EP2367751A1 - Vorrichtung zur produktion von wasserstoff mit hilfe eines elektronenzyklotronresonanzplasmas - Google Patents

Vorrichtung zur produktion von wasserstoff mit hilfe eines elektronenzyklotronresonanzplasmas

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Publication number
EP2367751A1
EP2367751A1 EP09753152A EP09753152A EP2367751A1 EP 2367751 A1 EP2367751 A1 EP 2367751A1 EP 09753152 A EP09753152 A EP 09753152A EP 09753152 A EP09753152 A EP 09753152A EP 2367751 A1 EP2367751 A1 EP 2367751A1
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EP
European Patent Office
Prior art keywords
chamber
hydrogen
plasma
oxygen
freezing
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP09753152A
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English (en)
French (fr)
Inventor
Denis Hitz
Marc-Yves Delaunay
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication of EP2367751A1 publication Critical patent/EP2367751A1/de
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042Decomposition of water
    • C01B3/045Decomposition of water in gaseous phase
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02Preparation of oxygen
    • C01B13/0203Preparation of oxygen from inorganic compounds
    • C01B13/0207Water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02Preparation of oxygen
    • C01B13/0229Purification or separation processes
    • C01B13/0248Physical processing only
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0655Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of hydrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/08Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05HPLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00Generating plasma; Handling plasma
    • H05H1/02Arrangements for confining plasma by electric or magnetic fields; Arrangements for heating plasma
    • H05H1/16Arrangements for confining plasma by electric or magnetic fields; Arrangements for heating plasma using externally-applied electric and magnetic fields
    • H05H1/18Arrangements for confining plasma by electric or magnetic fields; Arrangements for heating plasma using externally-applied electric and magnetic fields wherein the fields oscillate at very high frequency, e.g. in the microwave range, e.g. using cyclotron resonance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0875Gas
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046Purification by cryogenic separation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00Purification or separation of specific gases
    • C01B2210/0043Impurity removed
    • C01B2210/0053Hydrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/86Processes or apparatus using other separation and/or other processing means using electrical phenomena, e.g. Corona discharge, electrolysis or magnetic field
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/10Hydrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/50Oxygen or special cases, e.g. isotope-mixtures or low purity O2
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • Electron cyclotron resonance plasma hydrogen production device
  • the present invention relates to a device for producing hydrogen from an electron cyclotron resonance plasma.
  • Hydrogen (H 2 ) appears today as a very interesting energy vector, which is expected to become increasingly important and which could, in the long term, be a good substitute for oil and fossil fuels, whose reserves will decline sharply in the coming decades. In this perspective, it is necessary to develop efficient processes for the production of hydrogen.
  • a first technique is to use steam reforming. This is a technique for converting light hydrocarbons such as methane into synthesis gas by reaction with water vapor on a catalyst.
  • the two main chemical reactions of this method are the production of synthesis gas and the conversion of CO: CH 4 + H 2 O ⁇ co + 3H 2
  • a second method is to use a partial oxidation technique: it is an exothermic technique and generally without oxidation catalyst of products such as natural gas, heavy oil residues, coal.
  • the production of synthesis gas is given by the reaction: C n H n + (Y 2 ) O 2 ⁇ nCO + (Y 2 ) H 2
  • a fourth way is to perform an electrolysis of water: it is a technique of dissociation of water by passage of an electric current according to the reaction: H 7 O ⁇ H 7 + -O 7
  • an electrolyte cell consists of two electrodes, an anode and a cathode, connected to a DC generator The electrodes are immersed in an electrolyte serving as a conducting medium.
  • This electrolyte is generally an acidic or basic aqueous solution, a proton exchange membrane (H + ) or an oxygen ion conducting membrane (O 2). " ).
  • thermochemical cycle this process uses a series of chemical reactions.
  • An example is the use of the iodine-sulfur cycle based on the decomposition of two acids at high temperature: sulfuric acid produces oxygen and sulfur dioxide, and hydroiodic acid produces hydrogen and hydrogen. 'iodine.
  • a sixth way considered is biomass: obtained by photosynthesis of carbon dioxide and water, it uses solar energy to produce molecules of the type C 6 H 9 O 4 . Then there is a thermochemical treatment according to the reaction:
  • a seventh technique involves the photo-electrolysis of water: it is a process that uses the dissociation of the water molecule by an electric current produced by the illumination of a semiconductor photocatalyst (TiO 2 , AsGa ).
