WO2003097524A1 - Method for producing pure gases, in particular hydrogen and oxygen - Google Patents

Method for producing pure gases, in particular hydrogen and oxygen Download PDF

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Publication number
WO2003097524A1
WO2003097524A1 PCT/FR2003/001454 FR0301454W WO03097524A1 WO 2003097524 A1 WO2003097524 A1 WO 2003097524A1 FR 0301454 W FR0301454 W FR 0301454W WO 03097524 A1 WO03097524 A1 WO 03097524A1
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Prior art keywords
gases
hydrogen
oxygen
separation
water
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PCT/FR2003/001454
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French (fr)
Inventor
Nils Kongmark
Harald Wirth
Klaus RÖHRICH
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Creative Services Sarl
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Priority to AU2003254531A priority Critical patent/AU2003254531A1/en
Priority to EP03752799A priority patent/EP1506131A1/en
Publication of WO2003097524A1 publication Critical patent/WO2003097524A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2475—Membrane reactors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds
    • C01B13/0207—Water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C01B3/045—Decomposition of water in gaseous phase
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00157—Controlling the temperature by means of a burner
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0053—Hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a method for the production of separated gases, in particular in the production of hydrogen and oxygen by thermal dissociation of water.
  • the invention targets the manufacture of compact devices, possibly mobile, for the production of hydrogen.
  • the invention is based on the principle of a p reactor. ex with membranes as presented in several documents 1 . It claims to improve such devices (1) by accelerating the process of evaporation of water, (2) by heating to a very high temperature by combustion of a gas with pure oxygen, and (3) by supplying this oxygen as an outgoing gas associated with the production of hydrogen. These improvements are intended to provide the principle of a compact device which can optionally be installed p. eg in a fuel cell car replacing the hydrogen storage system.
  • Fossil energy sources are limited. World oil production will peak for a time between 2004 and 2008 and then decline and never increase again (K.S. Deffeys, 2001). Petroleum is a precious raw material, which should be used for lubricants and the manufacture of other products. Today and in the years to come 85% of all oil extracted is burned, either in engines of different types or for domestic and industrial heating. Even if this delay forecast is wrong for a few years, the disappearance of oil and other fossil energy sources is an established fact. The invention helps to replace petroleum as an energy source.
  • the object of the present invention is to allow the control of the production of a gas mixture and of the separation of the gases in a gas mixture, in particular if the gas mixture is water vapor.
  • the invention is based on several known facts.
  • the first is that the efficiency of heat transfer to a liquid object is linked to the relation of its surface 5 in contact with the heat source to its volume V.
  • the S / V relationship is ⁇ 1
  • a liquid in droplets in a warm environment eg. eg steam, can reach a relative ratio of more than 200.
  • Table 1 Comparison of combustion temperatures of gases in air and with oxygen.
  • the invention By burning a fuel, the invention employs thermodynamic phenomena that certain oxidation reactions give off high energies, making it possible to reach temperatures exceeding
  • the fuel is burned with pure oxygen leaving the device. We get more combustion efficient and clean, without production of nitrogen oxides and with a minimum of carbon oxides.
  • the degree of dissociation depends on the temperature of the water vapor reached.
  • Table 2 Example of the (approximate) degree of dissociation of water molecules in percent of the total mass at atmospheric pressure. Gas components are separated, p. ex hydrogen and oxygen created in the dissociation of water. The separation is carried out using ceramic or metallic membranes to separate the gas molecules by molecular sieving or by ion transport, separation arrangements by means of nozzles, or any other physical or chemical means.
  • the quantities of gas extracted are linked to their stoichiometric presence in the initial gas or liquid.
  • H 2 0 For the extraction of hydrogen and oxygen from water (H 2 0), two parts (in number of molecules) of hydrogen (H 2 ) and one part of oxygen (0 2 ) will be extracted - Because the energy vector (combustible gas) and the source of hydrogen (water) are physically separated, the gases leaving, in particular hydrogen, do not contain any contamination from small quantities of water. This fact is important, since it is no longer necessary to add a gas purification stage before its use p. eg in a fuel cell.
