EP1177332A1 - Procede et dispositif d'obtention d'hydrogene - Google Patents

Procede et dispositif d'obtention d'hydrogene

Info

Publication number
EP1177332A1
EP1177332A1 EP00926800A EP00926800A EP1177332A1 EP 1177332 A1 EP1177332 A1 EP 1177332A1 EP 00926800 A EP00926800 A EP 00926800A EP 00926800 A EP00926800 A EP 00926800A EP 1177332 A1 EP1177332 A1 EP 1177332A1
Authority
EP
European Patent Office
Prior art keywords
hollow
fibers
hollow micro
electrolyte
micro fibers
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Withdrawn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
EP00926800A
Other languages
German (de)
English (en)
Inventor
Klaus Rennebeck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP1177332A1 publication Critical patent/EP1177332A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a method and a device for the production of hydrogen by electrolysis, in particular at atmospheric pressure or at a pressure up to 30 bar.
  • electrolysers are constructed with bipolar electrolysis cells. These electrolytic cells have planar bipolar foil diaphragms which carry the cathode on one side and the anode on the other side, separated by the diaphragm thickness. On both sides of the diaphragm there are equal volumes of electrolyte and liquid. When voltage is applied to the electrodes, hydrogen is released on the cathode side and oxygen from the electrolyte volume on the anode side.
  • Electrolysers are particularly interesting for use in hydrogen-powered vehicles in order to generate the fuel required for these vehicles on board the vehicle.
  • the prior art planar electrolysers are not suitable for this purpose, since they require a large volume and since liquid turbulence occurs in the electrolytes when the vehicle is moving, and thus the built-in electrolyzer.
  • these known electrolysers have the disadvantage that the bipolar, flat films have to be stabilized in many places due to their small thickness, which requires considerable construction effort.
  • the object of the present invention is accordingly to specify a method by which it is possible to generate hydrogen by electrolysis with only a small space requirement, and which can be used in particular on board a motor vehicle. Furthermore, it is an object of the invention to provide a device which is suitable for carrying out the method. According to the invention, this object is achieved by a method according to claim 1 or an apparatus according to claim 8.
  • a first electrolyte is provided in the interior of a hollow micro fiber, which carries anode and cathode separately on its wall surfaces, a second electrolyte being provided outside the hollow fiber in such a way that it flushes around its outer wall, and wherein a voltage is applied between the anode and cathode.
  • the expression “rinsing” is to be understood in connection with the method according to the invention in such a way that the outer wall of the hollow fiber is in contact with the electrolyte fluid. An optimal process management is guaranteed if essentially the entire outer surface of the micro hollow fiber with the liquid electrolyte in The electrolyte liquids are preferably supplied continuously so that the amount of electrolytes present in and around the hollow fiber is kept constant at all times.
  • the reaction products generated, in particular the hydrogen generated, can be fed to a subsequent sequence for use or further processing.
  • a follow-up sequence can be, for example, a fuel cell.
  • Fuel cells of this type are increasingly being used for individual power generation, for example in electric vehicles, or for providing drinking water, for example on space stations and the like.
  • the fuel requirement for such fuel cells can be at least partially covered, which has the advantage that storage of the hydrogen required for the fuel cell associated with the known inconveniences can be avoided or at least reduced.
  • the voltage supply required for the method according to the invention can come from various sources, depending on the area of application.
  • a power supply by a photovoltaic element, an electrodynamo, solar cells and in the event that the method according to the invention is carried out in a vehicle, by a wind anemometer, an impeller drive or by partial recovery of the braking power.
  • the fibers used for the process according to the invention are hollow micro fibers, which means that their equivalent outer diameters are in the range from a few tenths of a micron to a few millimeters.
  • nanofibers has also become increasingly common to refer to fibers with a diameter of less than 10 ⁇ m.
  • micro hollow fibers in connection with the present invention is used both by conventional methods, such as e.g. to understand the spinning process, micro hollow fibers produced as well as the tubes or straws with the corresponding diameter, which are wound from thin foils.
