US20130276771A1 - Method of generating thermal energy - Google Patents

Method of generating thermal energy Download PDF

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US20130276771A1
US20130276771A1 US13/824,563 US201113824563A US2013276771A1 US 20130276771 A1 US20130276771 A1 US 20130276771A1 US 201113824563 A US201113824563 A US 201113824563A US 2013276771 A1 US2013276771 A1 US 2013276771A1
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hydrogen
oxygen
metal
absorbed
atmosphere
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Aleksander Jerzy Groszek
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Microscal Two Ltd
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Microscal Two Ltd
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Assigned to MICROSCAL LIMITED reassignment MICROSCAL LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GROSZEK, ALEKSANDER JERZY
Assigned to MICROSCAL TWO LIMITED reassignment MICROSCAL TWO LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MICROSCAL LIMITED
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    • F24J1/00—
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24V—COLLECTION, PRODUCTION OR USE OF HEAT NOT OTHERWISE PROVIDED FOR
    • F24V30/00—Apparatus or devices using heat produced by exothermal chemical reactions other than combustion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • 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
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0026—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof of one single metal or a rare earth metal; Treatment thereof
    • 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
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention relates to a method of generating thermal energy and an energy storage apparatus.
  • the present invention also relates to the use of a metal having hydrogen absorbed thereon to generate thermal energy.
  • Methods of generating thermal energy are of use in many different industries. Particularly of use are methods of storing potential thermal energy which may be released at an appropriate time. It is also of use to be able to recharge the energy source, so that more thermal energy can be generated.
  • WO2009/040539 describes a method of activating compositions comprising transition metals selected from at least one of gold, nickel, copper, ruthenium, molybdenum and platinum.
  • heat may be generated by the physical and chemical interactions of solid surfaces with gases.
  • the heat evolution may be measured using flow-through microcalorimetry.
  • a flow-through microcalorimeter may be used to measure the uptake of gases, heat evolution, the sorption of gases and their displacement with carrier gases at a range of temperatures and pressures.
  • a method of generating thermal energy comprising:
  • a metal having hydrogen absorbed thereon to generate thermal energy by exposing the metal having hydrogen absorbed thereon to an atmosphere comprising oxygen and/or an oxygen source, optionally after the surface has been activated with an atmosphere comprising water.
  • an energy storage apparatus comprising:
  • a method of generating thermal energy comprising:
  • generating thermal energy includes generating heat.
  • the present inventor has surprisingly found that if the surface of a metal is activated with water either before, simultaneously or after (preferably before or after) it is contacted with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon then when the metal is subsequently exposed to an atmosphere comprising oxygen and/or an oxygen source, the heat generated by the reaction of the oxygen and/or oxygen source with the absorbed hydrogen is significantly more than if the metal is not treated or activated with water.
  • This result is surprising, since typically, when looking to activate metal surfaces water is avoided.
  • WO2009/040539 teaches that “in one embodiment of the present invention, preferably prior to activation of the composition, the composition is exposed to a vacuum.
  • Treatment of the composition in this way has the advantage that unwanted water and gaseous impurities are removed from the composition prior to activation.
  • the composition is exposed to an atmosphere comprising nitrogen prior to activation”.
  • absorption does not preclude adsorption of gases on to the surface of the metal.
  • the metal used in the present invention is a transition metal.
  • the metal may be an alloy of the metal.
  • the metal is selected from one or more of gold, nickel, copper, ruthenium, molybdenum, tungsten, cobalt, silver, platinum, iron, palladium and mixtures of one or more thereof. More preferably the metal is palladium or gold. Most preferably still, the metal is palladium.
  • the metal is preferably in the form of powders, particles, fibres, flakes or sponges and may be deposited on a support. Suitable supports include TiO 2 , silica, graphite or iron oxides.
  • the metal preferably has a purity of at least 99% and most preferably a purity of at least 99.99%. The purity of the metal may be measured using atomic spectroscopy.
  • the metals used in the method described may comprise absorbed oxygen. At least some of this oxygen may be removed or at least partially removed during exposure of the metal to hydrogen. Exposure to hydrogen may at least partially reduce the oxides, but preferably some hydrogen is absorbed by the reduced metal atoms or on the unreduced metal oxide groups in the form of chemisorbed atoms.
  • step (i) the surface of the metal is exposed to an atmosphere comprising hydrogen and/or hydrogen source to form a surface having hydrogen absorbed thereon.
  • hydrogen can be absorbed onto the surface of the metal at room temperature, advantageously for example at a temperature in the range of from 10 to 30° C. It may also be carried out at temperatures from 10 to 130° C. It may be preferable for the hydrogen absorption at to be carried out at an elevated temperature.
  • the metal is or comprises gold
  • hydrogen absorption is carried out at from 20 to 130° C.