  • This process does not produce greenhouse gas gas but has a relatively low conversion efficiency.
  • Another method of producing hydrogen gas by microwave plasma is proposed in document WO2006 / 123883. This method uses the dissociation of gaseous molecules by impact electronic. The disclosed method consists of injecting microwave frequencies into a dielectric tube containing a gas or a vapor of the type H 2 O or CH 4 under reduced pressure, of the order of 50-300 torr. This microwave power causes the ionization and / or dissociation of the gas, thereby releasing hydrogen (initiation of a microwave plasma). At the end of the tube, a palladium separator separates the hydrogen gas diffusion.
  • the present invention aims to provide a device for producing hydrogen by electron cyclotron resonance plasma from water, allowing efficient dissociation of water molecules and simple separation of the products formed. not necessarily requiring significant magnetic fields.
  • the invention proposes a device for producing hydrogen with an electron cyclotron resonance plasma comprising: a vacuum-sealed chamber intended to contain a plasma,
  • a magnetic structure for generating a magnetic field in said chamber and for generating a plasma along the magnetic field lines, the module of said magnetic field having a magnetic mirror configuration with at least one electronic cyclotron resonance zone for dissociating the molecules at least partially; of water introduced in the vapor phase and for at least partially ionizing the products of the dissociation, said device being characterized in that said magnetic mirror configuration is such that the modulus of said magnetic field exhibits a non-punctual, substantially constant and substantially equal minimum the magnetic field corresponding to the electron cyclotron resonance, extended at least partially along said chamber, so that said plasma has the shape of a plasma ply; said steam injection means injecting said vapor in the form of a supersonic jet, said injection means comprising a planar nozzle and a debarker, said debarker being adapted to shape said jet of vapor so as to that it is directed along the axis of said chamber; said device comprising: at least one selective cryogenic condenser for freezing the oxygen resulting from the dissociation
  • Magnetic field substantially equal to the magnetic field corresponding to the electron cyclotron resonance a magnetic field equal to ⁇ 10% near the magnetic field corresponding to the electron cyclotron resonance.
  • Magnetic field that is substantially constant in the resonance magnetic field is understood to mean a magnetic field that does not deviate by more than 10% from the resonance magnetic field.
  • the device according to the invention is based on the combined use of a cyclotron resonance plasma of electrons and at least one selective cryogenic condenser.
  • This non-CO 2 emitting device uses no electrodes, ohmic heating, membrane or high temperatures.
  • the electrons acquire energy. They will then be able to dissociate the water molecules, then ionize the dissociation products. Thanks to the electroneutrality of the plasma, these ions will follow the electrons along the magnetic field lines.
  • the mirror configuration of the magnetic field forms a profile of the magnetic field comprising a non-local minimum, called a "flat field" minimum, whose value of the magnetic field module is equal to the value of the magnetic resonance field at ⁇ 10%
  • This value of the modulus of the minimum magnetic field equal to or very close to the electron cyclotron resonance is extended at least partially along the sealed chamber of the device, typically over a length greater than 10 cm, between the two maxima of the magnetic field , thereby obtaining an extended sheet of hot plasma.
  • the value of the module inside the chamber is constant over the entire height of said chamber for a given z on the axis of the chamber.
  • the electrons will be able to acquire a large amount of energy in order to efficiently dissociate the water molecules and to ionize the dissociation products.
  • the oxygen resulting from the dissociation of the water molecules will be trapped more efficiently all along the sealed chamber and over a great length.
  • the operating pressure of the considered plasma machine being less than 5.10 -3 mbar
  • the oxygen is cryocondensed while the hydrogen remains in gaseous form.
  • cryogenic condensers forming the wall of the plasma chamber, cooled to a temperature such that the two elements, hydrogen and oxygen, composing the plasma are in different phases (hydrogen gas and solid oxygen), one can trap the oxygen in solid form without trapping the hydrogen that will be recovered by other means.
  • the temperature of the condenser depends on the partial pressures of hydrogen from of the initial density of the plasma which is itself a function of the microwave frequency injected.
  • hydrogen recovery means such as a conventional pumping system (turbomolecular pump for example) to pump hydrogen. It is also possible to advantageously use the fact that the ionized particles follow, by electroneutrality of the plasma, the electrons which are guided by the magnetic field lines.
