CN101426734A

CN101426734A - Process for producing a disinfectant by electrochemical activation (eca) of water, disinfectant produced in such a manner and use thereof

Info

Publication number: CN101426734A
Application number: CNA2007800138787A
Authority: CN
Inventors: 彼得·萨拉瑟; 克里斯琴·费希尔; 伯恩德·乔斯特; 史蒂文·格罗斯; 沃尔克马·施密特
Original assignee: ACTIDES GmbH
Current assignee: ACTIDES GmbH
Priority date: 2006-02-17
Filing date: 2007-02-14
Publication date: 2009-05-06
Anticipated expiration: 2027-02-14
Also published as: DE102006007931A1; CN101426734B

Abstract

A process is proposed for producing a disinfectant by electrochemical activation (ECA) of water, by adding to the water to be disinfected an electrolyte solution, in particular a sodium chloride or potassium chloride solution, and subjecting the electrolyte-solution-charged water in the form of a dilute water/electrolyte solution to an electric current in an electrolysis reactor having a cathode space having a cathode and also an anode space spatially separated from the cathode space and having an anode, by applying direct current to the electrodes, in order to put the water/electrolyte solution into a metastable state suitable for disinfection.; In order to ensure reliable disinfectant action of the electrochemically activated water, with high reproducibility, the invention provides that the pH of the dilute water/electrolyte solution in the anode space of the reactor is controlled to a value between 2.5 and 3.5, in particular to a value in the region of 3, in such a manner that the potential of the anodic oxidation is controlled (potential-controlled anodic oxidation, PAO). The invention further relates to a disinfectant produced in such a manner and also to use thereof.

Description

Prepare the method for sterilizing agent by electrochemically-activated water, with the sterilizing agent and the application thereof of this method preparation

The present invention relates to prepare sterilizing agent through electrochemical activation (ECA) water, wherein, in water, add electrolyte solution, particularly sodium-chlor and/or Klorvess Liquid and the water that is added with electrolyte solution make it stand galvanic action by anode and cathode being applied volts DS with water/ionogen dilute solution form in electrolysis reactor, be fit to the disinfectant metastable state so that water/ionogen dilute solution is in, this reactor comprises that at least one cathode compartment that is provided with negative electrode and at least one are spatially especially by barrier film or saturating film separately and be provided with the anodic anolyte compartment.The invention still further relates to sterilizing agent and application thereof with this method preparation.

The method of electrochemical activation or processing is known to the sterilization of water particularly.In the case, make ionogen, neutral salt particularly, dilute solution such as sodium-chlor (CaCl) or salt, Repone K (KCl) or its analogue, warp applies voltage on anode and cathode in electrolysis reactor, is transformed into to be applicable to the disinfectant activated state, its common tool metastable state character, and because of the kind of water and the processing parameter regulated different, sustainable long-time.Electrolysis reactor has a cathode compartment that is provided with one or more negative electrodes and one and is provided with one or more anodic anolyte compartment, wherein anolyte compartment and cathode compartment are spatially separated mutually by means of (particularly the leading ionic) barrier film of a conduction or with a kind of saturating film with described character, with the mixing of water/electrolyte solution of preventing to exist in two Room.When using the electrolyte solution of high density, when electrolysis, generally make every effort to transform fully basically the reactant that is added and (when adding sodium chloride solution, be converted into chlorine and caustic soda (NaOH), when adding Klorvess Liquid, change into chlorine and Ke Xingjia (KOH)), so that the chlorine productive rate reaches maximum, in contrast, water/electrolyte solution will be in obvious dilution mode when electrochemical activation, usually concentration is 20g/l to the maximum, preferably be 10g/l to the maximum, import electrolysis reactor and only transform minimum part, so that the physics of solution and chemical property change in an advantageous manner, and the redox potential that is added with electrolytical water is improved, thereby the effect that is sterilized.Comparatively speaking, the reaction conditions during electrochemical activation is such as pressure, and temperature is selected than the demulcent condition during electrolysis of electric current geometric ratio chloro-alkali usually.This electrochemical treatment is referred to as in the application's scope " electrochemical activation ", and its advantage is that the material of the various concentration that produce during electrochemical activation has the compatible and environmental protection compatibility of good health especially, also reaches German tap water regulation.

During as electrolysis, during electrochemical activation, go up the generation oxygenizement at anode (being the electrode of lotus positive electricity), and go up the generation reductive action at negative electrode (being the electrode of bear electricity).When using rare neutral salt solution such as sodium chloride solution, mainly produce hydrogen by following molecular balance formula (1) on the negative electrode:

2H ₂O+2e ^-→H ₂+2OH ^- (1)

It is behind solution vent gas body, and for example the anolyte compartment by reactor discharges.In addition, the water in the cathode compartment of electrolysis reactor/ionogen dilute solution is alkalescence through forming hydroxide ion.

Especially produce chemical oxidizing agent oxygen (O by following molecular balance formula (2) and (3) on the anode ₂) and (Cl ₂), they are known to be effective to the sterilization of water.Must note in addition, owing to form H ₃O ⁺It is acid that ion, the water in the electrolysis reactor anolyte compartment/ionogen dilute solution are:

6H ₂O→O ₂+4H ₃O ⁺+4e ^- (2)

2Cl ^-→Cl ₂+2e ^- (3)

Chlorine becomes hypochlorite ion (OCl by following balanced reaction (4) at dissociation in water again ^-) and chlorion (Cl ^-), they again can with from electrolytical suitable positively charged ion such as Na ⁺Or with proton or H ₃O ⁺-ionic reaction becomes corresponding (sodium) salt or corresponding acid, i.e. hypochlorous acid (HClO) and hydrogenchloride or dilute hydrochloric acid (HCl):

Cl ₂+3H ₂O<＝>2H ₃O ⁺+OCl ^-+Cl ^- (4)

In addition, produce other material by the above-mentioned material that forms through secondary reaction on anode, its same known sterilization to water is effective.These are particularly related to hydrogen peroxide (H ₂O ₂, reaction formula (5)), ozone (reaction formula (6)), dioxide peroxide (ClO ₂Reaction formula (7)), chlorate anions (ClO ₃ ^-Reaction formula (8)) and different atomic group (reaction formula (9) and (10))

4H ₂O→H ₂O ₂+2H ₃O ⁺+2e ^- (5)

O ₂+3H ₂O→O ₃+2H ₃O ⁺+2e ^- (6)

Cl ^-+4OH ^-→ClO ₂+2H ₂O+5e ^- (7)

3OCl ^-→ClO ₃+2Cl ^- (8)

5H ₂O→HO ₂·+3H ₃O ⁺+3e ^- (9)

H ₂O ₂+H ₂O→HO ₂·+H ₃O ⁺+e ^- (10)

The shortcoming of electrochemical activation method especially lacks quality control, because the necessary parameter of enough sterilizations to water is the method that experience is determined mostly, amount such as electrolyte solution adding, voltage or the electric current and the similar parameters of regulating, not only depend on used electrolysis reactor, such as reaction volume, its annode area and cathode area, the residence time of water to be sterilized in the reactor, and depend on the composition separately of wanting disinfectant water, particularly its electric conductivity and redox potential thereof especially.In the case, to the processing parameter of certain water-usually by rule of thumb-determine, these parameters can cause satisfied disinfection to this water, and only can cause having very inadequate disinfection when another kind of water.

In addition, to point out by means of the solution general (on significance degree) of electrochemical activation manufacturing is assorted undesirable product is arranged especially, wherein often only produce chlorine (Cl by above-mentioned reaction formula (3) by prior art ₂), undesirable exactly to produce sterilizing agent though it is requirement in common electrochemical process at electrochemical activation, because it causes that electrochemical activation solution has a kind of smell of stimulation.In addition, because the component of the electrochemical activation solution of the above-mentioned parameter surging of its dependence does not have the explanation of reliability, the weather resistance of relevant electrochemical activation solution or storage characteristics, therefore in fact at first consider only product itself, actually so far this method-especially because its usability that differs from or inadequately guarantee enough sterilizations-in market, can not implement.

The method of making sterilizing agent by means of electrochemical activation is for example known by DE 202005008695U1.

Therefore, the objective of the invention is to further develop this specification sheets and start described type, the method for preparing sterilizing agent by electrochemical activation (ECA) water, this method keeps the high disinfection of sterilizing agent constant or guarantee to treat the high disinfection of sterilized water basically, and it especially also satisfies German tap water regulation.Purpose of the present invention also relates to sterilizing agent and the application thereof by means of this method preparation.

See that on Technology this purpose is adjusted between the 2.5-3.5 by the pH-value with the Zhong Shui of electrolysis reactor anolyte compartment/ionogen dilute solution and solves under the situation of the method for the above-mentioned type.About sterilizing agent itself, solving the problem that the present invention mainly exists is the sterilizing agent of making by means of this method, and its form is water/ionogen dilute solution on the anode of electrochemical activation, and wherein, the pH-value of sterilizing agent is between 2.5-3.5.

Shockingly find, when regulating the pH value of the water to be sterilized that the electrolysis reactor Zhong Shui of anolyte compartment/ionogen dilute solution promptly wherein sneaks into ionogen such as sodium-chlor or Klorvess Liquid, its value is transferred between about 2.5-about 3.5, be preferably the value between about 2.7-about 3.3, especially about 2.8-about 3.2, the value between about 2.9-about 3.1 for example, as in about 3.0 value, not only show and in fact still keep it having the in fact any tap water of forming and the disinfection of undrinkable water, and enough storage effects are arranged, it no longer needs further sterilisation step, and especially can continue to keep under rapid loaded situation.Control the anodic oxidation (PAO) that the Zhong Shui of the electrolysis reactor anolyte compartment/pH value of ionogen dilute solution causes control of Electric potentials by the present invention, wherein especially preferably regulate redox potential between about 1240mV and the about 1360mV, be preferably between the about 1360mV of about 1280mV-, between the about 1360mV of especially about 1320mV-.Research is not only pointed out, use intestinal bacteria, Pseudomonas aeruginosa and urine streptococcus as the test bacterium, by the inventive method 1:400 that water/the ionogen dilute solution is being diluted on the negative electrode by the electrochemical activation preparation under the anodic oxidation in control of Electric potentials the time, in about 30 seconds, can reduce and be higher than 4 10 powers, and be subjected to the pipeline of returning of visual visible microbial film or lawn invasion and attack, in 2 to 4 weeks, virtually completely free lawn.Therefore, the extent of dilution of 1:400 is the disinfectant that is suitable for tap water and undrinkable water or swimming-pool water, is the most effective extent of dilution.As following also to illustrate in greater detail, certainly also may, will carry out water/ionogen dilute solution on the anode of electrochemical activation according to the inventive method, be used in many other application purposes in dense mode.In addition, also certainly, when sterilized water, for example only in the limited timed interval, dilution anode water/electrolyte solution high density or little is added in the water to be sterilized, guaranteeing to carry out effective emergent management under the disaster scenarios it that occurs in tubing system, this dilution can the about 1:200 of for example about 1:100-, and wherein extent of dilution depends on various applicable cases in principle.

