WO2013181261A2 - Procédé de et dispositif pour optimiser un système de génération d'hydrogène - Google Patents

Procédé de et dispositif pour optimiser un système de génération d'hydrogène Download PDF

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Publication number
WO2013181261A2
WO2013181261A2 PCT/US2013/043129 US2013043129W WO2013181261A2 WO 2013181261 A2 WO2013181261 A2 WO 2013181261A2 US 2013043129 W US2013043129 W US 2013043129W WO 2013181261 A2 WO2013181261 A2 WO 2013181261A2
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hydrogen
voltage
reaction
catalyst
metal
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PCT/US2013/043129
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English (en)
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WO2013181261A3 (fr
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Jeffrey M. Carey
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Marine Power Products Incorporated
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to hydrogen production. More specifically, the present invention relates to the optimization of a hydrogen generating system.
  • Hydrogen is commonly produced from hydrocarbon fossil fuels.
  • hydrocarbon fossil fuels One of the significant problems of using hydrocarbon fossil fuels to generate hydrogen is that the process generates carbon dioxide (CO 2 ), a greenhouse gas.
  • CO 2 carbon dioxide
  • An alternative source for hydrogen production is water.
  • Currently available methods of generating hydrogen from water include biological hydrogen production, electrolysis of water, chemical production, and thermochemical production. Some researchers report that Group IV transitional metals react with water and generate hydrogen gas and a metal hydroxide.
  • the factors that are used for the system optimization include catalyst optimization treatment at the preparation stage (Redox/ pre- generation) of the catalysts, the selection of an optimal catalyst formulation, chloride ion (C1-) optimization (removal) during the operational stage (generation) of the catalysts, sodium ion (Na+) removal, sediment removal, and filtration of the water used.
  • the time for preparing and optimizing the electrodes for hydrogen production is able to be shortened by applying a pre- selected range of base voltage, pulse voltages, and/or incrementally increased voltages.
  • a base voltage of 150mV-400mV with an additional pulse voltage up to 0.8V is used to optimize the efficiency of the hydrogen production system.
  • a voltage of 1.1 V is the highest overall voltage applied.
  • a constant voltage 1.1V is applied at the electrodes during the hydrogen gas generation stage.
  • a voltage less than IV is applied at the electrodes during the hydrogen gas generation stage.
  • various formulations are chosen to optimize the efficiency of the hydrogen production system.
  • 25mg/L of Al is used and an optimized reaction rate (hydrogen production rate) is able to be obtained by increasing the amount of silver used.
  • the reaction rate is doubled when 50mg of silver is used compared to when 25mg of silver is used.
  • the reaction rate is tripled when a triple amount of the silver is used.
  • a pre- selected/incremental amount of silver is able to be added until the highest hydrogen production rate/amount is reached. By adjusting the amount of silver added, the efficiency of the hydrogen production system is able to be optimized.
  • a person of ordinary skill in the art appreciates that other chemical ratios (such as various ratios of the starting materials, e.g., Al : Ag : Cu) are able to be optimized/adjusted to optimize the reaction rate.
  • chloride ion is important at the catalysts preparation (Redox) stage, but the chloride ion is able to act negatively to the efficiency of the hydrogen production during normal operation (after the catalysts preparation stage).
  • devices and methods are used to remove chloride ions from the hydrogen production system during the operational phase (generation stage) stage. The removal of a chloride ion is able to prevent the precipitation of silver, because silver chloride has a low solubility in water solution.
  • a person of ordinary skill in the art appreciates that any other devices and methods that are able to be used to prevent the precipitation of the starting materials or the reacting chemical substances. Other methods and devices are able to be used to optimize the efficiency of hydrogen production system, such as adding another chemical substance that can form a precipitation with the chloride ions such that the chloride ions are able to be removed from the system.
  • Other aspects are able to be used to optimize the efficiency of the hydrogen production system, such as sodium ion (Na+) removal, sediment removal, and filtration of the water.
  • Sediment is able to build up during the hydrogen production reactions.
  • the sediments are able to come from the metal ions and minerals from the water supply. Removal of the sediments, such as MgO and CaO, that are building up in the reaction, is able to prevent the precipitation of the reacting chemical substance and/or prevent the clogging of the fluid transportation such that the efficiency of the hydrogen production system is able to be optimized.
  • Water filtration is another aspect that is able to be used to optimize the efficiency of the hydrogen generation system.
  • the filtration is able to be done by various ways to remove unwanted ions and chemical substances, such as ion exchange membrane and size exclusion membranes. Distillation is also able to be used to purify the water used in the system.
  • a person of ordinary skill in the art appreciates that any other methods and devices that can be used to remove unwanted particles, ions, and any other chemical substances are within the scope of the present invention.
  • a method of optimizing a hydrogen producing system comprising producing hydrogen gas using a hydrogen producing formulation containing Al(OH)x, copper, and silver, wherein x is 1, 2, 3, or 4 and removing a chemical substance that reduces the efficiency of the producing hydrogen gas.