  • the device for cryocondensation of oxygen is placed in the magnetic field lines, then it can advantageously be place hydrogen cryocondensation devices outside the magnetic field lines.
  • the device according to the invention does not use a method of thermal agitation of the water molecules, but on the other hand breaks the atomic bonds by collisions with the electrons of the plasma.
  • said chamber comprises means for injecting water vapor injecting water vapor along the longitudinal axis AA 'of the chamber directly into the hot plasma.
  • the device according to the invention may also have one or more of the following characteristics, considered individually or in any technically possible combination:
  • said at least one selective cryogenic condenser for freezing oxygen forms the inner wall of said chamber
  • said at least one cryogenic selective condenser for freezing oxygen is located at said minimum non-point magnetic field
  • said at least one selective cryogenic condenser for freezing oxygen is an annular condenser surrounding said plasma present in said chamber;
  • said at least one selective cryogenic condenser for freezing the oxygen resulting from the dissociation without freezing the hydrogen resulting from the dissociation is at a temperature of between 6 and 40 ° C. for a mean pressure substantially equal to 5.10 -3 mbar in said chamber;
  • said device comprises a plurality of selective cryogenic condensers for freezing the annular oxygen surrounding said plasma; said device comprises a second cryogenic condenser for freezing the oxygen resulting from the dissociation placed at the end of said a chamber between said magnetic mirror configuration and said hydrogen recovery means;
  • said magnetic structure comprises a plurality of permanent magnets; said plurality of permanent magnets has the same sense of magnetization;
  • said magnetic structure comprises permanent magnets whose poles face each other in the zone of injection of the water vapor;
  • said magnetic structure comprises permanent magnets whose poles face each other in the hydrogen recovery zone;
  • said permanent magnets located in the water vapor injection zone have a different polarity of said permanent magnets located in the hydrogen recovery zone;
  • said magnetic structure comprises permanent magnets of different sizes and having either the same magnetization or different magnetizations
  • said magnetic structure comprises coils at ambient temperature and / or superconducting coils at low or high critical temperature, said low or high Tc; said device comprises non-dissociated water recovery means, said non-dissociated water recovery means being substantially arranged along the steam injection axis (AA ');
  • said non-dissociated water recovery means forms a diaphragm around said steam injection means, so as to define the shape of the jet of water vapor;
  • said means for recovering non-dissociated water are formed by a cryogenic condenser
  • said device comprises at least one non-dissociated water reinjection system in the vapor phase and issuing from said non-dissociated water recovery means;
  • said device comprises a mesh having a mesh for stopping the propagation of high frequency waves;
  • said grid is inserted between the plasma of the chamber and said at least one selective cryogenic condenser for freezing the oxygen resulting from the dissociation, so as to protect said at least one cryogenic condenser of the high frequency waves;
  • said grid is formed by a metal mobile cylinder comprising solid portions and perforated portions for the at least partial protection of said at least one cryogenic condenser of the high frequency waves;
  • said device comprises an enclosure capable of recovering oxygen when the temperature of said at least one cryogenic condenser for freezing oxygen is high;
  • said means for recovering the hydrogen resulting from the dissociation are placed outside said magnetic mirror configuration:
  • said means for recovering the hydrogen resulting from the dissociation comprise a pump for pumping hydrogen in the gas phase;
  • said means for recovering the hydrogen resulting from the dissociation comprise at least one cryogenic condenser for freezing the hydrogen; said device comprises an enclosure capable of recovering hydrogen when the temperature of said at least one cryogenic condenser for freezing hydrogen is high;
  • said means for injecting a high-frequency wave inside said chamber comprises an input window placed in a high magnetic field so that the plasma diffuses towards the chamber and thus avoid impacts of the plasma on said window ;
  • said module of said minimum magnetic field is between 90% of said electronic cyclotron resonance value and said electronic cyclotron resonance value; said device comprises means for injecting high-frequency multifrequency waves.
  • FIG. 1 is a representation of the phase diagrams of hydrogen and oxygen with the corresponding values at the triple point of each element;
  • FIG. 2 shows a top view of a first embodiment of the device according to the invention
  • FIG. 3 shows a top view of a second embodiment of the device according to the invention.
  • FIG. 4 shows a top view of a third embodiment of the device according to the invention.
  • FIG. 5 shows a top view of a fourth embodiment of the device according to the invention
  • - Figure 6 shows a top view of a fifth embodiment of the device according to the invention
  • FIG. 7 shows a top view of a sixth embodiment of the device according to the invention.
