WO2012052763A1 - Procédé de production d'énergie thermique - Google Patents

Procédé de production d'énergie thermique Download PDF

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Publication number
WO2012052763A1
WO2012052763A1 PCT/GB2011/052029 GB2011052029W WO2012052763A1 WO 2012052763 A1 WO2012052763 A1 WO 2012052763A1 GB 2011052029 W GB2011052029 W GB 2011052029W WO 2012052763 A1 WO2012052763 A1 WO 2012052763A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
oxygen
metal
absorbed
atmosphere
Prior art date
Application number
PCT/GB2011/052029
Other languages
English (en)
Inventor
Aleksander Jerzy Groszek
Original Assignee
Microscal Two Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Microscal Two Limited filed Critical Microscal Two Limited
Priority to CN201180061220XA priority Critical patent/CN103328906A/zh
Priority to US13/824,563 priority patent/US20130276771A1/en
Priority to AU2011317344A priority patent/AU2011317344B2/en
Priority to CA2815148A priority patent/CA2815148A1/fr
Priority to JP2013534383A priority patent/JP2013543577A/ja
Priority to EP11776495.1A priority patent/EP2630415A1/fr
Publication of WO2012052763A1 publication Critical patent/WO2012052763A1/fr
Priority to ZA2013/02750A priority patent/ZA201302750B/en