  • the chemical substance comprises CI " .
  • the chemical substance comprises Na + .
  • the chemical substance comprises a sediment.
  • the removing the chemical substance comprises using a filter.
  • the filter comprises a reverse osmosis filter.
  • the filter comprises a PTFE membrane.
  • the filter comprises an ion exchange filter.
  • the filter comprises a Downs Cell.
  • the removing the chemical substance comprises controlling a CI " concentration to prevent a formation of AgCl precipitation.
  • the method further comprises applying a voltage to Al metal, Cu metal, Ag metal, or a combination thereof. In other embodiments, the voltage is no less than 1.1V. In some other embodiments, the hydrogen gas is produced at a voltage no greater than IV.
  • a method of making a hydrogen generating system comprises preparing a hydrogen generating catalyst containing aluminum, copper, and silver and applying a pulsed voltage to the hydrogen generating catalyst.
  • the method further comprises applying a voltage incrementally until a drop of a current.
  • the method further comprises increasing a density of the hydrogen generating catalyst on an electrode.
  • the method further comprises applying a voltage to the aluminum, wherein the aluminum comprises an aluminum metal.
  • the method further comprises applying a voltage to the copper, wherein the aluminum comprises a copper metal.
  • the method further comprises adding aluminum metal to increase a rate of hydrogen gas production until an applied current drops.
  • the method further comprises adding AgCl (s) .
  • the method further comprises adding HCl (aq) .
  • a hydrogen producing system comprises a hydrogen producing catalyst containing Al(OH)x, copper, and silver, wherein x is 1, 2, 3, or 4, a hydrogen generating voltage applied to the hydrogen producing catalyst to generate hydrogen gas, and a catalyst regenerating device to regenerate the hydrogen producing catalyst to a chemical state generating the hydrogen gas when the hydrogen generating voltage is applied.
  • the hydrogen producing system further comprises applying a catalyst preparing voltage to aluminum metal, copper metal, or a combination thereof.
  • the catalyst preparing voltage is higher than 1.1V.
  • the hydrogen generating voltage is lower than IV.
  • the catalyst regenerating device comprises a light.
  • the catalyst regenerating device comprises copper, silver, or both in a chemical state capable of coordinating with OH " .
  • the hydrogen producing system further comprises a computer automatic controlling system.
  • the computer automatic controlling system optimizes a hydrogen producing rate automatically.
  • FIG. 1 illustrates a hydrogen generating system in accordance with some
  • FIGS 2A and 2B illustrate the generation and regeneration reactions in accordance with some embodiments.
  • Figure 3 illustrates the overall reaction of a system in accordance with some embodiments.
  • Figure 4 illustrates a process of a hydrogen generating reaction in accordance with some embodiments.
  • Figure 5 illustrates a setup in accordance with some embodiments.
  • Figure 6 illustrates a method of electric -hydrolysis reaction for hydrogen production in accordance with some embodiments.
  • Figure 1 illustrates a system 100 in accordance with some embodiments.
  • the apparatus for the hydrogen generation through water decomposition includes: a main reactor 102, an oxidizer reactor 104, a heat source 108, and a computer- control system 106.
  • the main reactor 102 is a chamber where hydrogen is generated.
  • the main reactor 102 contains electrodes 102A, reactants, catalysts, and solvents contained therewithin.
  • the electrodes 102A contain iron, graphite, stainless steel, alloy, or any other proper materials.
  • the stainless steel includes Stainless 302, 316, 316L, 421.
  • the electrodes are metal alloy, such as Fe/Al or Fe/Cr/Mn and Fe/Si/Mn alloys. In some embodiments, the alloys have a Fe/Al mole or weight ratio of 97/3, 95/5, or 93/7.
  • a pre-generation voltage is applied to the electrodes 102A. In some embodiments, the voltage is provided by a power source 102B. In some embodiments, the pre-generation voltage applied is between 0.8V and 3.0V. Alternatively, the pre-generation voltage applied is about 5V or any voltage between 0.2V and 10.0V.
  • a pre-generation voltage of -2.5V or 0V is applied to a graphite electrode and +1.7V is applied to aluminum metal for 15 minutes, a pre-generation voltage of 1.4V is applied to copper metal for 10 minutes, and a pre-generation voltage of 1.0V is applied to silver metal for 5 minutes when ionizing the metals in the reaction solution.
  • a pre-generation voltage of -2.5V is applied to a graphite electrode and a pre- generation voltage of +2.5V is applied to aluminium, copper, and silver metals concurrently for about 30 minutes when ionizing the metals into the reaction solution.
  • a voltage between -0.4V and -0.9V is applied to a stainless steel electrode (cathode).
  • the voltage range mentioned above is an example, and other possible voltages are able to be applied.
  • the reactants and catalysts of the system include the hydrogen-generating substance, water, and salts.