  • FIG. 2 is a simplified representation of a device 1 for producing hydrogen by an electron cyclotron resonance plasma according to a first embodiment of the invention.
  • the device 1 comprises:
  • a sealed chamber 2 of parallelepipedal shape (hereinafter referred to as an enclosure thereafter) under vacuum;
  • a first cryogenic condenser 11 for trapping the oxygen forming the side wall of the sealed chamber 2;
  • a second cryogenic condenser 12 for trapping the oxygen located perpendicular to the axis AA 'of the chamber 2; a pump 13 for recovering hydrogen in gaseous form;
  • water vapor injection means 14 in the chamber 2 composed of a chamber in which steam prevails, this chamber being connected to the sealed chamber 2 by a nozzle 24 so as to create a supersonic jet water vapor.
  • the jet of water vapor is shaped with debarkers 25 consisting of pipes in which circulates a liquid whose temperature is around 5 ° C.
  • the water vapor which comes into contact with the debarkers 25 is immediately condensed and flows along the debarkers 25.
  • the jet of steam is thus limited in radial dimension and is oriented along the longitudinal axis AA 'of the chamber 2;
  • cryogenic condenser 16 for trapping non-dissociated water vapor so as to have a high directivity of the steam jet
  • the chamber 2 is evacuated, the vacuum being effected by means of pumping ad hoc. In order to have the least impurities in the chamber 2, a residual vacuum of at least 10 -4 mbar is required During operation of the device 1, the working pressure of the chamber 2 is typically less than or equal to 5.10 "3 mbar, this pressure being related to the partial pressure of water vapor injected into the chamber 2.
  • the magnetic structure formed by the eight bars of permanent magnets 3, 4, 5, 6, 7, 8, 9, 10 surrounding the chamber 2, produces inside the chamber 2 an axial magnetic field whose configuration of the module corresponds to a magnetic mirror type configuration whose profile has at least two maxima (B max ) at abscissae located respectively in the injection and extraction zones and a non-point minimum (Bmin) extended at least partially along of room 2 and located between the two maxima (B max ).
  • the two maxima (B max ) have a value greater than the value of the magnetic field (B r ⁇ S ) for which the electron cyclotron resonance is obtained.
  • the minimum (B m m) is a so-called flat field minimum, the value of which is equal to or slightly less than the value for which electronic cyclotron resonance is obtained over a large abscissa length.
  • the magnetic mirror configuration is a so-called minimum-B configuration: the electrons of the plasma are confined in a magnetic well.
  • the electrons follow magnetic field lines thanks to Laplace's law; and, thanks to the electroneutrality of the plasma, these ions will follow the electrons on the magnetic field lines.
  • the microwaves injected into the plasma tend to propagate through the plasma to the resonance zone. Indeed, the transfer of energy from the microwave power injected into the electrons of the plasma occurs at a magnetic field location (B r ⁇ S ) such that the electron cyclotron resonance condition is established, that is to say when there is equality between the pulsation of the high frequency wave ⁇ HF and the cyclotron pulsation of the electron: where q ⁇ is the charge of the electron (Cb); B r ⁇ S is the magnetic field corresponding to the resonance (T); m ⁇ is the mass of the electron.
  • a microwave generator not shown, is placed outside the chamber 2; this generator injects high frequency waves into the chamber 2 via the propagation means 15.
  • the frequency range of the microwaves can range from GHz to 100 GHz, the most common generator being the 2.45 GHz magnetron commonly used to domestic microwave ovens.
  • B r ⁇ S 0.0875 T.
  • transistors power for miniature hydrogen production devices (for embedded systems for example), it is also possible to use transistors power. Indeed, there are now field effect transistors capable of delivering about 60 W at 14.5 GHz.
  • the input window of the high frequency waves is placed in a zone of strong magnetic field, for example at the first maxima (B max ) of the profile 20 of the module of the axial magnetic field, so that the plasma diffuses in the direction of the plasma chamber 2 and not to the entrance window, so as to avoid any bombardment of this window by the plasma, thus ensuring an unlimited lifetime.
  • the steam injection means 14 in the chamber 2 are preferably placed near the microwave propagation means (however, another location may also be chosen for reasons of convenience).
  • Water is introduced into the plasma chamber 2 in the form of a supersonic vapor jet in order to obtain a high directivity of water vapor in order to direct the water vapor directly into the hot plasma towards the resonance zone of the chamber 2.