  • hollow micro fibers can be produced by spinning with very small wall thicknesses of approximately 0.01 to 15 ⁇ m and equivalent outer diameters down to 0.5 to 35 ⁇ m. Due to their small dimensions, these hollow micro fibers have textile properties, ie they can be easily bent without breaking.
  • the hollow micro fibers can be produced with highly precise dimensions, the fluctuation ranges of wall thickness and equivalent outside diameter being no more than ⁇ 6%. The precision of maintaining the sizes of the diameter and in particular the wall thickness ensures a homogeneous reaction process over the entire length of the hollow fiber.
  • hollow fibers in particular can be produced with an equivalent outer diameter of approximately 0.28 to 10 mm.
  • equivalent outer diameter means in the case of tubes made of structured foils that diameter which corresponds to a peripheral surface which is equal to the actual peripheral surface of the structured tube.
  • the length of the straws or spiral tubes thus produced is generally preferably between about 0.03 m and 3.00 m, a length of about 0.5 to about 1.0 for the use of the straws in the process according to the invention for the production of hydrogen by electrolysis m is preferred. It is possible to implement any desired and technically meaningful length-diameter ratio.
  • After shaping the straws or spiral tubes they can be fired ceramic.
  • the foils can be extruded together with the electrode material before they are further processed into straws or spiral tubes.
  • the sol-gel process can be used in particular to produce the films.
  • All proven diaphragm materials from bipolar diaphragm technology such as, for example, nano-carbon hollow fibers, polyether ether ketone (PEEK), polyether ketone ketone, polymethylpentene (TPX), zirconium oxide, PTFE, polymers, can be used as starting materials for the hollow micro fibers used in the process according to the invention Proteins, mixed oxides, spinels and zeolites.
  • the diaphragm films or polymer films are coated on both sides with the electrode material. Metals such as z. B. magnesium, aluminum or spinels etc.
  • the vacuum plasma spraying process has proven to be a very suitable method for producing the electrodes.
  • the coating process injects the spray material in powder form into a plasma jet, melts it and carries it with it, in order to then be deposited on the film as a layer.
  • targeted coatings with the electrode material with different surface morphology can be realized, whereby the voltage losses during water electrolysis can be considerably reduced.
  • One example here is vacuum plasma spraying of gas-atomized NiAlMo powder, with a highly structured surface, a so-called Ranay nickel, being produced by largely leaching out the Al content.
  • a highly structured surface is desirable in order to enable effective application or storage of catalysts for the process according to the invention.
  • Another possibility for producing such a highly structured or cancellous surface of the electrode material is a method which is known under the expression "anodic oxidation”.
  • a catalyst material suitable for the reaction used in the process according to the invention for example TiOi, WO 3 , VO5, Pt, Ru, is applied to the electrode layer or into the cancellous surface thereof.
  • the catalyst is applied in the form of clusters. It must be in a porous state in order not to hinder the passage of ions through the hollow micro-fiber membrane.
  • structured, e.g. Pleated, or curved or corrugated foils for the production of straw or spiral tubes can further increase the surface area of the straws or tubes available for the reaction.
  • Another advantage of using structured foils is the increased flexural strength that the straws and tubes made from them have.
  • the density of the hollow fiber wall should be designed for the process according to the invention in such a way that the ions of the electrolyte can diffuse through them, but the reaction products formed no longer. In this way it is ensured that the reaction products are separated and thus each can be used for its own further use.
  • the first electrolyte and the second electrolyte preferably have the same composition.
  • the electrolyte liquids can be, for example, all known, suitable liquid electrolytes. Pure water is particularly suitable due to its complete usability as an electrolyte and potassium hydroxide lye.
  • the use of high-purity water and KHO lye ensures the longest possible service life of the micro hollow fiber used, since the water can be completely broken down into its components hydrogen gas and oxygen gas.
  • waste water for one or both of the electrolyte liquids, which, however, should be pre-filtered to prevent possible clogging of the hollow micro fibers.