  • the water used has a salinity of about 1.5% by weight. Other suitable percentages of salinity are able to be used, such as sea water, which has salinity about 3.8%.
  • the salts used are able to include NaCl (sodium chloride), CaCl 2 (calcium chloride), Na 2 C0 3 , or other suitable ion sources.
  • the gases generated, such as hydrogen, are transferred out through the pipe 102C. After or during the reaction, the solution in the main reactor 102 flows to the oxidizer reactor 104 for oxygen reactions. In some embodiments, HCl (aq) is added to the solution to facilitate the hydrogen generating reaction.
  • the oxidizer reactor 104 is configured for photolysis or thermolysis for the oxygen-liberation reactions.
  • the light source 104A generates light for the photolysis reaction.
  • a heat source (not shown in the figure) generates heat for thermolysis.
  • the temperature for the thermolysis reaction is less than 200 °C. In other embodiments, the temperature for the thermolysis reaction is equal to or above 200 °C.
  • the heat source transfers and/or collects environmental heat to be used by the system 100. The gases generated are transferred through the pipe 104C.
  • the heat source for the hydrogen generating reaction is able to be an independent heat exchanger 108.
  • the heat source is able to be installed in the main reactor 102 or in any other suitable chambers.
  • the computer-controller 106 controls the operations of the system 100 and monitors the status of the reaction conditions in each of the reaction reactors.
  • the computer-controller 106 contains a controlling software application 106 A to control and monitor reaction conditions, such as pH value, temperature, salinity, applied voltage (pre hydrogen generating stage, hydrogen generating stage, and/or both), purity and quantity of the gases generated, water level, catalyst formulation, catalyst reaction characteristics, and solution level in the main reactor 102 and the oxidizer reactor 104.
  • reaction conditions such as pH value, temperature, salinity, applied voltage (pre hydrogen generating stage, hydrogen generating stage, and/or both), purity and quantity of the gases generated, water level, catalyst formulation, catalyst reaction characteristics, and solution level in the main reactor 102 and the oxidizer reactor 104.
  • the computer-controller 106 is able to be used for any other purposes, including controlling and adjusting the reaction conditions.
  • reaction reactors 102 and 104 are able to be combined into a single reactor. Additional reaction reactors are able to be added. Reactions
  • a system uses the following reactions to generate hydrogen by decomposing water: (1) REDOX reaction, (2) pre-generation reaction, (3) generation reaction, (4) regeneration reaction, (5) second hydrogen reaction, and (6) oxygen reaction.
  • the REDOX reaction prepares a prehydrogen-generating substance by oxidizing or reducing the starting materials. Subsequently, the hydrogen-generating substance reacts with water or hydroxide. The REDOX reaction is illustrated in equation (1). Equation (2) illustrates that the prehydrogen-generating substance reacts with water to form the hydrogen- generating substance. A person skilled in the art will appreciate that the hydrogen-generating substance is able to carry a certain amount of surrounding water in its surrounding sphere.
  • M and its ion form represent the core of the hydrogen- generating substance and x and y represent charge parameters for an oxidation state or reaction stoichiometry.
  • REDOX reaction is one exemplary model, and the starting material is not required to go through the REDOX reaction to become an active catalyst and/or a hydrogen-generating substance for the hydrogen generation.
  • the pre-generation reaction is a step of setting up the AID (Active Ion Displacement) condition for the generation reaction.
  • the pre-generation reaction applies a minimum starting voltage (eg. 0.5V DC) to the electrodes in the solution that contains the hydrogen-generating substance.
  • the pre-generation reaction makes the hydrogen- generating substance, such as [Al(OH) 3 -xH 2 O] complex, compact onto/couple with the Fe electrode surface.
  • the pre-generation reaction is a process that requires a low applied voltage. In some embodiments, it is observed that the pH of the solution is raised during the pre- generation reaction, and it is able to result from the liberation of the OH " groups to the solution.
  • the generation reaction generates hydrogen and depletes the hydrogen-generating substance.
  • the hydrogen-generating substance is [Al(OH) 3 ]
  • the generation reaction generates hydrogen gas and produces a depleted hydrogen- generating substance, [Al(OH) 4 ] ⁇
  • the substance [Al(OH) 3 ] is used herein as an example.
  • the hydrogen-generating substance is also able to be [M(OH) 4 ] " , [M(OH) 3 ], [M(OH) 2 ] + ,
  • the generation reaction is achieved by an active ion
  • Equation (3) is an example that illustrates some embodiments of the present invention.
  • the [M(OH) y -z(H 2 0)] p y is able to be [Al ( ⁇ ) 3 ⁇ ( ⁇ 2 0)] and the [M(OH) y+1 -(z-l)(H 2 0)] p y l is able to be [Al
  • the hydrogen-generating substance is also able to be in other chemical states, contain any other suitable number of hydroxide groups, or contain other suitable ligands.
  • external heat aids the AID reaction.