  • the extracted gases are directed either to external users or to use in the device itself.
  • the gases produced as well as the exhaust gas from the crucible pass through heat exchangers. Heat can be used to preheat water or for any other purpose.
  • Exhaust gas can also be used to achieve additional goals.
  • Inert materials recently developed and resistant to high temperatures are used. The evolution of such materials is promising for future improvements of the invention.
  • One embodiment of the invention may be the separation of hydrogen and oxygen from liquid water.
  • the container is made of heat resistant material.
  • One or more crucibles are mounted inside the reactor. Inside the crucible is burned acetylene- (C 2 H 2 ) with oxygen. To start the device, either oxygen from the air or oxygen from a storage container is used. When the machine is running, there will be enough oxygen production to support the combustion of acetylene.
  • the temperature can reach 3000 ° K and more.
  • Sprinklers mounted in the walls of the reactor inject small droplets of water. One or more nozzles are used to split the liquid into droplets one size in the order of one micrometer before exposure to heat for conversion. The water evaporates either through the hot gas in the reactor or in contact with the surface of the crucible.
  • the conversion of liquid into vapor is carried out by irradiation, convection and conduction.
  • the vapor is converted to a gas mixture by thermal dissociation by means of irradiation, convection and conduction.
  • the gas mixture is further heated by irradiation, convection and conduction, until a desired degree of dissociation is reached.
  • the thermal equilibrium is reached in very short times, below a millisecond depending on the power of the crucibles and the total amount of material in the reactor.
  • Some parts of the reactor walls are made of permeable materials for the gas components to be extracted.
  • the surface of the parts is chosen according to the permeability of the materials in order to ensure the relationship between the quantities extracted.
  • the jets inject the quantity of water corresponding exactly to the quantities of gas removed.
  • Two or more separation processes are carried out in parallel, resulting in the simultaneous extraction of two or more separate gases or mixtures of gases from the initial gas mixture.
  • Two or more separation processes are carried out in consecutive stages, such that two or more gases or distinct mixtures of gases are successively extracted from the initial mixture of gases.
  • the gases remain mechanically separated in caves above the permeable surfaces. They are directed to their next use by pipe systems and possibly pumps. Specifically, the oxygen will be compressed to be re-injected into the acetylene circuit.
  • the gas caves serve as the first thermal insulation.
  • thermos bottle system The complete system of the reactor with the gas collection caves is in a system of several layers of thermal insulation comprising vacuum insulation (thermos bottle system).
  • the inlets for the combustion gas and for the water pass through the various insulation stages and are thus preheated.
  • FIG. 1 shows the operating principle as described above, in particular the gas flows.
  • the volume of a reactor (1) comprises a crucible (2) and two caverns (3 and 4) for assembling the separate gases. They are extracted through permeable membranes almost exclusively for oxygen (5) and for hydrogen (6).
  • the water is led by a line (7) to the nozzle (8) inside the reactor.
  • the spout (9) of the crucible is supplied by a line of combustible gas (10), the exhaust gases exit through pipes (11).
  • the separated gases are routed through gas lines.
  • a line (12) is used for oxygen, which will be added to the fuel gas circuit.
  • the other line (13) will lead the hydrogen to its destination.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Fuel Cell (AREA)

Abstract

The invention concerns the control of production of separate gases, in particular in the production of hydrogen and oxygen by thermal dissociation of water. It concerns the manufacture of compact appliances, optionally mobile, for hydrogen production. The invention aims at improvement of such appliances. The volume of a reactor (1) holds evaporated water. It comprises a crucible (2) and two cavities (3 and 4) for collecting the separate gases. The gases are extracted through oxygen-permeable (5) and hydrogen-permeable (6) membranes. The water is conveyed by a conduit (7) towards a jet nozzle (8) inside the reactor. The spout (9) of the crucible is fed by a fuel gas conduit (10), the exhaust gases are discharged through the gas conduits. One conduit (12) is used for oxygen, which will be added to the fuel gas circuit. The other conduit (13) will transport hydrogen to its destination. The inventive device is particularly designed for mobile production of hydrogen on a small scale.