Find in addition, the pH value of the sterilizing agent of the water on the electrolysis reactor anode/ionogen dilute solution form is adjusted to pH value scope of the present invention, the pH value that can not cause water to be sterilized can drop to the pH value enduringly, and do not require owing to be than tart pH value to the application of many potential electrochemical activations, for example to tap water, this one side is very little (for example about 1:300-1:500 of its extent of dilution) to the dosage of the sterilizing agent of water sterilization necessity, it presses the buffer capacity of water and fixed and also in remollescent water very, then cause the pH value to drop to and make an appointment with-0.2 more, the pH value rises over time on the other hand, and this estimates that the metastability material decomposition when electrochemical activation produces as ozone, different (consulting above-mentioned molecular balance formula) such as atomic groups.But still reach remarkable disinfection as mentioned above.

In addition, produce chlorine by above-mentioned reaction formula (3) with inferior limit, be electrochemical activation, anodic water/ionogen dilute solution to cause this sterilizing agent, a kind of very weak chlorine flavor is arranged at most, is the general smell that does not have chlorine fully when this disinfectant product adds in the entry with suitable extent of dilution.Along with the anodic oxidation of control of Electric potentials especially produces hypochlorite, as the compound of clorox (NaClO) and hypochlorous acid (HClO), metastable state free radical, as replacing chlorine (Cl with more a spot of hydrogenchloride ₂), the balance of promptly above-mentioned reaction formula (4) guides significantly by moving right through side of the present invention.

Spatial isolation based on the anolyte compartment, produce efficient, the sterilization purposes of the water of electrochemical activation/ionogen dilute solution wherein prevents a kind of mixing and the therefore formation suitable material less to water sterilization at anodic electrochemical activation product that produces and the product that produces at cathode compartment from cathode compartment.This can be for example by means of barrier film, saturating film or analogue, it makes a kind of conduction that has, but basically the solution sealing the anolyte compartment in the electrolytic reaction chamber is separated with cathode compartment.For example have in this respect by porousness zirconium white (ZnO ₂) and or porousness aluminum oxide (Al ₂O ₃) a kind of barrier film/saturating film of making is suitable.

Usually in inventive concept, " regulate the scope of pH value " in addition to 2.5-3.5, be meant and be derived from barrier film/saturating film and the isolating electrolysis reactor of the cathode compartment anolyte compartment that has electricity to lead ability through, the solution that overflows-or electrochemical activation, this pH value of anodic water/ionogen dilute solution promptly is to regulate the pH value like this to make in the reactor end in anolyte compartment's adjusting pH value.Correspondingly the redox potential of " control water/ionogen dilute solution " is to the value between 1240mV and the 1360mV, it carries out like this, by effusive solution in the anolyte compartment of electrolysis reactor or electrochemical activation, anodic, the water/electrolyte solution of dilution-be a kind of its this value of regulating in this anolyte compartment of reduction-oxidation current potential that this reduction-oxidation current potential is promptly controlled like this that has in the reactor end.This reduction-oxidation current potential is equipped with standard electrode (NHE) or standard hydrogen electrode (SHE)." adjusting " is the static preregulated any means parameter of a kind of suitable more or less (minder), also be a kind of when reactor is operated, be a kind of method parameter of dynamic adjustments.

PH value in the water/ionogen dilute solution of anolyte compartment can be regulated by diverse ways in principle.For example can in the ionogen of wanting disinfectant water to replenish, add an amount of acid in principle to this,, in a preferred embodiment, the pH value is adjusted to value range of the present invention as mineral acid or organic acid, and (other) acid of not batching.By above-mentioned, the molecular balance that takes place at anode is significantly, and at this moment the oxidizing reaction of carrying out at anode produces many times proton or H ₃O ⁺Ion makes the pH value along with reduction.By this reason can, the pH value is adjusted in the scope of the invention by its reaction of carrying out at anode separately, wherein when electrochemical activation, improve the conversion that obtains at anode, obtain that a kind of bigger proton produces and along with a kind of lower pH value at anode.Because the conversion that electrochemical activation obtains can improve once more at predetermined reactor geometricdrawing, wherein regulate interelectrode electric current or wherein apply higher voltage (this make interelectrode electric current higher) on the electrode and also in reactor the residence time of water/ionogen dilute solution improve (even perhaps predetermined continuous or semi-continuous method carry out-and delay through the volumetric flow rate of the water/ionogen dilute solution of reactor) and/or the more electrolyte solution of wherein batching, be more sodium chloride solution/Klorvess Liquid, also add higher reaction volume.As what begin to mention, and the total concn of sodium chloride/potassium chloride still is no more than 20g/l.

On the other hand, because the pH value of water/ionogen dilute solution depends on electrolytical conversion in the anolyte compartment of reactor, also can directly or indirectly measure the pH value, to obtain first value in this method, for example, by means of habitual control techniques equipment, as by means of PID controller-can be adjusted to by rated value of the present invention.Predetermined by an embodiment preferred of the present invention, the pH value of water/ionogen dilute solution is directly measured with pH meter.The pH value current measurement through flowing through between electrode indirectly (for example by must on electrode, applying necessary voltage) of replacing or be anticipated that water/ionogen dilute solution in addition and/or the pH of water/ionogen dilute solution to reach this electric current indirect by therein the residence time-or a kind of (partly) continuation method in service-measure through the volumetric flow rate of ionogen reactor by itself.

Clearly, by the preferred embodiment of the inventive method as seen, the pH value of the Zhong Shui of the anolyte compartment/ionogen dilute solution of electrolysis reactor is to control by the electrolyte solution of control interpolation respective amount, add more electrolyte solution as the pH-value must be reduced the time for controlling to the scope of the invention, be more reactant, then add a small amount of less educt of electrolyte solution when being controlled at the scope of the invention when the pH value must improve.For example the assignment of the respective amount of sodium chloride/potassium chloride solution can be for example by means of volume pump for electrolyte solution, and therefore the gained water/electrolyte solution before entering electrolysis reactor preferably mixes as far as possible, so that electrolysis reactor evenly moves.As suitable mixing equipment, particularly a kind of spherical mixing chamber is reliably, imports water/ionogen dilute solution through a kind of spherical agitator betwixt.

Visible in preferred embodiments interchangeable or another kind of method, the pH value of the water of anolyte compartment/ionogen dilute solution can be controlled by mobile electric current between control electrode, wherein, for example apply suitable voltage on the electrolysis reactor electrode, to guarantee to reach the necessary electric current of pH scope of the present invention.Interchangeable in addition or another kind of method can be by being controlled in the electrolysis reactor or flowing through the residence time of electrolysis reactor and/or the volumetric flow rate of itself is controlled in the pH value of anodic water/ionogen dilute solution.In all cases, one or more parameters are to keep steady state value or be adjusted to steady state value basically.

For the predetermined electrolysis reactor of reactor geometric shape is demarcated with water to be sterilized, promptly for regulate with control water/ionogen dilute solution the pH value in value scope of the present invention, carry out necessary processing parameter in advance, carry out a kind of favourable processing arrangement, with the pH value of regulating the electrolysis reactor Zhong Shui of anolyte compartment/ionogen dilute solution to the value between the 2.5-3.5, especially the value between the 2.7-3.3, should there be electric current to give regularly electrolysis reactor interelectrode, determines to depend on residence time (Tv) in its electrolysis reactor of forming separately of water to be sterilized and/or depend on the flow through liquid flow volume (V ') of electrolysis reactor of the water/ionogen dilute solution of composition separately of wanting sterilized water.Thereby predict the favourable embodiment of the present invention, wherein flow through residence time (Tv) of electrolysis reactor and/or liquid flow volume (V ') and depend on electrical conductivity of water (k) and/or water hardness and determine.Because particularly electrical conductivity of water to reach pH value of the present invention in reactor or under the situation of (partly) continuation method operation water/necessary residence time of ionogen dilute solution considerable influence is arranged, relative liquid flow volume by reactor there is considerable influence, this method also can, at first to respectively wanting disinfectant water to determine suitable residence time/liquid flow volume.Wherein, determine that this dependence is to apply suitable current on the electrode of reactor, for example, can experience determine and preferably (also can determine the dosage of electrolyte solution equally) and keep constant.Thereby can predict, residence time or liquid flow volume replace depending on that the function that the electrical conductivity of water of will sterilizing can be used as the representative hardness of water determines electrical conductivity of water, just the contained ionic total concn of water becomes ratio only by its hardness with electrical conductivity of water therein, and just the concentration of calcium ion and magnesium ion is caused.

A preferred embodiment can see in this relation, residence time (Tv) and/or liquid flow volume (V ') determine by following linear relation:

Tv＝k ₁·κ+k ₂

And/or

(V’)＝k ₃·H+k ₄

K wherein ₁, k ₂, k ₃And k ₄It is the reactor characteristic constant, described linear relation for example can be determined by plain mode, wherein, water with different electric conductivitys in certain residence time in reactor or have under the certain liquid flow volume that flows through reactor and under ionogen that certain (especially constant) batches and interelectrode certain (especially constant) electric current in electrolysis reactor, carry out electrochemical activation and thereby regulate the pH value in scope of the present invention, obtain thus the residence time of necessity of different water or the relation of liquid flow volume and electrical conductivity of water, and reactor moves with a kind of corresponding liquid flow volume (or residence time).

