EP0074963A1 - Constructive elements of electrolysis cells - Google Patents
Constructive elements of electrolysis cellsInfo
- Publication number
- EP0074963A1 EP0074963A1 EP19820900783 EP82900783A EP0074963A1 EP 0074963 A1 EP0074963 A1 EP 0074963A1 EP 19820900783 EP19820900783 EP 19820900783 EP 82900783 A EP82900783 A EP 82900783A EP 0074963 A1 EP0074963 A1 EP 0074963A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- cells according
- electrochemical
- base body
- oxide layer
- 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- Withdrawn
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 15
- 238000000034 method Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
Definitions
- the separator must be sufficiently thin and porous to increase the electrical resistance of the cell as little as possible, be corrosion-resistant to the highly concentrated potassium hydroxide solution, and have sufficient mechanical properties to be easily installed in an industrial cell.
- Other examples are electrodes, which should be insulating in certain places, the walls of cells which are exposed to the interface between the electrolytes and the gas phase, or the passage of the electrodes through the cell walls.
- the invention described here is therefore a component of an electrochemical electrolysis cell, which consists of a metallic base material, which is either directly coated with a thin oxide layer, or which still has a suitable intermediate layer between the oxide layer and the base material.
- a separator for an electrolysis cell consists of a fine-meshed network of steel wire with a mesh size of -30 ⁇ m, which was covered with a 2 ⁇ m thick layer of TiO 2 using the CVD process and then treated at elevated temperature in concentrated potassium hydroxide solution .
- the component thus obtained is corrosion-resistant, flexible and can easily be installed in an electrolysis cell.
- a separator for an electrolysis cell consists of a fine-mesh network made of austenitic steel, which was first provided with a 1 ⁇ m thick TiN layer and then with a 1 ⁇ m thick Al 2 O 3 layer using the CVD process.
- Example 3 A separator for an electrolysis cell consists of a felt made of rustproof, ferritic steel, which in its entire volume is first of all coated with a 0.5 ⁇ m to 1 ⁇ m thick layer of TiC using the CVD process and then with a 1 ⁇ m layer thick layer of Al 2 O 3 was coated.
- Example 4 An electrode holder that is exposed to both the electrolyte and the corrosive gases in the cell consists of a ferritic, stainless steel, which is initially coated with a 2 ⁇ m thick TiC layer and then with a 1 ⁇ m thick Al 2 O 3 Layer was provided using the CVD process.
- the insulating, ceramic layers can consist not only of Al 2 O 3 or TiO 2 but also of other ceramic materials, such as zirconium oxide, zirconates, titanates and similar substances.
- the intermediate layer can consist of carbides, nitrides or borides of the elements Ti, Zr, Nb, Te or the like.
- CVD process is particularly suitable for the application of the layers, other processes, e.g. Plasma spraying, flame spraying and the like are used.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Les elements constructifs destines a la fabrication de cellules d'electrolyse, sont electriquement isolants, resistants aux produits chimiques contenus dans les cellules et presentent une solidite et une flexibilite leur permettant d'etre utilises dans des cellules d'electrolyse industrielle. Les elements constructifs sont remarquables en ce qu'ils sont constitues par un corps de base metallique revetu d'une mince couche d'oxyde. Entre la couche d'oxyde et le corps de base peut etre disposee une couche intermediaire. Les elements constructifs peuvent constituer des separateurs, des porte-electrodes, des parois etc...The constructive elements intended for the manufacture of electrolysis cells, are electrically insulating, resistant to the chemicals contained in the cells and have a solidity and flexibility allowing them to be used in industrial electrolysis cells. The constructive elements are remarkable in that they are constituted by a metallic base body coated with a thin layer of oxide. Between the oxide layer and the base body can be arranged an intermediate layer. The constructive elements can constitute separators, electrode holders, walls, etc.