  • This jet is from a nozzle 24 itself serving as an orifice to an enclosure where the water vapor is.
  • Debarbers 25 are placed at the outlet of the nozzle 24 in order to define the angular opening of the jet.
  • These debarkers 25 consist of pipes in which circulates a liquid whose temperature is close to 5 ° C (a lower temperature would lead to solidification of the water on the debarkers). The water vapor which comes into contact with the debarkers 25 is immediately condensed and flows along the debarkers 25.
  • a cryogenic condenser 16 formed for example by a cryogenic ring, is placed at the level of the first maxima (B max ) of the magnetic field, whose profile 20 represents the modulus of the magnetic field along the chamber 2.
  • the cryogenic condenser 16 whose temperature is around 200 K, is used as a diaphragm for the purpose of trapping by cryocondensation the water vapor located in the outer part of the jet of steam.
  • the condenser 16 also avoids the non-dissociated water saturation of the main cryogenic condensers 11 and 12 necessary for the dissociation of the ionized elements.
  • the device heats the cold walls of the condenser to recover water cold walls in liquid or gaseous form to be reinjected into the device 1 by the pump 17 recycling.
  • the cryogenic condenser 16 can be interchangeably replaced by a liquid condenser comprising a vertical pipe in which a pressure gradient is established (from 10 "3 mbar to 10 2 mbar or 1 bar). vapor in the liquid form, flows along the vertical pipe by gravity and is advantageously recycled via the pump
  • the magnetic structure is formed by the rod-shaped permanent magnets 3, 4, 5, 6, 7, 8, 9 and 10 having the same magnetization direction for all the magnets.
  • the orientation of the permanent magnets 3, 4, 5, 6, 7, 8, 9 and 10 is such that the magnetic profile 20 has a magnetic mirror configuration formed by a non-point minimum-B, said to "minimum field" flat "extended over a large part of the length of the device along the axis AA 'and located between two maximum values (B max ) of the magnetic field.
  • B max maximum values of the field are quite high, of the order of 0.15 T to 0.3 T, so as to limit the axial leakage of the plasma; the maximum values can also reach several Tesla.
  • the value of the minimum-B is a value equal to or less than the value of the resonance magnetic field (B r ⁇ S ) of the order of 90% of B r ⁇ S , that is to say approximately 0.08T.
  • This value of the magnetic field equal to or slightly less than the electron cyclotron resonance is extended over a large part of the length of the device, of the order of 25 cm.
  • the electrons will be able to acquire a large amount of energy in order to effectively dissociate the water molecules over the entire length of the device 1.
  • the plasma in the form of a long column extends over a large part of the chamber, with a high density at the outlet of the vapor jet and a pressure gradient along the chamber 2.
  • the device 1 does not provide for radial confinement of the plasma due to the radial inhomogeneity of the magnetic field.
  • the ionized particles forming the plasma tend to undergo a radial drift, according to a phenomenon known in plasma physics.
  • Cryogenic condensers 11 and 12 are cold-walled condensers, called cryo-panels or cryogenic panels.
  • the condenser 11 is advantageously placed on the inner surface of the chamber 2 so as to condense the desired ionized particles.
  • the cold walls of the condenser 1 1 have a temperature of around 20 - 3OK, for example, so as to condense all the elements present in the chamber 2 except the hydrogen which remains in gaseous form at this temperature under the working pressure of 0.1 Pa. .
  • the cryogenic condenser 12 is advantageously placed in the axis of the vapor jet 14 outside the plasma before a hydrogen pumping system, so as to condense the ionized oxygen particles and the undissociated water vapor.
  • a high frequency grid 21 is placed in front of the cryopannels 1 1 so as to protect the cryopannels and to prevent their heating by the microwaves, the mesh of the RF grid (21) being determined as a function of the wavelength of the microwave. It will be noted that, according to the grid shown in FIG. 2, a tile on the abscissa substantially corresponds to 1 cm. The dimensions of each magnet have been calculated so as to obtain, in the plasma chamber, a long resonance zone, where the electrons take enough energy to dissociate the water molecules and at least partially ionize the dissociation products.
  • FIG. 3 is a variant of the previous figure (the means in common between the devices 1 and 30 have the same reference numbers and perform the same functions).
  • the device 30 according to this second embodiment differs from the device 1 of FIG. 2 in that it comprises a plurality of cryogenic condensers 31, 32, 33, 34 with cold walls of the cryo-panel type or cryogenic panel placed at the same time. 2.