Description

DISPOSITIF POUR LA PRODUCTION DES GAZ PURS, EN PARTICULIER D'HYDROGENE ET D'OXYGENE, A PARTIR DES MELANGES DE GAZ OU DES LIQUIDES, POUR L'APPROVISIONNEMENT MOBILE ET STATIONNAIRE D'ENERGIE DEVICE FOR THE PRODUCTION OF PURE GASES, IN PARTICULAR HYDROGEN AND OXYGEN, FROM MIXTURES OF GASES OR LIQUIDS, FOR THE MOBILE AND STATIONARY ENERGY SUPPLY
La présente invention concerne une méthode pour la production des gaz séparés, en particulier dans la production d'hydrogène et d'oxygène par dissociation thermique d'eau. L'invention cible à la fabrication des appareils compacts, éventuellement mobiles, pour la production d'hydrogène. L'invention est basée sur le principe d'un réacteur p. ex à membranes comme présenté dans plusieurs documents1. Elle revendique d'améliorer de tels appareils (1) par l'accélération du processus d' évaporation de l'eau, (2) par le chauffage à une très haute température par combustion d'un gaz avec de l'oxygène pur, et (3) par fournir cet oxygène comme gaz sortant associé à la production d'hydrogène. Ces améliorations ont comme but de fournir le principe d'un appareil compact qui peut éventuellement être installé p. ex dans une voiture à pile à combustible remplaçant le système de stockage d'hydrogène .The present invention relates to a method for the production of separated gases, in particular in the production of hydrogen and oxygen by thermal dissociation of water. The invention targets the manufacture of compact devices, possibly mobile, for the production of hydrogen. The invention is based on the principle of a p reactor. ex with membranes as presented in several documents 1 . It claims to improve such devices (1) by accelerating the process of evaporation of water, (2) by heating to a very high temperature by combustion of a gas with pure oxygen, and (3) by supplying this oxygen as an outgoing gas associated with the production of hydrogen. These improvements are intended to provide the principle of a compact device which can optionally be installed p. eg in a fuel cell car replacing the hydrogen storage system.
Les sources d'énergie fossiles sont limitées. La production mondiale de pétrole fera une pointe un moment entre 2004 et 2008 et elle diminuera ensuite pour n' encore augmenter jamais (K.S. Deffeys, 2001) . Le pétrole est une matière brute précieuse, qui devrait être employée pour des lubrifiants et la fabrication d'autres produits. Aujourd'hui et dans les années à venir 85% de tout pétrole extrait est brûlé, soit dans les moteurs de différents types soit pour le chauffage domestique et industriel. Même si cette prévision de délai est erronée de quelques années, la disparition du pétrole et d'autres sources fossiles d'énergie est un fait établi. L'invention aide à remplacer le pétrole comme source d'énergie.Fossil energy sources are limited. World oil production will peak for a time between 2004 and 2008 and then decline and never increase again (K.S. Deffeys, 2001). Petroleum is a precious raw material, which should be used for lubricants and the manufacture of other products. Today and in the years to come 85% of all oil extracted is burned, either in engines of different types or for domestic and industrial heating. Even if this delay forecast is wrong for a few years, the disappearance of oil and other fossil energy sources is an established fact. The invention helps to replace petroleum as an energy source.
Les émissions des gaz toxiques ou hasardeux à l'environnement seront des problèmes fortement croissants si on continue de brûler le pétrole. L'invention revendique de réduire rigoureusement de telles émissions ou même de les éliminer.Emissions of toxic or hazardous gases to the environment will be greatly increasing problems if we continue to burn oil. The invention claims to drastically reduce or even eliminate such emissions.
90% de la surface de notre planète est couvert par l'eau et est ainsi un énorme réservoir d'hydrogène. L'utilisation de l'énergie inhérente dans l'hydrogène n'a pas été exploitée économiquement. La présente invention revendique avoir trouvé une manière d'extraire l'hydrogène de l'eau en utilisant plusieurs sciences.90% of the surface of our planet is covered by water and is thus a huge reservoir of hydrogen. The use of the energy inherent in hydrogen has not been exploited economically. The The present invention claims to have found a way to extract hydrogen from water using several sciences.
