EP0131724B1 - Woven diaphragm for aqueous electrolytes - Google Patents
Woven diaphragm for aqueous electrolytes Download PDFInfo
- Publication number
- EP0131724B1 EP0131724B1 EP84106154A EP84106154A EP0131724B1 EP 0131724 B1 EP0131724 B1 EP 0131724B1 EP 84106154 A EP84106154 A EP 84106154A EP 84106154 A EP84106154 A EP 84106154A EP 0131724 B1 EP0131724 B1 EP 0131724B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- threads
- diaphragm
- diaphragm according
- electrolysis
- twisted
- 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.)
- Expired
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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
Definitions
- the present invention relates to a woven diaphra 9 "i) for aqueous electrolytes such as alkali chloride solutions, hydrochloric acid solutions and for the water electrolysis of water mixed with acids and / or alkalis.
- aqueous electrolytes such as alkali chloride solutions, hydrochloric acid solutions and for the water electrolysis of water mixed with acids and / or alkalis.
- non-woven fibers made of asbestos fibers have been used as diaphragms in alkali chloride electrolysis.
- the need to largely replace asbestos has already led to proposals to use fluorocarbon polymers for diaphragms in the form of fabrics or foils, possibly including inorganic fiber structures.
- PVC fabrics have been used in the diaphragm process for hydrochloric acid electrolysis.
- Polytetrafluoroethylene fiber fabrics which have been rendered hydrophilic by an acid and / or radiation treatment have already been proposed for water electrolysis.
- EP-0 068 226 discloses diaphragms which are woven from monofilament threads, these diaphragms which are made from fluorinated polymers being hydrophobic, so that the surfaces of the filaments are treated oxidatively in an additional process step.
- An ideal diaphragm must therefore meet a variety of requirements, such as resistance to the electrolytes and the reaction products, sufficient porosity for the electrolyte passage, good separation properties for the reaction products and low ohmic resistance.
- the present invention now provides diaphragms that are characterized by their weave.
- the present invention relates to a woven diaphragm for electrolytic processes with warp and weft threads made of multifilament threads, which is characterized in that the weft multifilament is untwisted or up to max. 200 tours, preferably up to max. 50 tours, twisted per meter.
- the warp thread multifile can have a twist of 0 to 400 turns per meter, preferably about 100 to 200 turns per meter.
- Warp and weft threads are preferably woven in a plain weave, particularly preferably in a grosgrain weave.
- PVDF Polyvinylidene fluoride
- PPS polyphenylene sulfide
- Ryton trademark of Philipps Petroleum
- fluorocarbon polymers are polyethylene tetrafluoroethylene and copolymers, or polytetrafluoroethylene, especially for sodium chloride electrolysis.
- threads composed of continuous filaments are used in particular. If twisted threads are used as warp threads, these can also be constructed from staple fibers, weaving with spinning flake auxiliaries and, if appropriate, the auxiliary being subsequently removed. If untwisted continuous threads are used as warp threads, the multifilament must be treated with finishing or layering agents before weaving.
- a twisting with at least 100 tours / m eliminates the use of such means and the effort for their subsequent removal.
- Preferred diaphragms according to the invention have 4 to 28 wefts per cm, preferably 8 to 20 wefts per cm.
- the titer should be 280 to 1100 dtex, single or double, preferably 300 to 600 dtex, double.
- the individual thread is preferably composed of 20 to 70 individual filaments, preferably 35 to 55 individual filaments.
- the chain preferably consists of 25 to 100 warp threads per cm, particularly preferably 45 to 70 warp threads per cm.
- the titer is preferably also 280 to 1100 dtex, particularly preferably 350 to 700 dtex.
- the warp thread can also have a twist of 0 to 400 turns per meter, preferably 100 to 150 turns per meter.
- Warp and weft are preferably selected within the above limits so that the diaphragm has a weight of 200 to 600 g / m 2 , particularly preferably 300 to 500 g / m 2 .
- the cloth After weaving, the cloth can be compacted by calendering.
- the voltage drop in the electrolysis at the diaphragm is increased as a result, but a purer quality of the gaseous electrolysis products is achieved.
- the multifilament is woven in a grosgrain weave with 57 warp threads per cm and 11.5 weft threads twice per cm.