Description
Bauteile von Elektrolysezellen Components of electrolytic cells
In allen Elektrolysezellen, wie z.B. für die Erzeugung von Chlor, von Wasserstoff und Sauerstoff, von Hypochlorit, Persul fat, usf., gibt es Bauteile, die gegenüber dem Elektrolyten und den stromleitenden Elektroden elektrisch isoliert sein müssen. Die Anforderungen die an diese Bauteile gestellt werden, sind mehr oder weniger anspruchsvoll je nachdem um welche Bauteile es sich handelt. Abgesehen von der Korrosionsbeständigkeit gegenüber dem Elektrolyten oder anderen sich in der Zelle befindliche Stoffen, wie z.B. Chlor oder Sauerstoff, bei den Betriebsbedingungen, müssen sie eine gewisse mechanische Festigkeit, oder andere spezifische Eigenschaften aufweisen. Ein besonders anspruchvolles Beispiel ist der Separator in Wasserelektrolysezellen, die bei hohem Druck und Temperatur über 100ºC arbeiten. Der Separator muss genügend dünn und porös sein , um den elektrischen Widerstand der Zelle so wenig wie möglich zu erhöhen, gegenüber der stark konzentrierten Kalilauge korrosionsbeständi sein, und genügend mechanische Eigenschaften besitzen, um in einer industriellen Zelle einfach eingebaut zu werden. Andere Beispiele sind Elektroden, die an gewissen Stellen isolierend sein sollten, oder die Wandungen von Zellen die der Grenzfläche zwischen den Elektrolyten und der Gasphase ausgesetzt sind, oder die Durchführung der Elektroden durch die Zellwandungen.In all electrolytic cells, e.g. For the production of chlorine, hydrogen and oxygen, hypochlorite, persulfate, etc., there are components that must be electrically insulated from the electrolyte and the current-carrying electrodes. The demands placed on these components are more or less demanding depending on which components are involved. Apart from the corrosion resistance to the electrolyte or other substances in the cell, e.g. Chlorine or oxygen, under operating conditions, must have some mechanical strength, or other specific properties. A particularly demanding example is the separator in water electrolysis cells that operate at high pressure and temperature above 100ºC. The separator must be sufficiently thin and porous to increase the electrical resistance of the cell as little as possible, be corrosion-resistant to the highly concentrated potassium hydroxide solution, and have sufficient mechanical properties to be easily installed in an industrial cell. Other examples are electrodes, which should be insulating in certain places, the walls of cells which are exposed to the interface between the electrolytes and the gas phase, or the passage of the electrodes through the cell walls.
Beim heutigen Stand der Technik werden meist Kunststoffe eingesetzt. Keramische Substanzen, wie z.B. Aluminiumoxyd oder K2 O - 6TiO2 werden ebenfalls vorgeschlagen. Alle diese Lösungen befriedigen jedoch nicht vollauf. Entweder mangelt es an Korrosionsfestigkeit, oder an den notwendigen mechanischen Eigenschaften, oder an der Möglichkeit einer komplizierten Formgebung die eine optimale Zellenkonstruktion erlauben würde.
Es wurde nun überraschenderweise gefunden, dass man korrosionsbeständige, elektrisch isolierende Elektrolysezellenbauteile sehr komplexer Form mit ausgezeichneten mechanischen Eigenschaften erhalten kann, indem man auf einem billigen, metallischen, leicht zu bearbeitenden Grundwerkstoff mit Hilfe des CVD-Verf ahrens eine dünne Schicht eines keramischen Materials wie z.B. Aluminiumoxyd aufbringt. Es hat sich überrasche derweise weiterhin gezeigt, dass man die Widerstandsfähigkeit dieser Bauteile gegenüber den in der Elektrolysezelle herrschenden Bedingungen noch stark erhöhen kann, wenn man zwischen den Grundwerkstoff und die isolierende Oxydschicht eine Zwischenschicht aus z.B. Titankarbid oder ähnlichen Verbindungen anbringt.In today's state of the art, plastics are mostly used. Ceramic substances such as aluminum oxide or K 2 O - 6TiO 2 are also proposed. However, all of these solutions are not entirely satisfactory. Either there is a lack of corrosion resistance, or the necessary mechanical properties, or the possibility of a complicated shape that would allow an optimal cell construction. Surprisingly, it has now been found that corrosion-resistant, electrically insulating electrolytic cell components of very complex shape with excellent mechanical properties can be obtained by using a CVD method to apply a thin layer of a ceramic material such as, for example, to a cheap, metallic, easily machined base material Aluminum oxide. Surprisingly, it has also been shown that the resistance of these components to the conditions prevailing in the electrolysis cell can be greatly increased if an intermediate layer of, for example, titanium carbide or similar compounds is applied between the base material and the insulating oxide layer.
Die hier beschriebene Erfindung ist also ein Bauteil einer elektrochemischen Elektrolysezelle, der aus einem metallischem Grundwerkstoff besteht, der entweder direkt mi t einer dünnen Oxydschicht überzogen ist, oder der zwischen der Oxydschicht und dem Grundwerkstoff noch eine geeignete Zwischenschicht besitzt.The invention described here is therefore a component of an electrochemical electrolysis cell, which consists of a metallic base material, which is either directly coated with a thin oxide layer, or which still has a suitable intermediate layer between the oxide layer and the base material.