Actuellement il n' existe aucune solution praticable de la production d'hydrogène adaptée aux besoins de petits consommateurs, spécifiquement dans des véhicules de transports (voitures, camions ou bus actionnés par des piles à combustible) . Dans ce secteur la consommation d'hydrogène s'élève de 50 à 400 litres de gaz (à 20°C et 1 bar) par kilomètre parcouru. L'invention ouvre la porte à la construction des petites stations de production d'hydrogène fiable, compact et mobile.Currently there is no practicable solution for the production of hydrogen adapted to the needs of small consumers, specifically in transport vehicles (cars, trucks or buses powered by fuel cells). In this sector, hydrogen consumption rises from 50 to 400 liters of gas (at 20 ° C and 1 bar) per kilometer traveled. The invention opens the door to the construction of small reliable, compact and mobile hydrogen production stations.
L'objet de la présente invention est de permettre le contrôle de la production d'un mélange de gaz et de la séparation des gaz dans un mélange de gaz, en particulier si le mélange de gaz est du vapeur d' eau.The object of the present invention is to allow the control of the production of a gas mixture and of the separation of the gases in a gas mixture, in particular if the gas mixture is water vapor.
L'invention est basée sur plusieurs faits connus.The invention is based on several known facts.
Le premier est que l'efficacité du transfert thermique vers un objet liquide est lié à la relation de sa surface 5 en contact avec la source de chaleur à son volume V. Quand le liquide est tenu dans un récipient et la chaleur est fournie par un chauffage dans l' intérieur du récipient, la relation S/V est < 1, tandis qu'un liquide en gouttelettes dans un environnement chaud, p. ex du vapeur, peut atteindre un rapport relatif de plus de 200.The first is that the efficiency of heat transfer to a liquid object is linked to the relation of its surface 5 in contact with the heat source to its volume V. When the liquid is held in a container and the heat is supplied by a heating inside the container, the S / V relationship is <1, while a liquid in droplets in a warm environment, eg. eg steam, can reach a relative ratio of more than 200.
Figure imgf000004_0001
Figure imgf000004_0001
Tableau 1 : Comparaison des températures de combustion de gaz dans l'air et avec de l'oxygène.Table 1: Comparison of combustion temperatures of gases in air and with oxygen.
En brûlant un combustible l' invention emploie des phénomènes thermodynamique que certaines réactions d' oxydation dégagent des énergies élevées, permettant d'atteindre des températures excédantBy burning a fuel, the invention employs thermodynamic phenomena that certain oxidation reactions give off high energies, making it possible to reach temperatures exceeding
3000 °K. Plus spécifiquement, le combustible est brûlé avec de l'oxygène pur sortant de l'appareil. On obtient la combustion plus efficace et propre, sans production d'oxydes d'azote et avec un minimum d'oxydes de carbone.3000 ° K. More specifically, the fuel is burned with pure oxygen leaving the device. We get more combustion efficient and clean, without production of nitrogen oxides and with a minimum of carbon oxides.
A de telles températures les molécules dans le gaz sont partiellement dissociées. Le degré de dissociation dépend de la température du vapeur d'eau atteinte.At such temperatures the molecules in the gas are partially dissociated. The degree of dissociation depends on the temperature of the water vapor reached.
Figure imgf000005_0001
Figure imgf000005_0001
Tableau 2 : Exemple du degré de dissociation (approximatif) des molécules d' eau en pour cent de la masse totale à pression atmosphérique . On sépare des composants du gaz, p. ex l'hydrogène et l'oxygène créés dans la dissociation de l'eau. La séparation est effectuée en utilisant des membranes céramiques ou métalliques pour séparer les molécules de gaz par tamisage moléculaire ou par transport ionique, des arrangements de séparation au moyen de tuyères, ou tous les autres moyens physiques ou chimiques.Table 2: Example of the (approximate) degree of dissociation of water molecules in percent of the total mass at atmospheric pressure. Gas components are separated, p. ex hydrogen and oxygen created in the dissociation of water. The separation is carried out using ceramic or metallic membranes to separate the gas molecules by molecular sieving or by ion transport, separation arrangements by means of nozzles, or any other physical or chemical means.
