CA2143448C - Electrolysis apparatus for producing hydrogen - Google Patents

Electrolysis apparatus for producing hydrogen Download PDF

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Publication number
CA2143448C
CA2143448C CA002143448A CA2143448A CA2143448C CA 2143448 C CA2143448 C CA 2143448C CA 002143448 A CA002143448 A CA 002143448A CA 2143448 A CA2143448 A CA 2143448A CA 2143448 C CA2143448 C CA 2143448C
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Canada
Prior art keywords
liquid
electrolytic cell
interior space
pressure shell
oxygen
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Expired - Fee Related
Application number
CA002143448A
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French (fr)
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CA2143448A1 (en
Inventor
Jyrki Leppanen
Jukka-Pekka Nieminen
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Neste Oyj
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Neste Oyj
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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/05Pressure cells
    • 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
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/133Renewable energy sources, e.g. sunlight

Abstract

In an electrolysis apparatus according to the invention for producing hydrogen by decomposing electrolysis liquid with the aid of electric current into hydrogen and oxygen in a pressurized electrolytic cell, an electrolytic cell is placed within a liquid-filled pressure shell maintained pressurized with the pressure of a gas produced in electrolysis. Said liquid can be selected, for instance, among the following group; silicon oils or fats, fluorized oils, crude oil-based or synthetic oils, or water.

Description

Electrolysis Apparatus For Producing Hydrogen The present invention relates to an electrolysis apparatus for producing hydrogen by decomposing electrolytic liquid into hydrogen and oxygen in a pressurized electrolytic cell.
Hydrogen is an ideal and non-polluting source of energy in special applications in which no conventional energy sources are available. Therefore, for instance in devices using electric current and located in sparsely populated and rough regions photovoltaic modules can be used for producing electric current. Such installations are frequently unmanned and require automatic or remote control operation. Also such installations have to be operated when there is no sunlight. Storing electricity merely in batteries would require a large number of batteries, which are heavy in weight and require maintenance.
Using hydrogen for storing energy is one of the means to recover the surplus energy produced by solar cells, whereby water is decomposed into hydrogen and oxygen. Thereby, electricity may, if needed, be produced with the aid of a fuel cell from hydrogen. In order to reduce the size of the hydrogen storages required, the hydrogen must, however, be pressurized, and additional energy must be used in the pressurization.
It is known in the art to accomplish the decomposition of water into hydrogen and oxygen in electrolytic cells operating under pressure and thus producing hydrogen directly in pressurized form, so that no separate pressurization is needed. However increased leakage is a drawback of pressurizing electrolytic cells.

It is also known in the art to place an electrolytic cell into a separate pressure shell, whereby the differential pressure between the inside and outside of the electrolytic cell substantially reduces and the leakages decrease.
Thus, in a known apparatus the pressure shell is pressur-ized with the aid of nitrogen gas, and the apparatus comprises members for maintaining the pressure within the electrolytic cell lower than the pressure of the pressure shell. Use of separate pressurizing gas requires, however, containers for the pressurizing gases and need for supple-menting the pressurizing gas. Thus the system disclosed in the patent is not suitable for installations operating e.g.
automatically in remote areas.
It is known from G.B. Patent 1,518,234, 19/07/78, to place the electrolytic plates inside a pressure shell, whereby the pressure of hydrogen gas prevails inside the pressure shell. However, in the design according to said patent there is not a closed electrolytic cell placed within a pressure shell but the electrodes used in decomposing an electrolytic liquid (HCI) are positioned to be hanging directly inside the pressure shell. The apparatus disclosed in G.B. Patent 1,518,234 is an apparatus intended for large-scale production of hydrogen, having a great need of power, a complicated and expensive design, e.g. due to apparatus needed in purification.
Also known is an electrolysis apparatus is disclosed for producing hydrogen from water, in which apparatus, an electrolytic cell is placed inside a pressure shell and in which the pressure shell is pressurized by conducting oxygen produced in the electrolysis into the pressure shell. The great compressibility of gas causes, however, that the control of the pressure may be slow because the volume of the mantle can be great, particularly if within the pressure shell also other devices are placed in addition to the electrolytic cell, such as water separators. Oxygen may moreover cause, for instance, electrochemical corrosion in moist spaces, for instance in a space between the mantle and the electrolytic cells.
The present invention relates to a pressurized electrolysis apparatus used for producing hydrogen in which drawbacks occurring in the systems as those described above have been solved, and which can be advantageously applied in auto-matic solar energy applications operating without surveil-lance and continuous maintenance.
The electrolysis apparatus according to the invention for producing hydrogen by decomposing an electrolytic liquid with the aid of electric current into hydrogen and oxygen in a pressurized electrolytic cell is characterized in that a closed electrolytic cell is placed in a pressure shell maintained pressurized with the aid of the pressure of a gas produced in electrolysis.
In accordance with this invention an electrolysis apparatus for producing hydrogen by decomposing electrolytic liquid into hydrogen and oxygen with the aid of electric current includes a closed pressure shell defining an interior space, the interior space of the pressure shell being filled with a liquid. A closed pressurized electrolytic cell is arranged in that interior space of the pressure shell and has an interior space which is isolated from and not in flow communication with the interior space of the pressure shell. Means are provided for directing electrolytic liquid into the electrolytic cell to be decomposed so that pressurized hydrogen and oxygen gas is produced. Means remove the pressurized hydrogen and oxygen ~w~