  • each cryogenic condenser 31, 32, 33, 34 among the four shown is placed between a succession of magnets.
  • a metal cylinder 35 movable along the axis AA 'is inserted between the condensers 31, 32, 33, 34 and the plasma.
  • the metal cylinder 35 is used as a screen for protecting the condensers 31, 32, 33, 34.
  • the cylinder 35 comprises solid portions and perforated portions 37 by a mesh, said mesh corresponding to the wavelength of the microwaves used.
  • the oxygen dissociated by the plasma is trapped by the cold walls of the condensers 31, 32, 33, 34.
  • the cold walls of the condensers 31, 32, 33, 34 have a temperature close to 20 -3OK for example so as to condense all the elements present in the chamber 2 except the hydrogen which remains in gaseous form.
  • the solid parts are placed in front of the cold walls of the condensers 31, 32, 33, 34. In this position, the device is stopped allowing the recovery of oxygen by regeneration of the cold walls of the condensers 31, 32, 33, 34 by heating them.
  • Figure 4 is a variant of the previous figure (the means in common between devices 30 and 40 have the same reference numbers and perform the same functions).
  • the device 40 according to this third embodiment differs from the device 30 of FIG. 3 in that it comprises a mobile metal cylinder 41 having a particular arrangement of the solid parts 36 and the perforated parts 37.
  • the arrangement of these solid parts 36 and of these grid portions 37 is such that in a first position of the cylinder 41 three cryogenic condensers, for example 31, 32 and 34 are in operation, that is to say they trap the hydrogen elements, and a cryogenic condenser, for example 33, is in a regeneration process. In this way, the device 40 can operate without interruption. As soon as a wall of a condenser 31, 32, 33, or 34 is saturated, it is sufficient to move the movable cylinder 41 in different positions so as to mask the oxygen saturated wall plasma in order to regenerate it during operation of the device.
  • the different condensers 31, 32, 33, 34 at different distances from the center of the chamber 2 where the hot plasma is seated.
  • the condenser 34 placed near the jet of steam will be further away from the center of the chamber 2 so as to protect it from splashing water from the jet of steam that would come to freeze excessively on the cold wall.
  • the condenser 31 located near the hydrogen recovery system in gaseous form can be placed closer to the plasma or the center of the chamber 2 so as to pump the last oxygen atoms remaining in this zone.
  • Figure 5 is a variant of the previous figure (the means in common between the devices 40 and 50 have the same reference numbers and perform the same functions).
  • the device 50 according to this fourth embodiment differs from the device 40 of Figure 4 in that it comprises a nose 51 of ferromagnetic material to increase the efficiency of the magnetic mirror located in the microwave injection zone.
  • the added piece is a substantially elongated piece of iron or ferro-cobalt for example and including the means of propagation of high-frequency waves 15 and surrounding the stream of water vapor 14.
  • the arrangement and the material of the nose 51 make it possible to increase the first maxima (B max ) of the profile 53 without modifying the minimum-
  • the profile 53 representing the intensity of the axial magnetic field present in the chamber 2.
  • the maximum value B max of the profile 53 may be three times greater than the maximum value B max of the profile 20 detailed in the preceding embodiments of the invention illustrated with reference to FIGS. 2 to 4, which ensures better confinement of the plasma.
  • the value of the minimum-B is equal to or slightly less than the value of the magnetic resonance field (B r ⁇ S ) of the order of 90% of B r ⁇ S , that is to say approximately 0.08T.
  • This value of the magnetic field equal to or slightly less than the electron cyclotron resonance is extended over a large part of the length of the device, of the order of 25 cm.
  • Figure 6 is a variant of the previous figure (the means in common between the devices 50 and 60 have the same reference numbers and perform the same functions).
  • the device 60 according to this fifth embodiment differs from the device 50 of FIG. 5 in that it comprises a second ferromagnetic nose 52 placed at a second maxima B max of the profile 56.
  • the profile 56 representing the intensity of the magnetic field has two maximas whose intensity is higher than the maxima of the previous embodiments, thus ensuring better confinement of the plasma.
  • Figure 7 is a simplified representation of a sixth embodiment of a device 70 for producing hydrogen by an electron cyclotron resonance plasma.