In another preferred embodiment of the inventive method, proposed and/or the given residence time of the water/electrolyte solution in the electrolysis reactor under water/electrolyte solution is flowed through the given liquid flow volume of electrolysis reactor, the pH value of the Zhong Shui of electrolysis reactor anolyte compartment/ionogen dilute solution is adjusted to pH value between 2.5 and 3.5, especially the value between the 2.7-3.3 has determined that interelectrode static state should have electric current (I _Soll, _Stat) more depend on the composition of wanting sterilized water.Advantage in this case is to have determined that static state should have electric current (I _{Soll, stat}) depend on electrical conductivity of water (k) and/or depend on water hardness.In addition, preferably can propose, static state should have electric current I again _{Soll, stat}Can press linear relationship and try to achieve,

_Isoll，stat＝k ₁·κ+k ₂

And/or I _{Soll, stat}=k ₃H+k ₄

K wherein ₁, k ₂, k ₃And k ₄It is the reactor characteristic constant.

Except the anode potential of the above-mentioned type of static state control more or less electrolysis reactor, for the function of assurance dynamic adjustments as the time dependent actual parameter of possibility carries out, in a particularly preferred embodiment of the inventive method, propose, electric current (I should be arranged in the interelectrode static state of predetermined electrolysis reactor _{Soll, stat}) down between the pH value to 2.5 and 3.5 of regulating the electrolysis reactor Zhong Shui of anolyte compartment/ionogen dilute solution, especially between the 2.7-3.3, obtain residence time separately of depending on water/electrolyte solution in the electrolysis reactor and/or water/electrolyte solution flow through electrolysis reactor the liquid flow volume dynamically electric current (I should be arranged _{Soll, dyn}), therefore can the field control reactor with keep water/electrolyte solution on the electrochemical activation anode because of the different pH value of surveyed actual parameter such as residence time or liquid flow volume in about 3 scope.

Dynamically electric current (I should be arranged _{Soll, dyn}) equally preferably try to achieve by the following formula linear relationship

I _soll，dyn＝k ₅·Tv+k ₆

And/or

I _soll，dyn＝k ₇·V’+k ₈

Wherein, k ₅, k ₆, k ₇And k ₈It is the reactor characteristic constant.

Regulation and control had both comprised because of the different static state of each time institute water regulates component, comprises that again preferably always passing on the electrode of electrolysis reactor during regulation and control to have electric current (I because of the different dynamic adjustments component of actual measurement parameter _Soll, _Ges), it should have electric current (I for static state _{Soll, stat}) and dynamically electric current (I should be arranged _{Soll, dyn}) summation:

I _soll，ges＝I _soll，stat+I _soll，dyn

Such just as already mentioned, the amount of the electrolyte solution of batching is not only for the preset of reactor, and at run duration, preferred basic maintenance is constant, wherein, reactor for example can be in its optimum regime operation with certain water liquid flow volume (or with water certain residence time in reactor) all the time, and for example when the maximum load along with high request carried out disinfection to water with the low rest time that requires, then in order to overcome maximum load, reactor (for example can be closed on the one hand often, in rest time), be used for anode electrochemical activatory water/ionogen dilute solution holder of being produced and prepare one on the other hand.

The optimum benefits of controlling the dynamic adjustments component according to the present invention is, when water/ionogen dilute solution in electrolysis reactor or flow through the measured residence time of electrolysis reactor and/or the liquid flow volume surveyed when descending, under the situation of this residence time of being surveyed and/or the reduction of liquid flow volume, mobile total current (I between electrode _{Soll, ges}) also can be because of dynamic component (I _{Soll, dyn}) descend and reduce.Have now found that, under the situation that electrochemical activation carries out continuously, can produce small bubbles especially, particularly oxygen of from water to be sterilized, emitting and chlorine, thereby the transformation efficiency and the pH-value that raises subsequently of gained when reducing electrochemical activation, and thereby can detect the reactor of flowing through the liquid flow volume reduce.In order to offset this effect, the of short duration reduction of mobile electric current proves favourable between the electrode of electrolysis reactor, and of short duration reduction electric current can assign to carry out by the dynamic state part that electric current should be arranged.Form in electrolysis reactor for eliminating because of the small bubbles due to certain labile equilibrium, and return the operation of the electrochemical activation sterilized water that is suitable for being entirely satisfactory, this dynamic regulation or adjusting measure also can be suitable for not being subjected to defined water of the present invention/electric Jie's pH value of solution value conduct, and the function of water conductivity or hardness carries out the influence of static control.

According to a favourable embodiment of the inventive method, the alkali metal chloride form that electrolyte solution can be pure basically especially adds with sodium-chlor (NaCl) and/or Klorvess Liquid (KCl) form.In preferred embodiment, electrolyte solution adds with saturated alkali metal chloride solution in principle.In order to guarantee high reproducibility, alkali metal chloride adds with high purity, promptly its should be substantially can other halide ionss, bromine ion-containing (Br not just ^-), fluorion (F ^-) and iodide ion, oxygen-free halogen ion is as hypochlorite (ClO ^-), chlorite (ClO ₂ ^-), chlorate anions (ClO ₃ ^-), cross chlorate anions (ClO ₄ ^-), bromate (BrO ₃ ^-) etc.It is substantially free of heavy metal in addition, particularly from this metal of antimony (Sb), arsenic (As), plumbous (Pb), cadmium (Cd), chromium (Cr), nickel (Ni), mercury (Hg), selenium (Se), iron (Fe) and manganese (Mn), and preferably be substantially free of the alkaline-earth metal that causes hard water, particularly calcium (Ca) and magnesium (Mg).

The ratio specific conductivity of electrolyte solution (before electrochemically-activated water that it is batched) can preferably be adjusted to about 1.510 ⁵μ S/cm and about 3.510 ⁵Value between the μ S/cm is especially about 1.810 ⁵μ S/cm and about 2.810 ⁵Value between the μ S/cm, preferably about 2.010 ⁵μ S/cm and about 2.510 ⁵Between the μ S/cm.

The electrolyte concentration of the water that in electrolysis reactor, is added/ionogen dilute solution (after in the electrochemically-activated water of promptly batching), the electrolyte concentration of water/alkali metal chloride solution particularly, particularly the concentration of alkali metal chloride should be no more than the value of about 20g/l as mentioned above basically.In favourable scheme, its value should be adjusted between about 0.1g/l and the about 10g/l, between the about 5g/l of particularly about 0.1g/l-, between the about 3g/l of preferably about 0.1g/l-(respectively being every liter of gram number of ionogen or alkali metal chloride).This concentration is proved to be the water/electrolyte solution of suitable electrochemical activation or the best disinfection and the storage effect of water/alkali metal chloride solution, and adjustable economize on electricity separates the scope of appropriate pH value to about 3 of the electrochemical activation anode water/ionogen dilute solution of reactor outlet, and to the redox potential of SHE (standard hydrogen electrode) scope for about 1340mV.

The a kind of of the inventive method further develops, its essence is that the pH value of not controlling the Zhong Shui of electrolysis reactor anolyte compartment/ionogen dilute solution just causes the electrochemical activation of water significantly to improve, this further develops regulation, before adding electrolyte solution, the value of the ratio conductivity adjustment of electrolytic activation water to paramount 350 μ S/cm will be treated.Now shockingly find, by before the adding electrolyte solution, regulating the ratio specific conductivity of institute's water or former water like this to the highest about 350 μ S/cm, the preferred value between about 0.055 μ S/cm and about 150 μ S/cm, and especially between 0.055 μ S/cm and about 100 μ S/cm (electric conductivity of institute's water generally all improves many times in all cases), guaranteed disinfection and storage effect even the circulation ratio of better of the inventive method about the sterilizing agent sterilizing agent of anode electrochemical activatory water/ionogen dilute solution form.And in fact be not subjected to the influence of institute's water.A kind of like this " stdn " of used former water not only can very be regulated processing parameter simply, as residence time in electrolysis reactor of voltage or electric current, water/ionogen dilute solution, amount of the electrolyte solution of batching etc., and allow to use the water of forming in fact arbitrarily and not damage the sterilizing agent of gained with simple method, guaranteed the anodic oxidation of the Zhong Shui of the electrolysis reactor anolyte compartment/ionogen dilute solution of reliable control of Electric potentials thus.

In addition, remove at least substantially even the concentration treating may contain in the electrochemically-activated water hour also can also be changed into some ion of the material that is harmful to health in the electrochemical activation process.With the bromide anion is example, its as the time with the frequent processing drinking water of ozone, the bromate of tool carcinogenesis in the time of can being oxidized to high density.In practice, this can check as the function of water feature infeeding the batch process water of upstream of electrolyte solution of electrolysis reactor, when needing or constantly with preferred operate continuously conductivity measurement pond or electrode by coming deionization than specific conductivity or go mineral materialization, this also will explain below in detail.

" than the specific conductivity " of water or water/ionogen dilute solution is meant specific ionic conductivity in the present invention, and it is based on the water that dissolving removable ion wherein causes or the electric conductivity of water/electrolyte solution.

According to preferred development, before adding electrolyte solution, will treat that the hardness of electrochemically-activated water is adjusted between the about 12 ° of dH of about 0-, especially at the about 4 ° of dH of about 0-, preferably at the about 2 ° of dH of 0-, for example about 1 ° of dH and 2 ° of dH.In this connection, " hardness " means the divalent alkaline-earth metal ion is calcium (Ca), magnesium (Mg), the concentration of strontium (Sr) and barium (Ba), back two kinds in fact inoperative.1 ° of dH is equivalent to the concentration of the alkaline-earth metal ions of 0.179mmol/l, and the concentration of 2 ° of dH is 0.358mmol/l, and the rest may be inferred.This mode of carrying out in advance is particularly suitable for the harder calcic and/or the water of magnesium, and this is for the work-ing life of improving electrolysis reactor or prolongs the maintenance intervals time.When at the very strong water of electroconductibility, to worry especially when promptly having the water of high total ion concentration, water is not easy to through ion exchange softening, because the alkaline-earth metal ions of each divalence will substitute and carries out ion-exchange through two monovalent alkalimetal ions, and therefore specific conductivity adds up to high.Owing to this reason, suitable is, water is at first softening and specific conductivity is dropped within the scope of the invention.