- the diaphragm is installed in a test electrolysis cell with graphite electrodes.
- the graphite electrodes have vertical slots in a known manner.
- the electrodes were 11 cm high and 7.3 cm wide. The distance between the electrodes was 4 mm.
- the diaphragm was clamped between the electrode frames with rubber seals. 23% hydrochloric acid is introduced into the electrode chambers separated by the diaphragm. On the cathode side together with hydrogen and on the anode side together with chlorine the depleted hydrochloric acid escapes in 18%.
- the temperature of the hydrochloric acid was 85 ° C.
- the electrolysis was operated at a current density of 5 kA / m 2 . A voltage drop of 2.32 volts is measured between the electrodes. On the cathode side, there was 2.7% chlorine in the hydrogen and the purity of the chlorine on the anode side was 99.7%.
- Example 1 The diaphragm used in Example 1 was additionally calendered under heat and pressure. The electrolysis was carried out in the same manner as in Example 1. There was a voltage drop of 2.43 volts. The hydrogen on the cathode side had 0.7% chlorine, the purity of the chlorine on the anode was 99.5%.
- Example 1 A diaphragm as in Example 1 was used and the electrolysis was carried out in the same way as in Example 1. However, 1% orthodichlorobenzene was added to the hydrochloric acid as an organic impurity. The result was a voltage drop of 2.36 volts, a purity of the chlorine of 99.8% and contamination of the hydrogen gas with 1% chlorine.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
Die vorliegende Er' dung betrifft ein gewebtes Diaphra9"'i) für wäßrige Elektrolyte wie Alkalichloridlösungen, Salzsäurelösungen und für die Wasserelektrolyse von mit Säuren und/oder Alkalien versetztem Wasser.The present invention relates to a woven diaphra 9 "i) for aqueous electrolytes such as alkali chloride solutions, hydrochloric acid solutions and for the water electrolysis of water mixed with acids and / or alkalis.
Bezüglich der Technik der Elektrolyse nach dem Diaphragmaverfahren wird auf die einschlägige Handbuchliteratur, wie den Aufsatz von Hund und Minz in: Winnacker-Küchler: "Chemische Technologie", Band 2 "Anorganische Technologie I", S. 379 (1982), insbesondere S. 392, S. 404 ff, sowie S. 442 ff, verwiesen.With regard to the technology of electrolysis using the diaphragm method, reference is made to the relevant manual literature, such as the essay by Hund and Mint in: Winnacker-Küchler: "Chemische Technologie", Volume 2 "Inorganische Technologie I", p. 379 (1982), in particular p. 392, pp. 404 ff and p. 442 ff.
Als Diaphragmen wurden bisher bei der Alkalichloridelektrolyse insbesondere Wirrfaservliese aus Asbestfasern eingesetzt. Die Notwendigkeit, Asbest weitgehend zu ersetzen, hat auch bereits zu Vorschlägen geführt, Fluorkohlenstoffpolymerisate für Diaphragmen in Form von Geweben oder Folien, gegebenenfalls unter Einschluß anorganischer Faserstrukturen, einzusetzen.Until now, in particular, non-woven fibers made of asbestos fibers have been used as diaphragms in alkali chloride electrolysis. The need to largely replace asbestos has already led to proposals to use fluorocarbon polymers for diaphragms in the form of fabrics or foils, possibly including inorganic fiber structures.
Beim Diaphragmaverfahren für die Salzsäureelektrolyse wurden bisher insbesondere PVC-Gewebe eingesetzt.PVC fabrics have been used in the diaphragm process for hydrochloric acid electrolysis.
Für die Wasserelektrolyse wurden bereits Polytetrafluorethylen-Fasergewebe, die durch eine Säure- und/oder Bestrahlungsbehandlung hydrophil gemacht wurden, vorgeschlagen.Polytetrafluoroethylene fiber fabrics which have been rendered hydrophilic by an acid and / or radiation treatment have already been proposed for water electrolysis.