  • human urine can be used as the electrolyte liquid.
  • the constituents hydrogen and oxygen in the urine can be excreted as gases and synthesized to pure water in a subsequent synthesis method, for example in a fuel cell unit.
  • the constituents in the wastewater or urine, which cannot be regenerated in this process, are deposited on the inner and outer walls of the hollow fibers over time, so that they have to be flushed against one another.
  • the service life is approximately 20,000 operating hours, depending on the diameter of the fiber.
  • the method according to the invention is preferably carried out in such a way that the first electrolyte is divided into a plurality of partial streams which are introduced into a plurality of micro hollow fibers lying in parallel planes, and that the second electrolyte is provided in such a way that it covers the outer walls of the micro hollow fibers lying in parallel planes washed around.
  • the micro hollow fibers used in the method are thus one above the other in a stack, the exact arrangement being explained in more detail in connection with the explanation of the device according to the invention.
  • the electrodes of the individual hollow micro fibers are connected in parallel in this arrangement, so that the same voltage is applied to each fiber. To this In this way, equal amounts of reaction products are extracted from all fibers.
  • This type of process control is characterized by a particularly high effectiveness in terms of both simplicity and space-saving arrangement.
  • the method according to the invention is preferably carried out in this way with an arrangement consisting of approximately 100,000 to 900,000 hollow micro fibers.
  • the method is carried out at a temperature below approximately 100 ° C. and in particular below approximately 95 ° C.
  • the low temperatures are particularly advantageous when used in a vehicle, since this reduces the risk of the resulting gases igniting.
  • the method according to the invention can be carried out in this way at atmospheric pressure, which simplifies the construction of the device necessary for carrying out the method.
  • the catalysts according to the invention can also be carried out at the low temperatures mentioned by means of catalysts located on the electrodes. However, the catalysts can also be replaced by so-called “gap capillaries”. These are molecular sieves.
  • At least one of the electrolytes is stored in the interior of one or more storage micro-hollow fibers before being introduced into the interior or before being provided around the outer wall of the micro-hollow fiber (s).
  • These hollow storage fibers thus function as a tank in which the liquid electrolytes are kept until they are used.
  • Nano-carbon hollow fibers, PTFE, PEEK, PEEKK, TPX have proven to be particularly suitable materials for these hollow storage fibers.
  • the hollow storage fibers preferably have an equivalent outer diameter of approximately 3 ⁇ m to 25 ⁇ m, in particular approximately 10 ⁇ m to 25 ⁇ m, and a wall thickness of approximately 10 ⁇ m to 3 ⁇ m.
  • the walls of the hollow storage fibers are designed to be parapermeable or semi-permeable, so that the liquid to be stored is also stored inside the fiber wall.
  • the storage volume can thus be increased in a simple manner.
  • the described type of storage of the electrolysis liquids required for the method according to the invention means that there is a sloshing back and forth Liquids in motion, eg avoided during acceleration and the
  • the device suitable for carrying out the method according to the invention has a multiplicity of stacked hollow micro fibers, the inner and outer surfaces of which support the anodes or cathodes, the ends of the hollow micro fibers being bound in a frame in a dimensionally stable manner.
  • the stacked hollow micro fibers thus form a disk of finite thickness, which is delimited by the frame.
  • the hollow fiber can be bound in the frame in any suitable manner, for example by casting the hollow fiber ends with the frame.
  • the ends of the hollow fibers are exposed on the outer circumference of the frame, so that access to the interior of the hollow fiber, that is to say to the hollow fiber lumen, is ensured.
  • the hollow micro fibers are arranged parallel to one another within the stack and the frame has a rectangular or square shape.
  • the hollow micro fibers of a stack thus all have essentially the same length.
  • the frame can also be designed as an annular flange in which the hollow micro fibers are randomly stacked and held. This arrangement has the advantage of requiring little time in the manufacturing process and contributing to an extremely low reject rate.