gases from the electrolytic cell, and the apparatus includes means for pressurizing the interior space of the pressure shell and maintaining the pressurization in that interior space at a level to obtain the pressurized hydrogen and oxygen from the electrolytic cell. The pressurizing means comprises means for directing at least a portion of the pressurized hydrogen or oxygen gas removed from the electrolytic cell into connection with the liquid in the interior space of the pressure shell.
The electrolytic liquid fed into the electrolytic cell contains water but it may contain any auxiliary substances promoting the operation of the electrolytic cell used, such as acids or bases. The term "water" will below refer to any such electrolytic liquid.
In an apparatus according to the invention, normal advantages provided by pressurization are gained, i.e. the occurrence of leakages from the electrolytic cell can be minimized. In addition, a great number of other advantages are achieved with the aid of the invention. With the aid of the present invention pressurization with variable pressures can be provided without having to use a separate protective gas for the pressurization and the control thereof. The amount of gas required in pressurization is very small. It is to be noted particularly that in the apparatus of the invention, not only hydrogen produced in the electrolytic cell can be used for the pressurization gas but also oxygen without any risk of corrosion.
In the most common embodiment of the invention the electro-lytic cell is placed within a pressure-resistant pressure shell, and the pressure shell is filled with a liquid. In addition, the pressure shell is connected with a pipe to the pressure gas source, this being a gas produced in the electrolytic cell. Naturally, either oxygen or hydrogen may be used as pressurizing gas. The pressure shell is preferably entirely filled with a liquid, whereby the inertia of the control caused by the compressibility of the gas can be avoided, which may occur if only gas were used for the pressurization of the pressure shell.
In the pressure shell any liquid can be used which is non-conducting, inert to hydrogen or oxygen, non-corroding for the materials used, and resistant to working temperature conditions. The price and non-toxicity are also aspects to be considered.
Thus, in the apparatus of the invention, for instance silicon oil or fats, fluorized oils, oil-based or synthetic lubricants, distilled or ion-exchanged water, or mixtures of any one mentioned can be used for the pressurization liquid. The problem of the last mentioned substance is, however, its poor frost-resistance and that it may cause electrochemical corrosion, especially in association with oxygen. Conventional hydrocarbon containing oils cannot be used with oxygen, either.
Examples of pressurization liquids particularly appropriate also for use with oxygen are especially silicon oils and fats, such as "Dow Corning 200 Fluid"* manufactured by Company Dow Corning or "Rhodosil"* oil by Company Rhone-Poulenc.
It is conventional that the hydrogen gas and the oxygen gas from the electrolytic cell are first conducted through water separators for separating the water following the gases. The water separators in the apparatus according to * Tradename - 4a -the invention can be preferably placed within the pressure shell, whereby the water separators need not be pressure-resistant. However the water separators are preferably placed outside the pressure shell so that the volume of the pressure shell and the volume of the requisite pressuri-zation liquid is as small as possible.
The water separated in the water separators from the gases is returned into the electrolytic cell. According to one advantageous procedure, the water from the water separator of the hydrogen gas is conducted to the water separator of the oxygen gas, from which the water is returned into the electrolytic cell. Hereby the water separator of the hydrogen gas can be provided with a liquid surface height sensor to control the valve placed in the water return line. As the surface rises to the top height, the valve opens, and the water is able to flow from the water separator of the hydrogen gas to the water separator of the oxygen gas. After the surface has gone down into the lower height, the valve shuts down.
