EP1167579B1 - Procédé d'électrolyse chlore-alcali dans des cellules à membrane utilisant un sel non-purifié - Google Patents

Procédé d'électrolyse chlore-alcali dans des cellules à membrane utilisant un sel non-purifié Download PDF

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Publication number
EP1167579B1
EP1167579B1 EP01114430A EP01114430A EP1167579B1 EP 1167579 B1 EP1167579 B1 EP 1167579B1 EP 01114430 A EP01114430 A EP 01114430A EP 01114430 A EP01114430 A EP 01114430A EP 1167579 B1 EP1167579 B1 EP 1167579B1
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Prior art keywords
anode
membrane
process according
cathode
chlorine
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German (de)
English (en)
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EP1167579A1 (fr
Inventor
Jakob Dr.-Ing. Jörissen
Simon Dipl.-Ing.(Fh) Schnitzler
Ulrich Dipl.-Ing. Stemick
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Siemens AG
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Siemens AG
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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

  • Chlorine-based disinfectants for drinking water and swimming pools are indispensable because of their long-term effectiveness, especially for the disinfection of swimming pool water.
  • the use, and especially the transport and storage of elemental chlorine are associated with safety risks. Its use in water can lead to the undesirable formation of toxic chlorinated compounds from organic contaminants.
  • sodium hypochlorite solutions An alternative to the use of elemental chlorine is the use of sodium hypochlorite solutions.
  • the use of sodium hypochlorite solutions has the following advantages: The transport and handling of sodium hypochlorite are less dangerous than with chlorine gas, and inconvenience is easier to manage.
  • sodium hypochlorite solutions are very easy to dose and the hypochlorous acid formed from the sodium hypochlorite in the water at neutral pH acts as a strong oxidizer but is not chlorinating.
  • the process according to the invention relates to systems based on brine-based membrane cells.
  • US Pat. No. 4,230,544 describes a device and a corresponding chloralkali electrolysis process in which the electrolytic process, in particular in the anode space, is controlled by the pH value and the selection of the electrode. This is done in such a way that the amount of oxygen formed at the anode or the current efficiency of the oxygen production and the current efficiency of the membrane for the transfer of hydroxide ions from the cathode space to the anode space are chemically substantially equivalent.
  • the object of the invention is therefore to provide a chloralkali electrolysis process in which, in spite of the simplifications required for small installations (no brine cleaning, no complete degassing) a stable and reliable condition is achieved.
  • the abovementioned disadvantages of the hitherto available small plants should be avoided, but at the same time the chloralkali electrolysis process according to the invention should at least be equal in terms of costs.
  • a produced by further processing of the products of chlorine electrolysis sodium hypochlorite solution should show optimum product quality.
  • FIG. 4 shows by way of example the acidic state of the membrane obtained in carrying out the chloralkali electrolysis process according to the invention in the device according to the invention or a part thereof, namely the electrolysis cell.
  • the chloralkali electrolysis process according to the invention is characterized in that the membrane is in an acid state during electrolysis.
  • the term "acidic" state or “alkaline” state of a membrane has hitherto been known to the person skilled in the art within the context of the reaction of unpurified sodium sulfate with sodium hydroxide solution and sulfuric acid [Jörissen, J .; Simmrock, KH: "The behavior of ion exchange membranes in electrolysis and electrodialysis of sodium sulphate", 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 Dusseldorf (1996)].
  • the membrane (e) is usually destroyed by the use of impure brine by the then contained in it impurities such as calcium and magnesium salts. This happens due to precipitation of these substances on / in the membrane.
  • the chloralkali electrolysis process according to the invention is characterized by an acidic environment for the membrane;
  • the irreversible damage to the membrane is prevented by the impurities present in the non-purified brine.