  • the metal is or comprises nickel, preferably hydrogen absorption is carried out at from 150 to 250° C.
  • the metal When the metal is of comprises copper, preferably hydrogen absorption is carried out at from 120 to 180° C. When the metal is or comprises ruthenium, preferably hydrogen absorption is carried out at from 50 to 200° C. When the metal is or comprises molybdenum, preferably hydrogen absorption is carried out at from 150 to 250° C. When the metal is or comprises tungsten, preferably hydrogen absorption is carried out at from 150 to 250° C. When the metal is or comprises cobalt, preferably hydrogen absorption is carried out at from 150 to 250° C. When the metal is or comprises silver, preferably hydrogen absorption is carried out at from 150 to 250° C. When the metal is or comprises platinum, preferably hydrogen absorption is carried out at from 50 to 150° C. When the metal is or comprises iron, preferably hydrogen absorption is carried out at from 150 to 250° C. When the metal is or comprises palladium, preferably hydrogen absorption is carried out at from 10 to 130° C.
  • the surface of the metal is exposed to an atmosphere comprising from 0.1% to 100% vol of hydrogen, optionally mixed with an inert gas, to preferably obtain a chemisorbed hydrogen content per gram of metal, from 5 to 100 ⁇ mol. More preferably, the surface of the metal is exposed to atmosphere comprising from 80% vol to 100% vol of hydrogen, optionally mixed with an inert gas, to obtain a hydrogen content of the metal ranging from 5 to 50 ⁇ mol per gram of the metal.
  • the absorbed, preferably chemisorbed, hydrogen content per gram of metal is from 5 to 100 ⁇ mol. More preferably after step (i) the absorbed, preferably chemisorbed, hydrogen content is from 5 to 50 ⁇ mol per gram of the metal.
  • step (i) the surface is exposed to an atmosphere comprising from 0.5 to 150 ⁇ mol of hydrogen per 0.1 to 500 m 2 /g specific surface area of the metal. More preferably, in step (i) the surface is exposed to an atmosphere comprising from 1 to 100 ⁇ mol of hydrogen per 0.1 to 500 m 2 /g specific surface area of the metal.
  • step (i) the surface of the metal is exposed to an atmosphere comprising hydrogen and/or a hydrogen source to form a surface which contains chemisorbed hydrogen atoms.
  • a surface of a metal having hydrogen absorbed thereon preferably means that the surface of the metal has hydrogen atoms chemisorbed thereon.
  • a surface is capable of producing intense heat evolution on contact with molecular oxygen.
  • a metal powder containing at least 10 micromoles of chemisorbed hydrogen atoms will interact with approximately 0.5 micromoles of molecular oxygen to produce at least 300 kJmol ⁇ 1 of heat, and preferably at least 500 kJmol 1 .
  • the surface of the metal Prior to exposing the surface of a metal to an atmosphere comprising hydrogen and/or a hydrogen source to absorb hydrogen thereon, the surface of the metal is purged with an inert gas, preferably at approximately 120° C. In this way, gaseous and other impurities present on the surface of the metal may be removed.
  • an atmosphere comprising hydrogen and/or a hydrogen source Prior to exposure of the surface of the metal with an atmosphere comprising hydrogen and/or a hydrogen source, it may be exposed to an atmosphere comprising nitrogen and/or a noble gas.
  • the noble gas may be selected from argon, neon, helium, or a mixture of two or more thereof. More preferably the noble gas comprises one of at least argon and neon. Most preferably the noble gas comprises argon.
  • Absorption of hydrogen onto the surface of a metal may be measured by a thermal conductivity detector which senses and determines the amount of hydrogen in the effluent emerging from the FMC (Flow-through Microcalorimetry) containing the metal sorbent.
  • a thermal conductivity detector which senses and determines the amount of hydrogen in the effluent emerging from the FMC (Flow-through Microcalorimetry) containing the metal sorbent.
  • Such detectors are know in the art, for example those described in Kung, H. H et al, Journal of Physical Chemistry B 2005, 109, 5498-5502.
  • step (ii) exposing the surface having hydrogen absorbed thereon to an atmosphere comprising oxygen and/or an oxygen source) at least some of the hydrogen which is absorbed onto the surface of the metal is desorbed.
  • this allows regulation and a substantially even distribution of the strongly absorbed hydrogen atoms on the surface of the metal. Therefore, preferably, after step (i) and before step (ii) at least a portion of the hydrogen which is absorbed on the surface of the metal is desorbed. Desorbing at least a portion of the absorbed hydrogen may be achieved by flowing an inert gas or nitrogen over the surface having hydrogen absorbed thereon.
  • nitrogen gas is used to desorb at least a portion of the absorbed hydrogen from the surface of the metal.