As mentioned in the foregoing, the liquid-filled interior space of the pressure shell is connected with a pipe to a gas source provided by a hydrogen or oxygen gas under pressure produced in the electrolytic cell. Therefore, the pressure - 4b -WO 94/05830 ~ ~ ~ ~ pCT/FI93/00343 shell can be in conjunction with any point which is located in the pipes between the gas containers and the electrolytic cell. According to an advantageous alternative, the pressure shell is by means of a pipe connected with the upper part of the water separator used in the water removal from a gas. The pressurization liquid is prefer-s ably used in such quantity that the liquid surface rises at least to some extent into the pipe between the pressure shell and the gas pressure source, however considering a potential thermal expansion of the pressurization liquid.
As regards the operation, the pressure prevailing within the apparatus according to the invention is controlled directly with the pressure of a gas produced in the electrolytic cell. Since hydrogen and oxygen are produced in the electrolytic cell in volumetric ratio of 2:1, the volumes of the hydrogen storage and the oxygen storage are preferably in the same ratio. It is equally advantageous that the gaseous volumes of the water separators and the hydrogen a~ oxygen pipes in association therewith are in said ratio.
The invention is described below in greater detail, referring to the accompanying figures, in which:-Fig. 1 shows the principal design of an electrolysis apparatus according to the invention in which hydrogen pressure is used for controlling the pressure, and Fig. 2 presents an alternative embodiment in which oxygen pressure is used for controlling the pressure.
Figure 1 presents a pressure container 10 serving as a pressure shell. Inside the pressure shell 10 there is placed an electrolytic cell 11 provided with an inlet con-nector 12 of the electrolytic liquid, with outlet connectors 14 and 13 for hydrogen and oxygen, and respectively with electricity feeding lines 15. The interior of the pressure shell 10 is moreover filled with a liquid, e.g. silicon oil.
Electrolytic liquid, such as water, is conducted by means of gravitation into the electrolytic cell 11. The embodiment according to Figure 1 presents water separators 16 and 17 for separating ' 2.43448 water from hydrogen and oxygen.
Water is fed into the electrolytic cell 11 from a water pipe 18 and pump 19 through the pressure shell 10 through a water inlet line 20 conducted into the water separator 17 of the oxygen gas and further therefrom through a water inlet line 21 and a back pressure valve 22 positioned therein into an inlet connector 12, and further, into the electrolytic cell 11. The oxygen gas produced in the electrolytic cell I 1 is conducted through an oxygen outlet connector 13 and an oxygen outlet line 23 to the water separator 17 of oxygen. The water following the oxygen gas is separated in the water separator 17 and returns into the electrolytic cell 11 through line 21.
The hydrogen gas produced in the electrolytic cell 11 is conducted through a hydrogen outlet connector 14 and a hydrogen outlet line 25 to a water separator 16 of the hydrogen gas. From the water separator 16 a hydrogen outlet line 28 provided with a pressure sensor 26 and a valve 27 leads to a hydrogen gas storage container 29. Further a pipe 24 transmitting pressure is lead from the water separator 16 to the interior space of the pressure shell 10 for pressurizing thereof. In addition, a water pipe 31 provided with a valve 30 is conducted from the water separator 16 of the hydrogen gas to the water separator 17 of the oxygen gas, whereby the water following the hydrogen gas can be returned to the electrolytic cell 11 in the above-described manner.
The oxygen gas is conducted from the water separator 17 to the oxygen outlet line 32 and further for instance into an oxygen container (not shown) when also the oxygen is stored for later use. The oxygen outlet line 32 is provided with a pressure sensor 33 and a valve 34.
The pressure control in the apparatus as shown in Figure 1 can be accomplished preferably so that a pressure controller 35 has been connected with signal leads 36 and 37 to hydrogen and oxygen pressure sensors 26,33 and according to the signal provided by said pressure sensors 26,33, the pressure controller 35 opens and shuts through signal line 38,39 the valves 34,27 in the oxygen and hydrogen outlet lines WO 94/05830 ~ 14 3 4 4 S PGT/FI93/00343 32,28.
Figure 2 presents an apparatus according to figure 1 modified so that oxygen is used for pressurizing. The apparatus according to the invention is otherwise similar as in figure 1, except that the oxygen outlet pipe 24 is conducted into the pressure shell from the water separator for oxygen.
The above-described embodiments are intended merely to demonstrate, not to limit, the invention.

