EP2646373A1 - Cellule électrolytique pour produire de l'ozone destiné au traitement d'un liquide - Google Patents

Cellule électrolytique pour produire de l'ozone destiné au traitement d'un liquide

Info

Publication number
EP2646373A1
EP2646373A1 EP11799386.5A EP11799386A EP2646373A1 EP 2646373 A1 EP2646373 A1 EP 2646373A1 EP 11799386 A EP11799386 A EP 11799386A EP 2646373 A1 EP2646373 A1 EP 2646373A1
Authority
EP
European Patent Office
Prior art keywords
liquid
ozone
electrode
electrodes
cell
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Withdrawn
Application number
EP11799386.5A
Other languages
German (de)
English (en)
Inventor
Berthold Conradt
Peter Weidner
Ron Kemmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Brita SE
Original Assignee
Brita SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Brita SE filed Critical Brita SE
Publication of EP2646373A1 publication Critical patent/EP2646373A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C25B1/13—Ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4613—Inversing polarity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/46135—Voltage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46195—Cells containing solid electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/04—Oxidation reduction potential [ORP]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/23—O3
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/043—Treatment of partial or bypass streams
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00—Location of water treatment or water treatment device
    • C02F2307/10—Location of water treatment or water treatment device as part of a potable water dispenser, e.g. for use in homes or offices

Definitions

  • Electrolysis cell for generating ozone for the treatment of a liquid
  • the present invention relates to a Elektrolysezel ⁇ le for generating oxidants, in particular ozone, for treating a liquid, comprising
  • first and the second electrode are arranged at a distance from each other
  • a particulate solid electrolyte is arranged, which is traversed by the liquid.
  • the invention relates to a device for treating a liquid comprising
  • the invention relates to a method for generating ozone for the treatment of a liquid.
  • Liquid or drinking water-donating devices such as coolers, chillers, water bars or vending machines ⁇ , usually have elongated piping systems, which have inlets and outlets, via which the drinking water is supplied to the devices and discharged from them.
  • the risk of retrograde bacterial contamination of the drinking water by undesirable and often harmful to health germs such as bacteria, Pro ⁇ tists, fungi, parasites, viroids, viruses, algae or prions, which are in the piping systems of liquid or drinking water are located and can get stuck there.
  • touching the output Sufficient with the hand of a user to enter germs in the outlet piece which spread against the main flow direction of the drinking water within the device.
  • retrograde germination a hazard, but also of the pipeline system itself, in which also harmful germs can be found and spread.
  • the germs do not necessarily have to be killed.
  • Inactivation of the germs avoids the formation of biofilms.
  • These measures include, for example, the irradiation of the liquid with UV light or the displacement of the liquid with a cleaning agent.
  • the irradiation of the liquid with UV light has the disadvantage that the germs are inactivated only in the radiation range of the UV lamp, so that only a part of the germs are inactivated and the non inactivated ⁇ th germs can spread to other locations of the device on.
  • Oxidizing agents are in particular ozone, chlorine, chlorine dioxide, hydrogen peroxide and hydroxyl radicals (OH radicals).
  • oxidation ⁇ forward has the advantage that its concentration in the
  • Liquid or in drinking water can be controlled so that the germs are safely inactivated and the user is not exposed to health hazards. Furthermore, the Oxidizing agents are conveyed together with the liquid through the entire device, so that all Kirsab ⁇ cuts applied to the oxidizing agent and germs are inactivated everywhere.
  • ozone is generated by means of a so-called Koro ⁇ na-discharge method (corona discharge). With this method, gaseous ozone is generated, which is then introduced into the liquid to be treated. For this purpose, a mixing unit air / water is necessary. A gas separator is needed as residual gases must be destroyed, which are responsible for the
  • the "Fischer cell” known from the prior art, which is suitable for this purpose, comprises areal shaped electrodes which are pressed against a membrane located between the electrodes.
  • the electrodes used are made of lead oxide, which have the disadvantage, especially in the case of non-continuous operation of the device, that they release lead constituents into the liquid to be treated, which is unacceptable in terms of the user's health.
  • DE 10 2004 015 680 A1 discloses an electrolysis cell suitable for treating liquids, in which a solid electrolyte is arranged between the electrodes.
  • the solid electrolyte In order to ensure the stability of the electrolysis cell, the solid electrolyte must be provided in a relatively complex form, whereby a high space requirement is created.
  • the used membranes of a polymer solid electrolyte must be kept permanently moist, so as not to lose their functionality. This is disadvantageous for the storage, the easy transport and the replacement of a spent electrolysis cell.