  • the frame is designed as an annular flange and the hollow micro fibers are arranged in several planes lying parallel to one another, the hollow micro fibers lying in one plane being offset by 15 ° with respect to the hollow micro fibers of the next level.
  • the micro hollow fibers of a plane run parallel to one another.
  • the micro hollow fibers of a stack can be provided with a protective fabric in order to avoid damage.
  • This protective fabric is preferably attached to the inner edge of the frame so that it extends over the entire surface on which the hollow micro fibers are exposed within the frame.
  • Such a protective fabric is preferably attached to both the top and the bottom of the frame.
  • the protective fabric can be formed, for example, as a spunbonded fabric or gauze made of plastic or another suitable material.
  • micro hollow fibers of the device according to the invention have an equivalent outer diameter of approximately 1 ⁇ m to 1,000 ⁇ m, in particular of approximately 50 ⁇ m to 280 ⁇ m. Hollow fibers of these dimensions can be arranged in stacks and are easy to handle. They also offer an excellent surface to volume ratio.
  • such hollow micro fibers are used which have a wall thickness of approximately 0.01 ⁇ m to 15 ⁇ m.
  • wall thickness of approximately 0.01 ⁇ m to 15 ⁇ m.
  • the device In order to create a tank for the storage of the electrolyte liquid, the device preferably has a further stack of hollow micro fibers, the ends of which are each connected to one of the ends of each hollow hollow fiber of the first stack.
  • the electrolyte liquid can then be stored in the further stack of hollow micro fibers until it is used in the method according to the invention.
  • the stack of the hollow fibers required for the reaction and the stack of the hollow fibers used for the storage, the latter consisting for example of nano-carbon fibers, PTFE, PEEKK, TPX, are preferably arranged as staple fiber fabrics. net.
  • connection of the two stacks to one another can be, for example, a simple pipe or hose connection via which the liquid stored in the interior of the hollow fibers and, if appropriate, in their wall thicknesses, with the cavities and / or the exterior of the cavities required for the reaction. is connected.
  • a valve is installed in this hose or pipe connection in order to prevent the backflow of electrolyte liquid into the stack of hollow storage fibers.
  • An inlet regulator is preferably interposed between the two stacks and regulates the inlet of electrolyte liquid from the stack of storage fibers to the stack of the hollow fibers required for the reaction. In this way, the electrolyte liquid consumed in the process is continuously replaced. With an energy consumption of 5 kWh at the anodes, between 8 and 10 liters of water are consumed.
  • the various stacks can be connected to one another in a frame lying on top of one another.
  • the micro-hollow fibers of the further stack are preferably designed such that the electrolyte liquid is stored both in the inner cavity of the fibers and in their wall in order to achieve the largest possible storage volume. It is also possible to accommodate the frame with hollow storage fibers in a closed container so that the electrolyte liquid is stored both in the internal cavity or lumen of the fibers, optionally in the wall thereof and outside the fibers inside the container. Due to the small gaps between the fibers, an excessive sloshing of the stored liquid is also prevented in the outer space of the fibers.
  • the device has a storage medium in the form of a deposition material store for storing the hydrogen gas produced and / or a molecular sieve for storing oxygen produced.
  • a storage medium in the form of a deposition material store for storing the hydrogen gas produced and / or a molecular sieve for storing oxygen produced.
  • Figure lb shows a cross section through the micro hollow fiber of Figure la
  • Figure lc is a schematic representation of a hollow fiber stack
  • Figure 2 shows an alternative embodiment of a hollow fiber stack
  • Figure 3a shows the embodiment of Figure 2, but which has a protective fabric
  • Figure 3b shows the embodiment of Figure 3a in side view
  • Figure 3c is a perspective view of the embodiment of Figure 3a
  • FIG. 4a is a schematic illustration of a frame without a hollow micro fiber, in which the conductive connections to the electrodes are shown in particular
  • Figure 4b is a cross-sectional view of Figure 3a in elevation.