In addition, especially when water organic load or eutrophication, can advantageously the total organic carbon part (TOC, total organic carbon) for the treatment of electrochemically-activated water be adjusted to the highest about 25ppb (part per billion), especially the highest about 20ppb, preferably the highest about 15ppb.Correspondingly can relate to about oxygen requirement (COD, oxygen requirement), it is to regulate the highest about 7mgO of COD value in favourable mode ₂/ l, especially the highest about 5mgO ₂/ l, preferably the highest about 4mgO ₂/ l.

For regulating or reducing ratio specific conductivity and/or the hardness for the treatment of electrochemically-activated water, use for example saturating membrane method to be proved to be to suit, but obviously also can use suitable additive method as reverse osmosis, micro-filtration, nanofiltration, ultrafiltration or similarity method.For regulating or reducing total content of organic carbon (TOC) and/or the chemical oxygen demand (COD) for the treatment of electrochemically-activated water, for example can mention method for oxidation, especially by electromagnetic irradn (UV-irradiation) or other currently known methods in ultraviolet ray range.

Water/ionogen dilute solution that control adds to electrolysis reactor, especially the electrolyte concentration of water/alkali metal chloride solution, alkali metal chloride concentration particularly, preferably by control to the amount for the treatment of the electrolyte solution that electrochemically-activated water adds, for example by means of a kind of volume pump.In order to make it is a kind of uniform concentration distribution, treats that the water of electrochemical activation suitably carries out thorough mixing after electrolyte solution is metered into.

By preferred embodiment, corresponding water/alkali metal chloride the dilute aqueous soln that is added to electrolysis reactor of alkali metal chloride concentration of the water/alkali metal chloride dilute solution that can add to electrolysis reactor is controlled than the function of specific conductivity, determines at first that wherein the alkali metal chloride concentration that adds water/alkali metal chloride dilute solution in the electrolysis reactor adds the dependence of the ratio specific conductivity for the treatment of electrochemically-activated water and is used for which kind of purposes each.After determining this relation, need only measure representative electric conductivity, and change by means of the calibration curve that is converted into alkali metal concn to the alkali metal chloride concentration of water/alkali metal chloride dilute solution in the calibration curve mode.In the amount of learning that it provides the concentration of existing alkali metal chloride solution thereby can prepare each necessity, to reach desired concentration, suitable is to carry out by means of the electronics data processing element, and it has conductivity measurement battery or electrode on the one hand, and combination has corresponding metering mechanism on the other hand.

If alkali metal chloride concentration is to try to achieve by following linear calibration line (Kalibriergeraden) to the dependence of the ratio specific conductivity that adds water/alkali metal chloride dilute solution in the electrolysis reactor, then be proved to be suitable especially

κ _ges＝κ _w+d _κ/d[MeCl]·[MeCl]

κ in the formula _GesBe the ratio specific conductivity that adds entry/alkali metal chloride dilute solution to electrolysis reactor, κ _wBe each ratio specific conductivity that adds specific water to be sterilized, (measuring preferably the highest 350 μ S/cm before the adding electrolyte solution is tight), [MeCl] is the alkali metal chloride concentration to the water/alkali metal chloride dilute solution of electrolysis reactor input, and d _κ/ d[NaMe] be the slope of characteristic of the water of linear calibration line, i.e. constant d _κ/ d[MeCl] comply with the ratio specific conductivity that is in the content of institute's water and the electrolyte solution of batching thereof, such just as already mentioned, can adjusted value to the highest about 350 μ S/cm.For carrying out this correction, for example can treat the electric conductivity (κ of electrochemically-activated water known (for example measuring) to the storing solution of definite concentration known _w) under the alkali metal chloride solution of in water, batching, measure the total conductivity κ of water/alkali metal chloride dilute solution when adding the alkali metal chloride solution of different amounts _GesOn ordinate, introduce the total conductivity κ of water/alkali metal chloride dilute solution _GesObserved value, and on abscissa, introduce the electric metal chloride concentration [MeCl] of water/alkali metal chloride dilute solution.Obtain linear calibration line, wherein d like this _κ/ d[MeCl] on behalf of this straight slope and abscissa point of crossing, the factor represent k _wValue mentions that [MeCl] for example is preferably [NaCl] and/or [KCl].

Just as already described, not only about the preparation of sterilizing agent of the present invention, also about under the situation of sterilized water, using this sterilizing agent, water/ionogen the dilute solution of the electrochemical activation that it can advantageously use in the anolyte compartment to be produced specially, and can discard to produce in the cathode compartment and not too be suitable for disinfectant water/ionogen dilute solution.

Be sterilized water or other any medium, use sterilizing agent or with 1:500 with pure substantially form, especially to use be suitable to the diluent form of 1:400 part thinner, especially water.

The inventive method is particularly useful for sterilized water except preparing pure sterilizing agent itself, as tap water and undrinkable water, and rainwater, swimming-pool water, process water and trade effluent and analogue thereof.Aspect Technology, be favourable for example in this respect, shunt sterilized water when telling one thus, this shunting be through electrochemical activation and at least (or special) will add in the water to be sterilized as sterilizing agent in the shunting of anolyte compartment's electrochemical activation, and this sterilizing agent (as already mentioned) is added in the water to be sterilized with suitable dilution by service condition at every turn again.

At last, the inventive method is particularly suitable for continuous or semicontinuous carrying out, water wherein to be sterilized or flow through electrolysis reactor continuously or semi-continuously by the shunting that the present invention produces sterilizing agent through electrochemical activation.

The invention still further relates to a kind of sterilizing agent, it is a kind of by the inventive method anodic water/ionogen dilute solution (anolyte) form that make, electrochemical activation, its pH value is between about 2.5-about 3.5, between preferred about 2.7 and about 3.3, especially between about 2.8 to 3.2, and its redox potential is in preferred embodiments between about 1240mV and the about 1360mV, preferably between about 1280mV and about 1360mV, especially between about 1320mV and about 1360mV.

The electrochemical activation of making by the inventive method, anodic water/ionogen dilute solution can reach as sterilizing agent as can be used for the occasion that all need the zero defect sterilized water, it particularly must observe the tap water regulation, sterilization as area water supply, or hospital, school, beadhouse, middle-size and small-size industrial and commercial enterprises, the disinfection of drinking water of hotel or other catering industry enterprise and sportsmen association (for example, in the water of public health infrastructure, prepare), the railway station, the airport, the disinfection of drinking water of larger kitchens, add in sterilization of swimming-pool water or rainwater (for example in rainwater is handled, adding) or the water store tank at any kind of, be used for demineralization plant, as being used for preventing the mould propagation of fabric washing machine water in navigation or water desalination equipment in the inland, be used for the decolouring of dyehouse water, be used for trade effluent in fact arbitrarily, as sneak into water coolant and (for example be used to rotate lathe and mill machine, rig, cutting machine or other instrument machinery) be used for weather or the wetting system of air, be used for penetration equipment, as the additive of water with ready-mixed concrete and cement, when making electronics building slab and circuit as the additive of water, additive as the water that cuts flower, prepare the tap water and the waste water in raise livestock enterprise and slaughterhouse or the sterilization of this public utility that is used to sterilize, as hatch machine, milking unit and analogue thereof.Be used for instant sterilization in all cases or when normal enterprise will reach reliable sterilization, and stop unwelcome algae and/or mud formation.This sterilizing agent or form that can be pure substantially or especially when water treatment, reach about 1:500 with a kind of, preferably reach 1:400 extent of dilution form, add the thinner part as water, wherein under the situation of water treatment, for example dilution range proves suitable at about 1:400 in many cases.

Be the sterilizing agent of the anodic water/electrolyte solution mode of electrochemical activation of the present invention therefore equally can be with pure or especially with a kind of form of the suitable dilution food that carries out disinfection, as grain, flour, seasonings, fruit, vegetables, ice-creams and the ice cube used as refrigerant, meat, fish and seafood product during for example for transportation and sale storage, animal product and analogue thereof, wherein but nothing to find fault with, be without rebuke ground is eliminated mould, as spoilage organism etc., and therefore can reach the good health regularity of the storage stability that lives forever.

A kind of purposes of the sterilizing agent of the present invention's preparation is to be suitable for disinfection seed in addition, wherein can be used as the ensiling agent or store agent when bunker is stored at seed and cereal.

Another use range is that this sterilizing agent is used for sterilised packing container and packing, particularly health product, as food, medicine, sterilising member (as syringe, operation tableware etc.) with and analogue.

The use of this sterilizing agent can be suitable for reaction medium to carry out lyolysis and emulsion polymerization effect in addition, and wherein adding to reduce can sharply increase this necessary emulsifying agent and the polymerization degree, as the experiment illustration at preparation divinylbenzene ethylene rubber.

Another preferred use range is that this sterilizing agent can be used as and is used for the especially additive of water-soluble dye, lacquer, pigment, it has the effect of biocide, and as refrigerant and lubricant additive, as be used for industrial cooling recirculation system or be used for water base, oil base or the industrial lubricants of fatty group.

At last, this sterilizing agent also can be used as the additive of fuel and fuel oil, as fuel oil, gasoline, kerosene and like that.

In all cases, this sterilizing agent (especially basically under anoxybiotic condition) when suitably storing is the electrochemical activation of the inventive method, anodic water/electrolyte solution state, and to preserve about 6 months be no problem storing for it.

To consult under the accompanying drawing below by means of handling or the embodiment of disinfectant soup water is elaborated.Below, point out to implement to prepare be that anodic the water purified or electrochemical activation of dilute form on the other hand/the ionogen dilute solution is to carry out in identical electrolysis reactor, under show in the accompanying drawing

1. be the block diagram that is used for through first embodiment of the inventive method of electrochemical activation (ECA) sterilized water.

2. press the cross section schematic detail view of Fig. 1 electrolysis reactor.