Les quantités de gaz extraites sont liées à leur présence stœchiométrique dans le gaz ou le liquide initial. Pour l'extraction d'hydrogène et d'oxygène à partir d'eau (H20) , on extraira deux parts (en nombre de molécules) d'hydrogène (H2) et une part d'oxygène (02) - Parce-que le vecteur d'énergie (le gaz combustible) et la source d'hydrogène (l'eau) sont physiquement séparés, les gaz sortant, notamment l'hydrogène, ne contiennent aucune contamination à partir de faibles quantités d'eau. Ce fait est important, car il n'est plus nécessaire d'ajouter une étape d'épuration de gaz avant son utilisation p. ex dans une pile à combustible.The quantities of gas extracted are linked to their stoichiometric presence in the initial gas or liquid. For the extraction of hydrogen and oxygen from water (H 2 0), two parts (in number of molecules) of hydrogen (H 2 ) and one part of oxygen (0 2 ) will be extracted - Because the energy vector (combustible gas) and the source of hydrogen (water) are physically separated, the gases leaving, in particular hydrogen, do not contain any contamination from small quantities of water. This fact is important, since it is no longer necessary to add a gas purification stage before its use p. eg in a fuel cell.
Les gaz extraits sont dirigés soit vers des utilisateurs externes soit vers une utilisation dans le dispositif lui-même.The extracted gases are directed either to external users or to use in the device itself.
Les gaz produits aussi bien que le gaz d' échappement du creuset passent par des echangeurs de chaleur. La chaleur peut être employée pour préchauffer l'eau ou pour n'importe quel autre but.The gases produced as well as the exhaust gas from the crucible pass through heat exchangers. Heat can be used to preheat water or for any other purpose.
Le gaz d'échappement peut également servir à atteindre des objectifs supplémentaires. Des matériaux inertes récemment développés et résistants à hautes températures sont employés. L'évolution de tels matériaux est prometteuse pour de futures améliorations de l'invention.Exhaust gas can also be used to achieve additional goals. Inert materials recently developed and resistant to high temperatures are used. The evolution of such materials is promising for future improvements of the invention.
Une mode de réalisation de l' invention peut être la séparation d'hydrogène et oxygène à partir d'eau liquide.One embodiment of the invention may be the separation of hydrogen and oxygen from liquid water.
Le récipient (réacteur) est en matière résistant à la chaleur. A l'intérieur du réacteur sont montés un ou plusieurs creusets. A l'intérieur du creuset est brûlé de l'acétylène- (C2H2) avec de l'oxygène. Pour le démarrage de l'appareil on utilise soit l'oxygène de l'air soit l'oxygène d'un récipient de stockage. Quand la machine marche, la production d'oxygène sera suffisante pour soutenir la combustion d'acétylène. La température peut atteindre 3000°K et plus. Des gicleurs montés dans les parois du réacteur injectent des petites gouttelettes d'eau. Une ou plusieurs gicleurs sont utilisés pour fractionner le liquide en gouttelettes d'une taille dans l'ordre d'un micromètre avant exposition à la chaleur pour la conversion. L' eau évapore soit en traversant le gaz chaud dans le réacteur soit en contact avec la surface du creuset .The container (reactor) is made of heat resistant material. One or more crucibles are mounted inside the reactor. Inside the crucible is burned acetylene- (C 2 H 2 ) with oxygen. To start the device, either oxygen from the air or oxygen from a storage container is used. When the machine is running, there will be enough oxygen production to support the combustion of acetylene. The temperature can reach 3000 ° K and more. Sprinklers mounted in the walls of the reactor inject small droplets of water. One or more nozzles are used to split the liquid into droplets one size in the order of one micrometer before exposure to heat for conversion. The water evaporates either through the hot gas in the reactor or in contact with the surface of the crucible.