  • the device 70 comprises: a sealed chamber 72 of parallelepipedal shape (hereinafter referred to as an enclosure thereafter) under vacuum;
  • a first cryogenic condenser 81 for trapping the oxygen forming the lateral wall of the sealed chamber 72;
  • a second cryogenic condenser 82 for trapping the oxygen situated perpendicular to the axis of the chamber 72;
  • a pump 83 enabling the recovery of the hydrogen in gaseous form
  • water vapor injection means 84 in the chamber 72 composed of an enclosure containing water vapor, this chamber being connected to the sealed chamber 72 by a nozzle 94 so as to create a supersonic jet water vapor.
  • the stream of water vapor is shaped with debarkers 95 consist of pipes in which circulates a liquid whose temperature is around 5 ° C.
  • the water vapor which comes into contact with the debarkers 95 is immediately condensed and flows along the debarkers 95.
  • the jet of steam is thus limited in radial dimension and is oriented along the longitudinal axis AA 'of the chamber 72;
  • Microwave type high frequency wave injection means 85 formed by a waveguide or a coaxial cable equipped with a sealed high frequency window inside the chamber 72;
  • cryogenic condenser 86 for trapping non-dissociated water vapor so as to have a high directivity of the steam jet
  • the chamber 72 is evacuated, the vacuum being effected by means of pumping ad hoc. In order to have the least impurities in the 2, a residual vacuum of at least 10 -4 mbar is required During the operation of the device 70, the working pressure of the chamber 72 is typically less than or equal to 5.10 -3 mbar, this pressure being related to the partial pressure of water vapor injected into the chamber 2.
  • the magnetic structure is formed by the eight bars of permanent magnets 73, 74, 75, 76, 77, 78, 79, 80 surrounding the chamber 2.
  • the magnet bars 75, 76, 79, 80 have the same direction of magnetization along the longitudinal axis of the chamber 72, corresponding to the magnetization direction of the bars 3, 4, 5, 6, 7, 8, 9 and as shown in the preceding figures.
  • the magnetic profile 90 has a magnetic mirror-type configuration formed by a non-punctual minimum-B, referred to as a "flat-field minimum” extended at least partially along the chamber 2 and situated between two maximum values (B max ) of the magnetic field.
  • the maximum values of the field (B max ) are quite high, of the order of 0.15 T to 0.3 T, so as to limit the axial leakage of the plasma.
  • the bars of magnets 73, 74, 77, 78 are placed at the ends of the enclosure 2 and their direction of magnetization is perpendicular to the magnetization direction of the magnets 75, 76, 79, 80, the field lines created by these magnets 73, 77 and 74, 78 being in opposition.
  • the setting up of magnets with a direction of magnetization perpendicular to the direction of the longitudinal axis AA 'of the enclosure makes it possible to reduce the size of the magnets 75, 76, 79, 80 which make it possible to obtain a mirror configuration magnetic with a minimum-B flat field slightly less than or equal to the magnetic field of resonance.
  • the magnets located around the chamber 2 occupies less space than in the previous representations, which makes it possible to simplify the installation of the means for regenerating the cold walls of the cryogenic condensers present inside the chamber 2 .
  • the magnets 75, 79 and the magnets 76, 80 may be of different sizes thus changing the magnetic profile.
  • the magnets 76 and 80 may be smaller in size so as to provide an axial magnetic field with a value of the minimum-B, in the vicinity of the water vapor injection, close to the resonance magnetic field and a value the minimum-B lower than the resonance magnetic field at the zone of the chamber 2 near the extraction of hydrogen.
  • This variant makes it possible to have less energetic electrons at a zone close to the extraction of hydrogen with better confinement in order to be able to dissociate the water molecules still present in this zone. For this, we realize in this area a more conventional confinement with a profile with a strong field gradient, lowering the minimum-B and keeping the values of maxima (B max ) constant.
  • the invention has been mainly described with a means for extracting the gaseous hydrogen at the end of the chamber 2 and pumping the hydrogen axially; however, it is also possible to equip the device according to the invention with a hydrogen extraction means pumping hydrogen from the chamber radially at the end of the chamber of the device. Indeed, in the case of the use of a simple magnetic mirror configuration as shown in Figures 2 to 7, there may be a significant particle flow in the axis of the machine, the flow of particles being 'as much lower when B max is big. Radical pumping of the hydrogen makes it possible to obtain 100% pure hydrogen.
