CN103004868A - Low-corrosiveness oxidation potential sterilization water and preparation method thereof - Google Patents

Low-corrosiveness oxidation potential sterilization water and preparation method thereof Download PDF

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CN103004868A
CN103004868A CN2012105332714A CN201210533271A CN103004868A CN 103004868 A CN103004868 A CN 103004868A CN 2012105332714 A CN2012105332714 A CN 2012105332714A CN 201210533271 A CN201210533271 A CN 201210533271A CN 103004868 A CN103004868 A CN 103004868A
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copper
sterilized water
available chlorine
acid
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邵鹏飞
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Abstract

The invention relates to the field of sterilization and disinfection, and particularly relates to low-corrosiveness oxidation potential sterilization water and a preparation method thereof. The preparation method of the low-corrosiveness oxidation potential sterilization water comprises the following steps: (1) providing a pH regulator A unit; (2) providing an active chlorine provision unit B unit; and (3) mixing the A unit and the B unit to obtain a solution having strong oxidizing property, wherein the pH value of the solution having strong oxidizing property is 2-8, the oxidation-reduction potential is not lower than 600 mV, the active chlorine content is 3-5000 mg/L, and the total copper content is not higher than 2000 mg/L. Compared with the existing acidic oxidation potential water, the oxidation potential sterilization water provided by the invention can reduce corrosion to metal, thereby widening the application range.

Description

Oxidizing potential sterilized water of a kind of low-corrosiveness and preparation method thereof
Technical field
The present invention relates to the sterilizing field, particularly oxidizing potential sterilized water of a kind of low-corrosiveness and preparation method thereof.
Background technology
The concept of introducing redox potential in the sterilization field is to come from the acidic oxidized electric potential water generation machine of Japanese 20th century development and production eighties and the acidic oxidized electric potential water that is produced by the generation machine.Acidic oxidized electric potential water (is called for short: the water of EOW) refer to have high redox potential (ORP), low pH value characteristic and low concentration available chlorine (ACC).
The mechanism of acidic oxidized electric potential water sterilization is as follows:
At first, the microorganism of the most of kinds of occurring in nature lives in the environment of pH 4-9, and the pH value of acidic oxidized electric potential water can affect electric charge on the microbial biofilm and the absorption of nutriment, the activity of enzyme, and the toxicity of giving property or harmful substance of nutriment in the change environment, thereby quick killing microorganisms.
Secondly, because the distributions inside and outside microbial biofilm such as hydrogen ion, potassium ion, sodium ion are different, so that the inside and outside current potential of film has certain potential difference when reaching dynamic equilibrium, generally be about-700～+ 900mV.The inside and outside potential difference of the biomembrane of aerobic bacterium is generally+200～+ 800mV, and the inside and outside potential difference of the biomembrane of anaerobic bacteria is generally-700～+ 200mV.The factors such as the oxidation in the acidic oxidized electric potential water, reduction material and pH make its ORP be higher than 1100mV, have exceeded the scope of microorganism.Having high ORP (is to capture rapidly electronics behind the EOW contact microorganism of ORP＞1100mV), disturb the biomembrane balance, change biological transmembrane potential difference, the inside and outside osmotic pressure of film, the destruction that causes the enhancing of biomembrane permeability, cellular swelling and cellular metabolism enzyme, make intracellular organic matter overflow, dissolve, thus quick killing microorganisms.
At last, available chlorine can make the permeability of cell change, or biomembrane generation mechanicalness is broken, and impels the cell Dissolve things inside outwards to ooze out, and causes bacterium dead.And hypochlorous acid is neutral small-molecule substance, easily invades in the cell with protein generation oxidation or destroys its phosphate dehydrogenase, makes the glycometabolism imbalance cause bacterium dead, thus quick killing microorganisms.
The sterilizing ability of EOW system is to take as the leading factor with ACC, and low pH value and high ORP are the synergistic result of three of important promotion.This systematic collaboration effect far above single ACC, low pH value and high ORP effect simply add and, its ACC is higher, the pH value is lower, ORP is higher, the system synthesis sterilization effect is just better.
But existing acid oxidation potential sterilized water has general metal protection.
Summary of the invention
The first purpose of the present invention is to provide a kind of preparation method of oxidizing potential sterilized water of low-corrosiveness, has the technical matters of general metal protection to solve acid oxidation potential sterilized water of the prior art.
The second purpose of the present invention is to provide a kind of oxidizing potential sterilized water of low-corrosiveness, has the technical matters of general metal protection to solve acid oxidation potential sterilized water of the prior art.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of oxidizing potential sterilized water of low-corrosiveness may further comprise the steps:
(1) provides pH adjusting agent A unit;
(2) provide available chlorine that the unit B unit is provided;
(3) described A unit is mixed with described B unit, obtain strong oxidizing property solution, the pH value of described strong oxidizing property solution is between 2-8, and its redox potential is not less than 600mV, and its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
Preferably, the total copper in the described strong oxidizing property solution mainly comprises one or several in cupric, monovalence copper and the zerovalent copper.
Preferably, in step (1), also comprise: the preliminary treatment that part copper is removed in described A unit.
Preferably, in step (2), also comprise: the preliminary treatment that part copper is removed in described B unit.
Preferably, in step (3), also comprise: the post processing that the mixed mixed liquor in described A unit and described B unit is removed part copper.