La conversion du liquide en vapeur est effectuée par irradiation, convection et conduction. La vapeur est convertie en mélange de gaz, par dissociation thermique au moyen d'irradiation, de convection et de conduction. Le mélange de gaz est encore chauffé par irradiation, convection et conduction, jusqu'à ce qu'un degré souhaité de dissociation est atteint.The conversion of liquid into vapor is carried out by irradiation, convection and conduction. The vapor is converted to a gas mixture by thermal dissociation by means of irradiation, convection and conduction. The gas mixture is further heated by irradiation, convection and conduction, until a desired degree of dissociation is reached.
Dans le réacteur l' équilibre thermique est atteint dans des temps très courts, en dessous d'une milliseconde selon puissance des creusets et quantité de matière totale dans le réacteur. Quelques parties des parois du réacteur sont faites des matériaux perméables pour les composants de gaz à extraire. La surface des parties est choisie selon perméabilité des matériaux afin d'assurer la relation entre les quantités extraites.In the reactor the thermal equilibrium is reached in very short times, below a millisecond depending on the power of the crucibles and the total amount of material in the reactor. Some parts of the reactor walls are made of permeable materials for the gas components to be extracted. The surface of the parts is chosen according to the permeability of the materials in order to ensure the relationship between the quantities extracted.
Aujourd'hui il y a des matériaux résistants aux températures élevées avec une perméabilité ou porosité pour des gaz. Par exemple des oxydes de certains métaux sont exploités pour le transfert d'oxygène, par le mécanisme chimique de transport d'ions. Des produits de zircon étaient déjà utilisés pour fabriquer des membranes poreuses aux molécules d'hydrogène.Today there are materials resistant to high temperatures with permeability or porosity for gases. For example, oxides of certain metals are used for transfer oxygen, by the chemical ion transport mechanism. Zircon products were already used to make porous membranes with hydrogen molecules.
Les gicleurs injectent la quantité d'eau correspondante exactement aux quantités de gaz enlevées.The jets inject the quantity of water corresponding exactly to the quantities of gas removed.
Deux ou plusieurs procédés de séparation sont effectués en parallèle, ayant pour résultat l'extraction simultanée de deux ou plusieurs gaz ou mélanges distincts de gaz du mélange initial de gaz.Two or more separation processes are carried out in parallel, resulting in the simultaneous extraction of two or more separate gases or mixtures of gases from the initial gas mixture.
Deux ou plusieurs procédés de séparation sont effectués en étapes consécutives, telles que deux ou plusieurs gaz ou mélanges distincts de gaz sont extraits successivement du mélange initial de gaz .Two or more separation processes are carried out in consecutive stages, such that two or more gases or distinct mixtures of gases are successively extracted from the initial mixture of gases.
A l'extérieur du réacteur les gaz restent mécaniquement séparés dans des cavernes dessus les surfaces perméables. Ils sont dirigés vers leur utilisation suivante par des systèmes de tuyaux et éventuellement de pompes. Spécifiquement l'oxygène sera comprimé pour être re-injecté dans le circuit d'acétylène.Outside the reactor the gases remain mechanically separated in caves above the permeable surfaces. They are directed to their next use by pipe systems and possibly pumps. Specifically, the oxygen will be compressed to be re-injected into the acetylene circuit.
Les cavernes de gaz servent comme première isolation thermique.The gas caves serve as the first thermal insulation.
Le système complet du réacteur avec les cavernes de collection de gaz est dans un système de plusieurs couches d' isolation thermique comprenant d'isolation par vide (système bouteille thermos).The complete system of the reactor with the gas collection caves is in a system of several layers of thermal insulation comprising vacuum insulation (thermos bottle system).
Les entrées pour le gaz de combustion et pour l' eau traversent les différents stages d'isolation et ils sont ainsi préchauffés.The inlets for the combustion gas and for the water pass through the various insulation stages and are thus preheated.