So sind aus der EP-0 068 226 Diaphragmen bekannt, die aus monofilamenten Fäden gewebt sind, wobei diese Diaphragmen, die aus fluorierten Polymeren hergestellt sind, hydrophob sind, so daß die Oberflächen der Filamente in einem zusätzlichen Verfahrensschritt oxidativ behandelt werden.EP-0 068 226 discloses diaphragms which are woven from monofilament threads, these diaphragms which are made from fluorinated polymers being hydrophobic, so that the surfaces of the filaments are treated oxidatively in an additional process step.
Die in der britischen Patentschrift 1 036 416 beschriebenen Gewebe aus einer multifilamenten Gewebekonstruktion werden zusätzlich kalandert, heiß fixiert oder in heißem Wasser geschrumpft, um Diaphragmen zu erhalten, die für die Elektrolyse geeignet sind.The fabrics of a multifilament fabric construction described in British Patent 1,036,416 are additionally calendered, heat-fixed or shrunk in hot water in order to obtain diaphragms which are suitable for electrolysis.
Ein ideales Diaphragma muß also eine Vielzahl, einander teilweise wiedersprechender, Anforderungen erfüllen, wie Beständigkeit gegenüber den Elektrolyten und den Reaktionsprodukten, ausreichende Porosität für den Elektrolytdurchtritt, gute Trennwirkung für die Reaktionsprodukte sowie geringen Ohm'schen Widerstand.An ideal diaphragm must therefore meet a variety of requirements, such as resistance to the electrolytes and the reaction products, sufficient porosity for the electrolyte passage, good separation properties for the reaction products and low ohmic resistance.
Die vorliegende Erfindung stellt nun Diaphragmen zur Verfügung, die durch ihre Webart gekennzeichnet sind.The present invention now provides diaphragms that are characterized by their weave.
Gegenstand der vorliegenden Erfindung ist ein gewebtes Diaphragma für elektrolytische Prozesse mit Kett- und Schußfäden aus multifilen Fäden, das dadurch gekennzeichnet ist, daß die Schußfaden-Multifile unverdrillt oder bis max. 200 Touren, vorzugsweise bis max. 50 Touren, pro Meter verdrillt sind. Die Kettfaden-Multifile können eine Verdrillung von 0 bis 400 Touren pro Meter, vorzugsweise etwa 100 bis 200 Touren pro Meter, aufweisen.The present invention relates to a woven diaphragm for electrolytic processes with warp and weft threads made of multifilament threads, which is characterized in that the weft multifilament is untwisted or up to max. 200 tours, preferably up to max. 50 tours, twisted per meter. The warp thread multifile can have a twist of 0 to 400 turns per meter, preferably about 100 to 200 turns per meter.
Kett- und Schußfäden werden vorzugsweise in Leinwandbindung, besonders bevorzugt Leinwandripsbindung, verwebt.Warp and weft threads are preferably woven in a plain weave, particularly preferably in a grosgrain weave.
Es wurde gefunden, daß insbesondere die im wesentlichen unverdrillten oder geringtourig verdrillten Schußfäden dem Diaphragma eine Kapillarität verleihen, die eine ausreichende Porosität für den Elektrolytdurchtritt bei gleichzeitig guter Trennwirkung für die Elektrolyseprodukte bereitsteht.It has been found that, in particular, the essentially untwisted or low-speed twisted weft threads give the diaphragm a capillarity which is sufficient porosity for the electrolyte passage with a good separation effect for the electrolysis products.
Die chemische Beständigkeit gegen Elektrolyte und Elektrolyseprodukte wird durch die Auswahl des Fadenmaterials bewirkt. Bevorzugt werden Fluorkohlenstoffpolymerisate, gegebenenfalls mit einer Behandlung zur Hydrophilisierung, eingesetzt. Für die Salzsäureelektrolyse hat sich insbesondere Polyvinylidenfluorid ("PVDF") als besonders geeignet erwiesen, insbesondere wenn organische Verunreinigungen in der zu elektrolysierenden Salzsäure enthalten sind. Eine Hydrophilisierung von PVDF ist nicht notwendig.The chemical resistance to electrolytes and electrolysis products is achieved through the selection of the thread material. Fluorocarbon polymers, optionally with a treatment for hydrophilization, are preferably used. Polyvinylidene fluoride ("PVDF") in particular has proven to be particularly suitable for the hydrochloric acid electrolysis, in particular if organic impurities are present in the hydrochloric acid to be electrolyzed. Hydrophilization of PVDF is not necessary.