Beispiel 1. : Ein Separator für eine Elektrolysezelle besteht aus einem feinmaschigen Netz aus Stahldraht mit einer Maschenweite von -30 μm, das mit Hilfe des CVD-Verfahrens mit einer 2 ym dicken Schicht aus Tiθ2 überzogen und anschliessend bei erhöhter Temperatur in konzentrierter Kalilauge behandelt wurde. Der so erhal tene Bauteil ist korrosionsbeständig, flexibel und kann einfach in eine Elektrolysezelle eingebaut werden.Example 1. A separator for an electrolysis cell consists of a fine-meshed network of steel wire with a mesh size of -30 μm, which was covered with a 2 μm thick layer of TiO 2 using the CVD process and then treated at elevated temperature in concentrated potassium hydroxide solution . The component thus obtained is corrosion-resistant, flexible and can easily be installed in an electrolysis cell.
Beispiel 2. : Ein Separator für eine Elektrolysezelle besteht aus einem feinmaschigen Netz aus austeni ti schem Stahl , das zunächst mit einer 1 μm dicken TiN Schicht und darauf mit einer 1 μm dicken Al2O3 Schicht mit Hilfe des CVD-Verfahrens versehen wurde.
Beispiel 3.: Ein Separator für eine Elektrolysezelle besteht aus einem Filz aus rostfreiem, ferritischem Stahl , der in seinem ganzen Volumen mit Hilfe des CVD- Verfahrens zunächst mit einer 0,5 μm bis 1 μm dicken Schicht aus TiC und darauf mit einer 1 μm dicken Schicht aus Al2O3 übe rzogen wurde.Example 2. A separator for an electrolysis cell consists of a fine-mesh network made of austenitic steel, which was first provided with a 1 μm thick TiN layer and then with a 1 μm thick Al 2 O 3 layer using the CVD process. Example 3 .: A separator for an electrolysis cell consists of a felt made of rustproof, ferritic steel, which in its entire volume is first of all coated with a 0.5 μm to 1 μm thick layer of TiC using the CVD process and then with a 1 μm layer thick layer of Al 2 O 3 was coated.
Beispiel 4.: Eine Elektrodenhalterung, die in der Zelle sowohl dem Elektrolyten als auch den korrodierenden Gasen ausgesetzt ist, besteht aus einem ferritischem, nichtrostendem Stahl, der zunächst mit einer 2 μm dicken TiC Schicht und darauf mit einer 1 μm dicken AI2O3 Schicht mit Hilfe des CVD- Verfahrens versehen wurde.Example 4 .: An electrode holder that is exposed to both the electrolyte and the corrosive gases in the cell consists of a ferritic, stainless steel, which is initially coated with a 2 μm thick TiC layer and then with a 1 μm thick Al 2 O 3 Layer was provided using the CVD process.
Es versteht sich von selbst, dass die aufgeführten Beispiele nicht erschöpfend sind. So können z.B. die isolierende, keramische Schichten nicht nur aus AI2O3 oder TiO2 sondern auch aus anderen keramischen Stoffen, wie z.B. Zirkonoxyd, Zirkonaten, Titanaten und ähnliche Stoffe, bestehen. Die Zwischenschicht kann ausser aus TiC oder TiN aus Karbiden, Nitriden, oder Boriden der Elemente Ti, Zr, Nb, Te oder ähnliche bestehen.It goes without saying that the examples given are not exhaustive. For example, the insulating, ceramic layers can consist not only of Al 2 O 3 or TiO 2 but also of other ceramic materials, such as zirconium oxide, zirconates, titanates and similar substances. In addition to TiC or TiN, the intermediate layer can consist of carbides, nitrides or borides of the elements Ti, Zr, Nb, Te or the like.
Obwohl für das Aufbringen der Schichten das CVD-Verfahren besonders geeignet ist, können auch andere Verfahren, wie z.B. Plasmaspritzen, Flammspritzen und ähnliche angewandt werden.
Although the CVD process is particularly suitable for the application of the layers, other processes, e.g. Plasma spraying, flame spraying and the like are used.
Claims
1. Bauteil von elektrochemischen Elektrolysezellen dadurch gekennzeichnet, dass er aus einem metallischem Grundkörper besteht der mit einer dünnen Oxydschicht bedeckt ist1. Component of electrochemical electrolysis cells, characterized in that it consists of a metallic base body which is covered with a thin oxide layer
2. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 1 dadurch gekennzeichnet, dass sich zwischen dem Grundkörper und der Oxydschicht eine Zwischenschicht befindet.2. Component of electrochemical electrolytic cells according to claim 1, characterized in that there is an intermediate layer between the base body and the oxide layer.
3. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 1 und 2 dadurch gekennzeichnet, dass mindestens eine der beiden erwähnten Schichten mit Hilfe des CVD-Verfahrens aufgebracht wird.3. Component of electrochemical electrolytic cells according to claim 1 and 2, characterized in that at least one of the two layers mentioned is applied with the aid of the CVD method.
4. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 1 und 2 dadurch gekennzeichnet, dass die Oxydschicht aus Al2O3 besteht.4. Component of electrochemical electrolytic cells according to claim 1 and 2, characterized in that the oxide layer consists of Al 2 O 3 .
5. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 1 und 2 dadurch gekennzeichnet, dass die Oxydschicht aus TiO2 oder K2Ti6O13 besteht.5. Component of electrochemical electrolytic cells according to claim 1 and 2, characterized in that the oxide layer consists of TiO 2 or K 2 Ti 6 O 13 .
6. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 1 und 2 dadurch gekennzeichnet, dass die Oxydschicht aus einer d e r folgenden Verbindungen besteht: Zirkonoxyd, Zirkonate, Titanate, Niobate, Tantalate.6. Component of electrochemical electrolysis cells according to claim 1 and 2, characterized in that the oxide layer consists of one of the following compounds: zirconium oxide, zirconates, titanates, niobates, tantalates.
7. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 2 dadurch gekennzeichnet, dass die Zwischenschicht aus TiC, TiN oder TiBχ ( X = 1 bis 2 ) besteht.7. Component of electrochemical electrolysis cells according to claim 2, characterized in that the intermediate layer consists of TiC, TiN or TiB χ (X = 1 to 2).
8. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 2 dadurch gekennzeichnet, dass die Zwi s ch e n s ch i c h t aus einem Karbid, Nitrid oder Borid de r Elemente der 4., 5., oder 6. Gruppe des periodischen Systems der Elemente besteht.8. The component of electrochemical electrolysis cells according to claim 2, characterized in that the interchangeability consists of a carbide, nitride or boride of the elements of the 4th, 5th or 6th group of the periodic system of the elements.
9. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 1 bis 8 dadurch gekennzeichnet, dass d e r Grundkörper aus einem ferritischen oder austenitischen nichtrostendem Stahl 9. Component of electrochemical electrolytic cells according to claim 1 to 8, characterized in that the base body made of a ferritic or austenitic stainless steel
10. Bauteil von elektrochemischen Elektrolysezellen gemäss Anspruch 1 bis 9 dadurch gekennzeichnet, dass der Bauteil ein Separator ist, wobei der Grundkörper die Form eines Netzes oder eines Filzes besitzt. 10. Component of electrochemical electrolytic cells according to claim 1 to 9, characterized in that the component is a separator, wherein the base body has the shape of a network or a felt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1888/81 | 1981-03-20 | ||
| CH188881 | 1981-03-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0074963A1 true EP0074963A1 (en) | 1983-03-30 |
Family
ID=4220940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19820900783 Withdrawn EP0074963A1 (en) | 1981-03-20 | 1982-03-19 | Constructive elements of electrolysis cells |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0074963A1 (en) |
| WO (1) | WO1982003231A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100361548B1 (en) | 1999-04-19 | 2002-11-21 | 스미토모 긴조쿠 고교 가부시키가이샤 | Stainless steel product for producing polymer electrode fuel cell |
| DE10194846B4 (en) * | 2000-11-10 | 2008-02-28 | Honda Giken Kogyo K.K. | Process for the surface treatment of a stainless steel product for a fuel cell |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3222265A (en) * | 1958-10-29 | 1965-12-07 | Amalgamated Curacao Patents Co | Electrolysis method and apparatus employing a novel diaphragm |
| FR1255946A (en) * | 1958-10-29 | 1961-03-17 | Amalgamated Curacao Patents Co | Electrolysis diaphragm |
| US3248311A (en) * | 1962-03-29 | 1966-04-26 | Ethyl Corp | Manufacture of sodium |
| FR2067802A5 (en) * | 1969-11-18 | 1971-08-20 | Paris Rene | Metal boride electrodes |
| IT1115372B (en) * | 1977-07-15 | 1986-02-03 | Oronzio De Nora Impianti | TWO-STAGE CERAMIC MEMBRANES FOR ELECTROLYTIC CELLS |
| US4157943A (en) * | 1978-07-14 | 1979-06-12 | The International Nickel Company, Inc. | Composite electrode for electrolytic processes |
-
1982
- 1982-03-19 EP EP19820900783 patent/EP0074963A1/en not_active Withdrawn
- 1982-03-19 WO PCT/CH1982/000042 patent/WO1982003231A1/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8203231A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1982003231A1 (en) | 1982-09-30 |
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| AK | Designated contracting states |
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| 18D | Application deemed to be withdrawn |
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Inventor name: TANNENBERGER, HELMUT |