EP1167579A1 - Chloralkalielektrolyse-Verfahren in Membranzellen unter Elektrolyse von ungereinigtem Siedesalz - Google Patents
Chloralkalielektrolyse-Verfahren in Membranzellen unter Elektrolyse von ungereinigtem Siedesalz Download PDFInfo
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- EP1167579A1 EP1167579A1 EP01114430A EP01114430A EP1167579A1 EP 1167579 A1 EP1167579 A1 EP 1167579A1 EP 01114430 A EP01114430 A EP 01114430A EP 01114430 A EP01114430 A EP 01114430A EP 1167579 A1 EP1167579 A1 EP 1167579A1
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- anode
- membrane
- cathode
- chlorine
- sodium hydroxide
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- 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
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
Definitions
- the invention also relates to a device for carrying out the method.
- Disinfectant based on chlorine for drinking water and swimming pools are particularly suitable for the disinfection of swimming pool water indispensable.
- the application and especially the transport and the storage of elemental chlorine are, however, with safety risks connected. Its use in water can be toxic to undesirable formation chlorinated compounds lead from organic contaminants. Also has Chlorine lowers the pH value as a by-product Hydrochloric acid.
- the use is an alternative to the use of elemental chlorine of sodium hypochlorite solutions.
- the use of sodium hypochlorite solutions has the following advantages: The transportation and handling of sodium hypochlorite are less dangerous than with chlorine gas, accidents are easier manageable. Sodium hypochlorite solutions are also very easy to dose and that formed from the sodium hypochlorite in water at neutral pH Hypochlorous acid acts as a strong oxidizing agent, but is not chlorinating.
- Electrolysis plant to produce the sodium hypochlorite solution directly on site. This usually takes place by means of chlor-alkali electrolysis, also chlorine electrolysis called.
- Disinfection technology for water treatment currently exists Systems based on membrane cells and systems based on of continuous cells, as shown in FIG. 1.
- the method according to the invention relates to systems based on Brine-based membrane cells.
- the object of the invention is therefore to provide a chlor-alkali electrolysis process, despite the simplifications necessary for small systems (none Brine cleaning, no complete degassing) a stable and reliable Condition is reached.
- the aforementioned disadvantages of previously available small systems can be avoided, but at the same time Chloralkali electrolysis method according to the invention in terms of the cost thereof should be at least equal.
- a further processing of the Products of the chlorine electrolysis sodium hypochlorite solution produced an optimal Show product quality.
- the chlor-alkali electrolysis process according to the invention is characterized in that the membrane is in an acidic state during electrolysis.
- the term “acidic” or “alkaline” state of a membrane has hitherto been known to the person skilled in the art in the course of the reaction of unpurified sodium sulfate to sodium hydroxide solution and sulfuric acid [Jörissen, J .; Simmrock, KH: "The behavior of ion exchange membranes in electrolysis and electrodialysis of sodium sulfate", J. Appl. Electrochem. 21 (1991) 869-876; Jörissen, J .: “Ion exchange membranes in electrolysis and electro-organic synthesis", Progress Reports VDI, Series 3, No. 442, VDI-Verlag Düsseldorf (1996)].
- the membrane (s) is usually used of unpurified brine due to the contaminants it contains, such as calcium and destroyed magnesium salts. This happens due to precipitations of these Fabrics on / in the membrane.
- the chlor-alkali electrolysis process according to the invention is - as already mentioned - characterized by an acidic environment for the membrane; this will make the irreversible Damage to the membrane due to the presence in the unpurified brine Prevents contaminants.
- the precipitates occur as is in the frame the invention has shown, in chlorine electrolysis only in alkaline, but not in acidic area. If an acidic environment is present in the membrane according to the invention, the contaminants contained in the brine can pass through the membrane.
- the acidic environment is ensured according to the invention in that oxygen is also produced on the anode at the same time as the chlorine. Hydrogen ions (H 3 O + ) are produced as a by-product in the production of oxygen, and these acidify the anolyte very strongly. Since only dilute sodium hydroxide solution, below 20% by weight NaOH, preferably in the range from 2 to 5% by weight, is present in the cathode compartment in the process according to the invention, an acidic environment is stable in the membrane. An acidic boundary layer is therefore formed in front of the membrane in the cathode compartment due to the hydrogen ions. The membrane therefore has no direct contact with the sodium hydroxide solution and is in an acidic state.