  • at least 50%, at least 70%, at least 80% or at least 90% of the initially absorbed hydrogen is desorbed from the metal before step (ii) is carried out based on the total amount of hydrogen absorbed in the metal.
  • step (ii) is carried out based on the total amount of hydrogen absorbed in the metal.
  • at least 50%, at least 30%, at least 10% or at least 5% of the hydrogen which is absorbed in the metal remains absorbed in the metal based on the total amount of hydrogen absorbed in the metal.
  • 95% of the originally absorbed hydrogen is desorbed from the surface prior exposure of the surface to oxygen.
  • the surface of the metal is from 0.1% to 20% saturated with absorbed hydrogen.
  • the saturation of the surface with absorbed hydrogen is measured by determining the desorbed hydrogen with a thermal conductivity detector. More, preferably either after step (i) or after step (i) followed by a desorbtion step, the surface of the metal is from 0.1% to 10% saturated with the absorbed hydrogen.
  • the surface of the metal is activated with an atmosphere comprising water.
  • the surface may be activated by exposing it to an atmosphere comprising water before, or after the surface is contacted with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon.
  • the surface is activated by exposing it to an atmosphere comprising water before or after the surface is contacted with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon. More preferably still, the surface is activated by exposing it to an atmosphere comprising water after the surface is contacted with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon.
  • the atmosphere comprising water may, for example, comprise wet hydrogen gas, or a wet carrier gas.
  • the surface of the metal is exposed to an atmosphere comprising from 0.01 ⁇ mol to 100 ⁇ mol of water per gram of metal, from 0.01 to 80 ⁇ mol, from 0.01 to 10 ⁇ mol, from 0.1 to 5 ⁇ mol, or from 0.1 to 2 ⁇ mol of water per gram of metal. More preferably, the surface of the metal is exposed to atmosphere comprising from 1 to 10 ⁇ mol of water per gram of metal.
  • the present inventor has found that if low levels of water are used in the activation step (for example, less than 0.01 ⁇ mol of water per gram of metal) then the level of increase in generation of thermal energy upon exposure to oxygen compared to when the metal is not exposed to water is small.
  • the present inventor has also found that if high levels of water are used in the activation step (for example, greater than 100 ⁇ mol, or greater than 150 ⁇ mol, of water per gram of metal then the metal may be deactivated, it is thought that at such high levels the water prevents or reduces the interaction of the absorbed hydrogen with the oxygen and/or oxygen source.
  • high levels of water for example, greater than 100 ⁇ mol, or greater than 150 ⁇ mol, of water per gram of metal then the metal may be deactivated, it is thought that at such high levels the water prevents or reduces the interaction of the absorbed hydrogen with the oxygen and/or oxygen source.
  • the surface of the metal is exposed to water which is not generated by reaction of hydrogen and oxygen on the surface of the metal. Instead, preferably, “fresh”, new water is added to the system. The water is actively added to the system, it is not present as a result of a reaction.
  • the surface preferably having hydrogen absorbed thereon, is exposed to an atmosphere comprising from 1 to 500 ⁇ mol of water per 1 to 500 m 2 /g specific surface area of the metal. More preferably, the surface, preferably having hydrogen absorbed thereon, is exposed to an atmosphere comprising from 1 to 200 ⁇ mol of water per 1 to 200 m 2 /g specific surface area of the metal.
  • the oxygen source may be pure oxygen (oxygen gas having a purity of at least 95%, at least 99%, at least 99.99%), air, oxygen in an inert gas, or mixtures of one or more thereof.
  • the oxygen source may for example be or comprise hydrogen peroxide and/or ozone.
  • the surface having hydrogen absorbed thereon may be exposed to an atmosphere comprising one or more noble gases.
  • the noble gas may be selected from argon, neon, helium, or a mixture of two or more thereof. More preferably the noble gas comprises one of at least argon and neon. Most preferably the noble gas comprises argon.
  • step (ii) the surface of the metal having hydrogen absorbed thereon is exposed to an atmosphere comprising oxygen and/or an oxygen source wherein the oxygen reacts with the absorbed hydrogen to produce thermal energy.
  • the reaction is carried out under conditions such that water is not formed by the reaction of the oxygen and/or oxygen source with the absorbed hydrogen.
  • water is not formed by the reaction of the oxygen and/or oxygen source with the absorbed hydrogen.
  • step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising 0.05 to 100 ⁇ mol of oxygen per gram of metal. More preferably, in step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.1 to 50 ⁇ mol of oxygen per gram of metal, from 1 to 50 ⁇ mol of oxygen per gram of metal, or from 0.05 to 10 ⁇ mol of oxygen per gram of metal.
  • step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.05 to 200 ⁇ mol of oxygen per 0.1 to 300 m 2 /g specific surface area of the metal. More preferably, in step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.1 to 100 ⁇ mol of oxygen per 1 to 100 m 2 /g specific surface area of the metal.