Preferably, the pretreated method of part copper being removed in described A unit can be selected from and add in deactivator, membrane separation process, electrochemical process, chromatography, absorption method or the ion-exchange one or several.
Preferably, the pretreated method of part copper being removed in described B unit can be selected from and add in deactivator, membrane separation process, electrochemical process, chromatography, absorption method or the ion-exchange one or several.
Preferably, the described method that the mixed mixed liquor in A unit and B unit is removed the post processing of part copper can be selected from and add in deactivator, membrane separation process, electrochemical process, chromatography, absorption method or the ion-exchange one or several.
Preferably, the processing mode of described removal part copper is the fast processing mode, or processes under the cryogenic conditions, or transfers B unit ionic available chlorine to molecule-type available chlorine; Or transfer ion copper to nonionic derivative, make it and ionic active ingredient is distinguished, remove the purpose impurity copper after, return to again the stable form of available chlorine.
Preferably, described A unit is acidity or alkalescent.
Preferably, described B contains the unit one or more in double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite, and described available chlorine precursor substance refers to can generate with acid or water reaction the chlorine-bearing compound of available chlorine.
Preferably, described B unit is neutral or alkaline.
A kind of oxidizing potential sterilized water of low-corrosiveness comprises the A unit and the B unit that use front independent packing, and described A unit is pH adjusting agent; Described B unit provides the unit for available chlorine, described A unit with obtain strong oxidizing property solution after described B unit mixes, the pH value of described strong oxidizing property solution is between 2-8, its redox potential is not less than 600mV, its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
Preferably, the total copper in the described strong oxidizing property solution mainly comprises one or several in cupric, monovalence copper and the zerovalent copper.
Preferably, described B contains the unit one or more in double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite, and described available chlorine precursor substance refers to can generate with acid or water reaction the chlorine-bearing compound of available chlorine.
Preferably, described B unit is neutral or alkaline.
A kind of oxidizing potential sterilized water of low-corrosiveness, the pH value of described sterilized water is between 2-8, and its redox potential is not less than 600mV, and its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
Preferably, the total copper in the described sterilized water mainly comprises one or several in cupric, monovalence copper and the zerovalent copper.
Preferably, contain one or several of inorganic acid, organic acid, inorganic base, organic base, strong acid weak base salt, strong base-weak acid salt, weak acid and weak base salt or strong acid and strong base salt in the described sterilized water.
Preferably, available chlorine in the described sterilized water is by one or more generations of double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite, and described available chlorine precursor substance refers to can generate with acid or water reaction the chlorine-bearing compound of available chlorine.
Compare with existing acid oxidation potential sterilized water, the present invention has following advantage:
1, oxidizing potential sterilized water of the present invention can reduce corrosion of metal, thereby has enlarged range of application;
2, before use, A unit and the B unit of oxidizing potential sterilized water of the present invention are deposited separately, in the time will using, A unit and B unit are mixed again, and have solved the storage problem of oxidizing potential sterilized water, and be very easy to use;
3, in the process of preparation oxidizing potential sterilized water of the present invention, strengthen artificial controllability, can regulate according to the actual requirements pH value, available chlorine content and the redox potential of sterilized water.
Description of drawings
Fig. 1 is in the environment of pH=2.0-8.0, and the pH/ cupric is to copper corrosion effect schematic diagram;
Fig. 2-3 is in the oxidative environment of pH=2.0-8.0, and available chlorine and cupric synergy are to the schematic diagram of copper corrosion effect;
Fig. 4-5 is in the oxidative environment of pH=2.0-8.0, and pH and cupric synergy are to the schematic diagram of copper corrosion effect;
Fig. 6-9 is in the oxidative environment of pH=2.0-8.0, and the copper of different valence state is to the schematic diagram of copper corrosion effect;
Figure 10-13 is in the oxidative environment of pH=2.0-8.0, and the different total copper that form are to the schematic diagram of copper corrosion effect;
Figure 14 is in the oxidative environment of pH=2.0-8.0, and the hybrid mode of different A, B unit is to the schematic diagram that concerns of copper corrosion.
Embodiment
Below describe the present invention.
At present, for the acid oxidation potential sterilized water corrosion of metal has been launched Primary Study, the result who has announced shows that acidic oxidized electric potential water has general metal protection.But the research on mechanism to its corrosion does not carry out, and its corrosivity is considered to usually that peracid acidity (pH2-3) causes, even thinks that nearly neutral electrolyzed oxidizing water can avoid metal erosion.The result who has announced shows acidic oxidized electric potential water, to stainless steel substantially without corroding to mild corrosion, to carbon steel, copper, aluminium moderate to heavy corrosion, its conclusion widely different.
Acidic oxidized electric potential water mainly is that three aspect factor causes to corrosion of metal, the one, and system is acid, the replacing hydrogen reaction of hydrogen ion and active metal (iron, magnesium, zinc etc.); The 2nd, the oxidisability of system (available chlorine); The 3rd, the impact of other ion in the system.But acid and oxidisability is the physics and chemistry speciality of acidic oxidized electric potential water, also is the decisive factor of bactericidal property, and therefore, in a sense, bactericidal property and corrosion of metal are the paradox of coexistence.
Compare with electrolysis, chemical method prepares oxidizing potential solution, and by calculating the constituent content that can control in the solution, the Material Source of its A, B unit is wider general.But also caused the source of the impurity of introducing in the solution more complicated.
Below discuss total copper and the cupric corrosivity in the oxidative environment of pH=2-8.