- the acidic state stabilizes the membrane in that - unlike the small systems previously used for chlorine electrolysis - the chlorine gas in the form of a lean brine-free chlorine gas is taken from the anode compartment.
- the by the chosen process conditions avoids achievable operating state of the inventive method reliable deposits in the membrane and can be maintained long-term stable.
- a supply is required on the anode side in the method according to the invention saturated brine in particular only to the extent that the by the electrolysis-related consumption of anolyte is balanced.
- the chlorine electrolysis processes that have been customary up to now will be those in the anode compartment So lean brine does not recirculate, so the above does not occur mentioned adverse effects such as an increase in the concentration of interfering ions and so on.
- the chloride concentration of the anolyte in the anode compartment is the one according to the invention Chlor-alkali electrolysis process below the saturation limit, preferably below 50 g / l, particularly preferably in a range from 35 to 45 g / l.
- the supply of saturated brine on the anode side is preferably carried out according to the invention using one of the following methods, namely level control, hydrostatic Pressure control, conductivity measurement, density measurement or even one Combination of them. Such methods are known to the person skilled in the art.
- the supply of softened water on the cathode side is according to the invention via a measurement of the voltage of the cell, a conductivity measurement and / or Density measurement regulated.
- the method according to the invention is very special advantageous because the water supplied to the cathode compartment is softened tap water is.
- the acid is maintained Condition of the membrane separating the anode and cathode compartments is a cation exchange membrane used.
- the membrane is in particular to one that is formed on the basis of one or more polymers which is derivatized with acidic groups.
- acidic groups which the cation exchange function in the Provide membrane, are preferably sulfonic acid groups.
- the polymer must be one of the Conditions of the chlor-alkali electrolysis according to the invention also for a long time is stable, the requirements for the membrane in the course of implementation the inventive method is not as strict as the conditions for a corresponding membrane for chlorine electrolysis in large plants. This is because among other things due to the lower demands of the Membrane in the process according to the invention, for example because Concentration of NaOH in the cathode compartment in comparison with the large industrial ones Chlor-alkali electrolysis process ( ⁇ 33% by weight NaOH) kept significantly lower can be. On the other hand, it is the great advantage of the chlor-alkali electrolysis process according to the invention that that unpurified evaporated salt as the basis for the brine can be used without it being the case when using this Starting material known disadvantages would come.
- Membrane prefers polymer membranes based on perfluorinated hydrocarbons used, e.g. Nafion® from DuPont.
- one Anode which is made of a multilayer material based on titanium is formed and is not destroyed with increased oxygen formation.
- titanium anodes for oxygen development such as those used in the Steel strip galvanizing or sodium sulfate electrolysis can be used.
- Such electrodes, the carrier material of which is made of titanium are included Mixed oxides based on iridium oxide and tantalum oxide coated. Examples such electrodes preferably used on the basis of those mentioned above Metals are for example Electro Chemical Services / Eltech Type EC600 respectively EC625, or equivalent types from Heraeus Elektrochemie GmbH.
- the chlor-alkali electrolysis process according to the invention is particularly suitable to this, from the cathode side generated aqueous sodium hydroxide solution and the Chlorine gas produced on the anode side is a chlorine bleach or aqueous solution To produce sodium hypochlorite solution.
- a combination reactor is used following the chlor-alkali electrolysis process according to the invention, in the upper area, i.e. the area closest to the supply line of NaOH / H 2 , hydrogen is separated from the sodium hydroxide solution, in the middle area the Reaction of the chlorine with the sodium hydroxide solution takes place and in the lower area the resulting sodium hypochlorite solution is cooled.
- the lower area is the area closest to the supply line for Cl 2 .
- This example was carried out in a laboratory cell with a 52 mm diameter of the active area (approx. 20 cm 2 membrane area).
- a titanium sheet (Heraeus Elektrochemie GmbH, Rodenbach plant, Industriestr. 17, 63517 Rodenbach) was used as the anode, which was provided with a coating suitable for the simultaneous development of chlorine and oxygen.