  • US 6,254,762 discloses a two compartment electrolytic cell for the production of hydrogen peroxide. This system can be released ozone by selecting a suitable catalyst.
  • a main body of the electrolytic cell is divided into an anode chamber and a cathode chamber by means of an ion exchange membrane.
  • the ion exchange membrane has on a side facing the anode chamber on a gas diffusion anode, which is in close contact with her.
  • Cathode chamber is a gas diffusion cathode spaced apart from the Io ⁇ nensolermembran located, so that the cathode is connected to the upper side and the lower side of the main body of the electric ⁇ lysezelle is in contact to the cathode chamber in a
  • the supply and discharge ports each have a plug to prevent the ion exchange resin particles from flowing out.
  • the anode chamber has a hydrogen gas supply port and a gas excess discharge port formed in lower and upper parts of the anode chamber, respectively.
  • the cathode chamber has an oxygen gas supply port and a gas excess discharge port located in lower and upper, respectively Parts of the cathode chamber are formed.
  • Conductivity of the ultrapure water is practically zero. This is due to the fact that the two electrodes are electrically connected to one another via the ion exchange membrane and the ion exchange resin particles, which both have electrical conductivity.
  • Object of the present invention is therefore to provide an electrolytic cell, which is suitable for the treatment of other liquids as ultrapure water.
  • the object is achieved with an electrolytic cell of the type mentioned, in which the solid electrolyte is arranged in a limited by the first and the second electrode space.
  • a particulate solid electrolyte is to be understood as meaning an electrolyte which comprises a large number of solids with small dimensions.
  • the predominant particle size of the solid ⁇ electrolyte should be less than 1 mm.
  • Solid electrolyte can be present as a granulate, a suspension or a powder. Furthermore, the particulate solid electrolytes may also become a larger unit
  • particles with a mean diameter of 1 mm and more can be generated.
  • ozone yield describes the Proportion of ozone in the total amount of oxidants generated.
  • the conductivity of the liquid decreases with increasing purity.
  • a higher voltage is needed to generate the required current density.
  • ozone has the advantage that it decomposes into odorless oxygen and has a higher ef ⁇ fectivity in the inactivation of germs and possibly existing biofilms. Furthermore, the formation of disinfection by-products (DNP) such as chloroform is reduced.
  • DNP disinfection by-products
  • particle ⁇ shaped solid electrolyte may have high current densities are generated, without the two electrodes are short-circuited.
  • the solid electrolyte promotes the conduction of ions through the liquid from the first to the second electrode, so that
  • the electrolyzer ⁇ sezelle can therefore be operated more economically. Since it is possible to work with lower voltages in this embodiment, this contributes to the safety of the electrolysis cell. Furthermore, the electronics can be simplified.
  • the electrodes can be arranged at a very small distance from each other and yet be flowed through with a sufficiently high volume flow. As the distance decreases, the first and second surfaces of the electrodes can be reduced. Furthermore, the space requirement of the electrolytic cell decreases with decreasing distance of the two electrodes, so that they also in areas with low construction can be arranged, for example, directly in the inlet or outlet of a device for the treatment of a liquid.
  • each of the first and second electrodes can act alternately as the anode or cathode.
  • deposits on the electrodes are largely avoided. This is not possible in an electrolytic cell with separate supply ports for different gases without a relatively complex arrangement of automatically controlled valves.
  • the electrolysis cell thus comprises a housing having we ⁇ tendonss an inlet for the liquid to be treated and at least one outlet for the treated liquid, are located where ⁇ at all inlets and outlets between the first of or defined by the second electrode surfaces.
  • the electrolysis cell can be relatively compact, since no chamber has to be arranged on the side of each electrode facing away from the other electrode. In this sense, the electrolysis cell can be symmetrical with respect to an imaginary surface between the electrodes, so that a polarity reversal during operation is easily possible.
  • the particulate solid electrolyte is in one of the powder form, the granulated form, the sintered form and the extruded form.
  • the powder should comprise particles of very small particle size, in particular less than 0.5 mm.
  • the particulate solid electrolyte When sintering, one starts from the particulate solid electrolyte, wherein the grain size can also be chosen so that it corresponds to that of a powder.
  • the particulate solid electrolyte By a Temperaturbe ⁇ treatment and alternatively using a binder, the particulate solid electrolyte is converted into the sintered form. As a result, the particulate solid electrolyte ⁇ takes on a solid shape, so that it is easier to handle.
  • the particulate solid electrolyte can be represented in disk or plate form.
  • the solid electrolyte may be in extruded form. Again, the solid electrolyte after leaving a solid form, which corresponds in cross section to that of Extru ⁇ DERS. This can also be tubular. Again, the handling is improved.