  • the AID reaction is able to reduce water and associate the OH " group with the hydrogen-generating substance.
  • the AID reaction is further illustrated in equation (4), where [Al (OH) 3 -x(H 2 0)] is used as an example of the hydrogen-generating substance.
  • the x equivalent of water surrounding the core of the hydrogen-generating substance is used as an example.
  • the hydrogen-generating substance is able to use the water in the solution directly.
  • Figure 2A shows the reaction between the hydrogen-generating substance 208 and the water molecules 212.
  • the hydrogen-generating substance 208 is [Al (OH) 3 -x(H 2 0)], which reacts with the water molecules 212 and generates protons (FT) 216 or hydrogen 214.
  • the AID reactions are able to be assisted by an applied voltage, which is applied to the electrode 202. These mechanisms are described as examples.
  • a person skilled in the art would appreciate that the hydrogen gas is able to be generated through a hydride and a proton or any other suitable way of generating hydrogen gas.
  • the hydrides and protons described in this disclosure are able to bind/associate to the hydrogen- generating substance, be generated by the hydrogen-generating substance, and bind to other compounds in the solution. It is known by a person skilled in the art that amphoteric properties of aluminum hydroxides are able to add efficiency to the AID reaction of the generation reaction. It is observed that the pH of the solution is increased during the AID reaction, which is able to be resulted from the generation/liberation of the hydroxide in the AID reaction. In some embodiments, the pH value is able to be controlled by the flow rate/concentration of Catalyst Base Formulation (CBF) through the Reactor Core and Oxydizer. In some embodiments, the CBF is the hydrogen generation substance.
  • CBF Catalyst Base Formulation
  • the hydrogen-generating substance is able to generate hydrogen through protons, hydrides, or combinations thereof by a single molecule or by multi-molecules or atoms, such as alloys and a plurality of the same or different metal centers.
  • the regeneration reaction regenerates the hydrogen-generating substance from the depleted hydrogen-generating substance.
  • the [Al ( ⁇ ) 4 ⁇ ( ⁇ - 1)(H 2 0)] is able to be regenerated back to [Al (OH) 3 -x(H 2 0)] or to [Al (OH) 3 -(x- l)(H 2 0)] .
  • the generation reaction and the regeneration reactions make the whole reaction work in a catalytic manner until the hydrogen-generating substance converts to a less active or another stable state (unuseable compound).
  • [ ⁇ (OH y ] is the depleted hydrogen-generating substance
  • 2 M +X is a regenerating substance.
  • the regeneration reaction strips or liberates the hydroxide group bonded/associated to the depleted hydrogen-generating substance, so the hydrogen-generating substance regenerates from the state of depleted form, [ ⁇ ( ⁇ ], directly or indirectly back to the previous chemical state, such as [ ⁇ (OFf) ] .
  • the 2 M +X is acting as a hydroxide shuttle, such as Ag, Ag(OH), Cu, and Cu(OH) +1 , that removes or carries the hydroxide group from the depleted hydrogen-generating substance.
  • the above equation is an example to illustrate the concept of this disclosure.
  • the hydrogen-generating substance is able to be in other oxidation states, contain any other suitable number of hydroxide groups, or contain other suitable ligands.
  • the regeneration reaction is able to dissociate the OH " group away from the hydrogen- generating substance with which OH " originally bonds/associates.
  • the regeneration reaction is illustrated in equations (6) and (7) using [Al ( ⁇ ) 4 ⁇ ( ⁇ -1)( ⁇ 2 0)] " as the example of the depleted hydrogen-generating substance.
  • a person skilled in the art appreciates that the regeneration reaction is also able to occur between Ag(OH) r and Cu(OH) r , which are able to act as the hydroxide shuttle for each other.
  • R represents the numbers of hydroxides that are associated with the core of the hydroxide shuttle, and the value of R is able to be 0, 1, 2, or any other suitable number.
  • FIG. 2B illustrates a regeneration reaction in accordance with some embodiments.
  • the hydrogen-generating substance 208 binds/associates with the hydroxide group 206.
  • the hydroxide shuttles 203, 204, or 210 are able to take the hydroxide group 206 away from the depleted hydrogen-generating substance 208.
  • the hydroxide shuttle is able to be a silver ion 204, a copper ion 210, an aluminum ion (not shown in the figure), multi-ion center aggregation 203, or other chemicals that take up the hydroxide group 206.
  • the term "regeneration reaction” includes any reactions that revive the depleted hydrogen-generating substance back to the hydrogen-generating substance that is active as a catalyst for assisting the electric hydrolysis.
  • the term “hydroxide shuttle” is used as an illustration of the present invention, and the hydroxide shuttle is able to include any structure to remove any chemical substance from the hydrogen-generating substance. As such, the hydroxide shuttle is not limited to removing only hydroxyl groups. The hydroxide shuttle is able to act as a shuttle to remove hydrides, hydrogen, or other substances that bind to or associate with the hydrogen-generating substance. (5) Second Hydrogen Reaction
  • the generation reaction produces a depleted hydrogen- generating substance, which is bonded with the additional hydroxide group.
