WO2012041357A1 - Procédé de production d'un agent désinfectant à base d'acide hypochloreux ou d'hypochlorite par activation électrochimique d'une solution de chlorure - Google Patents

Procédé de production d'un agent désinfectant à base d'acide hypochloreux ou d'hypochlorite par activation électrochimique d'une solution de chlorure Download PDF

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Publication number
WO2012041357A1
WO2012041357A1 PCT/EP2010/006007 EP2010006007W WO2012041357A1 WO 2012041357 A1 WO2012041357 A1 WO 2012041357A1 EP 2010006007 W EP2010006007 W EP 2010006007W WO 2012041357 A1 WO2012041357 A1 WO 2012041357A1
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Prior art keywords
water
chloride solution
anode
electrolysis reactor
reactor
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PCT/EP2010/006007
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German (de)
English (en)
Inventor
Christian Fischer
Achim Wenner
Benjamin Pfeiffer
Frank Kandler
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Actides Berlin Gmbh
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Priority to PCT/EP2010/006007 priority Critical patent/WO2012041357A1/fr
Publication of WO2012041357A1 publication Critical patent/WO2012041357A1/fr

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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
    • C02F1/46—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
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/04—Hypochlorous acid
    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/026—Treating water for medical or cosmetic purposes
    • 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
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • 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
    • C02F2201/46145—Fluid flow
    • 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
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C02F2201/46185—Recycling the cathodic or anodic feed
    • 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
    • C02F2209/05—Conductivity or salinity
    • C02F2209/055—Hardness
    • 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
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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
    • C02F2209/40—Liquid flow rate

Definitions

  • the invention relates to a method for producing a hypochlorous acid (H0C1) and / or hypochlorite (0C1 ⁇ ) containing disinfectant by electrochemical activation of a dilute acid / chloride solution by adding a chloride solution to water and the thus obtained dilute water / chloride solution in the anode compartment of a Elektrolysereaktors having at least one cathode compartment with a cathode and at least one, of which by a membrane spatially separated anode compartment with an anode, is applied by applying an electrical voltage to the electrodes with an electric current to the chloride at least partially in hypochlorous acid and / or to transfer hypochlorite.
  • H0C1 hypochlorous acid
  • hypochlorite (0C1 ⁇ ⁇ ) containing disinfectant by electrochemical activation of a dilute acid / chloride solution by adding a chloride solution to water and the thus obtained dilute water / chloride solution in the anode compartment of a Elektroly
  • the method of electrochemical activation is known in particular for the disinfection of water.
  • a dilute solution of a chloride especially in the form of a neutral salt, such as sodium chloride (NaCl) or common salt, potassium chloride (KCl) or the like, in an electrolytic reactor by applying a voltage at the electrodes under anodic oxidation of a portion of the chloride ions primarily in hypochlorous .
  • a neutral salt such as sodium chloride (NaCl) or common salt, potassium chloride (KCl) or the like
  • H0C1 and / or their salts (hypochlorites, CIO ") converted electrolytic reactor includes a cathode chamber with one or more cathodes and an anode compartment comprising one or more anodes, wherein the anode chamber and the cathode chamber by means of an electrically conducting - in particular a for ion conductive - diaphragm or by means of a membrane with the properties mentioned spatially separated
  • CO FIRM ⁇ T10 COPY are to prevent mixing of the water / chloride solution in both rooms. While in electrolysis usually a substantially complete conversion of the reactants used - in the case of the use of a sodium chloride solution to chlorine gas (Cl 2 ) and sodium hydroxide (NaOH), in the case of the use of a potassium chloride solution to chlorine gas and potassium hydroxide (KOH) - is sought with the use of highly concentrated electrolyte solutions, primarily to maximize the chlorine gas yield, the water / chloride solution in contrast to the electrochemical activation in much diluted form, usually in a concentration of not more than 20 g / 1, preferably not more than 10 g / 1, the electrolysis reactor and reacted to a low contrast predominantly to HOC1 and / or OC1 " reacted, in particular, the redox potential of the mixed with the chloride as electrolyte water is increased, whereby a very effective disinfecting effect is obtained Reaction conditions, such as pressure, temperature, electrode st rome,
  • electrochemical activation is in particular the good health and environmental compatibility of the substances produced during the electrochemical activation in their respective concentrations, which for example also according to the German Drinking Water Ordinance (TrinkwV) are permitted.