Described cupric refers to that chemical valence state is the summation of copper of all forms of positive divalent.Described total copper refers to the summation of copper of all forms of various chemical valence states.
Chemical method prepares oxidizing potential solution, and the introducing of copper mainly contains three kinds of approach in the system, and one itself contains in employed acid-base modifier and the available chlorine or produces copper, such as copper chloride or hypochlorous acid copper or Kocide SD etc.; Its two, use and carry cupric impurity in the raw material secretly; Its three, the component of other effects of cupric is such as thickener, stabilizing agent, hardening agent etc.
Cupric is undertaken by following basic mode copper corrosion,
Cu 2++Cu＝2Cu +——1
Cu ++[O]＝Cu 2++e——2
In normal temperature, neutrality and non-oxidizable solution, reaction 2 be slowly, above-mentioned serial reaction can be understood as simple cupric corrosive effect and depends on cupric initial content (reaction 1), when cupric ran out, corrosion process finished.When cupric content was relatively stable, its corrosive effect changed little, and perhaps the corrosive effect that slowly carries out along with reaction 2 slowly strengthens.
In electrolyzed oxidizing water, the environment of the introducing of available chlorine and low pH, accelerated to react 2 carrying out, promoted metal and cupric direct product monovalence copper again to change cupric into, reduced cupric reduction, cupric content continues to increase state in the system in to the process of copper corrosion thereby make, and then has aggravated reaction 1 and carried out.
As from the foregoing, contain cupric electrolyzed oxidizing water, cupric and hydrogen ion and available chlorine interact, and the system that affected greatly is to corrosion of metal.
Simultaneously as can be known, monovalence copper or zerovalent copper (perhaps monovalence copper, the zerovalent copper in total copper) in stable environment be do not have corrosive, but in the oxidative environment of pH=2-8, monovalence copper constantly changes cupric (reaction 2) into, and form dynamically with cupric, the coexisting body of balance; Also there is cupric trend that is oxidized to simultaneously in zerovalent copper.Therefore, actual cupric amount that generates, the speed that namely changes and the amount of conversion of depending on of the corrosivity of monovalence copper and zerovalent copper.Can know also that thus always copper corrosion is actual is determined by cupric.So in the identical situation of total copper content, the active descending order of total copper corrosion is total copper that the zerovalent copper of total copper 〉=different proportion that 100% cupric forms, monovalence copper, cupric form; Again because monovalence copper is converted into the conversion trend that cupric trend is far longer than zerovalent copper, so total copper that total copper that total copper that 100% cupric forms＞100% monovalence copper forms＞100% zerovalent copper forms; Total copper that total copper that the monovalence copper of total copper 〉=different proportion that 100% monovalence copper forms and zerovalent copper form 〉=100% zerovalent copper forms.Because monovalence copper, zerovalent copper itself do not have corrosivity, and the constantly decay in oxidative environment of monovalence copper, therefore with the content of cupric content or total copper represent to have the copper of catalyzed corrosion more convenient with accurately.
See also Fig. 1, show among the figure: in the system of pH=2-8, the rising of hydrogen ion concentration makes system rise to some extent to corrosion of metal.Simultaneously as seen, cupric adding and content increase have increased system to corrosion of metal.Simultaneously as seen, hydrogen ion and cupric synergy have strengthened system to corrosion of metal.
See also Fig. 2-Fig. 3, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, cupric and available chlorine synergy, the system that affected makes system produce hop to metal protection to corrosion of metal.Wherein, different available chlorine content (3-5000ppm) during cupric concentration＞2000ppm, all can produce the hop to metal protection.Simultaneously as can be known, the reduction of available chlorine has reduced system to corrosion of metal, and has reduced the hop significance.
See also Fig. 4-Fig. 5, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, cupric and hydrogen ion synergy, the system that affected makes system produce hop to metal protection to corrosion of metal.Wherein, in the scope of pH2-8, during cupric concentration＞2000ppm, all can produce the hop to metal protection.Simultaneously as can be known, acid reduction has reduced system to corrosion of metal, and has reduced the hop significance.
Comparison diagram 1-Fig. 5 can reach a conclusion, and in the scope of pH=2-8, the metal protection of oxidizing potential sterilized water can be controlled or reduce to control cupric content at 3-5000ppm, at 0-2000ppm and available chlorine content.
Chemical method preparation oxidizing potential sterilized water, relating to Cu morphology and valence state has multiplely, as with typoiogical classification, then comprises copper oxide, free copper ion, slightly solubility mantoquita, with the chemical valence classification, then comprises zerovalent copper, monovalence copper, cupric.
See also Fig. 6-Fig. 9, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, available chlorine (3-5000ppm) acts synergistically with the copper of different valence state, to the similar characteristic of the active generation of corrosion of metal.The increase of copper content makes system produce hop to metal protection.Its corrosion activity is cupric＞monovalence copper＞zerovalent copper from large extremely little order.Wherein, cupric corrosion activity is the strongest, and it produces the concentration minimum (2000ppm) of corrosivity hop.The copper of other valence state, along with activity decreased, the concentration increase that corrosion activity reduces or hop is required (＞2000ppm).
See also Figure 10-Figure 13, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, available chlorine (3-5000ppm) acts synergistically from total copper of different compositions, to the similar characteristic of the active generation of corrosion of metal.The increase of total copper content makes system produce hop to metal protection.The different total copper that form have different corrosion activities, wherein, cupric corrosion activity is the strongest, the concentration minimum (2000ppm) of the total copper corrosion hop that therefore fully is comprised of cupric, under the same amount, its corrosivity is greater than total copper of the copper that contains other valence states.