  • the extruded shape can be reduced in size by a further process step in ⁇ example by cutting the extruded form.
  • the free space is completely filled with solid electrolyte.
  • the electrical resistance of the electrolytic cell is relatively constant from the beginning, which simplifies the Be ⁇ operation of the electrolysis cell. Otherwise, the electrical resistance after the first contact with the liquid ⁇ ness would decrease by swelling the particles because the swelling of the particles would cause a better coverage and a firmer contact Zvi ⁇ rule the particles and the electrode surfaces.
  • the distance between the two electrodes using the particulate solid electrolyte is 1.5 to 2.5 mm.
  • the first and second surfaces of the electrodes can be reduced as the distance decreases.
  • the space requirement of the electrolysis cell decreases with decreasing distance between the two electrodes, so that it can also be arranged in areas with a small installation space.
  • the current density between two electrodes increases with the conductivity of the liquid between the electrodes and the applied voltage, but decreases with increasing distance of the two electrodes to each other. If the distance of the electrodes from each other is reduced, the current density increases at the same voltage, whereby the current increases, which increases with the current density and the electrode surface. To return to the original current, the electrode area can be reduced.
  • the smaller the distance between the two electrodes the more compact the electrolytic cell can be configured.
  • the production of oxidants also increases with increasing current. It turned out that with one to the
  • Electrolytic cell applied average current density of more than 0.1 A / cm 2, the amount of ozone generated is sufficient to effectively disinfect liquids with a conductivity of 10 ⁇ / ⁇ or more. In the cell itself, significantly higher current densities can be achieved. This ensures that the majority of the drinking water with the inventive electrolysis cell without ⁇ additional measures such as softening or a full or partial desalination can be treated.
  • electrolytic cells according to the invention are mainly used for the production of ozone, but it can not be avoided that other oxidizing agents in the form of chlorine, chlorine dioxide, hydrogen peroxide and hydroxyl radicals (OH radicals) are formed. Since these also kill or at least inactivate germs, the formation of these is another
  • Oxidizing agent in this respect not disadvantageous. However, they lead to taste adverse changes in the liquid and can produce an unpleasant odor. As mentioned above, the formation of these and other oxidants and their disinfection by-products can not be prevented, however, using an increased current density, the ozone yield compared to the yield of the other oxidizing agents can be increased ge ⁇ .
  • the particulate solid electrolyte may be an ion exchanger, in particular a proton-conducting
  • Ion exchangers more particularly a zeolite or a polymer, still more particularly a tetrafluoroethylene polymer.
  • a sulfonated tetrafluoroethylene polymer such as Nafion has been found to be suitable. It is particularly effective if the ion exchanger is an acidified zeolite or a polymer.
  • Ion exchanger is a cation exchanger that provides protons. Acidified zeolites provide protons available so that a kind of "proton chain" is formed between the two electrodes, which contributes to increasing the conductivity ⁇ ness between the electrodes.
  • proton-conducting ion exchangers are compared with elec- rolysis cells without a proton-conducting solid electrolyte, the current flow and thus the current density at the same ⁇ bender voltage increases.
  • the acidified polymer may be a sulfonated tetrafluoroethylene polymer, such as e.g. Nafion, his.
  • the polymer can be extruded and then particulated.
  • the electrolysis cell can be further developed by a retaining device for retaining the particulate solid electrolyte in the electrolysis cell. This ensures that the particulate solid electrolyte is not flushed out of the space between the electrodes. This is particularly important when the pumbleför ⁇ -shaped solid electrolyte as a powder or powder of small
  • the retaining device can, for example, as a sieve with a particle size to the particle size
  • Electrolytic cell can be penetrated with a large volume flow.
  • the first and second electrodes comprise a carrier core and a diamond coating.
  • a carrier core may be any suitable material and in particular
  • the diamond coating is very durable, giving the electrodes a very long life because the diamond coating protects the electrodes greatly from corrosion by the oxidants such as ozone. Furthermore, it is prevented that components of the electrodes are discharged into the liquid, which may be harmful to the user, as may be the case with lead oxide electrodes, in particular in non-continuous operation of the electrolysis cell. Diamond as such is a very good insulator, so that no current density could be introduced into the liquid to be treated. Therefore, the diamond coating does not consist of pure diamond, but is doped,
  • the diamond coating is elekt ⁇ driven conductive for example with boron.
  • the diamond coating is about 5 to 10 ⁇ and can be applied to the carrier core with a vapor deposition process.