  • the regeneration reaction uses hydroxide shuttles to take the hydroxide group from the depleted hydrogen- generating substance. After taking the hydroxide group from the depleted hydrogen- generating substance, the hydroxide shuttle bonds with the hydroxide group. Subsequently, the second hydrogen reaction converts the hydroxide group bonded on the hydroxide shuttle into hydrogen proton/gas and metal oxide. For example, Ag 2+ or Ag + takes hydroxide from [Al (OH) 4 -(x-l)(H 2 0)] " and becomes Ag(OH) 2 or Ag(OH) through the regeneration reaction. The second hydrogen reaction converts Ag(OH) 2 into AgO and/or Ag 2 0 and hydrogen. In some embodiments, the above-mentioned reactions occur in the main reactor (e.g., reactor 102 in Figure 1).
  • the oxygen of the metal oxide which is generated in the second hydrogen reaction, is released from the metal oxide through photolysis, thermal decomposition, or other suitable chemical reactions or physical interactions.
  • the hydroxide shuttle is regenerated, and the hydroxide shuttle is able to take one or more hydroxide group from the depleted hydrogen-generating substance or other hydroxide shuttle having bonded hydroxide again.
  • the silver ion is regenerated from silver oxide (AgO) through an oxygen reaction.
  • the energy source of the photolysis for the oxygen reaction is visible light, UV waves, microwaves, radio frequency waves, gamma rays, x-rays, IR waves, or any other type of energy that a person skilled in the art would appreciate.
  • the metals that can be used as the hydroxide shuttle include aluminium, alumina, copper, iron, silver, zinc, magnesium, gallium, nickel, or any other metal or nonmetal material or compounds that are capable of taking up hydroxide groups.
  • the metal ion mentioned above is able to be in various oxidation states.
  • a silver ion is able to be Ag metal, Ag + , Ag 2+ or Ag 3+ .
  • the oxygen reaction is able to be performed with heat, light, or other suitable energy sources.
  • the second hydrogen reaction and the oxygen reaction are able to be part of the hydrogen-generating reactions, and the so-called hydroxide shuttles are able to be part of the hydrogen-generating substance.
  • FIG. 3 illustrates an overall reaction cycle 300 in accordance with some
  • the reaction begins with an aluminium (Al) metal 302.
  • Al metal 302 becomes Al 3+ 304.
  • the aluminium ion 304 is generated from other sources of Al ion such as bauxite, Na[Al(OH) 4 ], Al(OH) 3 , NaAlO 2 , Na 2 AlO 4 , Na 5 AlO 4 , NaAl u O 17 , or any other suitable Al ion sources.
  • the Al ion 304 reacts with water (H 2 O) 306, generating hydrogen gas 308 and the hydrogen-generating substance, aluminium hydroxide [ ⁇ 1( ⁇ ) 3 ⁇ ( ⁇ 2 ⁇ )] 310.
  • the hydrogen-generating substance 310 reacts with two surrounding water molecule. Hydrogen gas is generated in the generation reaction and the hydrogen-generating substance becomes a depleted hydrogen-generating substance, [Al(OH) 4 -(x-l)(H 2 O)] " , 312.
  • the regeneration reaction removes one OH " ion from [Al(OH) 4 -(x-l)(H 2 O)] " 312; thus, the depleted hydrogen-generating substance, [ ⁇ 1( ⁇ ) 4 ⁇ ( ⁇ - l)(H 2 O)] ⁇ , 312 becomes the substance [ ⁇ 1( ⁇ ) 3 ⁇ ( ⁇ -1)( ⁇ 2 ⁇ )] 314. Subsequently, the
  • [ ⁇ 1( ⁇ ) 3 ⁇ ( ⁇ -1)( ⁇ 2 ⁇ )] 314 associates with water and turns back into [ ⁇ 1( ⁇ ) 3 ⁇ ( ⁇ 2 ⁇ )] 310.
  • the hydrogen-generating substance works in a catalytic manner.
  • the regeneration reaction uses a copper ion 332 or a silver ion 352 as the hydroxide shuttle.
  • the copper ion 332 and the silver ion 352 are able to be generated through REDOX reactions from metal copper 330 and silver 350 or prepared from other suitable ion sources.
  • the hydroxide shuttles take up the hydroxide groups 316 and become a hydroxide-bonded hydroxide shuttle, such as Cu(OH) 2 334 or Ag(OH) 2 354.
  • the hydroxide shuttle is able to be in various oxidation states and bonded with various numbers of hydroxides 316.
  • the second hydrogen reaction generates more hydrogen and converts the hydroxide-bonded hydroxide shuttle, such as Ag(OH) 2 354, into a metal oxide, such as AgO or Ag 2 0 356, or a silver ion.