- the cathode was a chrome-nickel steel sheet (material no. 1.4571).
- the cell was formed from two 40 mm wide cell chambers between which a Nafion® 424 membrane (Dupont, Wilmington, Delaware, USA) was clamped and which were sealed off by the electrodes. The distances between the electrodes and the membrane were therefore 40 mm each.
- the cell walls were made of glass or acrylic glass (PMME) in order to observe the membrane and to recognize precipitates immediately.
- the cell chambers were mixed with magnetic stirring cores.
- a saturated brine from evaporated salt tablets (Axal®, Solvay, Hans-Böckler-Allee 20, 30173 Hanover) flowed into the anode compartment without further cleaning measures via a level control.
- the feed to the cathode compartment was regulated in such a way that the sodium hydroxide concentration reached 4% by weight.
- the current density was 2.25 kA / m 2 .
- the brine supply to the anode compartment was set at just under 30 g / h.
- a concentration of 3.6% by weight NaCl and 0.3% by weight HCl was analyzed in the anode compartment.
- the current yield for chlorine and sodium hydroxide solution was 65 to 70%.
- the sodium hypochlorite solution produced from it in an absorber had a pH of 11-12 and excellent stability.
- test facility ran for a total of three months under these conditions (about 2000 hours). After disassembling the cells were both the membrane as well as the electrodes in perfect condition.
- a second test plant with a 62 mm diameter of the active area was constructed with expanded metal electrodes, so that the electrode spacing could be reduced to approximately 2 mm.
- the titanium anode was coated by Electro Chemical Services / Eltech.
- a cathode made of expanded titanium was used to test the intermittent operation of practical production systems for sodium hypochlorite solution, which only run when needed. This is not attacked by hypochlorite, which is formed during the breaks from chlorine penetrating through the membrane.
- the current yield for chlorine and sodium hydroxide solution was constant at around 50%.
- the cell voltage started after switching on at room temperature with approx. 4.1 volts and then reached a constant approx. 3.8 volts after an approximately one-hour heating phase to approx. 55 ° C. There was no deterioration in the results during the entire test period. The membrane remained completely clear.
- a cell with an electrode area of 450 cm 2 was tested.
- the feed of the lean brine was level-controlled with the help of a small storage tank with a float switch.
- the cell was operated with a current of 100 A at a voltage of approximately 4.1 V.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
- einer Elektrolysezelle, die durch Unterteilung mit einer Membran einen Anodenraum mit einer Anode und einen Kathodenraum mit einer Kathode aufweist, kathodenraumseitig Wasser und anodenraumseitig eine gesättigte Sole, das heißt NaCI-Lösung zugeführt wird,
- durch Elektrolyse kathodenraumseitig ein Gemisch von wässriger Natronlauge und Wasserstoffgas hergestellt und anodenraumseitig unter Bildung einer Magersole Chlorgas hergestellt wird und
- am kathodenraumseitigen Auslass der Elektrolysezelle das Gemisch von Natronlauge und Wasserstoffgas entnommen wird und am anodenraumseitigen Auslass der Elektrolysezelle Chlorgas entnommen wird.