  • electrolysis oxidation also occurs at the anode (ie at the positively charged electrode) during electrochemical activation, while at the cathode (ie at the negatively charged electrode) there is oxidation takes place.
  • a diluted neutral salt solution such as a sodium chloride solution
  • hydrogen is generated at the cathode according to the following reaction equation (1):
  • secondary substances can be used to generate small amounts of other substances which are also known to be effective with respect to the disinfection of water. These are in particular small amounts of hydrogen peroxide (H 2 0 2 , reaction equation (5)) and ozone (0 3 , reaction equation (6)).
  • a disadvantage of the method of electrochemical activation has hitherto been in many cases the lack of quality control, as required for a sufficient disinfection of the water, mostly empirically determined process parameters, such as amount of added electrolyte or chloride solution, adjusted electrode voltage or -ström and the like, not only of the electrolysis reactor used, such as its reaction volume, its anode and cathode surface, the residence time of the water to be disinfected in the reactor, etc., but in particular the composition of the respective water to be disinfected, in particular its conductivity and its redox potential, depend. In this case, for a given water - mostly empirically - determined process parameters, which lead to a satisfactory disinfecting effect in this water, lead in another water to a very poor disinfecting effect.
  • a generic method for producing a disinfectant by means of electrochemical activation is known for example from WO 2007/093395 A2, which is hereby expressly made the subject of the present disclosure.
  • the cited document proposes to control the pH of the anodically obtained disinfectant ("Anolyte") to a value between 2.5 and 3.5.
  • hypochlorous acid reacts with the above-mentioned disadvantages to elemental chlorine (Cl 2 ), while at a pH above about 3.5, the redox potential of the electrochemically activated solution decreases and the hypochlorous acid dissociated from about a pH of 6 with elimination of their proton to hypochlorite, which is also disinfectant effective, but about 1 to 2 orders of magnitude lower than the hypochlorous acid itself.
  • this is from WO 2007/093395 A2 a very effective and reproducible method for generating a generic disinfectant means.
  • the water used for the electrochemical activation - or the dilute water / chloride solution - has the highest possible purity, in particular should be substantially free of other halide ions than chloride ions, ie those from the group bromide (Br ⁇ ), fluoride (F ⁇ ) and iodide (I " ), but also oxohalide ions, such as hypochlorite (CIO “ ), chlorite (C10 2 " ), Chlorate (C10 3 ⁇ ),
  • Perchlorate C10 4 ⁇
  • bromate Br0 3 ⁇
  • it should be substantially free of heavy metals, in particular those from the group antimony (Sb), arsenic (As), lead (Pb), cadmium (Cd) , Chromium (Cr), nickel (Ni), mercury (Hg), selenium (Se), iron (Fe) and manganese (Mn).
  • heavy metals in particular those from the group antimony (Sb), arsenic (As), lead (Pb), cadmium (Cd) , Chromium (Cr), nickel (Ni), mercury (Hg), selenium (Se), iron (Fe) and manganese (Mn).
  • WO 2007/093395 A2 proposes that the specific electrical conductivity of the water to be activated electrochemically before adding the chloride solution to a Value of at most 350 pS / cm or preferably lower, which increases the reproducibility of the method with respect to the disinfecting and depot effect of the disinfectant produced, virtually independent of the water used.
  • Such a "standardization" of the raw water used not only allows a particularly simple adjustment of the process parameters, such as electrode voltage or flow, residence time of the dilute water / chloride solution in the electrolysis reactor, amount of metered chloride solution, etc., but also makes a simple way Use of waters of practically any composition without any impairment of the resulting disinfectant possible, whereby a highly reliable and reproducible quality of the disinfectant is ensured.
  • ions which may be present in the water used for the electrochemical activation and which are converted into harmful substances during the electrochemical activation, even if only in low concentrations, can be eliminated as far as possible.
  • bromide ions may be mentioned, which - as in the case of ozonation which is frequently carried out in drinking water treatment - can be oxidized to bromate, which has a carcinogenic effect in higher concentrations.