Besonders geeignet ist auch Polyphenylensulfid ("PPS"), das unter dem Warenzeichen Ryton (Warenzeichen der Philipps Petroleum) erhältlich ist.Also particularly suitable is polyphenylene sulfide ("PPS"), which is available under the trademark Ryton (trademark of Philipps Petroleum).
Andere geeignete Fluorkohlenstoffpolymere sind Polyethylentetrafluorethylen und Copolymere, oder Polytetrafluorethylen, insbesondere für die Natriumchloridelektrolyse.Other suitable fluorocarbon polymers are polyethylene tetrafluoroethylene and copolymers, or polytetrafluoroethylene, especially for sodium chloride electrolysis.
Für die unverdrillten Schußfäden werden insbesondere aus Endlosfilamenten aufgebaute Fäden eingesetzt. Werden als Kettfäden verdrillte Fäden eingesetzt, können diese auch aus Stapelfasern aufgebaut sein, wobei mit Spinnflocke-Hilfsmittel verwebt wird und gegebenenfalls später das Hilfsmittel herausgelöst wird. Werden unverdrillte Endlosfäden als Kettfäden eingesetzt muß der Multifil vor dem Weben mit Avivage oder Schichtmitteln behandelt werden.For the untwisted weft threads, threads composed of continuous filaments are used in particular. If twisted threads are used as warp threads, these can also be constructed from staple fibers, weaving with spinning flake auxiliaries and, if appropriate, the auxiliary being subsequently removed. If untwisted continuous threads are used as warp threads, the multifilament must be treated with finishing or layering agents before weaving.
Eine Verdrillung mit mindestens 100 Touren/m erübrigt den Einsatz solcher Mittel und den Aufwand zu ihrer nachträglichen Entfernung.A twisting with at least 100 tours / m eliminates the use of such means and the effort for their subsequent removal.
Bevorzugte Diaphragmen nach der Erfindung weisen 4 bis 28 Schußfäden pro cm, vorzugsweise 8 bis 20 Schußfäden pro cm auf. Der Titer soll 280 bis 1100 dtex, einfach oder zweifach, betragen, vorzugsweise 300 bis 600 dtex, zweifach. Dabei ist der Einzelfaden vorzugsweise aus 20 bis 70 Einzelfilamenten, vorzugsweise 35 bis 55 Einzelfilamenten, aufgebaut.Preferred diaphragms according to the invention have 4 to 28 wefts per cm, preferably 8 to 20 wefts per cm. The titer should be 280 to 1100 dtex, single or double, preferably 300 to 600 dtex, double. The individual thread is preferably composed of 20 to 70 individual filaments, preferably 35 to 55 individual filaments.
Die Kette besteht vorzugsweise aus 25 bis 100 Kettfäden pro cm, besonders bevorzugt 45 bis 70 Kettfäden pro cm. Der Titer beträgt vorzugsweise ebenfalls 280 bis 1100 dtex, besonders bevorzugt 350 bis 700 dtex. Der Kettfaden kann ferner eine Verdrillung von 0 bis 400 Touren pro Meter, vorzugsweise 100 bis 150 Touren pro Meter, aufweisen.The chain preferably consists of 25 to 100 warp threads per cm, particularly preferably 45 to 70 warp threads per cm. The titer is preferably also 280 to 1100 dtex, particularly preferably 350 to 700 dtex. The warp thread can also have a twist of 0 to 400 turns per meter, preferably 100 to 150 turns per meter.
Kette und Schuß werden im Rahmen der o.g. Grenzen vorzugsweise so ausgewählt, daß das Diaphragma ein Gewicht von 200 bis 600 g/m2, besonders bevorzugt 300 bis 500 g/m2 aufweist.Warp and weft are preferably selected within the above limits so that the diaphragm has a weight of 200 to 600 g / m 2 , particularly preferably 300 to 500 g / m 2 .
Nach dem Weben kann eine Verdichtung des Tuches durch Kalandrieren erfolgen. Der Spannungsabfall bei der Elektrolyse am Diaphragma wird dadurch zwar erhöht, jedoch wird eine reinere Qualität der gasförmigen Elektrolyseprodukte erreicht.After weaving, the cloth can be compacted by calendering. The The voltage drop in the electrolysis at the diaphragm is increased as a result, but a purer quality of the gaseous electrolysis products is achieved.