  • the specific surface area of the metal may be measured by any suitable known technique, for example by a BET adsorption method.
  • oxygen may be provided as gaseous oxygen, or a source of oxygen, such as hydrogen peroxide.
  • the source of oxygen may be non-gaseous.
  • the present inventor has found that if the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising less than 0.05 ⁇ mol of oxygen per gram of metal then the significant thermal energy (or heat) is typically not generated.
  • the present inventor has surprisingly found that typically large heat evolutions are not observed. Without wishing to be bound to any particular theory it is thought that exposure of the surface having hydrogen absorbed thereon to excessive amounts of oxygen tends to produce water which is associated with low heat evolution. It is thought that evolution of high heats (for example, two, three, four, five or more times the heat of water formation) is not accompanied by the formation of water and appears to be related to the reaction (s) between the chemisorbed hydrogen and dissociated oxygen atoms.
  • the surface having hydrogen absorbed thereon may be exposed to a pulse of oxygen and/or a source of oxygen.
  • pulse is used to describe exposing a composition to a specified gas for a short period of time, typically seconds, or minutes. The length of exposure will depend on the desired amount of gas that is to be exposed to the composition and, for example, the flow rate of the gas etc.
  • a pulse as used herein is not a meant to describe a continuous or extended period of exposure of a gas to the composition.
  • a continuous flow of an atmosphere comprising oxygen for example oxygen diluted in an inert carrier gas may be used.
  • oxygen for example oxygen diluted in an inert carrier gas
  • the amount of oxygen does not exceed the limits stated above.
  • the surface having hydrogen absorbed thereon may be exposed to repeated pulses of oxygen and/or sources of oxygen.
  • the present inventor have found that by exposing the surface to repeated pulses of oxygen and/or sources of oxygen, large heat effects are seen after several pulses, until little or no heat effect is observed after further additions of pulses of oxygen and/or sources of oxygen. Without wishing to be bound by any particular theory, it is thought that heat effects are observed until all, or almost all of the hydrogen absorbed on the surface has been consumed.
  • the surface having hydrogen absorbed thereon After the surface having hydrogen absorbed thereon has been exposed to an atmosphere comprising oxygen and/or a source of oxygen, and preferably after at least some, and preferably all of the absorbed hydrogen has been consumed, the surface may be recharged by contacting it with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon. Thus, the surface may be “recharged” with absorbed hydrogen and the process may be repeated.
  • the method may be performed as a continuous process for the generation of thermal energy by repeating steps (i) and (ii) in turn.
  • a method of generating thermal energy comprising:
  • the present inventors have found that large amounts of thermal heat may be generated even in the absence of an activating water step.
  • Palladium is known to absorb hydrogen at ambient temperatures and atmospheric pressures.
  • the absorption of hydrogen is exothermic and it is generally accepted that it occurs after dissociation of hydrogen molecules into atoms. This process may take place during the exposure of palladium immersed in different inert atmospheres, such as nitrogen, helium and argon even when the partial pressure of hydrogen in the gas mixtures falls to very low values.
  • the preferential adsorption of hydrogen is very rapid at room temperatures, producing sharp evolution of heat. Desorption of the absorbed hydrogen with a flow of nitrogen is relatively slow at room temperatures, about 8000 volumes of nitrogen flow being required to completely desorb hydrogen at atmospheric pressures from 1 volume of a palladium powder at room temperatures.
  • the desorption times may be longer for fine powders and supported Pd particles, the rates of desorption being indicated by the shape of the heat endotherms.
  • the rates of desorption are relatively low allowing introduction of pulses of reactants, such as oxygen, into the flow of carrier gas, which then interact with the absorbed hydrogen.
  • the present inventor has surprisingly found that exceptionally high heat evolutions are observed when the surface comprises cobalt and iron.
  • the inventor has found that if the surface comprises only one of cobalt or iron, the exceptionally high heat evolutions are not observed. Accordingly, the combination of cobalt and iron results in an advantageous synergistic effect.
  • the surface comprises from 0.1 to 5 wt %, more preferably 0.5 to 2.5 wt %, more preferably still 0.8 to 1.5 wt %, most preferably 1 wt % cobalt relative to the amount of iron. If the surface comprises more than 5 wt % cobalt, no additional effect is observed relative to the effect observed when the surface comprises 1 wt % cobalt relative to the amount of iron. Accordingly, it is preferable that the amount of cobalt be as low as possible since cobalt is expensive.