Claims (13)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An electrolysis apparatus for producing hydrogen by decomposing electrolytic liquid into hydrogen and oxygen with the aid of electric current, the apparatus comprising:
a closed pressure shell defining an interior space, said interior space of said pressure shell being filled with a liquid;
a closed pressurized electrolytic cell arranged in said interior space of said pressure shell and having an interior space such that said interior space of said electrolytic cell is isolated from and not in flow communication with said interior space of said pressure shell;
means for directing electrolytic liquid into said electrolytic cell to be decomposed such that pressurized hydrogen and oxygen gases are produced;
means for removing the pressurized hydrogen and oxygen gases from said electrolytic cell; and means for pressurizing said interior space of said pressure shell and maintaining the pressurization in said interior space of said pressure shell at a level to obtain the pressurized hydrogen and oxygen from said electrolytic cell, said pressurizing means comprising means for directing at least a portion of the pressurized hydrogen or oxygen gas removed from said electrolytic cell into connection with the liquid in said interior space of said pressure shell.
2. An electrolysis apparatus for producing hydrogen by decomposing electrolytic liquid into hydrogen and oxygen with the aid of electric current, the apparatus comprising:
a closed pressure shell defining an interior space, said interior space of said pressure shell being filled with a liquid;
a closed pressurized electrolytic cell arranged in said interior space of said pressure shell and having an interior space such that said interior space of said electrolytic cell is isolated from and not in flow communication with said interior space of said pressure shell;
means for directing electrolytic liquid into said electrolytic cell to be decomposed such that pressurized hydrogen and oxygen gases are produced;
means for removing the pressurized hydrogen and oxygen gases from said electrolytic cell comprising a separate conduit leading from said electrolytic cell for each of said pressurized hydrogen and oxygen gases;
means for pressurizing said interior space of said pressure shell and maintaining the pressurization in said interior space of said pressure shell at a level to obtain the pressurized hydrogen and oxygen from said electrolytic cell, said pressurizing means comprising means for directing at least a portion of the pressurized hydrogen or oxygen gas removed from said electrolytic cell into connection with the liquid in said interior space of said pressure shell;
liquid separators, one in separate flow communication with each. of said conduits leading from said electrolytic cell, for separating the electrolysis liquid from a respective one of the pressurized hydrogen and oxygen gases; and conduit means for returning the separated electrolysis liquid into said electrolytic cell.
3. The electrolysis apparatus of claim 2, wherein at least one of said liquid separators is placed outside said pressure shell.
4. The electrolysis apparatus of claim 2, wherein at least one of said liquid separators is placed inside said pressure shell.
5. The electrolysis apparatus of claim 2, 3 or 4, wherein said conduit means further comprises a line connecting said liquid separators to each other.
6. The electrolysis apparatus of any one of claims 1 to 5, wherein said electrolytic cell is immersed in the liquid of the liquid-filled interior of the pressure shell.
7. An electrolysis apparatus for producing hydrogen by decomposing electrolytic liquid into hydrogen and oxygen with the aid of electric current, the apparatus comprising:
a closed pressure shell defining an interior space, said interior space of said pressure shell being filled with a liquid;
a closed pressurized electrolytic cell arranged in the liquid of said liquid-filled interior space of said pressure shell and having an interior space such that said interior space of said electrolytic cell is isolated from and not in flow communication with said liquid-filled interior space of said pressure shell;
means for directing electrolytic liquid into said electrolytic cell to be decomposed such that pressurized hydrogen and oxygen gases are produced;
means for removing the pressurized hydrogen and oxygen gases from said electrolytic cell; and means for pressurizing said liquid-filled interior space of said pressure shell and maintaining the pressurization in said liquid-filled interior space of said pressure shell at a level to obtain the pressurized hydrogen and oxygen from said electrolytic cell, said pressurizing means comprising means for directing at least a portion of the pressurized hydrogen or oxygen gas removed from said electrolytic cell into connection with the liquid in said liquid-filled interior space of said pressure shell.
8. The electrolysis apparatus of claim 7, wherein said means for removing the pressurized hydrogen and oxygen gases from said electrolytic cell comprises a separate conduit leading from said electrolytic cell for each of said pressurized hydrogen and oxygen gases, and said pressurizing means comprises means for directing at least a portion of the pressurized hydrogen gas removed from said electrolytic cell into said interior space of said pressure shell.
9. The electrolysis apparatus of claim 7, wherein said means for removing the pressurized hydrogen and oxygen gases from said electrolytic cell comprises a separate conduit leading from said electrolytic cell for each of said pressurized hydrogen and oxygen gases, and said pressurizing means comprises means for directing at least a portion of the pressurized oxygen gas removed from said electrolytic cell into said interior space of said pressure shell.
10. The electrolysis apparatus of claim 7, 8 or 9, in which the hydrogen and oxygen produced in the electrolytic cell is conducted into liquid separators for separating the electrolysis liquid from the gases, the separated electrolysis liquid being returned into said electrolytic cell.
11. The electrolysis apparatus according to claim 10, wherein at least one of said liquid separators is placed outside said pressure shell.
12. The electrolysis apparatus according to claim 10, wherein at least one of said liquid separators is placed inside said pressure shell.
13. The electrolysis apparatus of any one of claims 1 to 12, in which said liquid is selected from the group consisting of silicon oils and fats, fluorized oils, crude oils, synthetic oils, water, and mixtures thereof.
CA002143448A 1992-08-31 1993-08-31 Electrolysis apparatus for producing hydrogen Expired - Fee Related CA2143448C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI923904A FI90569C (en) 1992-08-31 1992-08-31 Electrolyser for hydrogen production
FI923904 1992-08-31
PCT/FI1993/000343 WO1994005830A1 (en) 1992-08-31 1993-08-31 Electrolysis apparatus for producing hydrogen