  • both the first and the second electrode have ei ⁇ ne diamond coating, a polarity reversal is possible, which should be done at regular intervals.
  • Umpolung means that not only one electrode always acts as an anode and the other as a cathode.
  • a Be ⁇ lag in particular by limescale, form, which is significantly reduced by the polarity reversal and distributed more uniformly on the two electrodes, so that the life of the electrolysis cell is increased. Otherwise, the electrolysis cell would cease to function after a shorter period of time, when a lime- containing liquid, for example tap water, is supplied to it.
  • the first and second surfaces are arranged planparal ⁇ lel to one another. This can be a
  • one is free to choose the geometrical shape of the electrodes.
  • the geometric shape of the electrodes has an influence on the current densities.
  • it is possible whiltau ⁇ chen rod-shaped electrodes in an ion exchange bed.
  • a different current density can be generated, with which the ozone yield can be controlled. It has been shown that the ozone yield increases with increasing current density in comparison to the other oxidizing agents.
  • the carrier core may be made of ceramic material or more generally comprise the ceramic material.
  • the carrier core can therefore consist exclusively of ceramic material or have other components in addition to the ceramic material and in particular ⁇ sondere be modified with organic components.
  • Ceramic material is particularly resistant to corrosion and therefore increases the life of the electrolysis cell. Furthermore, no harmful substances are released into the liquid flowing around the electrodes. Furthermore, it is possible that the first and the second surface have one or more projections. Peak discharges occur at the projections, so that high current densities are occasionally generated without the voltage having to be increased. The production of oxidants is thus made more efficient. In conjunction with the carrier material of a ceramic material, there is also the effect that the projections can be made very uniform, since the ceramics can be formed very precisely. The punctually high
  • Another aspect of the present invention relates to an apparatus for treating a liquid comprising
  • an electrolysis cell according to the invention for producing oxidizing agents and in particular ozone for the treatment of the liquid.
  • the electrodes can be arranged at a very small distance from each other and yet be flowed through with a sufficiently high volume flow. With decreasing distance, the first and second surfaces of the
  • Electrodes are reduced. Furthermore, the space requirement of the electrolytic cell decreases with decreasing distance of the two electric ⁇ so that it can be arranged in areas with little space, for example, directly in the inlet or outlet of the device.
  • a particulate solid electrolyte is arranged in the free space.
  • the parti ⁇ kelförmige solid electrolyte is good from the liquid to be enriched with the oxidant, fürström- bar.
  • Solid electrolyte promotes the conduction of ions through the liquid from the first to the second electrode, so that to generate the necessary current density lower voltages sufficient than in known electrolysis cells, the no
  • the electrolyzer ⁇ sezelle can therefore be operated more economically.
  • the device is adapted to reverse the polarity of the electrolysis cell so that the first and the second electrode yaw alternately as a cathode and as an anode ⁇ fun.
  • deposit formation is effectively counteracted so that the electrolysis cell remains functional for a reasonable amount of time even when ozone is generated from tap water.
  • the polarity reversal takes place in regular
  • the device is set up to apply a voltage above a threshold value to the electrodes.
  • the threshold value is in a variant at least 8 V / mm, based on the distance between the first and the second electrode, in particular at least
  • An ion exchanger for example a sulfonated fluoropolymer, is suitable for generating ozone from tap water.
  • the current flow can be ⁇ already after a relatively short time to break, so that the
  • Ozone production is greatly reduced.
  • the solid electrolyte is saturated with cations, in particular hardness-forming cations, so that its electrical conductivity decreases sharply.
  • the increase of the voltage above a suitable threshold causes a detachment of the bound cations.
  • the device is configured to detect a drop in current through the electrolytic cell and in response to the detection to increase the voltage at least temporarily to a value above ei ⁇ nes certain threshold value.
  • the device comprises a measuring device for determining at least one variable from the group comprising the conductivity, the ozone content and the oxidation-reduction potential of the liquid.
  • the cell can be activated (too little oxidant or ozone in the liquid) or deactivated (too much oxidant or ozone in the liquid).
  • Other determinable events for activating and deactivating the cell may be a time interval or time, or the delivery of untreated fluid into the device.
  • the device may be operated to produce or maintain a concentration of the oxidizing agent necessary to safely inactivate the germs. Thus that a too high concentration of the means of Oxidationsmit ⁇ is generated is prevented, which would cause unnecessary costs
  • Liquid taste is negatively influenced or limits for liquids (especially drinking water) are exceeded. Furthermore, the formation of disinfection by-products is reduced.
  • the device comprises a measuring device for determining the conductivity of the liquid, the device being set up to set a cell voltage as a function of the conductivity.