  • the inventors have found that the small size of gold particles supported on TiO 2 leads to a marked increase in the generation of heat produced by the reaction with oxygen. This may also be partly caused by an activating effect of the supporting TiO 2 . For palladium particles supported on an active carbon this effect was detected at temperatures exceeding 100° C. On the other hand, the heat generation by the interaction of oxygen with pure Pd powder at 25° C. is markedly greater than the heat generated at 125° C. For gold, conversely, the interaction with oxygen at 125° C. produces much more heat than that determined at room temperatures.
  • the palladium may be an alloy. Palladium may be present in combination with one or more of gold, nickel, copper, ruthenium, molybdenum, tungsten, cobalt, silver, platinum, iron.
  • the palladium is preferably in the form of powders, particles, fibres, flakes or sponges and may be deposited on a support.
  • the cobalt and iron may be an alloy or alloys. Cobalt and iron may be present in combination with one or more of gold, nickel, copper, ruthenium, molybdenum, tungsten, silver, platinum, palladium.
  • the cobalt and iron are preferably each in the form of powders, particles, fibres, flakes or sponges or mixtures thereof, or each deposited on a support. Preferably, the cobalt is deposited on the iron. Preferably, the iron is in the form of flakes. Most preferably, the cobalt and iron is an alloy.
  • a 1 wt % cobalt/iron alloy may be produced by co-grinding cobalt and iron powders in a Vibratory Ball Mill or by other conventional techniques. Similar alloys can be produced by, for example, co-grinding palladium and iron and nickel and iron.
  • the palladium or cobalt and iron may be deposited on a support, such as TiO 2 , silica, graphite or iron oxide.
  • the palladium or cobalt and iron respectively preferably have a purity of at least 99% and most preferably a purity of at least 99.99%.
  • the purity of the respective metals may be measured using atomic spectroscopy.
  • step (i) the surface of the palladium or cobalt and iron is exposed to an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon.
  • hydrogen can be absorbed onto the surface of the palladium at room temperature, for example at a temperature in the range of from 10 to 30° C.
  • the reaction may also be carried out at temperatures in the range of from 10 to 130° C.
  • the reaction wherein the surface comprises cobalt and iron may be carried out at from 180° C. to 220° C., preferably at from 190° C. to 210° C., more preferably at from 195° C. to 205° C.
  • the surface is exposed to atmosphere comprising from 1 to 100 ⁇ mol of hydrogen per gram of palladium or molar equivalent of cobalt and iron, from 10 to 50 ⁇ mol of hydrogen per gram of palladium or molar equivalent of cobalt and iron, from 50 to 100 ⁇ mol, or from 1 to 10 ⁇ mol of hydrogen per gram of palladium or molar equivalent of cobalt and iron. More preferably, the surface is exposed to an atmosphere comprising from 5 to 50 ⁇ mol of hydrogen per gram of palladium or molar equivalent of cobalt and iron.
  • the surface is exposed to an atmosphere comprising from 0.5 to 150 ⁇ mol of hydrogen per 0.1 to 500 m 2 /g specific surface area of the palladium or molar equivalent of cobalt and iron. More preferably, the surface is exposed to an atmosphere comprising from 1 to 100 ⁇ mol of hydrogen per 0.1 to 500 m 2 /g specific surface area of the palladium or molar equivalent of cobalt and iron.
  • step (i) the surface is exposed to an atmosphere comprising hydrogen to form a surface which is saturated with hydrogen absorbed thereon.
  • the surface Prior to exposing the surface of to an atmosphere comprising hydrogen to absorb hydrogen thereon, the surface is purged by an inert carrier gas, preferably at approximately 120° C. In this way, gaseous and other impurities present on the surface of the metal may be removed.
  • an atmosphere comprising nitrogen and/or a noble gas Prior to exposure of the surface with an atmosphere comprising hydrogen, it may be exposed to an atmosphere comprising nitrogen and/or a noble gas.
  • the noble gas may be selected from argon, neon, helium, or a mixture of two or more thereof. More preferably the noble gas comprises one of at least argon and neon. Most preferably the noble gas comprises argon.
  • step (ii) exposing the surface having hydrogen absorbed thereon to an atmosphere comprising oxygen
  • step (ii) exposing the surface having hydrogen absorbed thereon to an atmosphere comprising oxygen
  • step (ii) at least some of the hydrogen which is absorbed onto the surface is desorbed. Therefore, preferably, after step (i) and before step (ii) at least a portion of the hydrogen which is absorbed on the surface is desorbed. Desorbing at least a portion of the absorbed hydrogen may be achieved by flowing an inert gas over the surface having hydrogen absorbed thereon.
  • the surface is from 0.1% to 20% saturated with absorbed hydrogen. More, preferably either after step (i) or after step (i) followed by a desorbtion step, the surface of the metal is from 0.1% to 10% saturated with absorbed hydrogen.
  • the surface is activated with an atmosphere comprising water.