  • the precipitates occur, as has been shown in the invention, in the chlorine electrolysis only in the alkaline, but not in the 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 by producing oxygen at the anode simultaneously with the chlorine.
  • Hydrogen ions (H 3 O + ) are produced as a by-product of oxygen production, which acidify the anolyte very strongly. Since only a dilute sodium hydroxide solution, in the range of 2 to 5 wt .-% NaOH, is present in the cathode compartment in the inventive method, an acidic environment is stable in the membrane. Therefore, an acidic boundary layer is formed by the hydrogen ions in front of the membrane in the cathode compartment. The membrane therefore has no direct contact with the sodium hydroxide solution and is in an acidic state.
  • the acidic state of the membrane is stabilized by the fact that - unlike the hitherto customary small systems for Chlorelektrolyse- the chlorine gas in the form of a Magersolenfrelen chlorine gas is removed from the anode compartment.
  • the achievable by the selected process conditions operating state of the method according to the invention reliably prevents deposits in the membrane and can be maintained long-term stable.
  • the chloride concentration of the anolyte in the anode compartment is below the saturation limit in the chloralkali electrolysis process according to the invention, preferably below 50 g / l, particularly preferably in a range from 35 to 45 g / l.
  • the anode-side supply of saturated brine is carried out according to the invention preferably by means of one of the following methods, namely level control, hydrostatic pressure control, conductivity measurement, density measurement or a combination thereof. Such methods are known to the person skilled in the art.
  • the cathode-side supply of softened water is controlled according to the invention via a measurement of the voltage of the cell, a conductivity measurement and / or density measurement.
  • the method according to the invention is particularly advantageous, since the water supplied on the cathode chamber side is softened tap water.
  • the membrane separating the anode space and the cathode space is in an acidic state. Therefore, a single-layer membrane is preferably used. However, this is not a mandatory requirement of the method, as long as it is ensured that the boundary layer separating the cathode and the anode space is in the acidic state, as shown in FIG. 4. In a two-layer membrane, however, ensuring an acidic state is not reliably possible.
  • a cation exchange membrane is used to maintain the acidic state of the membrane separating the anode and cathode compartments.
  • the membrane is one formed on the basis of one or more polymers derivatized with acidic groups.
  • acidic groups which provide the cation exchange function in the membrane are preferably sulfonic acid groups.
  • the polymer must be one which is stable under the conditions of the chloralkali electrolyte according to the invention for an extended period of time, the requirements for the membrane in carrying out the process according to the invention not being as stringent as the conditions for a corresponding membrane in the chlorine electrolysis are in large plants.
  • This is due, inter alia, to the lower stresses of the membrane in this respect in the context of the method according to the invention, since, for example, the concentration of NaOH in the cathode compartment can be kept substantially lower in comparison with the large-scale industrial chloralkali electrolysis method ( ⁇ 33% by weight NaOH).
  • polymer membranes based on perfluorinated hydrocarbons for example for the membrane separating the cathode and the anode space, e.g. Nafion® from DuPont.
  • anodes are preferably used, on whose surfaces it comes in addition to the formation of chlorine gas from the chloride ions and also for the production of oxygen by oxidation of water.
  • the usual dimensionally stable anodes for the chloralkali electrolysis on the basis of titanium, coated with ruthenium-titanium oxides, are optimized for minimal oxygen formation and therefore not very suitable for the process according to the invention.
  • the strongly acidic anolyte according to the invention only little oxygen is produced on them. In addition, they are destroyed in conditions that lead to increased oxygenation.
  • an anode which is formed from a multi-layer material based on titanium and is not destroyed with increased oxygen formation.