Comparison diagram 1-Fig. 5 as can be known, when the metal protection of oxidizing potential sterilized water be controlled or be reduced to control cupric content (0-2000ppm) and available chlorine content (3-5000ppm) can, comparison diagram 6-Figure 13 so, control total copper content at 0-2000ppm and available chlorine content at 3-5000ppm, can control or reduce equally the metal protection of oxidizing potential sterilized water.
We know that free chlorine or its derivative can strengthen oxidisability and the bactericidal property of system.The A unit is added the B unit, can reduce to a certain extent the oxidisability of mixed liquor, reduced simultaneously the risk of the safety of the free chlorine band of gas.Therefore, preferentially take the A unit is added the addition manner of B unit.As shown in figure 14, the hybrid mode by control A, B unit adds the B unit with the A unit, can to a certain degree reduce corrosion of metal.The A unit is added the B unit, can take disposable adding or add in batches or slowly add or spray to add or the dropping mode.
As from the foregoing, the electrolyzed oxidizing water that contains cupric or total copper, cupric (perhaps the cupric in total copper and can be converted into cupric monovalence copper and zerovalent copper) interacts with hydrogen ion and available chlorine, and the system that affected greatly is to corrosion of metal.
The invention provides a kind of preparation method of oxidizing potential sterilized water of low-corrosiveness, may further comprise the steps:
(1) provides pH adjusting agent A unit;
(2) provide available chlorine that the unit B unit is provided;
(3) the A unit is mixed with the B unit, obtain strong oxidizing property solution, the pH value of strong oxidizing property solution is between 2-8, and its redox potential is not less than 600mV, and its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
The present invention also provides a kind of oxidizing potential sterilized water of low-corrosiveness, comprises A unit and the B unit of independent packing before using, and the A unit is pH adjusting agent; The B unit provides the unit for available chlorine, the A unit with obtain strong oxidizing property solution after the B unit mixes, the pH value of strong oxidizing property solution is between 2-8, its redox potential is not less than 600mV, its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
The A unit is acid or weakly alkaline solid or liquid, and wherein the pH value of liquid is preferably between 0-8, is preferably again between 1-6, is preferably between 1-5 again, also is preferably between 2-4, most preferably is between 2-3.
The A unit is selected from the combination of acidic materials or alkaline matter or acidic materials and alkaline matter.One or several of the optional precursor from inorganic acid, organic acid, strong acid weak base salt or acidic materials of its middle acid substance.Inorganic acid can be selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, chloric acid, perchloric acid, bromic acid, hyperbromic acid, metaperiodic acid, metaphosphoric acid, permanganic acid, hydrogen borate, the acid of hydrogen astatine, hydrogen telluric acid, the folded acid iodide of hydrogen, fluosilicic acid, chlorine plumbic acid, osmic acid, selenic acid, ferric acid, fluosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, niter cake, sulfurous acid or nitrous acid.Organic acid is optional from picric acid, Jiao's property picric acid, trifluoroacetic acid, trichloroacetic acid, acetic acid, formic acid, methanesulfonic acid, benzene sulfonic acid, KMD acid, 2-chloroethene mercaptan, ethanedioic acid, malonic acid, succinic acid, lactic acid, pyruvic acid, tartaric acid, malic acid, citric acid, benzoic acid, salicylic acid or caffeic acid.Common strong acid weak base salt is generally the strong acid salt of transition metal or the strong acid salt of amine substance, such as aluminium chloride, iron chloride, aluminum sulfate, iron sulfate, copper nitrate or ammonium chloride.The precursor of acidic materials refers to can be converted into the material of acidic materials in solution, such as the chloride derivative of acid, such as succinyl chloride.Wherein alkaline matter can be selected from one or several of inorganic base, organic base, strong base-weak acid salt.Inorganic base can be selected from alkali-metal hydroxide, such as sodium hydroxide, potassium hydroxide etc., also can be selected from the hydroxide of alkaline earth metal, such as slaked lime, barium hydroxide, magnesium hydroxide etc., also can be selected from the hydroxide of transition metal, such as zinc hydroxide, iron hydroxide etc.Organic base is optional from nitrogen substance, such as ammoniacal liquor, diethanol amine, triethylamine, natural alkaloid etc.Strong base-weak acid salt is such as sodium carbonate, sodium acetate, sodium phosphate, sodium citrate etc.The combined optional of its middle acid substance and alkaline matter is from the combination of weak acid and weak base salt such as ammonium citrate or strong acid weak base salt and strong base-weak acid salt or the combination of weak acid and its conjugate base.
The B unit can contain one or more in double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite.Hypochlorite can be selected from one or more of clorox, calcium hypochlorite, bleaching powder, bleaching powder extraction, magnesium hypochlorite.The double salt of hypochlorite can be selected from Efficacious Disinfeitant (Na 3PO 41/4NaOCl12H 2O).Chlorite can be selected from sodium chlorite, calcium chlorite.The available chlorine precursor substance refers to can generate with acid or water reaction the chlorine-bearing compound of activated state available chlorine, and its stability in the B unit is higher than in the mixed liquor of A, B unit, and the available chlorine precursor substance can be selected from one or more of sodium dichloro cyanurate, dichlord isocyanurice acid, sym-closene, toluene-sodium-sulfonchloramide, chlorate, perchlorate.