  • the oxygen reaction generates oxygen 358 and renews the metal oxide, such as AgO 356, into a renewed hydroxide shuttle.
  • the hydroxide shuttles work in a catalytic manner.
  • FIG. 4 further illustrates a process of the electrically controlled hydrogen-generation reaction 400 in accordance with some embodiments.
  • the process begins with preparing the starting material 402.
  • the hydrogen-generating substance is prepared by the REDOX reaction.
  • the hydrogen-generating substance reacts with water and becomes active hydrogen-generating substance.
  • the generation reaction makes the hydrogen-generating substance react with water or intramolecular hydrolysis reaction through an applied voltage potential to produce hydrogen gas via electric-hydrolysis reactions.
  • the hydrogen-generating substance becomes a depleted hydrogen-generating substance.
  • the regeneration reactions use hydroxide shuttles to regenerate the depleted hydrogen-generating substance.
  • the second hydrogen reaction and the oxygen reactions revive the hydroxide shuttle.
  • the hydrogen-generating substance is regenerated. After the step 412 the process goes back to the step 405, and the whole reaction works in a catalytic manner.
  • FIG. 5 illustrates a system 500 in accordance with some embodiments.
  • the apparatus 500 includes a preparation reactor 503, a main reactor 514, a
  • photochemical/oxidizer reactor 532 photochemical/oxidizer reactor 532
  • thermal converter 530 thermoconverting
  • the experiments are performed as follows.
  • the reaction begins with preparing a solution 501 containing 250mg of Al 502 metal, 50mg of Cu 504 metal, 25mg of Ag 506 metal, a graphite electrode 512 and 1 liter of water 508 having 1.5% NaCl 510 by weight.
  • a negative voltage of -1.7V is applied to the graphite electrode 512 and a positive is applied to the Al metal 502 for 15 minutes.
  • the first positive voltage applied to the Al metal 502 is removed, and a second positive voltage of 1.4V is applied to the Cu metal 504 for 10 minutes while the negative voltage of -2.5V is applied to the graphite electrode 512.
  • the second positive voltage is removed from the Cu metal 504, and a third positive voltage of 1.0V is applied to the Ag metal 506 for 5 minutes with the negative voltage still applied to the graphite electrode 512.
  • the temperature of the solution is maintained at 88 °F.
  • the procedures that are described above include ionizing the metals into the solution. In some embodiments, the procedures are for catalysts preparation.
  • the solution 501 is transferred to the main reaction vessel 514.
  • the main reaction vessel 514 contains aluminium ions 515, copper ions 517, silver ions 520, sodium ions 522, and chloride ions 524.
  • the term "ion" comprises all ligand states of a metal.
  • an aluminium ion includes Al 3+ or Al(OH) x , where the x represents the coordinated ligand numbers of the aluminium ion.
  • a voltage between 0.4V and 0.9V is applied to the cathode of the electrodes.
  • a voltage of 0.85V is applied to the cathode of the electrodes.
  • a voltage not exceeding 0.9V is applied to the cathode of the electrodes, because some experiments indicate that hydrogen production is reduced when a voltage exceeding 0.9V is applied.
  • the applied voltage of the anode is at 0V compared with a voltage on the standard hydrogen electrode.
  • the anode of the electrode is the reference electrode, which has a voltage of 0V.
  • the voltage is applied in a way that a negative charge is applied to the stainless steel electrode 516 and a positive charge is applied to the graphite electrode 518.
  • a hydrolysis reaction begins to occur when sufficient voltage is applied, and hydrogen gas 536 is generated at the stainless steel electrode 516 when the voltage is applied to the stainless steel electrode 516 and the graphite electrode 518.
  • the solution in the vessel 514 is transferred through the heater 530 and passed under the LED lights 532 to produce a photolysis reaction.
  • Oxygen gas 540 is collected at the outlet 538 during the photolysis reaction. The solution is transferred back to the main reaction vessel 514 for hydrogen production.
  • a control system 534 is connected to all the components of the system 500, including the preparation vessel 503, the main reaction vessel 514, valves 526, the heater 530 and/or heat exchanger, the LED lights 532, and all the electrodes 502, 504, 506, 512, 516, 518.
  • the control system 534 comprises one or more computers, which are able to automate the control of each of the components of the system 500. Accordingly, the control system 534 is able to automate the whole electric-hydrolysis process when predetermined conditions have been reached. For example, the control system 534 is able to initiate the reaction automatically by applying a voltage to the preparation vessel 503 when hydrogen gas is needed.
  • the control system 534 is able to stop the ionization process of the metals automatically when a preset condition has been reached, such as, a preset pH value or an applied voltage. Similarly, the control system 534 is able to transfer the solution 501 automatically to the various chambers or vessels by controlling the pump 528 and the valves 526.
  • the control system 534 is able to control the system 500 remotely.
  • the system 500 is able to be controlled through a website, over the Internet or using a telephone or PDA.
