre, ou la totalité, des caractéristiques suivantes, ainsi que des caractéristiques additionnelles telles que décrites et revendiquées, à savoir : un milieu réactionnel ; une anode en contact avec le milieu réactionnel ; une cathode en contact avec le milieu réactionnel, la cathode pouvant être en contact conducteur avec l'anode ; un catalyseur en suspension dans le milieu réactionnel, le catalyseur ayant un rapport élevé surface active/volume ; un sel dissous dans le milieu réactionnel ; un second catalyseur à rapport élevé surface active/volume ; un parcours conducteur connectant l'anode et la cathode ; un contrôleur dans le trajet conducteur ; une source d'énergie ; un récipient à réaction et une source d'énergie électrique configurée pour fournir un potentiel électrique entre la cathode et l'anode. L'invention concerne également un procédé de production d'hydrogène, un générateur d'énergie électrique et une batterie.
PCT/US2006/014122 2005-04-15 2006-04-14 Appareil et procede permettant une production controlable d'hydrogene a une vitesse acceleree WO2006113463A2 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007502769A (ja) * 2003-08-19 2007-02-15 グリフィン，リナド 水素を生成する装置および方法
WO2016079746A1 (fr) 2014-11-19 2016-05-26 Technion Research & Development Foundation Limited Procédés et système de production d'hydrogène par électrolyse de l'eau
WO2022187810A1 (fr) * 2021-03-01 2022-09-09 Verdagy, Inc. Systèmes et procédés pour la production d'hydrogène gazeux

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5110559A (en) * 1989-06-29 1992-05-05 Hitachi, Ltd. Hydrogen generating apparatus
US5639431A (en) * 1993-03-16 1997-06-17 Tokyo Gas Co. Ltd. Hydrogen producing apparatus
US5958091A (en) * 1994-05-23 1999-09-28 Ngk Insulators, Ltd. Hydrogen preparing apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5110559A (en) * 1989-06-29 1992-05-05 Hitachi, Ltd. Hydrogen generating apparatus
US5639431A (en) * 1993-03-16 1997-06-17 Tokyo Gas Co. Ltd. Hydrogen producing apparatus
US5958091A (en) * 1994-05-23 1999-09-28 Ngk Insulators, Ltd. Hydrogen preparing apparatus

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007502769A (ja) * 2003-08-19 2007-02-15 グリフィン，リナド 水素を生成する装置および方法
WO2016079746A1 (fr) 2014-11-19 2016-05-26 Technion Research & Development Foundation Limited Procédés et système de production d'hydrogène par électrolyse de l'eau
US10487408B2 (en) 2014-11-19 2019-11-26 Technion Research & Development Foundation Limited Methods and system for hydrogen production by water electrolysis
US11208729B2 (en) 2014-11-19 2021-12-28 Technion Research & Development Foundation Limited Methods and system for hydrogen production by water electrolysis
WO2022187810A1 (fr) * 2021-03-01 2022-09-09 Verdagy, Inc. Systèmes et procédés pour la production d'hydrogène gazeux
US11613816B2 (en) 2021-03-01 2023-03-28 Verdagy, Inc. Systems and methods to make hydrogen gas using metal oxyanions or non-metal oxyanions

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