The available chlorine of B unit is the stable form of available chlorine.The available chlorine of stable form refers to have better stability in the B unit, reacts the chlorine-bearing compound that can generate activated state available chlorine with acid or water.Available chlorine content should guarantee that the available chlorine content in A, the B unit mixed liquor is 3-5000mg/L in the B unit.
Available chlorine content is 3-5000mg/L in A unit and the B unit mixed liquor, wherein is preferably 3-4000mg/L, is preferably 3-3000mg/L again, also is preferably 3-2000mg/L, is preferably again 3-1000mg/L, most preferably is 30-500mg/L.
The B unit is neutral or alkaline solid or liquid, and wherein liquid is preferably pH and is not less than 8, is preferably pH again and is not less than 9, also is preferably pH and is not less than 10, is preferably again pH and is not less than 11, and more preferably pH is not less than 12, most preferably is pH and is not less than 13.
The pH control of B unit can be one or several of highly basic, middle highly basic, weak base or strong base-weak acid salt.The contained alkaline matter in B unit can be selected from alkali-metal hydroxide, such as sodium hydroxide, potassium hydroxide etc., also can be selected from the hydroxide of alkaline earth metal, such as slaked lime, barium hydroxide, magnesium hydroxide etc., also can be selected from the hydroxide of transition metal, such as zinc hydroxide, iron hydroxide etc., also can be selected from nitrogen substance, such as ammoniacal liquor, diethanol amine, triethylamine etc., also optional from the highly basic salt of weak acid, such as sodium carbonate, sodium acetate, sodium phosphate, sodium citrate etc.
The pH value of A unit and B unit mixed liquor wherein is preferably 3-8 between 2-8, be preferably 4-8 again, also is preferably 5-8, most preferably is 6-8.
Total copper content is not higher than 2000mg/L in A unit and the B unit mixed liquor, wherein is preferably not to be higher than 1750mg/L, is preferably not to be higher than 1500mg/L again, is preferably again not to be higher than 1250mg/L, also is preferably not to be higher than 750mg/L, most preferably is not to be higher than 500mg/L.
Control the method for total copper and cupric content, one is controlled total copper and cupric content of material in the AB unit mixed liquor by volume and the inherent component of adjusting A, B unit; Its two, by the preliminary treatment of A or (reaching) B unit, remove the total copper of part and cupric; Its three, by the post processing of AB unit mixed liquor, remove the total copper of part and cupric.
The total copper of described removal and cupric method can be selected one or several of following method, to remove or the total copper of masked segment and cupric.Can add total copper or cupric deactivator, such as precipitating reagent and Cu 2+Form precipitation-OH -, CO 3 2-, S 2-, such as chelating agent and Cu 2+Form large molecule chelate-EDTA; Also can utilize membrane separation process, such as reverse osmosis membrane, ion-selective membrane, filtration, ultrafiltration, nanofiltration; Also can utilize electrochemical process, such as electroosmose process, electrolysis; Also can utilize chromatography, absorption method or ion-exchange.
Contain the solution of available chlorine when reducing total copper or cupric by said method, available chlorine has certain loss usually, and its content need to redeterminate.In order to reduce the loss of available chlorine, can select the fast processing mode; Also can select to process under the cryogenic conditions; Also B unit ionic available chlorine can be transferred to molecule-type available chlorine (acidity), make it to distinguish with ionic substance; Also can transfer ion copper to nonionic derivative, make it with ionic active ingredient (as, hydrogen ion, clorox) distinguish.After removing purpose impurity (total copper or cupric), return to again stable form or the activation form of available chlorine.
The present invention also provides a kind of oxidizing potential sterilized water of low-corrosiveness, and the pH value of sterilized water is between 2-8, and its redox potential is not less than 600mV, and its available chlorine content is 3-5000mg/L, and its total copper content is not higher than 2000mg/L.
Its pH value is 2-8, wherein is preferably between 3-8, is preferably again between 4-8, is preferably between 5-8 again, most preferably is between 5-7.
The control of its pH value, can be separately by acidic materials or alkaline matter control or by acidic materials and alkaline matter co-controlling, make the oxidizing potential sterilized water of low-corrosiveness contain one or several of inorganic acid, organic acid, strong acid weak base salt, inorganic base, organic base, strong base-weak acid salt, weak acid and weak base salt or strong acid and strong base salt.
Described acidic materials can be selected from one or several of precursor of inorganic acid, organic acid, strong acid weak base salt, weak acid and weak base salt or acidic materials.Inorganic acid can be selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, chloric acid, perchloric acid, bromic acid, hyperbromic acid, metaperiodic acid, metaphosphoric acid, permanganic acid, hydrogen borate, the acid of hydrogen astatine, hydrogen telluric acid, the folded acid iodide of hydrogen, fluosilicic acid, chlorine plumbic acid, osmic acid, selenic acid, ferric acid, fluosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, niter cake, sulfurous acid or nitrous acid.Organic acid is optional from picric acid, Jiao's property picric acid, trifluoroacetic acid, trichloroacetic acid, acetic acid, formic acid, methanesulfonic acid, benzene sulfonic acid, KMD acid, 2-chloroethene mercaptan, ethanedioic acid, malonic acid, succinic acid, lactic acid, pyruvic acid, tartaric acid, malic acid, citric acid, benzoic acid, salicylic acid or caffeic acid.Common strong acid weak base salt is generally the strong acid salt of transition metal or the strong acid salt of amine substance, such as aluminium chloride, iron chloride, aluminum sulfate, iron sulfate, copper nitrate or ammonium chloride.The precursor of acidic materials refers to can be converted into the material of acidic materials in solution, such as the chloride derivative of acid, such as succinyl chloride.