  • the content of divalent cations such as the hardness formers calcium and magnesium, reduce, which can enforce the anode compartment of the cathode compartment separating membrane relatively easily, which is why the water used can also be additionally softened to the To increase the life of the electrolysis reactor and to extend its maintenance intervals.
  • EP 2 191 721 A1 proposes, in a generic method, adding to the water / chloride solution before entry into the electrolysis reactor a proton acceptor in the form of a buffer or a base.
  • a significantly increased yield of free chlorine in the form of the desired products HOCl or OCl can be ensured because the proton acceptor has a stoichiometric amount of anodically formed H 3 0 + ions according to the above reaction equation (2) can "catch" and thus the pH can be kept within the desired range of above about 2.5, even in the case of relatively high conversions of the added chloride solution, in which the equilibrium according to the above reaction equation (4) corresponds to the elemental chlorine (Cl 2 ) in the direction of hypochlorous acid (HOC1) or hypochlorite (0C1 ⁇ ) is shifted.
  • US Pat. No. 6,632,347 B1 likewise describes a generic process for producing a disinfectant which, for adjusting the pH of the chloride solution added to the electrolysis reactor, recirculates a portion of the solution containing electrochemical activation in the cathode compartment into the anode compartment of the reactor provides to compensate for either variations in the pH of the raw water used in each case or to increase the pH of the finished, anodically produced disinfectant as needed, while at the same time the proportion of accumulating catholyte should be reduced.
  • the invention is therefore based on the object to develop a method of the type mentioned in that at least as far as possible avoid the aforementioned disadvantages of the chloride consumption can be reduced in a simple and cost-effective manner, without affecting the yield of hypochlorous acid or hypochlorite.
  • this object is achieved in a method of the type mentioned in that the water / chloride solution is fed only to the anode compartment of the electrolysis reactor, while the cathode compartment of the electrolysis Is fed lysereaktors with not mixed with chloride ions water.
  • the embodiment of the invention thus makes it possible to reduce the consumption of chloride solution, which is usually added to the water used, in the form of an alkali metal chloride solution, e.g. a potassium chloride or, in particular, a sodium chloride solution is added to reduce about half, whereby the electrochemical reaction in the anode compartment, where the hypochlorous acid-based and / or hypochlorite-based disinfectant is produced, is not impaired.
  • an alkali metal chloride solution e.g. a potassium chloride or, in particular, a sodium chloride solution
  • the invention also offers in particular the possibility of using demineralized and / or distilled water or generally a "standardized" water for the water / chloride solution charged to the electrolysis reactor, wherein an advantageous embodiment of the method provides that the water used softens and / or demineralized. In this way, the reproducibility of the method with respect to the disinfecting and depot effect of the disinfectant produced is increased, virtually independent of the water used.
  • such "standardization" of the raw water used also not only ensures a particularly simple adjustment of the process parameters, such as electrode voltage or flow, residence time of the dilute water / chloride solution in the electrolysis reactor, amount of metered chloride solution, etc., but makes It also makes it possible to easily use waters of practically any composition without any impairment of the disinfectant obtained, thereby providing a highly reliable and reproducible zable quality of the disinfectant is guaranteed.
  • the content of divalent cations such as primarily the hardness formers calcium and magnesium, reduce, which can enforce the anode space of the cathode space separating membrane relatively easily.
  • the anode compartment of the electrolysis reactor with the water / chloride solution of softened and / or demineralized water and the cathode compartment of the electrolysis reactor with softened and / or demineralized water are fed, i. both electrochemical half-cells of the electrolysis reactor are fed with softened or demineralized water.
  • both electrochemical half-cells of the electrolysis reactor are fed with softened or demineralized water.
  • a cation-permeable membrane in particular a cation exchange membrane
  • a polymer electrolyte membrane commercially available under the trade name "Nafion TM" may be used in the cathode compartment of the electrolytic reactor.
  • Such a membrane is largely permeable to monovalent cations, so that the cations from the Anode space added water / chloride solution, such as potassium or in particular sodium ions, the membrane can pass from the anode compartment in the cathode compartment and provide in the cathode compartment for improved conductivity and consequently for a faster electrochemical reaction.
  • water / chloride solution such as potassium or in particular sodium ions
  • the cathode space of the electrolysis reactor is fed with a lower volume flow of water than the volume flow of dilute water / chloride solution through the anode space of the electrolysis reactor.