  • all of the processes of the system 500 are able to be all automated, triggered by at the occurrence of predetermined conditions, such as by using a preset timer or indicator of low fuel of a car.
  • Figure 6 illustrates a method of electric-catalytic -hydrolysis reaction 600 for hydrogen production in accordance with some embodiments.
  • the method begins at the step 602.
  • a step 604 aluminum, copper, and silver are ionized into a water solution, forming a hydrogen- generating catalyst.
  • the solution is maintained at approximately 90° F.
  • a voltage, between -0.4 and -0.9 volts, is applied to the solution or the cathode of the electrodes, thereby generating hydrogen gas.
  • the catalytic ability of the hydrogen-generating substance is regenerated by reacting with a first catalyst-reviving substance.
  • the first catalyst-reviving substance is regenerated by reacting with a second catalyst-reviving substance.
  • the second catalyst-reviving substance is regenerated by exposing it to a light, such as green LED lights.
  • the method 600 ends at a step 616.
  • some embodiments of the present invention are able to include the following chemical reactions: a REDOX reaction, a pre- generation reaction, a generation reaction, a regeneration reaction, a second hydrogen reaction, and an oxygen reaction.
  • some embodiments are able to include the following chemical reactions: a catalyst preparation reaction, a hydrogen generation reaction, a catalyst regeneration reaction, and a regeneration reaction to regenerate the catalyst regeneration substance.
  • HPS Hydrogen Generation Substrate
  • GEA Ground Electrode Assembly
  • the CBF of the HPS includes Al(OH) 3 and the CBF of the GEA includes CI " , F " and Br " .
  • the hydrogen producing reaction causes a depletion reaction of Al(OH) 3 and adding an OH " to the Al(OH) 3 .
  • CI " is consumed or depleted.
  • the ratios of the chemical compositions in the CBF are adjusted to have an optimized ratio, such that the hydrogen production rate is able to be optimized.
  • pulsing a voltage of direct current across the HPS and GEA electrodes allows Al(OH) 3 to be attracted to and remain on the HPS electrode, such that an active AID surface barrier is created, which leads to an optimal hydrogen production rate.
  • the following are factors that are able to be used to control the hydrogen production efficiency including (1) type of current, (2) polarity of current, (3) temperature, (4) applied base voltage and its range, (5) pulsed voltage and its range, (6) CBF molar ratios, and (7) voltage incremental timing and pulsing procedure.
  • Pre- generation reaction/phase is a process of (1) attraction, (2) collection, (3) consolidation, and (4) saturation of CBF compounds at the HPS and GEA electrodes.
  • a minimum initial voltage is applied and incrementally increased over time. As voltage increases, current is decreased until a maximum voltage is achieved.
  • the AID active barrier state is increased by applying a pulsed voltage.
  • Al(OH) 3 is added in the solution to enhance the active state and decrease the needed time for preparing the pre-generation phase. Once the preparation of the HPS/AID barrier is completed, temperature or pH of the CBF does not affect the barrier.
  • the Catalyst Base Formulation (CBF) of the present invention is able to be catalytic substances/chemicals for water reduction reactions.
  • the CBF comprises several metal compounds and various ions.
  • the CBF is able to be a stable, non reactive, non toxic and environmentally benign substance.
  • the AID prepared electrodes it is able to be an effective and efficient oxidizing and reducing agent.
  • the CBF contains various chemical substances having different chemical reactions occurring at different chambers.
  • MRC Main Reactor Core
  • Al(OH) 3 contained in the CFB reacts with H 2 0, which generates H + and Al(OH) " 4 .
  • the proton is reduced to become hydrogen gas.
  • the CBF is transferred from the MRC to an Accumulator.
  • Al(OH) " 4 becomes Al(OH) 3 and OH " .
  • the OH " reacts with Ag + and become Ag 2 0.
  • the solution in the Accumulator is transported to an Oxidizer.
  • Ag 2 0 is reduced to Ag°.
  • the CBF contains a composition having Ag metal, Cu metal, Al metal, CI " and distilled/deionized water. In some embodiments, the CBF contains a composition coming from a voltage applied Ag metal, a voltage applied Cu metal, and a voltage applied Al metal. In some embodiments, sodium ions are used.
  • different forms of CBF are chosen to control the hydrogen production rate. For example, a higher hydrogen production rate is achieved when smaller Ag particles are used, which is able to have a higher local Ag density on the electrodes.
  • the preparation of CBF includes the selection of a form of the CBF.
  • the selection of a form of the CBF includes having more available pre-selected ions in the solution, such as Ag + and Cu 2+ , and having a larger reacting surface area.
  • a method of CBF preparation procedure is provided. Water, Al metal, and Cu metal are placed in the MRC and the Accumulator. Next, AgCl (s) is added to the MRC and the Accumulator. HCl (aq) and NaCl (s) are added to the solution. A voltage is applied to the Al metal and Cu metal. More AgCl (s) , HCl (aq) and Al metal are added until the applied current drops to minimum. Also, more Al metal are added until the H 2 flow rate is maximized at the generation phase.