- Die Membran teilt die Elektrolysezelle in einen Anoden- und Kathodenraum;
- der Anodenraum ist der Raum zwischen Anode (positiver Elektrode) und Membran, bei gelochten Anoden zusätzlich der Raum hinter der Anode;
- der Kathodenraum ist der Raum zwischen Kathode (negativer Elektrode) und Membran, bei gelochten Kathoden zusätzlich der Raum hinter der Kathode;
- zwischen Anode und Kathode liegt eine elektrische Gleichspannung an;
- in den Anodenraum wird die Salzsole zudosiert. Die Salzsole enthält hauptsächlich gelöste (hydratisierte) Chlorid- und Natrium-Ionen;
- in den Kathodenraum wird Wasser zudosiert;
- an der Anode wird aus den Chlorid-Ionen Chlorgas produziert;
- Kationenaustauscher-Membranen sind im Idealfall nur für gelöste (hydratisierte) Kationen durchlässig;
- die Natrium-Ionen in der Salzsole können die Membran passieren und gelangen in den Kathodenraum;
- an der Kathode werden aus dem zudosierten Wasser Wasserstoffgas und Hydroxid-Ionen gebildet;
- aus den Natrium- und Hydroxid-Ionen entsteht Natronlauge;
- auf Grund der an den Elektroden ablaufenden Reaktionen und dem damit verbundenen lonentransport durch die Membran fließt zwischen Anode und Kathode der Zellstrom;
- als Maß für die Wirksamkeit der Membran wird die Stromausbeute angegeben. Sie gibt den Anteil des Zellstroms an, der für die Bildung der gewünschten Produkte (Chlor und Natronlauge) verwendet wird;
- die in den Anodenraum zudosierte Sole reagiert nur zu einem Teil ab. Die Sole verlässt den Anodenraum mit reduziertem Salzgehalt (Magersole). In der Zelle löst sich ein Teil des produzierten Chlors in der Magersole. Die Magersole wird nach Durchlaufen des Entgasungsbehälters wieder in einem Salzlösebehälter aufgesättigt und im Kreislauf gefahren, so dass kein Salz verloren geht.
- durch den Einsatz von Kationenaustauscher-Membranen, lässt sich salzfreie Natronlauge (Kathodenseite) und Chlorgas erzeugen, das von der Magersole abgetrennt wird.
- Austreten von Chlorgas;
- das in der Sole enthaltene Chlor kann im Solekreislauf ― insbesondere bei der Wiederaufsättigung mit Salz ― aus der Sole ausgasen und führt zu Umweltbelastungen und Korrosionsschäden;
- Schädigung der lonenaustauscher für die Solereinigung;
- gelöstes Chlor und Hypochlorit in der Sole zerstören die lonenaustauscher;
- Bildung von Chlorat;
- aus dem Hypochlorit in der Magersole kann durch verschiedene Reaktionen Chlorat entstehen, das sich im Kreislauf anreichert und zu Störungen führt.
- Die Sole wird aus Siedesalz und enthärtetem Wasser bereitet.
- Es wird keinerlei Reinigung der Sole durchgeführt.
- Die Magersole wird nicht vollständig entchlort. Daraus ergibt sich ein normaler Restchlorgehalt der Magersole von 5 bis 8 g/l.
- Um ein Ausgasen des Chlors zu verhindern, wird zusätzlich ein Teil der entstehenden Natronlauge in die Magersole dosiert.
- Die in der Anlage verwendete Sole weist sehr hohe Konzentrationen von Störstoffen auf.
- Da keine Ausschleusung aus dem Solekreislauf vorgesehen ist, steigt die Konzentration der Störstoffe stetig an. Dabei bilden sich jedoch in der Membran am Übergang vom sauren Medium des Anodenraums zum alkalischen Medium des Kathodenraums häufig Ausfällungen, vor allem von Calciumund Magnesiumsalzen, die anfangs zu einem starken Anstieg der Zellspannung und schließlich zu einer irreversiblen Schädigung der Membran führen. Dies geschieht häufig schon nach relativ kurzen Laufzeiten.
- Durch den hohen Chlorgehalt der Sole kommt es zur verstärkten Bildung von Chlorat.
- Durch die Zugabe von Natronlauge in die nicht vollständig entchlorte Magersole wird die Entwicklung von Chlorat unterstützt.
- Durch Nebenreaktionen, die durch die Zugabe der Natronlauge verstärkt werden, kann es zu massivem Austritt von Chlorgas aus dem Salzlösebehälter kommen.
- Da ein Teil der erzeugten Natronlauge der Magersole zudosiert wird, fehlt dieser in der erzeugten Natriumhypochlorit-Lösung, und sie weist nicht zu Hypochlorit umgesetztes Chlor auf. Dies beeinträchtigt die Stabilität des Produktes und kann zu einem Austritt von Chlorgas aus dem Produkt führen.