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Classifications

    • 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.
  • thermal energy may be generated by modifying the surfaces of the metal. It is one object of the present invention to overcome at least some of the disadvantages of the prior art or to provide a commercially useful alternative thereto. It is one object of the present invention to provide an effective, efficient and/or environmentally friendly method of generating thermal heat, preferably using low cost materials. It is a further object of the present invention to provide a rechargeable method of generating thermal energy.
  • a method of generating thermal energy comprising:
  • atmosphere comprising hydrogen and/or a
  • step (ii) wherein before performing step (ii) the surface is 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
  • the composition is exposed to an atmosphere comprising nitrogen prior to activation.
  • this document teaches away from exposing the composition to water, and indeed that water is unwanted.
  • 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 T1O 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
  • Exposure to hydrogen may at least
  • 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
  • hydrogen absorption is carried out at from 150 to 250°C.
  • the metal is of comprises copper
  • hydrogen absorption is carried out at from 120 to 180 °C.
  • the metal is or comprises ruthenium, preferably
  • hydrogen absorption is carried out at from 50 to 200 °C.
  • the metal is or comprises molybdenum, preferably hydrogen absorption is carried out at from 150 to 250°C.
  • the metal is or comprises tungsten, preferably hydrogen absorption is carried out at from 150 to 250°C.
  • the metal is or comprises cobalt, preferably hydrogen absorption is carried out at from 150 to 250°C.
  • the metal is or comprises silver, preferably hydrogen absorption is carried out at from 150 to 250°C.
  • the metal is or comprises platinum, preferably hydrogen absorption is carried out at from 50 to 150°C.
  • the metal is or comprises iron, preferably hydrogen absorption is carried out at from 150 to 250°C.
  • 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 pmol. 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 pmol per gram of the metal.
  • step (i) the absorbed, preferably
  • hydrogen content per gram of metal is from 5 to 100 pmol. More preferably after step (i) the absorbed, preferably chemisorbed, hydrogen content is from 5 to 50 pmol per gram of the metal.
  • step (i) the surface is exposed to an
  • atmosphere comprising from 0.5 to 150 pmol of hydrogen per 0.1 to 500 m 2 /g specific surface area of the metal.
  • step (i) the surface is exposed to an atmosphere comprising from 1 to 100 pmol 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.
  • hydrogen absorbed thereon preferably means that the surface of the metal has hydrogen atoms chemisorbed thereon.
  • such 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.
  • the metal 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.
  • 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
  • step (ii) exposing the surface having hydrogen absorbed thereon to an atmosphere comprising oxygen and/or an oxygen source) at least some of the
  • step (i) 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
  • 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 pmol to 100 pmol of water per gram of metal, from 0.01 to 80 pmol, from 0.01 to 10 pmol, from 0.1 to 5 pmol, or from 0.1 to 2 pmol of water per gram of metal. More preferably, the surface of the metal is exposed to atmosphere comprising from 1 to 10 pmol 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 pmol 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 pmol, or greater than 150 pmol, 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 pmol, or greater than 150 pmol, 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 pmol 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 pmol 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
  • the noble gas comprises argon.
  • 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.
  • relatively higher additions of water vapour may be tolerated.
  • step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising 0.05 to 100 pmol 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 pmol of oxygen per gram of metal, from 1 to 50 pmol of oxygen per gram of metal, or from 0.05 to 10 pmol of oxygen per gram of metal .
  • step (ii) the surface having hydrogen
  • step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.1 to 100 pmol 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
  • the 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 pmol of oxygen per gram of metal then the significant thermal energy (or heat) is typically not generated.
  • adsorbed hydrogen is not desorbed by an inert gas then 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
  • the surface may be recharged by contacting it with an atmosphere comprising hydrogen to form a surface having hydrogen absorbed thereon.
  • the surface may be
  • the method may be performed as a continuous process for the generation of thermal energy by repeating steps (i) and (ii) in turn.
  • thermal energy comprising:
  • 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
  • the present inventor has surprisingly found that
  • the surface comprises cobalt and iron.
  • 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.
  • the amount of cobalt be as low as possible since cobalt is expensive.
  • 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.
  • the iron is in the form of flakes.
  • 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 T1O 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.
  • reaction 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 pmol of hydrogen per gram of palladium or molar equivalent of cobalt and iron, from 10 to 50 pmol of hydrogen per gram of palladium or molar equivalent of cobalt and iron, from 50 to 100 pmol, or from 1 to 10 pmol 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 pmol of hydrogen per gram of palladium or molar equivalent of cobalt and iron.
  • the surface is exposed to an atmosphere
  • the surface is exposed to an atmosphere comprising from 1 to 100 pmol 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.
  • an atmosphere comprising hydrogen to form a surface which is saturated with hydrogen absorbed thereon.
  • the surface is purged by an inert carrier gas, preferably at approximately 120°C. In this way, gaseous and other gases
  • impurities present on the surface of the metal may be removed. 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.
  • the noble gas comprises argon.
  • step (ii) exposing the surface having hydrogen absorbed thereon to an atmosphere comprising oxygen) at least some of the hydrogen which is absorbed onto the surface is desorbed. Therefore,
  • 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.
  • 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
  • the surface is exposed to atmosphere comprising from 1 to 1000 pmol 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
  • palladium or cobalt and iron preferably, having hydrogen absorbed thereon is exposed to an atmosphere comprising from 1 to 200 pmol 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
  • 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
  • step (ii) the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 1 to 50 pmol of oxygen per gram of palladium or molar equivalent of cobalt and iron, or from 0.05 to 10 pmol 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 pmol of oxygen per gram of
  • the surface having hydrogen absorbed thereon is exposed to an atmosphere comprising from 0.05 to 200 pmol 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 pmol 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 x 10 7 Pa/g) . Most preferably the pressure is between atmospheric pressure (approximately 10 5 Pa/g) and 30 bar/g (3 x 10 6 Pa/g) .
  • energy storage apparatus comprising:
  • an energy storage apparatus comprising:
  • a vessel containing metal a means for contacting the metal with an atmosphere comprising hydrogen to absorb hydrogen onto the surface of the metal;
  • 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.
  • Figure 1 shows the heats of adsorption of hydrogen and oxygen on 5% Pd on active Carbon at 123°C.
  • Figure 2 shows the adsorption of H 2 , a pulse of H 2 0 and 0.45 pmol O2 in Argon
  • Figure 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.
  • Figure 4 shows heats of adsorption of oxygen on 0.327g of palladium with oxygen at 125°C.
  • Figure 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 0.45pmol of oxygen in argon .
  • Figure 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 pmol pulses of pure oxygen.
  • 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.
  • Figure 1 shows the results of the following experiment. Heat evolution at 123 C of a 10 micromole pulse of hydrogen and 0.45 micromole pulse of oxygen mixed with argon ( 1 cc of 1% vol of oxygen in argon) on 53 mg of Pd/carbon sample
  • the heat of adsorption of oxygen follows that produced by the hydrogen pulse and its partial desorption by the nitrogen carrier gas before its
  • Figure 2 shows the results of the following experiment. Heat evolutions produced by the interactions of 10 micromoles of hydrogen 5 pmol of water vapour and 0.45 micromole of oxygen mixed with argon on 0.259g 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.
  • 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.
  • Palladium seems to be especially effective at producing high heats with small amounts of oxygen. This may be because it is capable of absorbing more hydrogen than most of the other metals known at present and can do this at room
  • 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 O2 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 O2 and inert gases, or, pure oxygen
  • Figure 3 shows the heats produced by the interaction of 0.45 pmol 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.
  • 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.