  • a further advantage of such a procedure, in particular when using softened and / or demineralized water, is that the conductivity caused by electrochemically generated hydroxide ions (OH.sup.- 1 ) and preferably also by the membrane permeating alkali metal ions (K.sup. + , Na.sup. + ) In the cathode compartment lower dilution is increased so that the anode space in the going electrochemical conversion of the chloride ions is not inhibited.
  • the volume flow through the anode chamber of the electrolysis reactor may in this case preferably amount to at least twice, in particular at least three times, preferably at least four times and for example also about ten times or more, the volume flow through the cathode space of the electrolysis reactor.
  • inventive method contains a part of the volume flow of the exiting from the cathode compartment of the electrolysis reactor, hydroxide ions (OH-) water in the anode chamber of the electrolysis reactor or in the added this water / chloride solution.
  • OH- hydroxide ions
  • the invention offers the additional advantage that the partial recirculation of the cathodic - largely chloride-free - solution in the anode compartment of the electrolysis reactor the The chlorine content there does not change or remains constant, so that the control or regulation technically adjusted as a function of the chloride content parameters
  • Electrode current and voltage do not need to be changed.
  • the conductivity of the water / chloride solution in the anode space is thereby at most increased to an extent which likewise does not require any control or regulatory changes.
  • the invention also offers the possibility of adding a - also preferably substantially chloride-free - buffer, as is also known from EP 1 292 721 AI.
  • the hydrogen generated in the cathode compartment of the electrolysis reactor in the emerging from the cathode compartment water should preferably be removed before, not to according to the above reaction equation (8), a disintegration of the anodically produced, disinfectively active products HOC1 and / or to cause OC1 ".
  • the removal of hydrogen for example, by means of conventional outgassing
  • the pH of the disinfectant produced in the anode compartment of the electrolysis reactor to a value between 2.5 and 6, in particular between 2.5 and 5, preferably between 2.5 and 4, in particular, a pH range of from about 2.5 to about 3.5, or from about 2.7 to about 3.5, may be favorable to provide for substantially complete presence of the free chlorine in the form of hypochlorous Acid at a high redox potential of the disinfectant, eg in the range of about 1340 mV.
  • the used softened or demineralized water has a hardness between 0 and 4 dH, in particular between 0 and 2 dH.
  • hardness is in this context the concentration of divalent alkaline earth metal ions, ie calcium (Ca), magnesium (Mg), strontium (Sr) and barium (Ba), the latter two in practice usually play no role.
  • l ° dH corresponds to a concentration of alkaline earth metal ions of 0.179 mmol / l, 2 ° dH of a concentration of 0.358 mmol / 1 etc.
  • Such an adjustment of the hardness of the water used is expedient in particular for relatively hard, calcium- and / or magnesium-containing waters To increase the life of the electrolysis reactor or to extend its maintenance intervals.
  • an advantageous embodiment of the inventive method provides that the specific electrical conductivity of the water used to a value of at most 350 yS / cm, in particular at most 150 yS / cm, preferably at most 100 S / cm, such as at most about 50 yS
  • the method also allows advantageous use of standardized demineralized or deionized water, so-called demineralized water or "demineralised water,” with a specific electrical conductivity of less than 25 yS / cm.
  • the chloride concentration, in particular in the form of sodium and / or potassium chloride, the dilute water / chloride solution added to the anode compartment of the electrolysis reactor can advantageously be at a value of at most 20 g / l, in particular between 0.1 and 10 g / l, preferably be controlled between 0.1 and 5 g / 1.
  • the method according to the invention finally gives the possibility, as required, of a disinfectant having a free chlorine content in the form of HOC1 and / or OCl " in the range of about 20 mg / 1 to produce in the g / l range.
  • FIG. 1 is a schematic view of an electrolytic reactor including the charged starting materials and the products obtained, which can be used in a method according to the invention for producing a disinfectant based on hypochlorous acid and / or hypochlorite by electrochemical activation of a chloride solution; and a schematic process flow diagram of a process for preparing a hypochlorous acid-based hypochlorite-based disinfectant by electrochemical activation of a chloride solution using an electrolytic reactor shown in FIG. 1.