Described alkaline matter can be one or several of inorganic base, organic base, strong base-weak acid salt or weak acid and weak base salt.Inorganic base can be selected from alkali-metal hydroxide, such as sodium hydroxide, potassium hydroxide etc., also can be selected from the hydroxide of alkaline earth metal, such as slaked lime, barium hydroxide, magnesium hydroxide etc., also can be selected from the hydroxide of transition metal, such as zinc hydroxide, iron hydroxide etc.; Organic base is optional from nitrogen substance, such as ammoniacal liquor, diethanol amine, triethylamine, natural alkaloid etc.; Strong base-weak acid salt is such as sodium carbonate, sodium acetate, sodium phosphate, sodium citrate etc.
Described weak acid and weak base salt such as ammonium citrate, or the combination of strong acid weak base salt and strong base-weak acid salt.
Contained available chlorine can be by one or more generations of double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite.Hypochlorite can be selected from one or more of clorox, calcium hypochlorite, bleaching powder, bleaching powder extraction, magnesium hypochlorite.The double salt of hypochlorite can be selected from Efficacious Disinfeitant (Na 3PO 41/4NaOCl12H 2O).Chlorite can be selected from sodium chlorite, calcium chlorite.The available chlorine precursor substance refers to can generate with the reaction of acid or water the chlorine-bearing compound of activated state available chlorine, and the available chlorine precursor substance can be selected from one or more of sodium dichloro cyanurate, dichlord isocyanurice acid, sym-closene, toluene-sodium-sulfonchloramide, chlorate, perchlorate.
Its available chlorine content 3-5000mg/L wherein is preferably 3-4000mg/L, is preferably 3-3000mg/L again, is preferably again 3-2000mg/L, and more preferably 3-1000mg/L most preferably is 30-500mg/L.
Its total copper content is not higher than 2000mg/L, wherein is preferably not to be higher than 1750mg/L, is preferably not to be higher than 1500mg/L again, is preferably again not to be higher than 1250mg/L, also is preferably not to be higher than 1000mg/L, most preferably is not to be higher than 500mg/L.
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1: configuration 1000L highly acid oxidizing potential sterilized water (available chlorine content is 3mg/L)
Raw material A: citric acid-sodium citrate buffer (pH2-3), measure 1000L, can, sealing gets A unit (containing cupric 5g).
Raw material B: sodium dichloro cyanurate (available chlorine 0.25g/g), take by weighing 12g, packing gets B unit (the about 3g of available chlorine).
During use, the A unit is mixed with the B unit, make the dissolving of B unit, make 1000L highly acid oxidizing potential sterilized water (pH2-3, ORP1030-1130mV, ACC3mg/L, total copper 5mg/L, wherein cupric 5mg/L).At this moment, contain organic monoacid, strong base-weak acid salt in the solution.
Embodiment 2: configuration 1000L faintly acid oxidizing potential sterilized water (available chlorine content is 30mg/L)
Raw material A: lactic acid-sodium lactate buffer solution (pH3-5), measure 1000L, can, sealing gets A unit (containing cupric 24g).
Raw material B: sodium dichloro cyanurate (available chlorine 0.25g/g), take by weighing 120g, packing gets B unit (the about 30g of available chlorine contains cupric 1g).
During use, the B unit is added the A unit, make the dissolving of B unit, make 1000L faintly acid oxidizing potential sterilized water (pH3-5, ORP1000-1100mV, ACC30mg/L, total copper 25mg/L, wherein cupric 25mg/L).At this moment, the pH of solution is by acidic materials and alkaline matter co-controlling.
Embodiment 3: configuration 1000L subacidity oxidizing potential sterilized water (available chlorine content is 500mg/L)
Raw material A: phosphoric acid-buffer solution of sodium phosphate (pH5-7), measure 1000L, can, sealing gets the A unit.
Raw material B: sodium dichloro cyanurate (available chlorine 0.25g/g), take by weighing 2Kg, packing gets B unit (the about 500g of available chlorine contains cupric 50g).
During use, the A unit is added the B unit, make the dissolving of B unit, make 1000L subacidity oxidizing potential sterilized water (pH5-7, ORP900-1100mV, ACC500mg/L, total copper 50mg/L, wherein cupric 50mg/L).At this moment, contain inorganic acid, strong base-weak acid salt in the solution.
Embodiment 4: configuration 1000L faintly acid oxidizing potential sterilized water (available chlorine content is 1000mg/L)
Raw material A: aqueous sulfuric acid (pH2.5), measure 1000L, can, sealing gets A unit (containing monovalence copper 75g).
Raw material B: toluene-sodium-sulfonchloramide (available chlorine 0.25g/g), take by weighing 4Kg, add 120g sodium hydroxide, hybrid packed, get B unit (the about 1Kg of available chlorine).
During use, the A unit is slowly added B unit (being not less than 15 minutes), make B unit dissolving, make 1000L faintly acid oxidizing potential sterilized water (pH3-4, ORP1100-1200mV, ACC1000mg/L, total copper 75mg/L, wherein monovalence copper≤75mg/L).At this moment, contain strong acid, strong acid and strong base salt in the solution.