  • the device is also better suited for treating tap water whose conductivity may vary within certain limits.
  • the cell resistance can be determined by means of the measuring device, wherein the measuring device comprises a power supply for regulating the voltage as a function of the measured cell resistance.
  • the measuring device comprises a power supply for regulating the voltage as a function of the measured cell resistance.
  • the apparatus further comprises a tank for storing the liquid, and guide means for guiding the liquid in the apparatus, the electrolytic cell in the tank, in the inlet, arranged in the Füh ⁇ agent or in the outlet piece.
  • Inventive electrolysis cell requires little space, it can be arranged in all areas of the device.
  • the location at which the electrolytic cell is located coincides with the introduction of the oxidizing agent into the liquid, so that the electrolysis cell can be arranged at locations of the device which are critical for the microbial contamination, for example at the outlet or at the supply line for untreated liquid.
  • the outlet piece comprises a closable opening for selectively discharging the liquid, a supply element for supplying the liquid to the outlet piece, and a discharge element for discharging the liquid from the outlet piece and for guiding into the tank.
  • the outlet piece can be flushed with the treated liquid even if the liquid is not to be dispensed through the outlet piece.
  • the disinfecting effect of the liquid which is mixed with the oxidizing agent is used to supply the outlet piece
  • the outlet piece is a critical point for retrograde Ver ⁇ germination, as it represents the interface with the environment in which a high number of germs is located.
  • the liquid discharged from the outlet piece can be returned to the tank. Furthermore, it is also possible to operate the device so that the liquid is conveyed in the circuit ⁇ run. In this embodiment, a certain Recirculated volume of fluid within the apparatus, repeated with chert ⁇ oxidant and in particular ozone angerei and are brought to a specific concentration.
  • this embodiment Since on the one hand less or no fresh liquid ⁇ speed must be supplied, this embodiment has the effect that the amount of spent liquid can be reduced and thus also devices can be operated without outflow. On the other hand, the amount to be generated in the cell becomes
  • the cell can be switched on in dependence upon the determined value of the conductance of the oxidation-reduction potential or the ozone content and off, while the liquid ge ⁇ promotes the circulation, so that a certain concentration is never exceeded.
  • the oxidant and ozone concentration generated in the electrolysis cell can be adjusted by adjusting the
  • a conveying device for conveying the liquid within the device.
  • the device can also be operated without a conveyor, wherein the pressure of the supply line or the hydrostatic pressure in the tank cause the conveying of the treated liquid.
  • the liquid can be independent of structural conditions and
  • An embodiment of the device is characterized by a unit for reducing the concentration of the oxidizing agent.
  • This unit can be a UV lamp, activated carbon,
  • Glass fiber or other catalytically active element umfas ⁇ sen and may for example in the area of the outlet
  • This embodiment makes it possible to produce within the device a concentration of the oxidizing agent which is higher than that which is necessary for the use of the
  • Liquid, especially as drinking water, acceptable and zuläs ⁇ sig is. Furthermore, a high concentration of
  • the unit for reducing the concentration of the oxidizing agent may be disposed outside of the circulation circuit. But it can also be ⁇ classified within the circulation circuit. In this case, the liquid removal is in one disclosed embodiment by the user during the Umisselzpro ⁇ zesses not possible, and the unit is switched off for reducing the concentration of the oxidizing agent.
  • the device comprises a bypass with a first section and a second section, wherein the electrolysis cell is arranged in one of the sections.
  • bypass indicates, the first and second sections are fluidically connected in parallel.
  • the bypass allows easy replacement of the electrolysis cell, furthermore, with the choice of volume flows through the first and the second section, the enrichment of the liquid with ozone can be easily adjusted.
  • a treatment unit for example, a filter unit may be arranged to condition the flues ⁇ stechnik upstream of the electrolytic cell.
  • the portion other than the portion which contains the electrolytic cell by passing a portion of the fluid through the portion other than the portion which contains the electrolytic cell, and an after ⁇ following blending of the treated with the electrolytic cell liquid with the gas passing the other portion flues ⁇ stechnik the content of undesired substances such as bromide and iodide are reduced.
  • the ozone content will be sufficient even in the blended liquid for disinfection purposes.
  • the Oxidationsstoff- or ozone concentration does not necessarily have to be chosen so high that almost all germs are killed. Rather, one can speak of a safe disinfection, when the oxidant and ozone concentration at regular intervals by a corresponding activation of the electrolytic cell to a comparatively low value held ⁇ th is sufficient to inactivate the germs in many cases already. A certain number of germs can be tolerated, only it may not come to an increase. Thus, with a low oxidizing agent and ozone concentration and thus low energy consumption, the formation of biofilms can be counteracted.