  • the invention has been mainly described, in the embodiments illustrated with reference to FIGS. 2 to 7, with a hydrogen extraction at the end of the chamber effected by suction of the hydrogen in gaseous form by means of 'a pump. It is also possible, according to the invention, to introduce into the chamber 2 at the level of the hydrogen extraction zone and outside the magnetic field lines cold-wall cryogenic condensers for trapping hydrogen, such as cryo-panels solid or perforated and whose wall temperature is less than 5K.
  • cold-wall cryogenic condensers for trapping hydrogen, such as cryo-panels solid or perforated and whose wall temperature is less than 5K.
  • the invention has mainly been described with a magnetic configuration comprising a minimum-B equal to or less than the value corresponding to the magnetic resonance field whose value of the minimum-B is a constant value over a certain length of the chamber of the device corresponding to the distance between the two maxima (B max ); however, in another embodiment of the invention, the minimum-B of the magnetic configuration may oscillate around a minimum value, while remaining very close to this minimum value over a large distance from the chamber of the device corresponding to the distance between the two maxima (B max ).
  • the invention has been mainly described with a parallelepiped chamber surrounded by a magnetic structure formed by magnet bars and comprising cryogenic condensers in the form of a plate; however, the invention is also feasible with a cylindrical sealed plasma chamber surrounded by a magnetic structure formed by circular magnets and having cryogenic ring-shaped condensers positioned along the length of the plasma chamber.
  • the invention has been mainly described with a parallelepiped chamber surrounded by a magnetic structure formed by bars of magnets; however, part of the magnetic structure surrounding the plasma chamber such as the upper magnet bars may also be used as lower magnet bars of a magnetic structure surrounding a second sealed plasma chamber.
  • the invention has been mainly described with an axial magnetic field, however, it is also possible to add a radial component to the axial magnetic field, for the dissociation for example of other elements requiring the use of a magnetic field. radial and / or to prevent radial leakage of the plasma due to drift particles and thus ensure better confinement of the plasma.
  • the invention is not limited to the embodiment just described.

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EP09753152A 2008-09-30 2009-09-29 Vorrichtung zur produktion von wasserstoff mit hilfe eines elektronenzyklotronresonanzplasmas Withdrawn EP2367751A1 (de)

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FR0856613A FR2936505B1 (fr) 2008-09-30 2008-09-30 Dispositif de production d'hydrogene par plasma a la resonance cyclotron electronique
PCT/FR2009/051841 WO2010037960A1 (fr) 2008-09-30 2009-09-29 Dispositif de production d'hydrogene par plasma a la resonance cyclotron electronique

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JP6987402B2 (ja) 2016-08-31 2022-01-05 ワン サイエンティフィック,インコーポレイテッド 水の水素および酸素への変換を介して電力を発生させるためのシステム、装置および方法
CN109818122A (zh) * 2017-11-21 2019-05-28 核工业西南物理研究院 一种水冷型大功率电子回旋共振加热系统隔直器
CN109867261B (zh) * 2019-02-28 2024-01-26 山东师范大学 一种甲烷-二氧化碳等离子体催化重整装置及催化重整方法

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FR2583250B1 (fr) * 1985-06-07 1989-06-30 France Etat Procede et dispositif d'excitation d'un plasma par micro-ondes a la resonance cyclotronique electronique
IL102064A (en) * 1992-06-01 1995-03-30 Yeda Res & Dev Method and apparatus for the separate recovery of a high molecular weight gas and a low molecular weight gas from a gaseous starting mixture
EP0967628A2 (de) * 1996-10-08 1999-12-29 H.-P. Ehret ECR-Ionenquelle 2,45GHz
US6505472B1 (en) * 2001-08-20 2003-01-14 Praxair Technology, Inc. Cryogenic condensation system
EP1765745A4 (de) * 2003-06-30 2009-06-03 Bar Gadda Llc Dissoziation von molekularem wasser zu molekularem wasserstoff
US7384619B2 (en) * 2003-06-30 2008-06-10 Bar-Gadda, Llc Method for generating hydrogen from water or steam in a plasma
DE102004030717A1 (de) * 2004-06-25 2006-01-19 Mayer, Günter, Dipl.-Ing. Verfahren und Vorrichtung zur Speicherung von geothermer und regenerativer Energie durch die Umwandlung in chemische Energie
US20090084346A1 (en) * 2007-09-28 2009-04-02 General Electric Company Gas flow injector and method of injecting gas into a combustion system

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