La Figure 1 montre le principe de fonctionnement comme décrit ci-dessus, en particulière les flux des gaz. Le volume d'un réacteur (1) comporte un creuset (2) et deux cavernes (3 et 4) pour assembler les gaz séparés. Ils sont extraits à travers des membranes perméable quasi exclusivement pour oxygène (5) et pour hydrogène (6) . L'eau est conduite par une ligne (7) vers le gicleur (8) à l'intérieur du réacteur. Le bec (9) du creuset est alimenté par une ligne de gaz combustible (10), les gaz d'échappement sortent par des conduites (11) . Les gaz séparés sont acheminés dans des lignes de gaz. Une ligne (12) sert pour l'oxygène, qui sera ajouté au circuit de gaz combustible. L'autre ligne (13) conduira l'hydrogène vers sa destination. En employant les principes de la présente invention, il est possible de réaliser une unité mobile de production de gaz en petite taille, pour par exemple alimenter des piles à combustibles dans des voitures et des camions. Elle est également utile pour la production d'énergie électrique pour un usage domestique et industriel.Figure 1 shows the operating principle as described above, in particular the gas flows. The volume of a reactor (1) comprises a crucible (2) and two caverns (3 and 4) for assembling the separate gases. They are extracted through permeable membranes almost exclusively for oxygen (5) and for hydrogen (6). The water is led by a line (7) to the nozzle (8) inside the reactor. The spout (9) of the crucible is supplied by a line of combustible gas (10), the exhaust gases exit through pipes (11). The separated gases are routed through gas lines. A line (12) is used for oxygen, which will be added to the fuel gas circuit. The other line (13) will lead the hydrogen to its destination. By using the principles of the present invention, it is possible to make a mobile gas production unit in small size, for example to supply fuel cells in cars and trucks. It is also useful for the production of electrical energy for domestic and industrial use.
1 Documents particulièrement concernés avec la production d'hydrogène à partir de l'eau dissociée : GB 1 532 403 A (COMP GENERALE ELECTRICITE) 1 Documents particularly concerned with the production of hydrogen from dissociated water: GB 1 532 403 A (COMP GENERALE ELECTRICITE)
R. P. Omorjan et al. : " Applicability of a double-membrane reactor for thermal décomposition of water: a computer analysis" US 4 120 663 A (FALLY JACQUES) US 3 901 668 A (SEITZER WALTER H) US 3 901 669 A (SEITZER WALTER H) US 4 254 086 A (SANDERS ALFRED P) DE 43 02 089 A (RYDZEWSKI ROLAND DR ING) R. P. Omorjan et al. : "Applicability of a double-membrane reactor for thermal decomposition of water: a computer analysis" US 4 120 663 A (FALLY JACQUES) US 3 901 668 A (SEITZER WALTER H) US 3 901 669 A (SEITZER WALTER H) US 4 254 086 A (SANDERS ALFRED P) DE 43 02 089 A (RYDZEWSKI ROLAND DR ING)

Claims

REVENDICATIONS
1. Méthode pour contrôler la production et la séparation des gaz depuis de l'eau ou des solutions aqueuses, caractérisée en ce qu'un ou plusieurs creusets sont utilisés pour chauffer l'eau ou le liquide dans un volume réacteur, en brûlant des combustibles, en ce qu'un ou plusieurs des gaz séparés par la méthode et sortants du volume réacteur sont employés pour la combustion dans le ou les brûleurs afin d'atteindre des températures élevées, par le chauffage supplémentaire de cette vapeur jusqu'à ce qu'un degré de dissociation employable du vapeur en mélange de composants gazeux est atteint, et - par la séparation des gaz de ce mélange.1. Method for controlling the production and separation of gases from water or aqueous solutions, characterized in that one or more crucibles are used to heat the water or the liquid in a reactor volume, by burning fuels , in that one or more of the gases separated by the method and leaving the reactor volume are used for combustion in the burner (s) in order to reach high temperatures, by the additional heating of this vapor until a degree of employable dissociation of the vapor as a mixture of gaseous components is achieved, and - by the separation of the gases from this mixture.
2. Méthode selon la revendication 1, caractérisée en ce qu'une ou plusieurs gicleurs sont utilisés pour fractionner le liquide en gouttelettes d'une taille dans l'ordre d'un micromètre avant l'exposition à la chaleur pour la conversion accélérée et contrôlée du liquide en vapeur.2. Method according to claim 1, characterized in that one or more jets are used to fractionate the liquid into droplets of a size in the order of a micrometer before exposure to heat for accelerated and controlled conversion liquid vapor.