Embodiment 5: configuration 1000L subacidity oxidizing potential sterilized water (available chlorine content is 2000mg/L)
Raw material A: aqueous sulfuric acid (pH2.5), measure 500L, aqueous hydrochloric acid solution (pH2.5) is measured 500L, and two kinds of acid solutions are mixed, and packing gets A unit (containing monovalence copper 90g).
Raw material B: sym-closene (available chlorine 0.4g/g), take by weighing 5Kg, add 168g sodium carbonate, mix packing, get B unit (the about 2Kg of available chlorine contains monovalence copper 10g).
During use, the A unit is added the B unit in batches, make the dissolving of B unit, every crowd of addition 100L makes 1000L subacidity oxidizing potential sterilized water (pH5-7, ORP1100-1200mV, ACC2000mg/L, total copper 100mg/L, wherein monovalence copper≤100mg/L.
Embodiment 6: configuration 1000L subacidity oxidizing potential sterilized water (available chlorine content is 5000mg/L)
Raw material A: aqueous sulfuric acid (pH4.0), measure 1000L, add 1mol aluminium chloride, after the dissolving, can, sealing gets the A unit.
Raw material B: solid chlorine dioxide (available chlorine 0.2g/g), take by weighing 25Kg, add 17g sodium carbonate, mix packing, get B unit (the about 5Kg of available chlorine contains monovalence copper 150g).
During use, the A unit is added the B unit in batches, every crowd of addition 50L makes 1000L subacidity oxidizing potential sterilized water (pH5-7, ORP1100-1200mV, ACC5000mg/L, total copper 150mg/L, wherein monovalence copper≤150mg/L).
Embodiment 7: configuration 10L highly acid oxidizing potential sterilized water (available chlorine content is 3mg/L)
Raw material A: aqueous hydrochloric acid solution (pH2-3), measure 9.99L, can, sealing gets A unit (containing zerovalent copper 2g).
Raw material B: stable ClO 2 solution (sodium hydroxide is regulated for available chlorine 3mg/ml, pH10-11), measure 10ml, can, sealing gets B unit (available chlorine 30mg).
During use, the A unit is mixed with the B unit, make 10L highly acid oxidizing potential sterilized water (pH2-3, ORP1050-1150mV, ACC3mg/L, total copper 200mg/L, wherein zerovalent copper 200mg/L).At this moment, contain strong acid, strong acid and strong base salt in the solution.
Embodiment 8: configuration 10L faintly acid oxidizing potential sterilized water (available chlorine content is 250mg/L)
Raw material A: aqueous hydrochloric acid solution (pH3-3.5), measure 9.9L, can, sealing gets A unit (containing zerovalent copper 2g).
Raw material B: liquor natrii hypochloritis's (sodium hydroxide is regulated for available chlorine 25mg/ml, pH=10-11), measure 0.1L, can, sealing gets B unit (available chlorine 2.5g contains zerovalent copper 0.5g).
During use, the A unit is mixed with the B unit, make 10L faintly acid oxidizing potential sterilized water (pH3-5, ORP1000-1100mV, ACC250mg/L, total copper 250mg/L, wherein zerovalent copper 250mg/L).
Embodiment 9: configuration 10L subacidity oxidizing potential sterilized water (available chlorine content is 1000mg/L)
Raw material A: aqueous hydrochloric acid solution (pH5.0-6.0), measure 9L, can, sealing gets the A unit.
Raw material B: liquor natrii hypochloritis's (sodium hydroxide is regulated for available chlorine 10mg/ml, pH=7.5), measure 1L, can, sealing gets B unit (available chlorine 10g contains zerovalent copper 3g).
During use, the B unit is added the A unit, make 10L subacidity oxidizing potential sterilized water (pH5-7, ORP1000-1100mV, ACC1000mg/L, total copper 300mg/L, wherein zerovalent copper 300mg/L).At this moment, contain strong acid, strong acid and strong base salt in the solution.
Embodiment 10: configuration 10L faintly acid oxidizing potential sterilized water (available chlorine content is 1500mg/L)
Raw material A: aqueous hydrochloric acid solution (pH2-2.5), measure 9L, can, sealing gets A unit (containing cupric 3g).
Raw material B: liquor natrii hypochloritis's (sodium hydroxide-sodium carbonate is regulated for available chlorine 15mg/ml, pH=12.5), measure 1L, can, sealing gets B unit (available chlorine 15g contains monovalence copper 0.5g).
During use, the A unit is added the B unit, mix, make 10L faintly acid oxidizing potential sterilized water (pH3-5, ORP1050-1200mV, ACC1500mg/L, total copper 350mg/L, wherein cupric 300mg/L, monovalence copper 50mg/L).At this moment, contain strong acid, weak acid, strong acid and strong base salt, strong base-weak acid salt in the solution.
Embodiment 11: configuration 10L subacidity oxidizing potential sterilized water (available chlorine content is 2000mg/L)
Raw material A: aqueous hydrochloric acid solution (pH=3-3.5), measure 9.8L, can, sealing gets A unit (containing monovalence copper 3.5g).
Raw material B: liquor natrii hypochloritis's (slaked lime is regulated for available chlorine 100mg/ml, pH=12), measure 200ml, can, sealing gets B unit (available chlorine 20g contains cupric 0.5g).