3. press the cross section schematic detail view of Fig. 1 mixing tank.

4. be used for the block diagram through second embodiment of the inventive method of electrochemical activation (ECA) sterilized water, it is different from Fig. 1 embodiment, particularly by using a kind of electrolysis reactor of the pure water equipment of connecting.

Fig. 1 synoptic diagram shows, the suitable device that is used for continuous or semicontinuous enforcement the inventive method, this equipment passes through electrochemical activation (ECA) sterilized water in the anodic oxidation (PAO) of control of Electric potentials, it comprises a main water pipeline 1, wherein supply with and want disinfectant water, main water pipeline 1 can be the convertible pipeline of water supply water inlet pipe, swimming pool of for example a kind of hospital, middle-size and small-size industrial and commercial enterprises, hotel or other catering industry enterprise, or similar manufacturing.Linking on main water pipeline 1 has arm 2, and it has valve 3, especially is control valve, and filter 4 is housed, particularly be the aperture and be for example second filter of 80-100 μ m, and, down lead to the electrolysis reactor 6 that a Fig. 2 describes in detail again by a mixing tank 5 that in accompanying drawing 3, describes in detail.Therefore the electrolysis reactor 6 of can flowing through of the part liquid stream in the main water pipeline 1 that supplies water by means of control valve 3 may command by arm 2, wherein for example its part liquid stream that supplies water at main water pipeline 1 with 1/200 order of magnitude fork by arm 2.

Mixing tank 5 links to each other with the reservoir 7 that holds electrolyte solution (being sodium chloride saturated solution basically) here with arm 2 on the one hand on the other hand at input side, it can mix and pass through the conduit 8 arrival electrolysis reactors 6 of the outlet side of a common mixing tank 5 equably mutually in mixing tank 5, the conduit 9 that leads to mixing tank 5 from reservoir 7 also links so that quantitative electrolyte solution to be provided the water that provides at arm 2 with the volume pump that Fig. 1 does not show.Especially can see that by Fig. 3 the mixing tank 5 of the embodiment of the invention is that spherical mixing chamber constitutes it and keeps consistently the uniform mixing power and water to separate matter.It consists essentially of an about column shape container 51, and linking

inlet

2,9 in its opposite end or exporting 8 is ball 52 or other particulate material of arranging at the exemplary filler of pointing out of Fig. 3 wherein also.Separate matter solution by these filler power and waters and flow through through this, ball 52 is vibration active simultaneously, and thereby has guaranteed that the electrolyte solution of water and adding very mixes equably.

Learn that as Fig. 2 electrolysis reactor 6 comprises anode 61, its for example be in the present embodiment the hollow cylinder that constitutes by titanium its scribble the ruthenium dioxide (RuO of katalysis ₂) and distolaterally can link the anode of a power supply that does not show by an outside screw 61a at it, be furnished with other or replenish be added to ruthenium oxide for example also be one based on iridium dioxide (IrO ₂) or a kind of two kinds of (RuO ₂/ IrO ₂) mixture or other oxide compound such as titanium dioxide (TiO ₂), plumbic oxide (PbO ₂) and/or Manganse Dioxide (MnO ₂).Electrolysis reactor 6 also comprises a negative electrode 62, and it is aptly by stainless steel or analogous material such as nickel (Ni), platinum (Pt) etc. are made and the hollow cylinder placed coaxially with anode 61 in the present embodiment constitutes.The anchor clamps (not shown) that negative electrode 62 surrounds by means of its outside can be attached to the negative pole of not shown power supply, antianode 61 and negative electrode 62 are co-axial and are one betwixt and seal by means of tight circle 63, be mounted with tubular barrier film 64, it is between anode 61 and negative electrode 62, and annular reaction chamber and the annular reaction chamber in the anolyte compartment in the anolyte compartment separate.This barrier film 64 has stoped the liquid mixing that is arranged in anolyte compartment and cathode compartment, and represents that it does not particularly have big resistance to ion migration mobile.Barrier film 64 in the present embodiment, for example by electroconductibility or lead ionic, or hydraulic seal basically, porousness zirconium dioxide (ZrO ₂) constitute, another kind has the material such as the aluminum oxide (Al of in proportion little resistance ₂O ₃), ion-exchange membrane, particularly this material based on plastics can use equally.

Electrolysis reactor 6 has two

inlets

65a, 65b to enter the reaction chamber of reactor 6 by these two inlets from the 5 effusive water/electrolyte solutions of the mixing tank on pipeline 8, promptly infeeds this anolyte compartment and from infeeding the cathode compartment input that separates at interval by barrier film 64 here.The arm of for this reason being furnished with a for example about T-shape, this is not shown in Fig. 1.Reach in addition from Fig. 1 clearly from Fig. 3, electrolysis reactor 6 also has two

outlets

66a, 66b again.Discharge by this outlet by this outlet water/electrolyte solution behind the electrochemical activation in reactor 6.When outlet 66a is used for promptly discharging so-called " anolyte " from the water/electrolyte solution of anolyte compartment's discharging electrochemical activation of reactor 6, export 66b and be used for promptly discharging so-called catholyte by the cathode compartment discharging.In addition, can stipulate, when starting electrolysis reactor 6, can discard anolyte " the anodic water/electrolyte solution of electrochemical activation ", to remove relevant beginning quality deteriorated, as long as the electrolysis reactor operation does not still reach desired running status by specific time interval.

Be electrolysis reactor 6 used in the present invention below, provide with listed dimensional measurement:

Cathode compartment length: 18.5cm

Cathode compartment volume: 10ml

Cathode surface: 92.4cm ²

Anolyte compartment's length: 21.0cm

Anolyte compartment's volume: 7ml

Anode surface: 52.7cm ²

Negative electrode and anodic spacing: about 3mm (comprising barrier film)

Electrolysis reactor 6 is the water handling capacities that for example have 60-140lL/h, and bigger throughput is certainly arranged, the bigger reactor and/or a plurality of of wherein can packing into, parallel placed in-line reactor.The storage tank intercepting and capturing maximum load of the anodic water/ionogen dilute solution that is used for electrochemical activation can be closed and be described in detail by the next one to preferred electrolysis reactor 6 under full load, simultaneously, all the time when needing.

As seen export the cathode compartment input gas separator 10 of 66b from Fig. 1 again by electrolysis reactor 6, waste gas discharges from the vapor pipe 11 of separator by suitable configuration, and catholyte itself, promptly water/the electrolyte solution of being discharged by the cathode compartment of electrolysis reactor 6 passes through pipeline 12, for example discharges in the tubing system of zonal water exhaust system.Outlet 66a feeds storage tank 13 from the anolyte compartment of electrolysis reactor 6, anolyte comes out from 13, can join water main 1 by conduit 14, undertaken by arm 15 in embodiments of the present invention, it passes through the point of contact of the conduit 14 in the arm 15 sometimes, can control its following current or adverse current up and down by means of control valve 16,17.Another control valve 18 be placed in by the water main 1 of arm 15 bridge joints that the section on.Link storage tank 13 to the pipe 14 of the arm 15 of water main 1 configuration volume pumps 19 in addition, it is used to regulate anolyte and is formulated into water main 1 by storage tank 13.Waste pipe 20 is by the vapor pipe 11 of storage tank 20 inflow gas separators 10.The function of arm 15 is to add sterilizing agent, carries out also can infeeding with sterilizing agent normal in service stream by arm 15 at the whole water liquid of water main 1 mobile.In order to safeguard and to assemble arm 15 and from water main, separate by valve 16,17.

Electrolysis reactor 6 also is furnished with and fails the controllable voltage source that is shown specifically among Fig. 1, and to control desired electric current, this electric current is measured by the amperometer (not shown) between anode 61 and negative electrode 62.66a also has a pH meter (not shown equally) that is used for anolyte in outlet, and it is also configurable in addition in storage tank 13 for example.Be used to the to flow through supply regulated of water/ionogen dilute solution of electrolysis reactor of one (for example) integrated controllable pump (not shown equally) in reactor 6 is regulated its residence time thereby pump is adjusted in the liquid flow volume of the water/electrolyte solution in the reactor 6.The same operating device that does not have detailed description, for example in the mode of electronic data processing division, be configured to regulate the described parameter of control, for the pH value that will flow out the anolyte that discharges by outlet 66a from the anolyte compartment of reactor 2 just in time remains on between the 2.5-3.5, preferably, for example carry out by means of the PID-controller in about 3.0 scope.

In order to wash electrolytic reaction chamber 6, also dispose a reservoir 21 to hold washing liq, as acetate or analogue, and randomly a reservoir 22 is used to hold the exhausted washing liq, and storage tank 21 leads to the conduit 23 and reactor 6

inlet

65a, 65b (view 2) coupling connection of reactor 6 simultaneously, and water shoot 24 and reactor outlet 66a that flows into storage 22 by

reactor

6,66b (view 2) but phase coupling connection as required comes cleaning reaction chamber 6, i.e. its cathode compartment and especially its anolyte compartment like this.As what select, cleaning solution particularly also can directly infeed for example partial drainage system under the feelings of acetate.

For the work-ing life or the prolongation service intervals time of improving electrolysis reactor 6 also can connect unshowned softening installation among a Fig. 1 in advance, it keeps water hardness for example to be up to 4 ° (consult this paper, and press the embodiment that Fig. 4 describes).

Following brief description is by the industrial equipment of the sterilized water of the anodised electrochemical activation (ECA) under control of Electric potentials.