3. Méthode selon la revendication 1, caractérisée en ce que la conversion du liquide en vapeur est effectuée par irradiation, convection et conduction.3. Method according to claim 1, characterized in that the conversion of the liquid into vapor is carried out by irradiation, convection and conduction.
4. Méthode selon la revendication 1, caractérisée en ce que la vapeur est convertie en mélange de gaz par dissociation thermique au moyen d'irradiation, de convection et de conduction.4. Method according to claim 1, characterized in that the vapor is converted into a gas mixture by thermal dissociation by means of irradiation, convection and conduction.
5. Méthode selon les revendications 1, 2 et 4, caractérisée en ce que le mélange de gaz est encore chauffé par irradiation, convection et conduction, jusqu'à ce qu'un degré souhaité de dissociation est atteint.5. Method according to claims 1, 2 and 4, characterized in that the gas mixture is further heated by irradiation, convection and conduction, until a desired degree of dissociation is reached.
6. Méthode selon les revendications 1, 2, 3, et 4, caractérisée en ce qu'un ou plusieurs gaz ou mélanges distincts de gaz sont séparées du mélange initial de gaz.6. Method according to claims 1, 2, 3, and 4, characterized in that one or more gases or distinct mixtures of gases are separated from the initial mixture of gases.
7. Méthode selon la revendication 6, caractérisée en ce que deux ou plusieurs procédés de séparation sont effectués en parallèle, ayant pour résultat l'extraction simultanée de deux ou plusieurs gaz ou mélanges distincts de gaz du mélangé initial de gaz.7. Method according to claim 6, characterized in that two or more separation processes are carried out in parallel, resulting in the simultaneous extraction of two or more separate gases or mixtures of gases from the initial gas mixture.
8. Méthode selon la revendication 6, caractérisée en ce que deux ou plusieurs procédés de séparation sont effectués en étapes consécutives, telles que deux ou plusieurs gaz ou mélanges distincts de gaz sont extraits successivement du mélange initial de gaz .8. Method according to claim 6, characterized in that two or more separation processes are carried out in consecutive stages, such that two or more gases or distinct mixtures of gases are successively extracted from the initial mixture of gases.
9. Méthode selon les revendications 6, 7 et 8, caractérisée en ce que les quantités de gaz séparés du mélange de gaz sont en même proportions que dans le mélange initial de gaz, ainsi pour éviter un enrichissement de n'importe lequel des gaz à l'intérieur du réacteur.9. Method according to claims 6, 7 and 8, characterized in that the quantities of gases separated from the gas mixture are in the same proportions as in the initial gas mixture, thus to avoid enrichment of any of the gases to inside the reactor.
10. Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce qu'un ou plusieurs des gaz séparés sont utilisés pour préchauffer des composants dans le processus.10. Method according to any one of the preceding claims, characterized in that one or more of the separated gases are used to preheat components in the process.
11. Méthode selon l'une quelconque des revendications précédentes, caractérisée par un flux contrôlé des gaz avant séparation et après séparation. 11. Method according to any one of the preceding claims, characterized by a controlled flow of gases before separation and after separation.
12. Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce que les gaz d'échappement du creuset sont utilisés pour chauffer des composants dans le processus. 12. Method according to any one of the preceding claims, characterized in that the exhaust gases from the crucible are used to heat components in the process.
PCT/FR2003/001454 2002-05-17 2003-05-12 Method for producing pure gases, in particular hydrogen and oxygen WO2003097524A1 (en)

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FR0206061A FR2839713B1 (en) 2002-05-17 2002-05-17 DEVICE FOR THE PRODUCTION OF PURE GAS, IN PARTICULAR HYDROGEN AND OXYGEN, FROM GAS MIXTURES OR LIQUIDS, FOR THE MOBILE AND STATIONARY POWER SUPPLY
FR02/06061 2002-05-17

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WO2022167481A1 (en) * 2021-02-04 2022-08-11 Ultra High Temperature Processes Ltd Device and process for splitting water into hydrogen and oxygen by thermolysis

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FR2839713B1 (en) 2005-03-11

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