  • Conventional titanium anodes are suitable for oxygen evolution, as can be used, for example, in steel strip galvanizing or in sodium sulfate electrolysis.
  • Such electrodes whose support material consists of titanium are coated with mixed oxides based on iridium oxide and tantalum oxide. Examples of such preferably used electrodes based on the above-mentioned metals are, for example, Electro Chemical Services / Eltech type EC600 or EC625, or equivalent types from Heraeus Elektrochemie GmbH.
  • the chloralkali electrolysis process according to the invention is particularly suitable for producing a chlorine bleach or aqueous sodium hypochlorite solution from the aqueous sodium hydroxide solution produced on the cathode side and the chlorine gas produced on the anode side.
  • a combined reactor is used after the chloralkali electrolysis process according to the invention, in the upper, that is the supply line of NaOH / H 2 nearest area, hydrogen is separated from the sodium hydroxide, in the central region of the Reaction of the chlorine is carried out with the sodium hydroxide solution and in the lower part of the resulting sodium hypochlorite solution is cooled.
  • the lower area is the area closest to the Cl 2 supply line.
  • This example was performed in a laboratory cell with 52 mm diameter active area (about 20 cm 2 membrane area).
  • the anode used was a titanium sheet (Heraeus Elektrochemie GmbH, Rodenbach, Industriestr. 17, 63517 Rodenbach), 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 sandwiched by a Nafion® 424 membrane (Dupont, Wilmington, Delaware, USA) and terminated by the electrodes. The distances between the electrodes and the membrane were thus each 40 mm.
  • the cell walls were made of glass or acrylic glass (PMME) to observe the membrane and to detect precipitations immediately.
  • the mixing of the cell chambers was carried out with magnetic stirring cores.
  • a saturated brine of evaporated salt tablets (Axal®, Solvay, Hans-Böckler-Allee 20, 30173 Hannover) flowed into the anode compartment via a level control without any further cleaning measures.
  • the feed to the cathode compartment was controlled so that the sodium hydroxide concentration reached 4 wt .-%.
  • the current density was 2.25 kA / m 2 .
  • the brine supply to the anode compartment turned to just under 30 g / h.
  • a concentration of 3.6% by weight of NaCl and of 0.3% by weight of HCl was analyzed.
  • the water transport through the membrane with the Na + and H + ions increased so high that the supplied brine was completely transported away in the form of the gases chlorine and oxygen as well as through the membrane (no anolyte effluent).
  • the current yield for chlorine and caustic soda was 65 to 70%.
  • the sodium hypochlorite solution produced therefrom in an absorber had a pH of 11-12 and excellent stability.
  • the experimental plant ran for a total of three months under these conditions (about 2000 hours). After dissecting the cells, both the membranes and the electrodes were in perfect condition.
  • a second test facility with 62 mm diameter of the active area (about 30 cm 2 membrane area) was constructed with expanded metal electrodes, so that the electrode spacing could be lowered to about 2 mm.
  • the coating of the titanium anode was carried out by the company Electro Chemical Services / Eltech.
  • a cathode made of expanded titanium metal was used. This is not attacked by hypochlorite, which arises in the breaks from the membrane penetrating chlorine.
  • the plant ran with 2.25 kA / m 2 current density in the cycle of 6 hours of operation and 6 hours break 8 months. This corresponds to a mere operating time of about 2800 hours.
  • the current yield for chlorine and caustic soda was constant at about 50%.
  • the cell voltage started after switching on at room temperature with about 4.1 volts and then reached after approximately one hour of heating to about 55 ° C constant about 3.8 volts. There was no deterioration in the results throughout the trial period. The membrane remained completely clear.
  • a cell with an electrode area of 450 cm 2 was tested.
  • the Magersole feed was level controlled using a small reservoir with float switch.
  • the cell was operated with a current of 100A at a voltage of about 4.1V.
  • the production capacity of this plant was about 70 g / h. After a trial period of about 2 months with daily interruptions, 300 hours of continuous operation resulted in very constant relationships in current, voltage and generation quantity. After disassembly of the cell membranes and electrodes were in perfect condition.