Abstract

La présente invention a trait à un procédé de production d'énergie thermique, lequel procédé comprend les étapes consistant : (i) à mettre en contact la surface d'un métal avec une atmosphère comprenant de l'hydrogène en vue de former une surface sur laquelle de l'hydrogène a été absorbé ; et (ii) à exposer la surface sur laquelle de l'hydrogène a été absorbé à une atmosphère comprenant de l'oxygène, l'oxygène réagissant avec l'hydrogène absorbé pour produire de l'énergie thermique, ladite surface étant, avant de réaliser l'étape (ii), activée avec une atmosphère comprenant de l'eau.
PCT/GB2011/052029 2010-10-19 2011-10-19 Procédé de production d'énergie thermique WO2012052763A1 (fr)

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CN201180061220XA CN103328906A (zh) 2010-10-19 2011-10-19 一种产生热能的方法
US13/824,563 US20130276771A1 (en) 2010-10-19 2011-10-19 Method of generating thermal energy
AU2011317344A AU2011317344B2 (en) 2010-10-19 2011-10-19 A method of generating thermal energy
CA2815148A CA2815148A1 (fr) 2010-10-19 2011-10-19 Procede de production d'energie thermique
JP2013534383A JP2013543577A (ja) 2010-10-19 2011-10-19 熱エネルギーを発生させる方法
EP11776495.1A EP2630415A1 (fr) 2010-10-19 2011-10-19 Procédé de production d'énergie thermique
ZA2013/02750A ZA201302750B (en) 2010-10-19 2013-04-17 Method of generating thermal energy

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4730601A (en) * 1984-12-13 1988-03-15 The Garrett Corporation Steam engine reaction chamber, fuel composition therefore, and method of making and operating same
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

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51138934A (en) * 1975-05-27 1976-11-30 Agency Of Ind Science & Technol Method of accumulating and discharging thermal energy produced from me tallic tydride
US4118340A (en) * 1976-06-07 1978-10-03 National Distillers And Chemical Corporation Novel polymerization catalyst
JPS55108354A (en) * 1979-02-13 1980-08-20 Matsushita Electric Ind Co Ltd Heating apparatus
DE3013753A1 (de) * 1980-04-10 1981-10-15 Varta Batterie Ag, 3000 Hannover Hydrophober katalysator fuer rekombinatoren
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
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
JP2920860B2 (ja) * 1993-03-01 1999-07-19 日本電信電話株式会社 発熱装置
US6534033B1 (en) * 2000-01-07 2003-03-18 Millennium Cell, Inc. System for hydrogen generation
WO2002014214A1 (fr) * 2000-08-18 2002-02-21 Valery Armenakovich Grigoryan Procede de production d'hydrogene et d'energie thermique
US20050026007A1 (en) * 2003-07-28 2005-02-03 Herman Gregory S. Method and system for collection of hydrogen from anode effluents
JP4161948B2 (ja) * 2004-08-23 2008-10-08 トヨタ自動車株式会社 発熱システム及び熱供給方法
DE102007006512B4 (de) * 2006-02-13 2016-07-07 Falk-Thilo Ferse Verfahren und Vorrichtung zur Energiespeicherung sowie zur gesteuerten, verlustarmen Wärmeenergieumwandlung
JP5343003B2 (ja) * 2006-08-10 2013-11-13 リチャージャブル バッテリー コーポレイション 酸素活性ヒーターおよびその製造方法
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
FR2937630B1 (fr) * 2008-10-24 2011-05-06 Commissariat Energie Atomique Systeme catalytique pour la generation d'hydrogene par la reaction d'hydrolyse des borohydrures metalliques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4730601A (en) * 1984-12-13 1988-03-15 The Garrett Corporation Steam engine reaction chamber, fuel composition therefore, and method of making and operating same
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMISTRY AND INDUSTRY, 25 March 1965 (1965-03-25), pages 482 - 489
KUNG, H.H ET AL., JOURNAL OF PHYSICAL CHEMISTRY B, vol. 109, 2005, pages 5498 - 5502
THERMOCHIMICA ACTA, vol. 312, 1998, pages 133 - 143

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CN103328906A (zh) 2013-09-25
EP2630415A1 (fr) 2013-08-28
ZA201302750B (en) 2013-11-27
AU2011317344B2 (en) 2015-11-26
US20130276771A1 (en) 2013-10-24
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