  • FIGS. 1 a and 1 b show a micro hollow fiber which is suitable for carrying out the method according to the invention and is designated 1 in its entirety.
  • the micro hollow fiber is semipermeable, i.e. permeable to the protons generated during electrolysis, but impermeable to the gaseous reaction products.
  • the hollow fiber can be produced by spinning as well as by extrusion of a film and subsequent winding or turning of the film into a tube.
  • the proton conductivity of the fiber or film used to make the tube can be by sulfonation, i.e. can be increased by bathing in sulfuric acid.
  • the hollow fiber On their wall surfaces, the hollow fiber carries the two electrodes separated by the wall thickness, here the anode 2 outside and the cathode 3 inside.
  • the electrodes can be made of carbon paper, for example.
  • the carbon paper is applied to the membrane film before the winding or turning of the hollow fiber.
  • Another possibility is to metallize the foils, for example by anodic oxidation of metals, e.g. Aluminum.
  • the electrodes can each be coated on their outer surfaces with a catalyst, e.g. is formed as a spunbond.
  • FIG. 1 c The arrangement of the hollow micro fibers in a frame 4 is shown schematically in FIG. 1 c, in which the ends of the hollow micro fibers are firmly integrated, for example by casting are. In order not to endanger the clarity of the illustration, only four hollow fibers are enlarged in this figure and shown at a greater distance from one another. In practice, the individual hollow micro fibers 1 are packed tightly and are stacked over the entire height of the frame perpendicular to the plane of the figure.
  • the frame 4 is preferably rectangular or square, the hollow micro fibers 1 being arranged parallel to one another.
  • FIG. 2 Another possibility of arranging a hollow fiber stack is shown in FIG. 2.
  • the frame is designed here as an annular flange, in which the hollow micro fibers are integrated in a dimensionally stable manner.
  • the position of the hollow micro fibers is indicated here schematically in solid lines.
  • the micro hollow fibers themselves end flush with the outer edge of the frame 4.
  • the individual layers of the micro hollow fibers are offset from one another by 15 °, so that two mutually opposite flange ends 5 are produced, which are flattened here and on which no micro hollow fiber ends are exposed. At these ends 5 there is therefore space for the introduction of conductive connections to the electrodes in order to connect them to a voltage source.
  • Figures 3a to 3c show a frame 4 in the form of an annular flange, which corresponds to that of the embodiment of Fig. 2.
  • a protective fabric 6 is attached, which covers the circular surface delimited by the frame. This protective fabric 6 serves to avoid damage to the hollow micro fibers contained in the frame.
  • the open hollow fiber ends 7 (for reasons of clarity of the illustration, only a few hollow fiber ends are shown here enlarged) open to the outside.
  • An example of the dimensions of such a frame is given below:
  • a free hollow fiber surface of 3 to 6 m 2 can be achieved. This means that a large reaction surface is available in a very small space.
  • the frame can also be used for the frame.
  • the range has proven to be particularly suitable, in which the individual sizes deviate by ⁇ 50% from the information given above. Since the device according to the invention is designed as a flat disk in cross-section, as is best illustrated in FIG. 3b, several such devices can be stacked on top of one another in order to achieve a higher yield of hydrogen.
  • the individual stacks are to be arranged in a suitable pressure housing.
  • a suitable pressure housing Such housings are known in the prior art and are therefore not to be explained in more detail here.
  • FIG. 4a and 4b show a frame 4 of the device according to the invention, which is provided with connections 8, 9 for the two electrodes.
  • the frame 4 itself is made of a dielectric material. According to the arrangement shown in FIG. 4 a, a series connection of the electrodes of the hollow micro fibers contained in the frame 4 can be realized by stacking a plurality of frames.
  • FIG. 4b shows the frame 4 from FIG. 4a in cross-section, only one hollow micro fiber 2 being shown extending into the frame 4 to improve the clarity of the illustration.
  • One of the two electrodes 10 of the micro hollow fiber which can be designed as an anode or cathode, is located on the outer surface of the micro hollow fiber 1.