  • FIG. 2 suitable for continuous or semi-continuous implementation of a method according to the invention for Desinfek tion of water by electrochemical activation (ECA) branches from a main water line 1 via a Abzweiglei device 2 from water, which as raw water for the electrochemical mixing activation is used.
  • the main water line may for example be part of a public water supply system.
  • the branch line 2 is connected to a valve 3, in particular in the form of a control valve, and preferably before with a valve 3 upstream or downstream Filter F, in particular in the form of a fine filter with a hole width of, for example, about 80 to 100 ⁇ , equipped and opens downstream of the valve 3 and the filter F in a softener 4, which is equipped for example with a suitable ion exchange resin and contained in the water divalent hardener calcium and magnesium ions replaced by monovalent ions, such as sodium ions.
  • the softener 4 keeps the hardness of the water, for example, at a value of at most 2 ° dH (corresponding to a concentration of alkaline earth metal ions of 0.358 mmol / l), preferably at most l ° dH (corresponding to a concentration of alkaline earth metal ions of 0.179 mmol / l).
  • the effluent 5a of the water softener 4 opens into a desalination device 6 for reducing the specific electrical or ionic conductivity of the water, which may be formed in particular by a membrane system, such as a reverse osmosis plant or by a micro, nano or ultrafiltration plant and the specific electrical conductivity of the water, for example, to a value of at most about 100 S / cm or in particular also holds at most about 25 yS / cm, so that it is in the discharged via a line 7a from the desalting 6 water to substantially demineralized, so-called " VE water "is, which is thus standardized regardless of the water used in each case.
  • a membrane system such as a reverse osmosis plant or by a micro, nano or ultrafiltration plant
  • the specific electrical conductivity of the water for example, to a value of at most about 100 S / cm or in particular also holds at most about 25 yS / cm, so that it is in the discharged via a line 7a from the
  • a conductivity measuring device such as a conductivity cell, electrode or the like, may be arranged to monitor compliance with the particular desired value of the specific electrical conductivity of the water.
  • a discharge line 5b, 7b can lead from the softening plant 4 and / or from the desalting device 6, which discharge in the present embodiment into a common discharge line 8, via which the wastewater from the plants 4, 6 can be discarded.
  • measures may be taken to lower the carbon content of the water.
  • a UV oxidation system (not shown) which has the total organic carbon content (TOC) and / or the chemical oxygen demand (COD) to a value of, for example, at most about 25 ppb, in particular of at most about 20 ppb, or to a value of, for example, at most about 7 mg 0 2 / l, in particular of, for example, at most about 5 mg 0 2 / l, lowers.
  • TOC total organic carbon content
  • COOD chemical oxygen demand
  • the outlet 7a of the membrane unit 6 leads into a mixer Mi, which opens into an electrolysis reactor 10 explained in greater detail below with reference to FIG.
  • the branch line 2 is thus controllable by means of the control valve 3, softened and deionized part of the funded in the main water line 1 water in the electrolysis reactor 10, for example, a partial flow of funded in the main water line 1 water in the order of 1/200 on the Branch line 2 is branched off.
  • the mixer i is on the inlet side on the one hand - as already mentioned - with the outlet 7a of the membrane unit 6, on the other hand with a reservoir 11 for receiving a chloride solution, in particular in the form of a substantially saturated alkali metal chloride solution - in the present case, for example, a substantially saturated sodium chloride solution - , in which are mixed as homogeneously as possible in the mixer i and pass through a common, drain-side line 14 of the mixer Mi in the anode compartment 10a of the electrolysis reactor 10.
  • a chloride solution in particular in the form of a substantially saturated alkali metal chloride solution - in the present case, for example, a substantially saturated sodium chloride solution - , in which are mixed as homogeneously as possible in the mixer i and pass through a common, drain-side line 14 of the mixer Mi in the anode compartment 10a of the electrolysis reactor 10.
  • the line 12 leading from the reservoir 11 into the mixer Mi is further equipped with a metering pump 13 to add to the softened and desalinated water a defined amount of sodium chloride solution, eg in the range of about 1 to about 10 g / 1 NaCl.
  • the cathode chamber 10b of the electrolysis reactor 10 is fed directly with the softened and desalinated water leaving the membrane system 6, which takes place via a line 9 which branches off the outlet 7a of the membrane installation 6 upstream of the mixer Miaus.