  • the surface may be activated by exposing it to an atmosphere comprising water before, or after the surface is contacted with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon.
  • the surface is activated by exposing it to an atmosphere comprising water before or after the surface is contacted with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon. More preferably still, the surface is activated by exposing it to an atmosphere comprising water after the surface is contacted with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon.
  • the surface is exposed to an atmosphere comprising from 0.01 to 10000 ⁇ mol of water per gram of palladium or molar equivalent of cobalt and iron, from 0.1 to 5000 ⁇ mol of water per gram of palladium or molar equivalent of cobalt and iron, or from 0.1 to 2000 ⁇ mol of water per gram of palladium or molar equivalent of cobalt and iron. More preferably, the surface is exposed to atmosphere comprising from 1 to 1000 ⁇ mol of water per gram of palladium or molar equivalent of cobalt and iron.
  • the palladium or cobalt and iron preferably having hydrogen absorbed thereon, is exposed to an atmosphere comprising from 1 to 500 ⁇ mol of water per 1 to 500 m 2 /g specific surface area of the palladium or molar equivalent of cobalt and iron. More preferably, the palladium or cobalt and iron, preferably, having hydrogen absorbed thereon is exposed to an atmosphere comprising from 1 to 200 ⁇ mol of water per 1 to 200 m 2 /g specific surface area of the palladium or molar equivalent of cobalt and iron.
  • the surface is exposed to water which is not generated by reaction of hydrogen and oxygen on the surface. Instead, preferably, “fresh”, new oxygen is added to the system.
  • the oxygen source may be pure oxygen (oxygen gas having a purity of at least 95%, at least 99%, at least 99.99%), air, oxygen in an inert gas, or mixtures of one or more thereof.
  • the oxygen source may for example be or comprise hydrogen peroxide and/or ozone.
  • the surface having hydrogen absorbed thereon may be exposed to an atmosphere comprising one or more noble gases.
  • the noble gas may be selected from argon, neon, helium, or a mixture of two or more thereof. More preferably the noble gas comprises one of at least argon and neon. Most preferably the noble gas comprises argon.
  • the present inventor has surprisingly found that if argon is used as a carrier gas for the pulse of oxygen much larger amounts of heat are generated.
  • step (ii) the surface of the metal having hydrogen absorbed thereon is exposed to an atmosphere comprising oxygen wherein the oxygen reacts with the absorbed hydrogen to produce thermal energy.
  • step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.05 to 100 ⁇ mol of oxygen per gram of palladium or molar equivalent of cobalt and iron. More preferably, in step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 1 to 50 ⁇ mol of oxygen per gram of palladium or molar equivalent of cobalt and iron, or from 0.05 to 10 ⁇ mol of oxygen per gram of palladium or molar equivalent of cobalt and iron.
  • the present inventor has found that if the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising less than 0.05 ⁇ mol of oxygen per gram of palladium or molar equivalent of cobalt and iron then the significant thermal energy (or heat) is typically not generated.
  • the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.05 to 200 ⁇ mol of oxygen per 0.1 to 300 m 2 /g specific surface area of the palladium or molar equivalent of cobalt and iron. More preferably, the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.1 to 100 ⁇ mol of oxygen per 1 to 100 m 2 /g specific surface area of the palladium or molar equivalent of cobalt and iron.
  • the surface having hydrogen absorbed thereon may be exposed to a pulse of oxygen.
  • the surface having hydrogen absorbed thereon may be exposed to repeated pulses of oxygen.
  • the present inventors have found that by exposing the surface to repeated pulses of oxygen, large heat effects are seen after several pulses, until little or no heat effect is observed after further additions of pulses of oxygen. Without wishing to be bound by any particular theory, it is thought that heat effects are observed until all, or almost all of the hydrogen absorbed on the surface has been used.
  • the surface having hydrogen absorbed thereon After the surface having hydrogen absorbed thereon has been exposed to an atmosphere comprising oxygen, and preferably after at least some, and preferably all of the absorbed hydrogen has been consumed, the surface may be recharged by contacting it with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon. Thus, the surface may be “recharged” with absorbed hydrogen and the process may be repeated.
  • the present invention may be carried out at pressures from atmospheric pressure (approximately 10 5 Pa/g) to 150 bar/g (1.5 ⁇ 10 7 Pa/g). Most preferably the pressure is between atmospheric pressure (approximately 10 5 Pa/g) and 30 bar/g (3 ⁇ 10 6 Pa/g).
  • a metal having hydrogen absorbed thereon to generate thermal energy by exposing the metal having hydrogen absorbed thereon to an atmosphere comprising oxygen, optionally after the surface has been activated with an atmosphere comprising water.
  • an energy storage apparatus comprising:
  • the term “vessel” means a gas tight (air-tight) container, which comprises a means for introducing and releasing a specific gas, or mixture of gases, such that the atmosphere in the vessel may be controlled.