  • the following experiments show the effects of adding more of the one or more of the components of CBF and/or other chemical substances to the reaction media.
  • the substances are added to the MRC after a completed pre- generation phase reaction.
  • 100 ml of 5M HC1 is added.
  • the result shows an increase of the H 2 flow rate from 50 ml/min to 75 ml/min over a 2 hour period.
  • 50 ml of 10M H 2 S0 4 is added.
  • the result shows a short period, 2 min, of H 2 flow rate increases.
  • lOOmg of Na 2 (C0 3 ) 2 in 250 ml of water is added. The result shows that the hydrogen production is completely ceased and no change in the regeneration voltage and current.
  • sodium ion (Na + ) is removed from the system, because sodium ion is able to interfere with the hydrogen production reaction by affecting the chemical ratios in the CBF.
  • Na 2 C0 3 is added to the reaction solution. The addition of Na 2 C0 3 stops the hydrogen producing reaction. The sodium is able to react with Al(OH) 3 reducing active Al(OH) 3 in the solution, so the hydrogen producing reaction is slowed down or completely ceased.
  • Na + reacts with Al(OH) 4 " and forms NaAl(OH) 4 .
  • a reverse osmosis filter with PTFE (Polytetrafluoroethylene) membrane, or ion exchange filter is used to remove excess Na + from the reaction system.
  • PTFE Polytetrafluoroethylene
  • ion exchange filter is used to remove excess Na + from the reaction system.
  • any other devices and methods are able to be used, so long as the Na + is able to be removed from the reaction system.
  • Sediment removal a process of separating foreign sediment, debris, feedstock containment, and by-product compounds is performed.
  • the present invention is able to use various water sources like (sea)water, municipal, gray water and other water sources to produce H 2 and 0 2 .
  • the water source is able to bring in contaminate. Along time, trace contaminants buildup in the reaction chambers.
  • electrodeionization or ion exchange membrane is used to remove the sediments.
  • flushing the internal chambers is a method used to remove the sediments.
  • Downs Cell is used to remove the sediment.
  • sunlight and/or sodium hydroxide are used to remove chlorine in the system.
  • ions are charged to be removed from the system.
  • the water used for the hydrogen production reaction of the present invention includes the following properties, such as no solid precipitation, no dissolved solids, and no soluble compounds.
  • water used is distilled water.
  • the distilled water is able to come from using industrial waste heat to distill the water.
  • desalinization, deionizer, and membrane filtration system are used to filter the water used.
  • PTFE membrane is used to purify used water, and Al(OH) 3 and water are able to flow back to the system after the filtration process.
  • a first stage filtration system such as a pool filtration system, is able to be used to filter debris and bacteria/protein.
  • a second stage filtration system includes a PTFE membrane filtration system, which is able to filter out large molecules.
  • a third stage filtration system includes a flash steam distillation. Nitrates and sulfates, metal ions, and small molecule precipitates are trapped in the filter. Aromatics and dissolved gases are vented to the atmosphere.
  • a deionization device is included for filtering metal ions.
  • ultrafiltration membranes, ion exchange systems, and electrodeionization are used as the filtration system.
  • the water used is pre-treated with a reverse osmosis unit to remove an amount of the organic contaminant.
  • the term Aluminium used herein refers to all charge states and coordination numbers of the aluminium, such as Al 1+ , Al 2+ , Al 3+ , [Al(OH)] 2+ ,
  • the hydrogen producing reaction is optimized by selecting the electrodes, voltages, and current to be applied, selecting a CBF having a composition that is able to have an optimized hydrogen producing rate and/or duration, maintaining an optimized chlorine concentration, removing sodium and sediments, and pre-filtering water to be used.
  • the hydrogen production device is able to be used to generate hydrogen as a type of energy supply using environmentally non harmful chemicals and wasted heat.

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Abstract

La présente invention concerne un procédé de et un appareil pour optimiser un système de production d'hydrogène. Le procédé d'optimisation du système de production d'hydrogène comprend la production de gaz d'hydrogène en utilisant une formulation de production d'hydrogène et l'élimination d'une substance chimique qui réduit l'efficacité de production de gaz d'hydrogène. De plus, le système de production d'hydrogène comprend un catalyseur de production d'hydrogène, une tension de génération d'hydrogène appliquée au catalyseur de production d'hydrogène pour générer du gaz d'hydrogène, et un dispositif de régénération de catalyseur pour régénérer le catalyseur de production d'hydrogène à un état chimique capable de générer le gaz d'hydrogène lorsqu'une tension de génération d'hydrogène est appliquée.
PCT/US2013/043129 2012-05-31 2013-05-29 Procédé de et dispositif pour optimiser un système de génération d'hydrogène WO2013181261A2 (fr)

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