- einer Elektrolysezelle, die durch Unterteilung mit einer Membran einen Anodenraum mit einer Anode und einen Kathodenraum mit einer Kathode aufweist, kathodenraumseitig Wasser und anodenraumseitig eine gesättigte NaCI-Lösung zugeführt wird,
- durch Elektrolyse kathodenraumseitig ein Gemisch von wässriger Natronlauge und Wasserstoffgas hergestellt und anodenraumseitig unter Bildung einer Magersole Chlorgas hergestellt wird, wobei sich die Membran im sauren Zustand befindet, und
- am kathodenraumseitigen Auslass der Elektrolysezelle das Gemisch von Natronlauge und Wasserstoffgas entnommen wird und am anodenraumseitigen Auslass der Elektrolysezelle Chlorgas und Sauerstoff entnommen wird.
Claims (17)
- Chloralkalielektrolyse-Verfahren unter Einsatz einer Membranzelle, wobei das Verfahren die Schritte umfasst, dasseiner Elektrolysezelle, die durch Unterteilung mit einer Membran einen Anodenraum mit einer Anode und einen Kathodenraum mit einer Kathode aufweist, kathodenraumseitig Wasser und anodenraumseitig eine gesättigte NaCI-Lösung zugeführt wird,durch Elektrolyse kathodenraumseitig ein Gemisch von wässriger Natronlauge und Wasserstoffgas hergestellt und anodenraumseitig unter Bildung einer Magersole Chlorgas hergestellt wird, wobei sich die Membran im sauren Zustand befindet,am kathodenraumseitigen Auslass der Elektrolysezelle das Gemisch von Natronlauge und Wasserstoffgas entnommen wird undam anodenraumseitigen Auslass der Elektrolysezelle Chlorgas und Sauerstoff entnommen wird.
- Verfahren nach Anspruch 1, wobei das anodenseitig entnommene Chlorgas magersolenfrei ist.
- Verfahren nach Anspruch 1 oder 2, wobei die kathodenraumseitig hergestellte Natronlauge eine Konzentration von unter 20 Gew.-% NaOH, bevorzugt im Bereich von 2 bis 5 Gew.-% aufweist.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei die Membran einschichtig ist.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei es sich bei der Membran um eine Kationenaustauschermembran handelt.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei die Membran eine Membran aus einem Polymer ist, das mit Sulfonylgruppen derivatisiert ist.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei das Polymer ein Polymer auf der Basis perfluorierter Kohlenwasserstoffe ist.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei die anodenseitige Zufuhr an gesättigter Sole lediglich in dem Umfange erfolgt, dass der Verbrauch an Anolyt ausgeglichen wird.
- Verfahren nach Anspruch 8, wobei die Regelung der Zufuhr an gesättigter Sole anodenseitig mittels eines Verfahrens, ausgewählt aus hydrostatischer Druckregelung, Leitfähigkeitsmessung, Dichtemessung und Niveauregelung, erfolgt.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei die Regelung der Zufuhr an Wasser kathodenseitig mittels eines Verfahrens erfolgt, ausgewählt aus Spannungsüberwachung der Zelle, Leitfähigkeitsmessung und Dichtemessung.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei das kathodenraumseitig zugeführte Wasser Leitungswasser ist.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei die kathodenseitig erzeugte wässrige Natronlauge und das anodenseitig hergestellte Chlorgas zur Herstellung einer Chlorbleichlauge eingesetzt werden.
- Verfahren nach Anspruch 12, wobei die Chlorbleichlauge in einem Kombireaktor hergestellt wird, in dessen oberem Bereich Wasserstoff von der Natronlauge getrennt wird, in dessen mittleren Bereich die Reaktion des Chlors mit der Natronlauge erfolgt und in dessen unterem Bereich die entstehende Natriumhypochloritlösung gekühlt wird.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei eine beschichtete Anode eingesetzt wird, die aus einem Mehrschichtenmaterial auf der Basis von Titan gebildet ist.
- Verfahren nach Anspruch 14, wobei die Beschichtung der Anode im wesentlichen aus Mischoxiden, basierend auf Iridiumoxid und Tantaloxid, besteht.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei die Chloridkonzentration des Anolyten im Anodenraum unterhalb der Sättigungsgrenze liegt, bevorzugt unterhalb von 50 g/l, besonders bevorzugt in einem Bereich von 35 bis 45 g/l.