  • FIG. 1 shows the heats of adsorption of hydrogen and oxygen on 5% Pd on active Carbon at 123° C.
  • FIG. 2 shows the adsorption of H 2 , a pulse of H 2 O and 0.45 ⁇ mol O 2 in Argon
  • FIG. 3 shows the heats of exposure of a 0.259 g sample of palladium powder to oxygen after reduction with hydrogen at 25° C. Comparison of the heats of adsorption of equal amounts of pure oxygen and the oxygen mixed with argon.
  • FIG. 4 shows heats of adsorption of oxygen on 0.327 g of palladium with oxygen at 125° C.
  • FIG. 5 shows heats of exposure of a 0.053 g of palladium catalyst supported on an active carbon at 25° C. The palladium was exposed to two times 0.45 ⁇ mol of oxygen in argon.
  • FIG. 6 shows heats of exposure of a 0.53 g sample of palladium catalyst supported on an active carbon at 125° C. The sample was exposed to 2 ⁇ mol pulses of pure oxygen.
  • the surface energy measurements were carried out using a Microscal Flow-trough Microcalorimeter as described in Chemistry and Industry 25 Mar. 1965, pages 482 to 489 and Thermochimica Acta, 312, 1998, pages 133 to 143.
  • the adsorption experiments described herein were conducted by exchanging the flow of nitrogen for those of pure hydrogen, oxygen, noble gas or the gas under investigation.
  • the resulting exposures of the metals to the gases were maintained for seconds or minutes for the pulse experiments, or hours to achieve complete saturation, i.e. until no further uptake of the interacting gases was recorded by the thermal conductivity detector.
  • the pulses were separated by nitrogen flows long enough to remove any oxygen or noble gas that was not retained (absorbed) by the metal powders.
  • purification of the internal walls of the tubing was carried out in each case, before the exchanges, for example, by passing at least 100 cc of each gas through the tubing before their exchanges with nitrogen flows.
  • the abnormally high heat generated in this method can reach, for example five to twelve times higher than the heats of formation of gaseous water from molecular hydrogen and oxygen, which offers the development of new sources of energy for domestic and industrial purposes.
  • the sample of palladium was then exposed to a further 0.45 ⁇ mol of oxygen in an argon carrier gas. This time 1488 mJ of heat were evolved, which equates to 3306 kJ/mol of heat per mol of oxygen.
  • the sample of palladium was then exposed to a further 0.45 ⁇ mol of oxygen in a nitrogen carrier gas. This resulted in 618 mJ of heat being evolved, which equates to 1373 kJ/mol of heat per mol of oxygen.
  • the sample of palladium was then exposed to a further 0.45 ⁇ mol of oxygen in a nitrogen carrier gas. This resulted in 658 mJ of heat being evolved, which equates to 1456 kJ/mol of heat per mol of oxygen.
  • the sample of palladium was then exposed to a further 0.45 ⁇ mol of oxygen in a nitrogen carrier gas. This resulted in 668 mJ of heat being evolved, which equates to 1489 kJ/mol of heat per mol of oxygen.
  • the sample of palladium was then exposed to a further 0.45 ⁇ mol of oxygen in a helium carrier gas. This resulted in 544 mJ of heat being evolved, which equates to 1209 kJ/mol of heat per mol of oxygen.
  • the sample of palladium was then exposed to a further 0.45 ⁇ mol of oxygen in a nitrogen carrier gas. This resulted in 675 mJ of heat being evolved, which equates to 1500 kJ/mol of heat per mol of oxygen.
  • the sample of palladium was then exposed to a further 0.45 ⁇ mol of oxygen in a nitrogen carrier gas. This resulted in 630 mJ of heat being evolved, which equates to 1400 kJ/mol of heat per mol of oxygen.
  • FIG. 1 shows the results of the following experiment.
  • the heat of adsorption of oxygen follows that produced by the hydrogen pulse and its partial desorption by the nitrogen carrier gas before its interaction with 0.45 ⁇ mol of oxygen generating heat evolution of 1428 mJ equivalent to 3173 kJ/mol/O 2 .
  • This heat evolution exceeds that of the formation of water from molecular hydrogen and oxygen by a factor of 6.6.
  • the high heat evolution was obtained after the Pd particles deposited on an activated carbon were exposed to 5 ⁇ mol pulse of water before the interactions with hydrogen and oxygen. The water pulse was almost completely absorbed and is not visible in the figure.
  • FIG. 2 shows the results of the following experiment. Heat evolutions produced by the interactions of 10 micromoles of hydrogen 5 ⁇ mol of water vapour and 0.45 micromole of oxygen mixed with argon on 0.259 g of unsupported Pd powder at 25 C.