Die Erfindung wird nachfolgend anhand von Beispielen näher erläutert:The invention is explained in more detail below with the aid of examples:
Es wird ein Multifilament aus Polyvinylidenfluorid, bestehend aus 42 Einzelfilamenten und einem Titer von 550 dtex eingesetzt, für den Schußfaden unverdrillt, für den Kettfaden mit 130 Touren pro Meter verdrillt.A multifilament made of polyvinylidene fluoride, consisting of 42 individual filaments and a titer of 550 dtex, is used, untwisted for the weft thread, twisted at 130 turns per meter for the warp thread.
Das Multifilament wird in Leinwandripsbindung verwebt mit 57 Kettfäden pro cm und 11,5 Schußfäden zweifach pro cm.The multifilament is woven in a grosgrain weave with 57 warp threads per cm and 11.5 weft threads twice per cm.
Das Diaphragma wird in eine Versuchselektrolysezelle mit Graphitelektrodenn eingebaut. Die Graphitelektroden weisen in bekannter Weise vertikale Schlitze auf. Die Elektroden wiesen eine Höhe von 11 cm und eine Breite von 7,3 cm auf. Der Abstand der Elektroden betrug 4 mm. Das Diaphragma war mit Gummidichtungen zwischen den Elektrodenrahmen eingespannt. In die durch das Diaphragma getrennten Elektrodenkammern wird 23 %-ige Salzsäure eingeführt. Auf der Kathodenseite tritt zusammen mit Wasserstoff und auf der Anodenseite zusammen mit Chlor die verarmte Salzsäure 18 %-ig aus. Die Temperatur der Salzsäure betrug 85° C. Die Elektrolyse wurde mit einer Stromdichte von 5 kA/m2 betrieben. Zwischen den Elektroden wird ein Spannungsabfall von 2,32 Volt gemessen. Auf der Kathodenseite ergab sich ein Gehalt von 2,7 % Chlor im Wasserstoff die Reinheit des Chlors auf der Anodenseite betrug 99,7 %.The diaphragm is installed in a test electrolysis cell with graphite electrodes. The graphite electrodes have vertical slots in a known manner. The electrodes were 11 cm high and 7.3 cm wide. The distance between the electrodes was 4 mm. The diaphragm was clamped between the electrode frames with rubber seals. 23% hydrochloric acid is introduced into the electrode chambers separated by the diaphragm. On the cathode side together with hydrogen and on the anode side together with chlorine the depleted hydrochloric acid escapes in 18%. The temperature of the hydrochloric acid was 85 ° C. The electrolysis was operated at a current density of 5 kA / m 2 . A voltage drop of 2.32 volts is measured between the electrodes. On the cathode side, there was 2.7% chlorine in the hydrogen and the purity of the chlorine on the anode side was 99.7%.
Das in Beispiel 1 eingesetzte Diaphragma wurde zusätzlich unter Hitze und Druck kalandert. Die Elektrolyse wurde in gleicher Weise wie in Beispiel 1 durchgeführt. Es ergab sich ein Spannungsabfall von 2,43 Volt. Der kathodenseitig entstehende Wasserstoff wies 0,7 % Chlor auf, die Reinheit des an der Anode entstehenden Chlors betrug 99,5 %.The diaphragm used in Example 1 was additionally calendered under heat and pressure. The electrolysis was carried out in the same manner as in Example 1. There was a voltage drop of 2.43 volts. The hydrogen on the cathode side had 0.7% chlorine, the purity of the chlorine on the anode was 99.5%.