  • Another aspect of the present invention relates to a process for producing ozone for the treatment of a liquid, comprising the following steps:
  • Liquid-carrying parts are understood as meaning all parts of the device which come into contact with the liquid.
  • the generator for producing oxidizing agents, and in particular ozone is an electrolytic cell according to one of the exemplary embodiments presented above.
  • the determinable event is the exceeding or falling below a certain threshold value of the oxidation rate measured by the measuring device.
  • the oxidation ons-reduction potential varies with the concentration of the oxidizing agent generated, so that for example the Erzeu ⁇ supply of the oxidizing agent and can in particular be started by ozone when a predetermined threshold value can be exceeded, and stopped when a predetermined threshold is exceeded ,
  • concentration of the oxidizing agent, in particular, the ozone in the liquid can be held in raplba ⁇ ren thus limits, so that the device is operated efficiently and economically and permissible Maximalkonzentra ⁇ functions are not exceeded.
  • the determinable event may be the supply of unbehan ⁇ delter liquid in the device.
  • the untreated liquid has a high number of germs, so that the supply of untreated liquid into the device is an event that makes it necessary to increase the concentration of the oxidizing agent, in particular the ozone. So with ⁇ can also be a reliable inactivation caused crossing of germs without a measurement of the oxidation-reduction potential or the ozone concentration.
  • the determinable event may be a time interval or a time. It is thus possible to activate the electrolytic cell regularly for a certain period of time. For example, the electrolytic cell can be activated for a certain duration every two hours. Alternatively, a particular time may be chosen, for example during the night when the device is not usually used to activate the electrolytic cell.
  • the method includes applying a voltage above a threshold to the
  • the threshold is in one variant at least 8 V / mm, based on the distance between the first and second electrodes, especially at least 9 V / mm, more in particular ⁇ sondere 10 V / mm. These values are especially if the
  • Solid electrolyte comprises a strongly acidic ion exchanger, for example a sulfonated fluoropolymer, suitable for generating ozone from tap water.
  • a strongly acidic ion exchanger for example a sulfonated fluoropolymer, suitable for generating ozone from tap water.
  • the current flow can be ⁇ already after a relatively short time to break, so that the
  • Ozone production is greatly reduced.
  • the solid electrolyte is saturated with cations, in particular hardness-forming cations, so that its electrical conductivity decreases sharply.
  • the increase of tension up above a suitable threshold causes detachment of the bound cations.
  • the method includes detecting a decrease in a current through the
  • Electrolysis cell and at least temporarily increase the voltage across the electrodes to a value above a certain threshold value in response to the detection.
  • the Elect ⁇ rolysezelle is reversed, so that the first and second electrodes alternately function as a cathode and anode.
  • the polarity reversal can take place in particular at regular intervals. Ozone production thus remains relative
  • Figure 1 is a schematic representation of an electrolytic cell according to the invention according to a first
  • Figure 2 is a schematic representation of an electrolytic cell according to the invention according to a second
  • Figure 3 is a schematic representation of an electrolytic cell according to the invention according to a third
  • Figure 4 is a schematic representation of an inventive device
  • Figure 5 is a schematic representation of a bypass according to the invention.
  • the electrolytic cell 10i illustrated in Figure 1 to ⁇ holds a first electrode 12 having a first surface Fi and a second electrode 14 having a second area F 2, which face each other and are arranged at a distance A from each other.
  • the Elect ⁇ clear 12,14 each have a carrier core 17 on which a Diamond coating 28 is applied. In order to make the diamond coating 28 electrically conductive, it is doped.
  • the electrolytic cell 10 comprises a measuring device 26 for determining the cell resistance and for
  • the measuring device 26 is connected to a
  • Power supply 18 is connected for controlling the voltage as a function of the precisely measured ⁇ NEN cell resistance.
  • the two electrodes 12, 14 form a free space 15 which can be flowed through by liquid, for example water, and filled with a particulate solid electrolyte 20, which can be embodied as an ion exchanger 22 or as an acidified zeolite 24 or as a polymer 24.
  • a particulate solid electrolyte 20 which can be embodied as an ion exchanger 22 or as an acidified zeolite 24 or as a polymer 24.
  • polymer 24 in particular, a sulfonated tetrafluoroethylene polymer has been found suitable, for example, available under the trade name Nafion ⁇ . It may the example extruded and then ground to the desired particle size ⁇ .