Publications (2)

Publication Number Publication Date
CA2143448A1 CA2143448A1 (en) 1994-03-17
CA2143448C true CA2143448C (en) 2000-02-01

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CA002143448A Expired - Fee Related CA2143448C (en) 1992-08-31 1993-08-31 Electrolysis apparatus for producing hydrogen

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US (1) US5665211A (en)
EP (1) EP0656959B2 (en)
AT (1) ATE151820T1 (en)
AU (1) AU4961193A (en)
CA (1) CA2143448C (en)
DE (1) DE69309937T3 (en)
FI (1) FI90569C (en)
WO (1) WO1994005830A1 (en)

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CA2329672C (en) 2000-12-27 2009-12-22 Donald W. Kirk Bifurcated electrode of use in electrolytic cells
CA2333859A1 (en) 2001-02-01 2002-08-01 Donald W. Kirk Electrochemical cell stacks
US7559978B2 (en) * 2005-09-19 2009-07-14 General Electric Company Gas-liquid separator and method of operation
US20070215201A1 (en) * 2006-03-17 2007-09-20 Lawrence Curtin Photovoltaic cell with integral light transmitting waveguide in a ceramic sleeve
US7727373B2 (en) * 2006-03-17 2010-06-01 Lawrence Curtin Hydrogen absorption rod
DE102007051230B4 (en) * 2006-10-23 2010-04-08 SETT Solare Energietechnologien Thüringen GmbH electrolyzer
EP2060661A1 (en) * 2007-11-16 2009-05-20 AccaGen SA Electrolyser for producing substances
US9011651B2 (en) 2010-12-09 2015-04-21 Ut-Battelle, Llc Apparatus and method for the electrolysis of water
TWI465301B (en) * 2012-09-25 2014-12-21 Univ Southern Taiwan Sci & Tec Preparation device of porous alumina template
DE102018213404A1 (en) * 2018-08-09 2020-02-13 Siemens Aktiengesellschaft Electrolyser and method for operating an electrolyzer
GB2612067A (en) * 2021-10-20 2023-04-26 Francis Geary Paul Pressurised electrolyser

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DE2548699C3 (en) * 1975-10-30 1980-06-26 Linde Ag, 6200 Wiesbaden Device for the electrolysis of a liquid under pressure
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Publication number Publication date
WO1994005830A1 (en) 1994-03-17
CA2143448A1 (en) 1994-03-17
DE69309937D1 (en) 1997-05-22
FI90569C (en) 1994-02-25
EP0656959B2 (en) 2004-11-10
AU4961193A (en) 1994-03-29
DE69309937T2 (en) 1997-10-16
DE69309937T3 (en) 2005-04-07
EP0656959A1 (en) 1995-06-14
EP0656959B1 (en) 1997-04-16
FI90569B (en) 1993-11-15
US5665211A (en) 1997-09-09
ATE151820T1 (en) 1997-05-15
FI923904A0 (en) 1992-08-31

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