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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)

Claims (15)

  1. Procédé d'électrolyse à l'alcali et chlore en utilisant une cellule à membrane, qui comprend les stades dans lesquels :
    - on envoie à une cellule d'électrolyse, qui a par subdivision par une membrane une chambre anodique ayant une anode et une chambre cathodique ayant une cathode, de l'eau du côté de la chambre cathodique et une solution saturée de NaCl du côté de la chambre anodique ;
    - par électrolyse, on prépare du côté de la chambre cathodique un mélange de lessive de soude aqueuse et d'hydrogène gazeux et du côté de la chambre anodique, avec formation d'une saumure pauvre, du chlore gazeux, la membrane se trouvant à l'état acide ;
    - on soutire à la sortie de la cellule d'électrolyse du côté de la chambre cathodique le mélange de lessive de soude et d'hydrogène gazeux ; et
    - on soutire à la sortie de la cellule d'électrolyse du côté de la chambre anodique du chlore gazeux et de l'oxygène et on effectue un apport du côté anodique d'une saumure saturée seulement dans la mesure nécessaire à la compensation de la consommation de l'anolyte.
  2. Procédé suivant la revendication 1, dans lequel le chlore gazeux soutiré du côté anodique est exempt de saumure pauvre.
  3. Procédé suivant la revendication 1 ou 2, dans lequel la lessive de soude préparée du côté de la chambre cathodique a une concentration inférieure à 20 % en poids de NaOH, de préférence de l'ordre de 2 à 5 % en poids.
  4. Procédé suivant l'une des revendications précédentes, dans lequel la membrane est à une seule couche.
  5. Procédé suivant l'une des revendications précédentes, dans lequel la membrane est une membrane échangeuse de cations.
  6. Procédé suivant l'une des revendications précédentes, dans lequel la membrane est une membrane en polymère qui est greffée de groupes sulfonyles.
  7. Procédé suivant l'une des revendications précédentes, dans lequel le polymère est un polymère à base d'hydrocarbure perfluoré.
  8. Procédé suivant la revendication 7, dans lequel on effectue la régulation de l'apport de saumure saturée du côté anodique au moyen d'un procédé choisi parmi la régulation de la pression hydrostatique, la mesure de la conductivité, la mesure de la masse volumique et la régulation du niveau.
  9. Procédé suivant l'une des revendications précédentes, dans lequel on effectue la régulation de l'apport d'eau du côté cathodique au moyen d'un procédé choisi parmi le contrôle de la tension de la cellule, la mesure de la conductivité et la mesure de la masse volumique.
  10. Procédé suivant l'une des revendications précédentes, dans lequel l'eau apportée du côté de la chambre cathodique est de l'eau de distribution.
  11. Procédé suivant l'une des revendications précédentes, dans lequel la lessive de soude aqueuse produite du côté cathodique et le chlore gazeux produit du côté anodique sont utilisés pour produire de la solution de chlorure décolorant.
  12. Procédé suivant la revendication 11, dans lequel on prépare la solution de chlorure décolorant dans un réacteur combiné dans la partie supérieure duquel de l'hydrogène est séparé de la lessive de soude, dans la partie intermédiaire duquel s'effectue la réaction du chlore sur la lessive de soude s'effectue et dans la partie inférieure duquel la solution d'hypochlorite de sodium formée est refroidie.
  13. Procédé suivant l'une des revendications précédentes, dans lequel on utilise une anode revêtue qui est formée d'un matériau à plusieurs couches à base de titane.
  14. Procédé suivant la revendication 13, dans lequel le revêtement de l'anode est constitué essentiellement d'oxyde mixte à base d'oxyde d'iridium et d'oxyde de tantale.
  15. Procédé suivant l'une des revendications précédentes, dans lequel la concentration de l'anolyte en chlorure dans la chambre anodique est inférieure à la limite de saturation, en étant de préférence inférieure à 50 g/l et en étant notamment de préférence de l'ordre de 35 à 45 g/l.
EP01114430A 2000-06-24 2001-06-15 Procédé d'électrolyse chlore-alcali dans des cellules à membrane utilisant un sel non-purifié Expired - Lifetime EP1167579B1 (fr)

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

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EP1167579A1 EP1167579A1 (fr) 2002-01-02
EP1167579B1 true EP1167579B1 (fr) 2006-09-27

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EP (1) EP1167579B1 (fr)
AT (1) ATE340884T1 (fr)
DE (2) DE10031018B4 (fr)
DK (1) DK1167579T3 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003271236A1 (en) * 2003-03-25 2004-10-18 Vyacheslav Georgievich Gablenko Device for synthesising oxidants from agueous sodium chloride solution
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

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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

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DK1167579T3 (da) 2007-01-08
DE10031018A1 (de) 2002-01-31
ATE340884T1 (de) 2006-10-15
DE10031018B4 (de) 2007-02-22
DE50111075D1 (de) 2006-11-09
EP1167579A1 (fr) 2002-01-02

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