  • Solid electrolyte 20 is selected so that the liquid can flow with a sufficiently large volume flow between the two electrodes 12,14. It can the
  • Particle size diameter in the range of 10 ⁇ to 0.5 mm.
  • a retainer 25 is provided. This can for example be designed as a sieve having a mesh width ent ⁇ speaking or as a nonwoven layer. It is important that the pressure loss generated during the flow through the retaining device 25 or the
  • Flow resistance can be kept low.
  • the electrodes 12, 14 are subjected to a voltage.
  • a current density which ensures that at the anode following the current understanding, the following reactions can take place:
  • ozone is generated as an oxidizing agent, with which the water is enriched in the electrolytic cell 10i.
  • Been oxidant enriched with ozone in particular, it is gereichert with additional oxidizing agent and preferably with ozone at ⁇ .
  • the volume flow through the electrolytic cell 10i and the concentration of the ozone generated are chosen so that the ozone concentration in the entire liquid in the device 30 is sufficient to safely deactivate the germs present in the liquid and liquid-carrying parts without damaging the health limits on ⁇ steps and / or the water taste adversely modified or an unpleasant odor is triggered.
  • a volume flow of about 30 Lh- 1 through the electrolytic cell has proved to be suitable.
  • the average ozone concentration in the electrolytic cell is 50 micrograms ⁇ L ⁇ not exceed 1, otherwise unwanted by-products are generated to an increased extent in ⁇ play as bromate. However, locally in the
  • Electrolysis cell also produces a significantly higher ozone concentration, which in the tank to the maximum
  • FIG. 2 shows a second exemplary embodiment of an electrolytic cell IO 2 .
  • the free space is 15 empty. Otherwise, the electrolytic cell IO 2 corresponds to that shown in FIG.
  • FIG. 3 shows an electrolytic cell 10 3 according to a third exemplary embodiment.
  • a carrier core 17 As a carrier core 17, a ceramic material 29 is provided.
  • the first and the second surface Fi, F 2 have one or, as shown, several cracks before ⁇ 27, on which high current densities can be produced.
  • FIG. 4 shows an inventive device 30 is shown for treating a fluid, comprising a ⁇ genera tor 11 for generating ozone, which in the illustrated
  • Example is formed as an electrolytic cell 10 according to one of the embodiments shown in the Fi ⁇ gures 1 to 3 embodiments.
  • a control device 31 controls the operation of the electrolysis cell 10.
  • the device 30 comprises an inlet 32, with which an untreated liquid, in particular water, can be guided into the device 30.
  • the feed 32 opens into a treatment area 36 in which the liquid, in this case water, is mixed with oxidizing agent and, in particular, ozone.
  • the treatment area 36 comprises a tank 34 in which the water can be stored. Starting from the tank 34, a guide means 37 leads to a
  • Outlet 38 through which the treated water can be discharged, for example, to be drunk by a user. Furthermore, the outlet piece 38 has a closure element 40 with which an opening 42 for selectively discharging the treated water can be opened and closed. The outlet piece 38 has a feed element 39, which serves to bring the treated water up to the opening 42.
  • a discharge element 44 is provided in the outlet piece 38, with which the treated liquid from the outlet ⁇ piece 38 can be removed when the opening 42 is closed.
  • the removal element 44 is designed from ⁇ that the treated liquid is recycled to the tank 34th
  • the device 30 comprises a conveyor 46, for example a pump, with which the liquid can be circulated within the device 30.
  • a unit 48 for reducing the concentration of the oxidizing agent is also present, which is arranged in the region of the outlet piece 38 in the example shown. In the example shown, this is activated when fluid is removed via the outlet piece 38. When circulating the liquid, the unit 48 is normally switched off.
  • the generator 11 or the electrolytic cell 10 is arranged in the guide means 37, but can be mounted at any point of the device 30, for example in the
  • the measuring device 26 for determining the conductivity, the oxidation-reduction potential or the oxidation content of the liquid is not integrated in the illustrated example in the electrolytic cell 10, but disposed upstream of the electrolytic cell 10 and via a line 50 with the Electrolytic cell 10 connected.
  • the conductivity of the water can be measured anywhere on the device 30, for example in the guide means 37, as shown here.
  • Liquid which flows through the electrolytic cell 10, with oxidizing agent, preferably subjected to ozone.
  • the oxidizing agent preferably ozone
  • transported by the fluid within the device 30 is advantage.
  • the conveyor means 46 circulates the fluid in the closed closure member 40 within the Wennsmit ⁇ tel 37 in the direction of the arrows in a way, that the ozone is promoted to the outlet piece 38 and back into the tank 34th
  • the tank 34 and the guide means 36 and in particular the outlet piece 38 are flushed with the ozone-containing water, so that the necessary number of germs are inactivated and in particular a re ⁇ trograde bacterial contamination of the device 30 and the formation of biofilms in the device 30 is prevented.