Electrolysis reactor 6 at first depends on specific conductivity or is to depend on the representative hardness of wanting sterilized water (its pH value is in principle at neutral range in the present embodiment, promptly about 6-8) proofreaies and correct for the pH value in the anolyte compartment that makes reactor 6 and reach about 3 and obtain wherein making effective anolyte with sterilized water especially in the anolyte compartment at the suitable rated value of mobile electric current between electrode and by liquid flow volume or water/electrolyte solution residence time in reactor 6 of reactor.Basically along with wanting disinfectant water hardness (or specific conductivity) to raise, need provide with higher electric current and/or littler liquid flow volume, in order to regulate the pH value in 3 scope, water/ionogen the dilute solution of relevant its electrochemical activation of proper transformation, timing is at first regulated the liquid flow volume by reactor 6, this be equivalent to substantially accumulate virtue by the liquid fluid of reactor 6 preestablish-more accurately, be equivalent to liquid flow volume by arm 2 inflow reactors 6, for example be equivalent to about 1/200 of the water main 1 liquid stream of flowing through here, it (for example enters 1/400 of water main 1 liquid flow flowing here based on the amount that provides at water main 1 through the anolyte that pipeline 14 turns back to water main 1, and 1/400 being discarded during with catholyte of this approximately liquid stream), be used to sterilized water.Regulator solution stream in addition, its by by storer 7 suitably the preparation electrolyte solutions pH value that makes water/ionogen dilute solution in the electrochemical activation mode in 3 scope.After correction had the different water of different hardness, obtaining the following static state that is used in embodiments of the present invention should have electric current (I _{Soll, stat}) or be used for linear calibration line by the liquid flow volume of reactor 6:

(I) I _{Soll, stat}=0.418A, hardness [°]+0.953A

(II) V ' soll=-0.95l/h, hardness [°]+43.80l/h

After setting up above-mentioned linear calibration line, between the anode 61 of electrolysis reactor 6 and negative electrode 62 the mobile electric current each be adjusted to corresponding rated value according to its water hardness of will sterilizing.Equally also be applicable to the liquid flow volume of the water/ionogen dilute solution of the reactor 6 of flowing through.

Want the pH value of the employed anolyte of sterilized water to carry out like this in run duration control, the pH value that makes anolyte is the scope at pH3, particularly always electric current (I should be arranged by what other control was provided with altogether on the

electrode

61,62 of electrolysis reactor 6 _{Soll, ges}) dynamic part (Isoll dyn), consider in fact the liquid flow volume of measuring through reactor 6:

(III)I _soll，ges＝I _soll，stat+I _soll，dyn

I wherein _{Soll, dyn}=k ₇V '+k ₈Therefore the electric current that is provided with at electrode 61,62 depends on the pH value of being surveyed, when pH value above 3 (promptly work as the liquid flow volume V ' that is surveyed increases or the conversion of relevant electrochemical activation gained reduction), electric current increases; And the pH value is lower than 3 (promptly as the liquid flow volume V ' that measures-for example owing to form in reaction chamber that bubble reduces or work as the conversion that electrochemical activation obtains and increase), and electric current then reduces; And/or the liquid flow volume V ' by reactor reduces when the pH value is higher than 3; When dropping to, the pH value is lower than the raising of 3 liquid flow volume.When the amount of the electrolyte solution that will prepare preferably keeps substantially constant, setting other or that replenish also can be arranged, when the pH value surpasses 3 (i.e. the conversion that obtains at electrochemical activation reduces) by the more electrolyte solution of storage 7 preparations,, the pH value is lower than 3 (being that the conversion that electrochemical activation obtains improves) less electrolyte solution of preparation when dropping to.According to the present invention, may make very much in three the described parameter electric currents interelectrode electric current of reactor 6 (promptly) two, the liquid flow volume that flows through by reactor 6 (promptly, the liquid flow volume of water/ionogen dilute solution) and the amount of the electrolyte solution that will prepare keep constant, and only keep the pH value within the scope of the present invention by the 3rd parameter control.Regulate pH value redox potential when being controlled at 3 scope in the present invention, preferably at about 1340mV ± 20mV.

The sterilised liq of the electrochemical activation gained by the anodised control with control of Electric potentials of the present invention (it is the anolyte form when temporary in basin 13), by means of volume pump 19, ratio with about 1:400 adds water main 1 especially, is for the whole water that provide are here sterilized reliably.Because the anolyte of electrochemical activation; as already mentioned; be metastable condition; its add be used in the entry sterilization before; consider shielded and not possible to a great extent thermmal storage; this anolyte is stored in its storage tank 13 to have the sizable free surface of liquid planar, is up to about 14 days, and is preferably the highest about 48 hours.As above mentioned, may be up to about 6 months in the storage of the sterilizing agent that carries out the aforesaid method manufacturing own, should notice that simultaneously hermetic seal as far as possible seals corresponding hold-up vessel and also preferably alap temperature for example up to about 8 ℃.

Fig. 4 represents the exemplary process schema of another equipment, this equipment with continuous or semicontinuous enforcement the inventive method with by electrochemical activation (ECA) method sterilized water.Equipment comprises a main water pipeline 101, wherein supplies with and wants disinfectant water, for example, and with the water supply inlet duct of hospital, middle-size and small-size industrial and commercial enterprises, hotel or other catering industry enterprise, the water supply inlet duct of swimming pool transition duct or similar.Link arm 102 on water main 101, it disposes a valve 103 as control valve, and pays a filter (not shown) thus, particularly with a kind of form of second filter.

Arm 102 following current flow valves 103 enter softening agent 104, and it is furnished with a suitable ion exchange resin, and it replaces the calcium that causes hardness and the magnesium ion of discharging divalence through monovalent ion such as sodium in water.For work-ing life of improving electrolysis reactor 6 or in order to prolong the interval of maintenance, softening agent 104 keeps water hardness for example at the highest 4 ° of dH (being equivalent to alkaline-earth metal ions concentration 0.716mmol/l), preferably the highest 2 ° of dH (being equivalent to alkaline-earth metal ions concentration 0.358mmol/l).The draining 105 of softening agent 104 flows into an equipment 106 with the specific conductivity of reduction water or than the sub-rate of diversion, it is especially by a film device, as reverse osmosis unit or a kind of micro-strainer, nanofilter or ultrafiltration unit constitute, and the ratio specific conductivity of water remains on the value of the highest 350 μ S/cm, be up to 150 μ S/cm especially, preferably the highest 100 μ S/cm, draining 107 at film device 106 is provided with a conductivity measurement equipment 108, as a conductivity measurement unit, conductivity measurement electrode or similarly, observe expected value with each of monitoring water than specific conductivity.

To this, can propose especially when wanting the proportional high organic carbon content of disinfectant glassware for drinking water, the measure of then taking is the carbon content that reduces water.Here it reduces total organic carbon content (TOC) and/or chemical oxygen demand (COD) (COD) to the value, particularly the highest 20ppb or the highest 7mgO of the highest 25ppb for example to dispose a mixing tank that links UV-oxidation unit (not shown) 109 ₂/ l, particularly the highest 5mgO ₂/ l.For measuring and/or control the combination parameter of organic carbon contained in TOC value or COD value or other decision water, as dissolved organic carbon (DOC, dissolved organic carbon), configurable device well known in the prior art.Softening agent 104 and film device 106 in conjunction with the time can suspect equally, the arm 102 of the water liquid of electrochemical activation stream part by telling by water main 101, only on demand by softening agent 104, film device 106 or UV-oxidation unit (promptly when each limit value surpasses), and each installs and carries out bridge joint by means of the arm (not shown).

The draining 107 of film device 106 flows into mixing tank 109, and it flows into electrolysis reactor 6.The latter is equivalent to the embodiment that provides at Fig. 2 in this article.By arm 102, can regulate by means of control valve 103, the part liquid stream of the water of the softening and deionization that water main 101 the provides electrolysis reactor 6 of can flowing through, wherein the part liquid stream of the water that provides of water main 101 with 1/200 the order of magnitude through arm 102 shuntings.The ingress of mixing tank 109 be connected with the draining 107 of film device 106 on the one hand (just as already mentioned), be connected to admit electrolyte solution with admitting storage 111 on the other hand, particularly with a kind of saturated substantially basic metal sodium chloride solution (being sodium chloride solution in this article), its mutual as far as possible uniform mixing in mixing tank 109 also arrives electrolysis reactor 6 by the common waste side pipeline of a mixing tank 109.Enter the conduit 112 that mixing tank 109 advances from reservoir 111 and also be furnished with a volume pump 113, add quantitative sodium chloride solution with electrochemically-activated water.Mixing tank 109 can for example be a kind of spherical mixing chamber that constitutes by Fig. 3.With the water flux operation of 60-140l/h, the while is 1 described reason with reference to the accompanying drawings, preferably carries out with full load, and can close in case of necessity again for electrolysis reactor 6.

Also obviously obtain from Fig. 4, insert gas separator 115 by the outlet 66b of the cathode compartment of electrolysis reactor 6, by the waste gas here, hydrogen (H particularly ₂) discharge by the waste gas duct 116 of configuration arbitrarily, and catholyte itself is promptly discharged by the tubing system that conduit 117 for example enters endemic drainage system by the effusive water of the cathode compartment of electrolysis reactor 6/ionogen dilute solution.Vapor pipe 116 flows into a vapor pipe 118 that stores diluent air in the present embodiment, and it is equipped with one avoids the low pressure blower 119 of exploding.

Cathode compartment outlet 66a by electrolysis reactor 6 enters storage tank 122 by control valve 120 and conduit 121, and anolyte can be added to water main 101 by storage tank 122 by pipeline 123.By arm 124, this 124 siding by conduit 123 is divided into following current or adverse current, controls up and down by means of each control valve 125,126 at arm 124 in the present embodiment.Another control valve 127 is configured in the bridge joint sections of the arm 124 of water main 101.Also dispose a volume pump 128 in the arm 124 banded pipelines 123 of storage tank 122 and water main 101, it is used for being metered into anolyte in water main 101 by storage tank 122 controls.Arm 129 is especially for emit chlorine (Cl in case of necessity in anolyte ₂), feeding gas separator 130 by the air chamber of storage tank 122, this air chamber links to each other with a vapor pipe that is used for chlorine again.At the isolating liquid of gas separator, the water of condensation for example can equally for example enter the pipeline system of endemic blowdown system and discharges (not shown).It will be situated between with the anode electricity and separate the liquid form, just the form in the water/sodium-chlor dilute solution of electrolysis reactor anolyte compartment electrochemical activation adds arm 124, and its function is, flows by arm 124 and enters with sterilizing agent at the whole water liquid streams of water main 101 mobile when normal operation.In order to keep in repair or to assemble, at this moment arm 124 can separate from water main by valve 125,126.