  • the volumetric flow of softened and demineralized water supplied to the electrolysis reactor 10 can be set lower, for example by a factor of about 10, than the volume flow of softened and demineralized sodium chloride solution fed to the anode compartment 10a of the electrolysis reactor 10 via the conduit 14 a provided in the line 9 throttle valve 9a or by any other means for flow control and / or by appropriate (smaller) dimensioning of the cathode chamber 10b of the electrolysis reactor 10 can be done.
  • the electrolytic reactor 10 includes an anode 101, which is formed coated by a with catalytically active ruthenium dioxide (Ru0 2) when PRESENT embodiment, for example, carrier of titanium, to which the positive terminal 101a of an unspecified represented voltage source can be connected.
  • Ru0 2 catalytically active ruthenium dioxide
  • the electrolytic reactor 10 further includes a cathode 102 which is conveniently made of stainless steel or similar materials such as nickel (Ni), platinum (Pt), etc.
  • the cathode 102 is connectable to the negative pole 102a of the voltage source not further disclosed.
  • the membrane 104 prevents a mixing of the anode chamber 10a and the cathode. denraum 10b liquid and allows, however, a current flow, which is not a significant resistance in particular for the migration of cations.
  • the membrane 104 is formed in the present embodiment, for example in the form of an electrically or ionically conductive, but substantially liquid-tight polymer electrolyte membrane.
  • the electrolysis reactor 10 further has two inlets 14, 9 (see also Fig. 2), via which on the one hand from the
  • the electrolysis reactor 10 also has two outlets 103a, 103b, via which the water / chloride solution or the water after the electrochemical activation from the anode chamber 10a or from the Cathode space 10b of the reactor 10 can be discharged.
  • outlet 103a is for discharging the electrochemically activated solution containing hypochlorite generated from the anode space 10a of the reactor 10, ie for discharging the so-called "anolyte”
  • the outlet 103b serves to discharge the electrochemically activated water with the hydroxide ions from the cathode space 10b of the reactor 10 - ie for discharging the so-called "catholyte”.
  • the volume flow through the cathode space 10b of the reactor 10 can be selected to be smaller than that of the anode space 10a in order to minimize the amount of catholyte which is to be disposed of, at least for the most part, and also for good conductivity of the water to provide the cathode compartment 10b.
  • the cathodically produced hydroxide ions (OH " ) and, on the other hand, the sodium ions (Na + ), which can permeate the membrane 104 out of the anode space provide the anode space 10a of the electrolysis reactor 10, for example with a throughput of 60 to
  • the electrolysis reactor 10 always runs at full load, where it can be switched off as needed and peak loads can be intercepted via a storage tank for the electrochemically activated, anodic solution explained in more detail below. As can also be seen from FIGS.
  • the outlet 103b from the cathode compartment ends 10b of electrolytic reactor 10 for this purpose initially in a gas separator 15 from which the exhaust gas , in particular hydrogen (H 2 ), is discharged via an optionally provided exhaust pipe 16, while the catholyte itself, ie the cathode compartment of the electrolysis reactor 10 discharged basic water, via a line 17, for example, in the sewer K a municipal sewage system, is discharged.
  • exhaust line 16 may be fed with dilution air that is equipped with an explosion-proof low-pressure blower (not shown) to meet the safety requirements with respect to gaseous hydrogen.
  • the outlet 103a from the anode chamber 10a of the electrolysis reactor 10 opens via eg a control valve (not shown) and a line 20 into a storage tank 21, from which the anolyte or the disinfectant produced via a line 22 of the main water line 1 for the purpose of disinfection of the water carried herein.
  • a metering pump 23 which metered in the line 22 guided disinfectant via a mixer M 2 of the main water line 1.
  • the metering pump 23 may in particular be operated depending on the volume flow of water determined by a flow meter 24 arranged in the main water line 1 in order to always add the required amount of disinfectant to the water.
  • sensors 25 may also be provided in the conduit 20 connecting the anode compartment 10a of the reactor 10 to the storage tank 21. be seen.
  • the measured values obtained can, of course, also be used in the control parameters, such as electrode current and voltage, amount of added chloride solution, volume flows through or residence times in the electrolysis reactor 10, etc.