  • the control device 31 is adapted to a
  • the threshold value depends on the distance A, in particular sondere proportional to this distance A. Further, the STEU ⁇ er worn 31 can monitor the current between the electrodes 12,14. If it is detected that this drops sharply, then the voltage is temporarily increased above a threshold value. Subsequently, the normal operation is again generatenom ⁇ men.
  • the control device is also set up to carry out a regular reversal of polarity of the electrolytic cell 10.
  • the electrode 12,14 which acted as a cathode before the polarity reversal, becomes the anode.
  • the electrode 12,14 which acted as an anode before the polarity reversal, becomes the cathode.
  • FIG. 5 shows a bypass 52 which can be used at any point of the device 26 according to the invention.
  • the bypass 52 is arranged in the inlet 32, which divides into a first section 53 and a second section 55 and then rejoins.
  • the electrolysis cell 10 and a treatment unit 54 are arranged in section 55.
  • the specialistssein ⁇ standardized 54 is in the embodiment example shown in Figure 5
  • the bypass 52 further comprises an adjusting device 56 with which the ratio between the volume flow in the first section 53 and the volume flow in the second section 55 can be adjusted. In this way, the oxidizing agent and ozone concentration in the device 26 can be selected. Furthermore, the bypass 52 allows easy replacement of the
  • Electrolysis cell 10 or the treatment unit 54 may be configured so that all the water flows through the first portion 53. Then, the electrolytic cell 10 or the treatment unit 54 can be replaced without having to shut down the entire device 26. Furthermore, the entire bypass 52 or the second section 55 or the electrolysis cell 10 or the
  • Treatment unit 54 designed as a replaceable unit which can be very easily separated from the adjacent building units and reconnected with them.
  • a first Abklemmech 58i and a second Abklemmein ⁇ unit 58 2 are provided, which can be closed on the one hand to prevent the passage of the liquid and the ⁇ other hand, the assembly and disassembly of lying between them second portion 55 of the bypass 52 together therein angeord ⁇ Neten units, here the treatment unit 54 and the
  • Electrolysis cell 10 simplify.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

La présente invention concerne une cellule électrolytique pour produire des agents d'oxydation, notamment de l'ozone, destinés à traiter un liquide, ladite cellule comprenant une première électrode (12) et une seconde électrode (14). La première et la seconde électrode (12,14) sont disposées à une distance (A) l'une de l'autre. Entre la première et la seconde électrode (12,14) se trouve un électrolyte solide particulaire (20) qui peut être parcouru par le liquide. L'électrolyte solide (20) se trouve dans un espace libre délimité par la première et la seconde électrode (12,14).
EP11799386.5A 2010-12-03 2011-12-02 Cellule électrolytique pour produire de l'ozone destiné au traitement d'un liquide Withdrawn EP2646373A1 (fr)

Applications Claiming Priority (2)

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DE102010062433 2010-12-03
PCT/EP2011/071586 WO2012072784A1 (fr) 2010-12-03 2011-12-02 Cellule électrolytique pour produire de l'ozone destiné au traitement d'un liquide

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EP2697730A4 (fr) 2011-04-15 2015-04-15 Advanced Diamond Technologies Inc Système et procédé électrochimiques destinés à une génération sur site d'oxydants sous une densité de courant élevée
US10239772B2 (en) * 2015-05-28 2019-03-26 Advanced Diamond Technologies, Inc. Recycling loop method for preparation of high concentration ozone
US10858744B2 (en) 2016-10-20 2020-12-08 Advanced Diamond Technologies, Inc. Ozone generators, methods of making ozone generators, and methods of generating ozone
GB2557185A (en) * 2016-11-29 2018-06-20 Roseland Holdings Ltd Electrochemical cell assembly and method for operation of the same
GB2556949A (en) * 2016-11-29 2018-06-13 Roseland Holdings Ltd Electrochemical cell assembly and method for operation of the same
CA3066791A1 (fr) * 2017-07-12 2019-01-17 Axine Water Technologies Inc. Mode de fonctionnement d'un systeme de traitement des eaux usees
CN109626679A (zh) * 2019-02-27 2019-04-16 陆鑫 一种工业废水处理设备及其工业废水的处理方法
FR3094711B1 (fr) * 2019-04-03 2021-10-29 Waterdiam France Système d’amélioration et distribution d’eau
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US20130240458A1 (en) 2013-09-19

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