  • the absorption of hydrogen produces a heat evolution of 637 mJ following a 600 mJ in situ calibration peak.
  • the subsequent flow of nitrogen desorbing 3.3 micromole of the absorbed hydrogen is followed by a 5 ⁇ mol pulse of water vapour producing a 2 mJ heat effect to small to be visible in the figure.
  • a 0.45 micromole pulse of oxygen followed generating heat evolution of 2632 mJ equivalent to a molar heat of absorption of 5849 kJ/mol/02. This heat evolution exceeded the heat of formation of water from molecular hydrogen and oxygen by a factor of 12.1
  • This example shows the heats of interaction of molecular oxygen (0.45 micromoles) with 0.259 g of palladium powder after their reduction with hydrogen at 25° C.
  • the effective amounts of water vapour typically range between 1 to 50 micromoles per gram of palladium powders and preferably between 1 and 10 micromoles. In this example the amount of water to which the palladium powders were exposed was 20 micromoles per gram.
  • the high heat generation can be obtained continuously in an arrangement in which hydrogen and oxygen (it could be air, mixtures of O 2 and inert gases, or, pure oxygen) are passed through finely divided palladium maintaining appropriate proportions of chemisorbed hydrogen, coming into contact with oxygen in a regime not producing any water.
  • hydrogen and oxygen it could be air, mixtures of O 2 and inert gases, or, pure oxygen
  • FIG. 3 shows the heats produced by the interaction of 0.45 ⁇ mol pulses of oxygen with the sample of palladium powder containing the absorbed hydrogen.
  • the amount of the absorbed hydrogen constituted about 10% of the hydrogen that the Pd sample is capable of adsorbing at 25° C.
  • the rate of its desorption by nitrogen flow was relatively slow and the oxygen pulses interacting with the Pd sample encountered large numbers of the absorbed hydrogen atoms with which the oxygen pulses could interact.
  • Displacement of the nitrogen carrier gas by 0.45 ⁇ mol of oxygen mixed with argon produced heat evolutions that were on average 4.7 times higher than the heats of formation of water.
  • the 1% Cobalt/Iron catalyst is produced by co-grinding cobalt and iron powders in a Vibratory Ball Mill to produce an alloy.
  • Experiment 21 records heat evolution produced by continuous evolution of heat for 23 minutes after saturation of Co/Fe catalyst with hydrogen.

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US6534033B1 (en) * 2000-01-07 2003-03-18 Millennium Cell, Inc. System for hydrogen generation
US20050026007A1 (en) * 2003-07-28 2005-02-03 Herman Gregory S. Method and system for collection of hydrogen from anode effluents
WO2005118137A1 (fr) * 2004-06-04 2005-12-15 Microscal Limited Procede d'activation d'un catalyseur
WO2009040539A2 (fr) * 2007-09-26 2009-04-02 Microscal Limited Procédé d'activation d'une composition
US20100178240A1 (en) * 2008-10-24 2010-07-15 Commissariat A L'energie Atomique Catalytic system for generating hydrogen by the hydrolysis reaction of metal borohydrides
US8697027B2 (en) * 2008-08-27 2014-04-15 Alliant Techsystems Inc. Methods and systems of producing hydrogen and oxygen for power generation, and power source

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CA1200540A (fr) * 1983-10-24 1986-02-11 Atomic Energy Of Canada Limited - Energie Atomique Du Canada, Limitee Methode de fabrication d'un catalyseur au silice cristallin et au platine
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US4118340A (en) * 1976-06-07 1978-10-03 National Distillers And Chemical Corporation Novel polymerization catalyst
US5012719A (en) * 1987-06-12 1991-05-07 Gt-Devices Method of and apparatus for generating hydrogen and projectile accelerating apparatus and method incorporating same
US6534033B1 (en) * 2000-01-07 2003-03-18 Millennium Cell, Inc. System for hydrogen generation
US20050026007A1 (en) * 2003-07-28 2005-02-03 Herman Gregory S. Method and system for collection of hydrogen from anode effluents
WO2005118137A1 (fr) * 2004-06-04 2005-12-15 Microscal Limited Procede d'activation d'un catalyseur
WO2009040539A2 (fr) * 2007-09-26 2009-04-02 Microscal Limited Procédé d'activation d'une composition
US8697027B2 (en) * 2008-08-27 2014-04-15 Alliant Techsystems Inc. Methods and systems of producing hydrogen and oxygen for power generation, and power source
US20100178240A1 (en) * 2008-10-24 2010-07-15 Commissariat A L'energie Atomique Catalytic system for generating hydrogen by the hydrolysis reaction of metal borohydrides

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ZA201302750B (en) 2013-11-27
GB201017638D0 (en) 2010-12-01
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GB2484684A (en) 2012-04-25

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