  • the device according to FIG. 2 further comprises a control (not shown in the drawing), as known for example from the prior art mentioned in WO 2007/093395 A2 and EP 2 191 72 A1 as such.
  • the disinfectant in the form of the anodically produced electrochemically activated solution (anolyte), which has been prepared in the manner described above from demineralised water as raw water, has e.g. at a pH in the range of 3.0 and a redox potential in the range of 1340 mV (vs. SHE vs. vs NHE, standard and / or normal hydrogen electrode), a free chlorine concentration in the range of about 25 mg / 1 to about 1000 mg / l, corresponding to a concentration of particularly effective hypochlorous acid (HC10) in the range of about 18.5 mg / l to about 706 mg / l.
  • anodically produced electrochemically activated solution anolyte
  • HC10 particularly effective hypochlorous acid

Abstract

L'invention concerne un procédé de production d'un agent désinfectant contenant de l'acide hypochloreux (HOCl) et/ou de l'hypochlorite (OCl-) par activation électrochimique d'une solution de chlorure diluée à l'eau. Dans ledit procédé, de l'eau est ajoutée à une solution de chlorure et la solution de chlorure diluée à l'eau ainsi obtenue est placée dans l'espace anodique d'un réacteur d'électrolyse, qui comporte au moins un espace cathodique contenant une cathode et, séparé spatialement de celui-ci par une membrane, au moins un espace anodique contenant une anode. La solution de chlorure diluée à l'eau est alors soumise à l'action d'un courant électrique généré par l'application d'une tension électrique entre les électrodes dans le but de convertir au moins en partie le chlorure en acide hypochloreux et/ou en hypochlorite. Afin de minimiser la consommation de chlorure, l'invention prévoit d'introduire la solution de chlorure diluée à l'eau uniquement dans l'espace anodique du réacteur d'électrolyse, tandis que l'espace cathodique du réacteur d'électrolyse est alimenté en eau non mélangée avec des ions de chlorure.
PCT/EP2010/006007 2010-10-01 2010-10-01 Procédé de production d'un agent désinfectant à base d'acide hypochloreux ou d'hypochlorite par activation électrochimique d'une solution de chlorure WO2012041357A1 (fr)

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CN111533327A (zh) * 2020-04-10 2020-08-14 杭州清薇科技有限公司 一种用于改善水质和环境用的超氧化水制备方法及其应用
CN113529109A (zh) * 2021-08-03 2021-10-22 北京德义法正科技有限公司 次氯酸分子溶液制备装置
CN113564626A (zh) * 2021-09-14 2021-10-29 福建浩达智能科技股份有限公司 一种次氯酸电解槽
WO2021257377A1 (fr) * 2020-06-19 2021-12-23 Hien Tu Le Système et procédé de fabrication d'acide hypochloreux au moyen d'eau salée avec du bicarbonate de sodium
US11306402B2 (en) * 2017-08-25 2022-04-19 Blue Safety Gmbh Device for obtaining electrolysis products from an alkali metal chloride solution
CN114436375A (zh) * 2022-02-15 2022-05-06 浙江省农业科学院 农村生活污水剂量自调节消毒装置及其方法
US20220205114A1 (en) * 2020-08-06 2022-06-30 Briotech, Inc. Deployable, remotely-controlled, pure hypochlorous acid manufacturing system and method
WO2023115574A1 (fr) * 2021-12-24 2023-06-29 卡富环球有限公司 Machine de désinfection de l'eau à l'acide hypochloreux

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US11306402B2 (en) * 2017-08-25 2022-04-19 Blue Safety Gmbh Device for obtaining electrolysis products from an alkali metal chloride solution
CN111533327A (zh) * 2020-04-10 2020-08-14 杭州清薇科技有限公司 一种用于改善水质和环境用的超氧化水制备方法及其应用
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CN113564626A (zh) * 2021-09-14 2021-10-29 福建浩达智能科技股份有限公司 一种次氯酸电解槽
WO2023115574A1 (fr) * 2021-12-24 2023-06-29 卡富环球有限公司 Machine de désinfection de l'eau à l'acide hypochloreux
CN114436375A (zh) * 2022-02-15 2022-05-06 浙江省农业科学院 农村生活污水剂量自调节消毒装置及其方法

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