Es wurde ein Diaphragma wie in Beispiel 1 eingesetzt und die Elektrolyse in gleicher Weise wie in Beispiel 1 durchgeführt. Der Salzsäure wurde jedoch 1 % Orthodichlorbenzol als organische Verunreinigung zugesetzt. Es ergab sich ein Spannungsabfall von 2,36 Volt, eine Reinheit des Chlors von 99,8 % sowie eine Verunreinigung des Wasserstoffgases mit 1 % Chlor.A diaphragm as in Example 1 was used and the electrolysis was carried out in the same way as in Example 1. However, 1% orthodichlorobenzene was added to the hydrochloric acid as an organic impurity. The result was a voltage drop of 2.36 volts, a purity of the chlorine of 99.8% and contamination of the hydrogen gas with 1% chlorine.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3321159 | 1983-06-11 | ||
| DE19833321159 DE3321159A1 (en) | 1983-06-11 | 1983-06-11 | WOVEN DIAPHRAGMA FOR AQUEOUS ELECTROLYTE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0131724A2 EP0131724A2 (en) | 1985-01-23 |
| EP0131724A3 EP0131724A3 (en) | 1986-10-22 |
| EP0131724B1 true EP0131724B1 (en) | 1988-08-10 |
Family
ID=6201252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84106154A Expired EP0131724B1 (en) | 1983-06-11 | 1984-05-30 | Woven diaphragm for aqueous electrolytes |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4539082A (en) |
| EP (1) | EP0131724B1 (en) |
| DD (1) | DD222045A5 (en) |
| DE (2) | DE3321159A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4804449A (en) * | 1986-02-25 | 1989-02-14 | Sweeney Charles T | Electrolytic cell |
| US4707228A (en) * | 1986-06-06 | 1987-11-17 | Treadwell Corporation | Diaphragm for electrolytic and electrochemical cells |
| IT1205166B (en) * | 1987-06-22 | 1989-03-15 | Testori Spa Flli | POROUS SEPARATOR ELEMENT COMPLETELY CONSTITUTED BY POLYPHENYLENE SULFIDE, FOR WATER ELECTROLYSIS |
| FR2617872B1 (en) * | 1987-07-09 | 1989-11-24 | Rhone Poulenc Chimie | WOVEN DIAPHRAGM BASED ON VINYL POLYCHLORIDE; A PROCESS FOR ITS OBTAINMENT AND ITS USE IN THE ELECTROLYSIS OF HYDROCHLORIC ACID |
| DE102006023261A1 (en) | 2006-05-18 | 2007-11-22 | Bayer Materialscience Ag | Process for the production of chlorine from hydrogen chloride and oxygen |
| CN101372752B (en) * | 2007-08-21 | 2010-12-08 | 天津工业大学 | High temperature resistant alkaline water electrolytic cell barrier diaphragm and preparation thereof |
| BRPI0918582A2 (en) * | 2008-09-08 | 2015-12-01 | Saint Gobain Performance Plast | sanitary coupling set |
| CN103938337A (en) * | 2013-01-18 | 2014-07-23 | 东丽纤维研究所（中国）有限公司 | Diaphragm cloth for water electrolyser and method for producing diaphragm cloth |
| EP3447177B1 (en) * | 2016-04-18 | 2023-10-25 | Toray Industries, Inc. | Polyphenylene sulfide woven fabric for water electrolyser and manufacturing method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2942327A (en) * | 1957-08-15 | 1960-06-28 | Landers Corp | Coated fabric |
| BE632859A (en) * | 1962-05-28 | |||
| FR1470721A (en) * | 1965-03-04 | 1967-02-24 | Bayer Ag | Process for the preparation of olefin oxides |
| US4324606A (en) * | 1979-12-27 | 1982-04-13 | E. I. Du Pont De Nemours And Company | Process for forming a reinforced membrane |
| NO148267C (en) * | 1981-06-16 | 1983-09-07 | Norsk Hydro As | Water electrolysis diaphragm |
-
1983
- 1983-06-11 DE DE19833321159 patent/DE3321159A1/en not_active Withdrawn
-
1984
- 1984-05-30 DE DE8484106154T patent/DE3473302D1/en not_active Expired
- 1984-05-30 EP EP84106154A patent/EP0131724B1/en not_active Expired
- 1984-06-06 US US06/617,691 patent/US4539082A/en not_active Expired - Fee Related
- 1984-06-08 DD DD84263968A patent/DD222045A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0131724A3 (en) | 1986-10-22 |
| US4539082A (en) | 1985-09-03 |
| DD222045A5 (en) | 1985-05-08 |
| EP0131724A2 (en) | 1985-01-23 |
| DE3473302D1 (en) | 1988-09-15 |
| DE3321159A1 (en) | 1984-12-13 |
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