  • the electrode 10 of the micro hollow fiber 1 is in direct contact with the corresponding connector 9, which is applied to the frame circumference. From the other of the two micro hollow fiber electrodes (not shown) that are on the in- NEN surface of the micro hollow fiber is attached, a line leads from the frame up to the second terminal 8 of the frame 4th
  • the cathodes are arranged on the inner surfaces of the hollow micro fiber 1, the hydrogen of the electrolysis process is produced on the outer surfaces of the fibers which form the anode. In this case the anode contact to the housing is reached directly.
  • the hollow fibers intended for storage can be arranged in an analog fashion in an analog fashion, but the electrical supply lines are omitted.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé d'obtention de l'hydrogène par électrolyse, caractérisé en ce qu'on prépare un premier électrolyte dans l'espace intérieur d'une microfibre creuse qui porte sur sa surface de paroi, une anode et une cathode, séparées l'une de l'autre, en ce qu'un deuxième électrolyte est préparé à l'extérieur de la microfibre creuse, de telle façon qu'il baigne sa paroi extérieure, et en ce qu'une tension est appliquée entre l'anode et la cathode. Le dispositif selon l'invention, pour l'obtention d'hydrogène par électrolyse, présente une pluralité de microfibres creuses empilées, dont les surfaces intérieures et extérieures portent les anodes ou les cathodes, les extrémités des microfibres creuses étant liées de façon indéformable dans un cadre.
EP00926800A 1999-04-25 2000-04-04 Procede et dispositif d'obtention d'hydrogene Withdrawn EP1177332A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19918680 1999-04-25
DE19918680 1999-04-25
PCT/EP2000/002973 WO2000065129A1 (fr) 1999-04-25 2000-04-04 Procede et dispositif d'obtention d'hydrogene

Publications (1)

Publication Number Publication Date
EP1177332A1 true EP1177332A1 (fr) 2002-02-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00926800A Withdrawn EP1177332A1 (fr) 1999-04-25 2000-04-04 Procede et dispositif d'obtention d'hydrogene

Country Status (6)

Country Link
EP (1) EP1177332A1 (fr)
JP (1) JP2002543285A (fr)
AU (1) AU4542600A (fr)
CA (1) CA2371170A1 (fr)
DE (1) DE10016591C2 (fr)
WO (1) WO2000065129A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002038495A1 (fr) * 2000-11-12 2002-05-16 Klaus Rennebeck Procede et dispositif permettant de produire de l'hydrogene au moyen d'un dispositif de reformage catalytique a microfibres creuses
EP1329968A3 (fr) * 2002-01-04 2007-04-04 Klaus Rennebeck Couche ayant une fonction, procédé de fabrication d'une telle couche ayant une fonction et son utilisation
DE10359509B4 (de) * 2003-11-28 2005-12-29 Roiner, Franz, Prof. Verfahren zur Herstellung eines oder mehrerer Gase
US10390494B2 (en) * 2016-01-20 2019-08-27 Nano Evaporative Technologies, Inc. Hydroponic electroculture system and methods of use

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6004691A (en) * 1995-10-30 1999-12-21 Eshraghi; Ray R. Fibrous battery cells
JP3061866B2 (ja) * 1996-01-21 2000-07-10 クラウス レンベック， セラミック材料からなる微小中空繊維、その製造方法及びその使用
JP3215650B2 (ja) * 1996-05-23 2001-10-09 日本碍子株式会社 電気化学セル、その製造方法および電気化学装置
ATE293711T1 (de) * 1998-03-01 2005-05-15 Klaus Rennebeck Verfahren und vorrichtung zur gewinnung von synthesegas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0065129A1 *

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Publication number Publication date
JP2002543285A (ja) 2002-12-17
CA2371170A1 (fr) 2000-11-02
AU4542600A (en) 2000-11-10
DE10016591C2 (de) 2003-04-10
DE10016591A1 (de) 2000-10-26
WO2000065129A1 (fr) 2000-11-02

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