In addition, can stipulate, when starting, electrolysis reactor 110 can discard " anolyte " by certain time interval, just electrochemical activation, anodic water/electrolyte solution, for with its eliminating, because of as long as electrolysis reactor 110 operations still do not meet the requirements of running status, quality that begins is not good enough then just closes for it.For this reason another pipeline 132 by valve 120, be parallel in the pipeline 121 of the storage tank 122 that leads and enter in the tubing system of region water exhaust system, (by the switch of valve 120) also can eliminate anolyte.

Equipment by Fig. 4 also comprises a control 133, for example in electronics mathematics processing unit mode, when linking with needs with control valve 120 on the one hand, it controls conduit 121 or conduit 132 up and down, link by control of Electric potentials 134 and electrolysis reactor 6 on the other hand, with in electrolysis reactor 6, (Fig. 2) is to control the desired electric current of for example measuring (not shown) with amperometer between anode 61 and negative electrode 62.This is by the technical reason that begins to mention, promptly regulate pH value in about 3 scope and be to obtain the scope of redox potential at about 1340mV in addition in electrochemical activation anode water/ionogen dilute solution, the ratio specific conductivity that the present invention regulates former water with plain mode is up to 350 μ S/cm, and in fact this all be fine to all water with any inclusion.For this reason, wherein the conduit 66a that is come out by the anolyte compartment of electrolysis reactor 6 disposes a pH meter (not shown) aptly, preferably also dispose a conductivity measurement unit, or conductivity measurement electrode (not shown equally), it can be control 133, it obtains desired process parameter by the amount of the former water adding of pump 113 controls sodium chloride solution.At this moment the sodium-chlor total concn in the inlet 114 of electrolysis reactor 6 should be no more than and be about 20g/l, preferably is no more than about 10g/l.Control 133 can also be a requirement that the controllable pump (not shown) of integration passes through electrolysis reactor 6 with control water/electrolyte solution in reactor 6, wherein therefore by means of the adjustable water saving of pump/ionogen dilute solution process or liquid flow volume or residence time in reactor 6.

Be the summary that is used for through electrochemical activation (ECA) working method of the equipment of sterilized water under the oxidation of control of Electric potentials anodic below.

Hardness is the scope (the concentration 0.179mmol/l that is equivalent to alkaline-earth metal ions Ca and Mg) of about 1 ° of d to provide the softening pipe 104 of the volume part of about 1:200 of water-at first enter for example to soften to by the arm water of water main 101 by arm 102-for example be at water main 101.In film device 106, its specific conductivity drops to for example about 50 μ S/cm, for example can also for example reduce by oxygenolysis greater than about 25ppb water when higher organic carbon content is arranged thus.

Make with this softening and deionization and in case of necessity the water of oxide treatment make a kind of calibrating mode, with obtain about the amount of the sodium-chlor that is added to the water by means of volume pump 113 and resulting water/sodium-chlor dilute solution by manufacturing always than the relation between the specific conductivity.Sodium chloride concentration adds to electrolysis reactor this, the dependency of the ratio specific conductivity of water/sodium-chlor dilute solution thereby be the linear calibration line that can press mode is especially inferred.

κ _ges＝κ _w+d _κ/d[NaCl]·[NaCl]

κ wherein _GesBe ratio specific conductivity to the water/ionogen dilute solution of electrolysis reactor adding, κ _wBe the ratio specific conductivity of wanting disinfectant water (directly add, promptly its specific conductivity is about 50 μ S/cm under this situation) before adding ionogen that adds, [NaCl] is the sodium chloride concentration of the water/ionogen dilute solution of adding, and d _κ/ d[NaCl] be the slope of the water of linear calibration line than electric rate.

Reactor 6 is for to wanting disinfectant water to proofread and correct then, obtain at electrode 61, the suitable rated value of the electric current that flows through between 62 and the liquid flow volume that is fit to by reactor 6 or water/ionogen dilute solution are in residence time that reactor 6 particularly is fit in the anolyte compartment, wherein produce effective anolyte of wanting sterilized water, reach about 3 with the pH value in the anolyte compartment that obtains reactor 6 in the anolyte compartment.Thereby the specific conductivity that has raising in principle then to want disinfectant water provide higher electric current and/or less liquid flow volume (or higher residence time) with reach regulate the pH value in 3 scope with the suitable conversion water/ionogen dilute solution of electrochemical activation.

Wanting the used anolyte of disinfectant water during operation is to control the pH value always like this to make the pH value of anolyte will be in the scope of pH3, particularly by the corresponding electrode 61 that is adjusted in

electrolysis reactor

6,62 added electric currents consider that simultaneously water/sodium chloride solution is by the liquid flow volume of reactor 6 and/or by carrying out the preparation of corresponding chlorinated sodium solution by means of volume pump 113.Controlling the preferably about constant 1340mV of redox potential ± 20mV SHE in the scope of pH value 3 like this.

By the sterilised liq form of this electrochemical activation method by the present invention control with the anodic oxidation gained of control of Electric potentials, it is stored in the form that stores in the storage tank 122 with the anolyte form, be for example to add water main 101 with the 1:400 share by means of volume pump 128, the sterilization of the water that provides in order to ensure whole this respects.Catholyte can discharge by pipeline 132.

Comparative example

By means of Fig. 4 (A) apparatus shown prepare the anode water/ionogen dilute solution (anolyte) of electrochemical activation with same equipment but be connected inverse osmosis device 106 in order to the electric conductivity that reduces institute's water, and connected ion-exchanger (104) (B) prepared anolyte compare.

Employed former water

Electric conductivity (κ _w): 543 μ S/cm;

Total hardness: 14.3 ° of dH (comprising 10.7 ° of dH carbonate)

PH value: 7.63.

Former water (A) after reducing specific conductivity:

Specific conductivity (k _w): 89 μ S/cm;

PH value: 7.25.

The anolyte that comes out by (A)

Electric conductivity: 9820 μ S/cm;

Free chlorine: 50.6mg/l (fluctuation);

Total chlorine: 56.6mg/l (fluctuation);

Combined chloride: 6.00mg/l (fluctuation);

PH value: 4.00 (fluctuations).

The anolyte that comes out by (B):

Specific conductivity: 3950 μ S/cm;

Free chlorine: 19.9mg/l;

Total chlorine: 19.9mg/l;

Combined chloride:＜0.05mg/l;

PH value: 3.10.

Experiment shows, when not reducing specific conductivity, handle this paper be the former water of 14.3 ° of dH (being equivalent to alkaline-earth metal ions 2.560mmol/l) than the about 550 μ S/cm of electric rate and hardness the time, in fact even during the sodium chloride solution of the higher amount of batching, can not accurately regulate the pH value in 3 scope.Equally also be suitable for redox potential at 1340mV scope (to SHE).(A) is opposite with method, and reproducibility is relatively poor under the situation of (B), and the hurried rising of chlorine number, so that there is the danger of no longer satisfying German tap water regulation (TrinkwV).Therefore can not foretell the disinfection of anolyte definitely reliably.

Claims

1. the method for preparing sterilizing agent by electrochemical activation (ECA) water, wherein in water, add electrolyte solution, particularly sodium-chlor and/or Klorvess Liquid, and comprising that at least one cathode compartment that is provided with negative electrode (62) and at least one are provided with anode (61), especially in the electrolysis reactor (6) of the anolyte compartment that barrier film or saturating film and cathode compartment separate, at electrode (61,62) apply volts DS on, make the water of the water/ionogen dilute solution form that is added with electrolyte solution accept galvanic action, water/ionogen dilute solution is in is fit to the disinfectant metastable state, it is characterized in that, the pH value of the Zhong Shui of anolyte compartment/ionogen dilute solution is controlled at value between the 2.5-3.5.

2. the described method of claim 1 is characterized in that, the pH of the Zhong Shui of anolyte compartment/ionogen dilute solution is controlled at a value between the 2.7-3.3, is controlled at a value between the 2.8-3.2 especially.

3. claim 1 or 2 described methods is characterized in that, with the value of oxidation reduction potential control between 1240mV and 1360mV of the Zhong Shui of anolyte compartment/ionogen dilute solution.

4. described method one of among the claim 1-3 is characterized in that, with the value of oxidation reduction potential control between 1280mV and 1360mV of the Zhong Shui of anolyte compartment/ionogen dilute solution, and a special value between 1320mV and 1360mV.

5. described method one of among the claim 1-4 is characterized in that the pH value of the Zhong Shui of anolyte compartment/ionogen dilute solution is directly measured with pH meter.

6. described method one of among the claim 1-5 is characterized in that, the pH value of the Zhong Shui of anolyte compartment/ionogen dilute solution is measured indirectly by the electric current that flows through between electrode (61,62).

7. described method one of among the claim 1-6 is characterized in that, with solution in electrolysis reactor or flow through the pH value that residence time (Tv) of electrolysis reactor and/or volumetric flow rate (V ') are measured the Zhong Shui of anolyte compartment/ionogen dilute solution indirectly.

8. described method one of among the claim 1-7 is characterized in that, the respective amount that adds electrolyte solution by control is controlled the pH value of the Zhong Shui of anolyte compartment/ionogen dilute solution.

9. described method one of among the claim 1-8 is characterized in that, controls the pH value of the Zhong Shui of anolyte compartment/ionogen dilute solution by the electric current that is flow through between control electrode (61,62).

10. described method one of among the claim 1-9, it is characterized in that, by control solution in electrolysis reactor (6) or flow through the pH value that residence time (Tv) of electrolysis reactor (6) and/or volumetric flow rate (V ') are controlled the Zhong Shui of anolyte compartment/ionogen dilute solution.

11. described method one of among the claim 1-10, it is characterized in that, for the pH value with the Zhong Shui of the anolyte compartment/ionogen dilute solution of electrolysis reactor (6) is controlled between the 2.5-3.5, special pH value between 2.7-3.3, electrode (61 in electrolysis reactor (6), 62) should have between under the predetermined situation of current value, measure with water to be sterilized form separately and in the reactor that becomes the residence time (Tv) and/or with water form separately and the volumetric flow rate of the water/ionogen dilute solution of the electrolysis reactor of flowing through (6) that becomes (V ').