- Vorrichtung zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 16.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10031018A DE10031018B4 (de) | 2000-06-24 | 2000-06-24 | Chloralkalielektrolyse-Verfahren in Membranzellen unter Elektrolyse von ungereinigtem Siedesalz |
DE10031018 | 2000-06-24 |
Publications (2)
Publication Number | Publication Date |
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EP1167579A1 true EP1167579A1 (de) | 2002-01-02 |
EP1167579B1 EP1167579B1 (de) | 2006-09-27 |
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EP01114430A Expired - Lifetime EP1167579B1 (de) | 2000-06-24 | 2001-06-15 | Chloralkalielektrolyse-Verfahren in Membranzellen unter Elektrolyse von ungereinigtem Siedesalz |
Country Status (4)
Country | Link |
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EP (1) | EP1167579B1 (de) |
AT (1) | ATE340884T1 (de) |
DE (2) | DE10031018B4 (de) |
DK (1) | DK1167579T3 (de) |
Families Citing this family (3)
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WO2004085709A1 (fr) * | 2003-03-25 | 2004-10-07 | Gablenko Vyacheslav Georgievic | Dispositif de synthese d'antioxydants a partir d'une solution aqueuse de chlorure de sodium |
DE102015003911A1 (de) | 2015-03-27 | 2016-09-29 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Verfahren zur Desinfektion von Schwimmbecken-, Trink- und Gebrauchswasser sowie zur Herstellung eines Desinfektionsmittelkonzentrats |
US11998875B2 (en) | 2021-12-22 | 2024-06-04 | The Research Foundation for The State University of New York York | System and method for electrochemical ocean alkalinity enhancement |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4230544A (en) * | 1979-08-31 | 1980-10-28 | Ionics Inc. | Method and apparatus for controlling anode pH in membrane chlor-alkali cells |
US4528077A (en) * | 1982-07-02 | 1985-07-09 | Olin Corporation | Membrane electrolytic cell for minimizing hypochlorite and chlorate formation |
DE29718331U1 (de) * | 1997-10-17 | 1998-01-22 | Dinotec GmbH, 63477 Maintal | Elektrolyseanlage zur Hertellung einer wäßrigen Natriumhypochloritlösung |
-
2000
- 2000-06-24 DE DE10031018A patent/DE10031018B4/de not_active Expired - Fee Related
-
2001
- 2001-06-15 AT AT01114430T patent/ATE340884T1/de active
- 2001-06-15 EP EP01114430A patent/EP1167579B1/de not_active Expired - Lifetime
- 2001-06-15 DE DE50111075T patent/DE50111075D1/de not_active Expired - Lifetime
- 2001-06-15 DK DK01114430T patent/DK1167579T3/da active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4230544A (en) * | 1979-08-31 | 1980-10-28 | Ionics Inc. | Method and apparatus for controlling anode pH in membrane chlor-alkali cells |
US4528077A (en) * | 1982-07-02 | 1985-07-09 | Olin Corporation | Membrane electrolytic cell for minimizing hypochlorite and chlorate formation |
DE29718331U1 (de) * | 1997-10-17 | 1998-01-22 | Dinotec GmbH, 63477 Maintal | Elektrolyseanlage zur Hertellung einer wäßrigen Natriumhypochloritlösung |
Non-Patent Citations (1)
Title |
---|
JOERISSEN J ET AL: "THE BEHAVIOUR OF ION EXCHANGE MEMBRANES IN ELECTROLYSIS AND ELECTRODIALYSIS OF SODIUM SULPHATE", JOURNAL OF APPLIED ELECTROCHEMISTRY, CHAPMAN AND HALL. LONDON, GB, vol. 21, no. 10, 1 October 1991 (1991-10-01), pages 869 - 876, XP000371841, ISSN: 0021-891X * |
Also Published As
Publication number | Publication date |
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ATE340884T1 (de) | 2006-10-15 |
DE10031018A1 (de) | 2002-01-31 |
EP1167579B1 (de) | 2006-09-27 |
DE50111075D1 (de) | 2006-11-09 |
DK1167579T3 (da) | 2007-01-08 |
DE10031018B4 (de) | 2007-02-22 |
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