12. the described method of claim 11 is characterized in that, with in the electrolysis reactor (6) or the residence time (Tv) of the electrolysis reactor of flowing through (6) and/or volumetric flow rate (V ') measure as the function of the water conductivity (K) and/or the water hardness (H).

13. claim 11 or 12 described methods is characterized in that, residence time (Tv) and/or volumetric flow rate (V ') are pressed the alignment equation and are calculated

Tv＝k ₁·κ+k ₂

And/or

V’＝k ₃·H+k ₄

K in the formula ₁, k ₂, k ₃And k ₄It is the reactor characteristic constant.

14. described method one of among the claim 1-13, it is characterized in that, for the pH value of water/ionogen dilute solution in control electrolysis reactor (6) between 2.5-3.5, especially the pH value between the 2.7-3.3, for residence time (Tv) of water/aqueous electrolyte liquid in the predetermined electrolysis reactor (6) and/or predetermined water/electrolyte solution is flow through the volumetric flow rate (V ') of electrolysis reactor (6), determine that because of the composition separately of water to be sterilized is different static state between electrode (61,62) should have electric current (I _{Soll, stat}).

15. the described method of claim 14 is characterized in that, static state should be had electric current (I _{Soll, stat}) measure as the function of water conductivity (κ) and/or hardness (H).

16. claim 14 or 15 described methods is characterized in that static state should have electric current I _{Soll, stat}Try to achieve by the following formula linear equation

I _soll，stat＝k ₁·κ+k ₂

And/or

I _soll，stat＝k ₃·H+k ₄

17. described method one of among the claim 14-16, it is characterized in that, between the pH value to 2.5 and 3.5 for control electrolysis reactor (6) Zhong Shui of anolyte compartment/ionogen dilute solution, especially to the pH value between the 2.7-3.3, static state in predetermined electrolysis reactor between electrode (61,62) should have electric current (I _{Soll, stat}) under, measuring with what each residence time of water/electrolyte solution in the electrolysis reactor (Tv) and/or water/electrolyte solution flowed through that the volumetric flow rate separately of electrolysis reactor (6) becomes dynamically should have electric current (I _{Soll, dyn}).

18. the described method of claim 17 is characterized in that, dynamically electric current (I should be arranged _{Soll, dyn}) try to achieve by the following formula linear equation

I _soll，dyn＝k ₅·Tv+k ₆

And/or

I _soll，dyn＝k ₇·V’+k ₈

Wherein, k ₅, k ₆, k ₇And k ₈It is the reactor characteristic constant.

19. described method one of among the claim 14-18 is characterized in that always passing to have electric current (I on the electrode (61,62) of electrolysis reactor (6) _{Soll, ges}), it should have electric current (I for static state _{Soll, stat}) and dynamically electric current (I should be arranged _{Soll, dyn}) summation:

I _soll，ges＝I _soll，stat+I _soll，dyn

20. described method one of among the claim 11-19 is characterized in that, makes the electrolyte solution amount of batching keep constant substantially.

21. described method one of among the claim 1-20 is characterized in that, with pure basically alkali metal chloride solution form, especially the form with sodium-chlor (NaCl) and/or Repone K (KCl) solution adds with electrolyte solution.

22. described method one of among the claim 1-21 is characterized in that, with saturated substantially solution, especially the form with saturated substantially alkali metal chloride solution adds with electrolyte solution.

23. described method one of among the claim 1-22 is characterized in that, with the ratio conductivity adjustment to 1.510 of electrolyte solution ⁵μ S/cm and 3.510 ⁵Value between the μ S/cm is especially 1.810 ⁵μ S/cm and 2.810 ⁵Between the μ S/cm, preferably 2.010 ⁵μ S/cm and 2.510 ⁵Between the μ S/cm.

24. described method one of among the claim 1-23, it is characterized in that, the degree that will add the electrolyte concentration, particularly alkali metal chloride of water/ionogen dilute solution, the especially water/alkali metal chloride solution in the electrolysis reactor (10) is controlled at and is up to 20g/l.

25. described method one of among the claim 1-24, it is characterized in that, water/ionogen dilute solution to electrolysis reactor (10) adding, the electrolyte concentration of water/alkali metal chloride dilute solution particularly, basic metal sodium chloride concentration particularly, be adjusted to the value between the 0.1g/l-10g/l, especially between 0.1g/l-5g/l, preferably between 0.1g/l-3g/l.

26. described method one of among the claim 1-25 is characterized in that, before adding electrolyte solution, the specific conductivity for the treatment of the water of electrochemical activation is adjusted to the value of the highest 350 μ S/cm.

27. described method one of among the claim 1-26, it is characterized in that, before adding electrolyte solution, the specific conductivity for the treatment of the water of electrochemical activation is adjusted to value between the 0.055 μ S/cm-150 μ S/cm, especially between the 0.055 μ S/cm-100 μ S/cm.

28. described method one of among the claim 1-27 is characterized in that, before adding electrolyte solution, the water hardness for the treatment of electrochemical activation is adjusted to the 0-12 ° of value between the dH, especially arrives between the 0-4 ° of dH, preferably arrives between the 0-2 ° of dH.

29. described method one of among the claim 1-28 is characterized in that, the total content of organic carbon (TOC, total organic carbon) for the treatment of the water of electrochemical activation is adjusted to the TOC value of the highest 25ppb, especially the highest 20ppb, preferably the highest 15ppb.

30. described method one of among the claim 1-29 is characterized in that, chemical oxygen demand (COD) (COD chemical oxygen demand (COD)) is adjusted to the highest 7mg O ₂The COD value of/l, especially the highest 5mg O ₂/ l, preferably the highest 4mg O ₂/ l.

31. described method one of among the claim 1-29 is characterized in that, uses embrane method, regulates specific conductivity and/or the hardness for the treatment of electrochemically-activated water as reverse osmosis membrane, micro-filtration, nanofiltration or ultrafiltration.

32. described method one of among the claim 28-31 is characterized in that, uses method for oxidation, particularly by means of the electromagnetic irradn in the ultraviolet range (UV-irradiation), regulates the total content of organic carbon (TOC) and/or the chemical oxygen demand (COD) of electrochemically-activated water.

33. described method one of among the claim 1-32, it is characterized in that, the amount that adds electrolyte solution by control in the water for the treatment of electrochemical activation is controlled and add water/ionogen dilute solution in electrolysis reactor (10), the electrolyte concentration in water/basic metal chlorination dilute solution particularly, alkali metal chloride concentration particularly.

34. the described method of claim 33, it is characterized in that, when the water for the treatment of electrochemical activation that all situations is used has down determined that in advance alkali metal chloride concentration adds the funtcional relationship of ratio specific conductivity of water/alkali metal chloride dilute solution to institute in the electrolysis reactor (10), the middle alkali metal chloride concentration that adds water/basic metal sodium-chlor dilute solution of electrolysis reactor (10) is controlled as the corresponding function than specific conductivity that electrolysis reactor (10) adds water/basic metal sodium chloride solution.

35. the described method of claim 34 is characterized in that, alkali metal chloride concentration is pressed following formula linear calibration line computation to adding the funtcional relationship of the ratio specific conductivity of water/alkali metal chloride dilute solution in the electrolysis reactor (10)

κ _ges＝κ _w+dκ/d[MeCl]·[MeCl]

κ in the formula _GesBe the ratio specific conductivity that adds water/alkali metal chloride dilute solution in the electrolysis reactor, κ _wBe each ratio specific conductivity that adds water to be sterilized, [MeCl] is the alkali metal chloride concentration of water/alkali metal chloride dilute solution, and d κ/d[MeCl] be the slope of the water of linear calibration line than specific conductivity.

36. described method one of among the claim 1-35 is characterized in that, sterilizing agent is made in the water/ionogen dilute solution special use of the electrochemical activation that the anolyte compartment is produced.

37. described method one of among the claim 1-36 is characterized in that, this sterilizing agent is with simple basically form, or with 1: 500 at the most, especially 1: 400 part of thinner especially the diluent form of water use.

38. described method one of among the claim 1-37 is characterized in that continuous or semicontinuous the carrying out of this method.

39. described method one of among the claim 1-38 is characterized in that, this method water such as tap water and undrinkable water, rainwater, swimming-pool water, service water and trade effluent that is used to sterilize.

40. the described method of claim 39 is characterized in that, tells one shunting from water to be sterilized, and this stock stream is carried out electrochemical activation, and to the major general anolyte compartment the shunting of electrochemical activation add in the water to be sterilized as sterilizing agent.

41. by the sterilizing agent of water/ionogen dilute solution form described method preparation one of among the claim 1-40, that activated through the electrochemistry anode, its pH value is between 2.5-3.5.

42. the described sterilizing agent of claim 41 is characterized in that, its pH value is between 2.7-3.3, especially between 2.8-3.2.

43. claim 41 or 42 described sterilizing agents is characterized in that its redox potential is between 1240mV and 1360mV.

44. described sterilizing agent one of among the claim 41-43 is characterized in that its redox potential is between 1280mV-1360mV, especially between 1320mV-1360mV.

45. described Application of disinfectants one of among the claim 41-44, it is used for sterilized water, as tap water and undrinkable water, rainwater, swimming-pool water, process water and trade effluent.

46. described Application of disinfectants one of among the claim 41-44, it is used for sterilised foodstuff, as grain, seasonings, fruit, vegetables, ice-creams and animal product.

47. described Application of disinfectants one of among the claim 41-44, it is used for disinfection seed.

48. described Application of disinfectants one of among the claim 41-44, it is used for sterilised packing container and wrapping material, especially for health product, as food, medicine and sterilizing objects.

49. described Application of disinfectants one of among the claim 41-44, it is as the additive of solvent polymeric and emulsion polymerization medium.

50. described Application of disinfectants one of among the claim 41-44, it is as the additive of colored paint, varnish and pigment.

51. described Application of disinfectants one of among the claim 41-44, it is as refrigerant and lubricant additive.

52. described Application of disinfectants one of among the claim 41-44, it is as the additive of power fuel and fuel such as fuel oil, gasoline and kerosene.