During use, the A unit is added the B unit in batches, every crowd of addition 50ml makes 10L subacidity oxidizing potential sterilized water (pH5-7, ORP1000-1200mV, ACC2000mg/L, total copper 400mg/L, wherein cupric 50mg/L, monovalence copper 350mg/L).
Embodiment 12: configuration 10L subacidity oxidizing potential sterilized water (available chlorine content is 2500mg/L)
Raw material A: aqueous hydrochloric acid solution (pH2-3), measure 9.75L, can, sealing gets A unit (containing cupric 4g, monovalence copper 0.5g).
Raw material B: liquor natrii hypochloritis's (diethylamine is regulated for available chlorine 100mg/ml, pH=12), measure 250ml, can, sealing gets B unit (available chlorine 25g).
During use, the A unit is slowly added B unit (time is not less than 1 minute), make 10L subacidity oxidizing potential sterilized water (pH5-7, ORP1000-1200mV, ACC2500mg/L, total copper 450mg/L, wherein cupric 400mg/L, monovalence copper 50mg/L).
Embodiment 13: configuration 10L highly acid oxidizing potential sterilized water (available chlorine content is 3000mg/L)
Raw material A: aqueous hydrochloric acid solution (pH2.0-3.0), measure 9L, can, sealing gets the A unit.
Raw material B: the hypochlorite generator prepares liquor natrii hypochloritis's (sodium bicarbonate is regulated for available chlorine 30mg/ml, pH=8.0), measures 1L, can, and sealing gets B unit (available chlorine 30g contains cupric 4.5g, monovalence copper 0.5g).
During use, A unit slow (being no less than 5 minutes) is added the B unit, make 10L highly acid oxidizing potential sterilized water (pH2-3, ORP1200-1400mV, ACC3000mg/L, total copper 500mg/L, wherein cupric 450mg/L, monovalence copper 50mg/L).
Embodiment 14: configuration 10L faintly acid oxidizing potential sterilized water (available chlorine content is 3500mg/L)
Raw material A: acetic acid aqueous solution (pH3.0-4.0), measure 9.65L, add 0.001mol aluminium chloride, after the dissolving, packing gets A unit (containing cupric 4g, monovalence copper 0.5g).
Raw material B: the hypochlorite generator prepares liquor natrii hypochloritis's (sodium carbonate is regulated for available chlorine 0.1g/ml, pH=8.5), measures 350ml, and packing gets B unit (available chlorine 35g contains cupric 1g).
During use, the spraying of A unit is added the B unit, make 10L faintly acid oxidizing potential sterilized water (pH3-5, ORP1000-1200mV, ACC3500mg/L, total copper 550mg/L, wherein cupric 500mg/L, monovalence copper 50mg/L).At this moment, contain weak acid-weak acid strong alkali salt buffer system in the solution.
Embodiment 15: configuration 10L subacidity oxidizing potential sterilized water (available chlorine content is 4000mg/L)
Raw material A: acetic acid-sodium acetate solution (pH5.0-5.5), measure 9.6L, can, sealing gets A unit (containing cupric 3g, monovalence copper 2g).
Raw material B: the hypochlorite generator prepares liquor natrii hypochloritis's (aluminium hydroxide is regulated for available chlorine 0.1g/ml, pH=9.0), measures 0.4L, can, and sealing gets B unit (available chlorine 40g contains cupric 0.5g, monovalence copper 0.5g).
During use, the A unit is added dropwise to the B unit, makes 10L subacidity oxidizing potential sterilized water (pH5-7, ORP1000-1200mV, ACC4000mg/L, total copper 600mg/L, wherein cupric 350mg/L, monovalence copper 250mg/L).At this moment, contain acetic acid-sodium acetate buffer system in the solution.
Embodiment 16: configuration 10L faintly acid oxidizing potential sterilized water (available chlorine content is 5000mg/L)
Raw material A: acid solution (0.1M acetic acid, 0.01M hydrochloric acid), measure 9.5L, can, sealing gets A unit (containing cupric 6g).
Raw material B: the liquor natrii hypochloritis (available chlorine 0.1g/ml,, triethanolamine is regulated pH=14), measure 500ml, filling and sealing gets B unit (available chlorine 50g contains zerovalent copper 0.5g).
During use, the A unit is added the B unit, make 10L faintly acid oxidizing potential sterilized water (pH3-5, ORP1100-1300mV, ACC5000mg/L, total copper 650mg/L, wherein cupric 600mg/L, zerovalent copper 50mg/L).At this moment, contain acetic acid-sodium acetate buffer system in the solution.
Embodiment 17: configuration 10L acid oxidation potential sterilized water (available chlorine content is 3mg/L)
Raw material A: citric acid solution (0.01M), measure 9L, can, sealing gets A unit (containing zerovalent copper 6.9g).
Raw material B: liquor natrii hypochloritis's (available chlorine 30mg/L contains sodium hydroxide 0.24M), measure 1L, filling and sealing gets B unit (available chlorine 30mg contains cupric 0.1g).
During use, the A unit is added the B unit in batches, every crowd of 400ml makes 10L acid oxidation potential sterilized water (pH6.95, ORP700mV, ACC3mg/L, total copper 700mg/L, wherein cupric 10mg/L, zerovalent copper 690mg/L).At this moment, solution contains sal limonis buffer solution.
Embodiment 18: configuration 10L faintly acid oxidizing potential sterilized water (available chlorine content is 1000mg/L)
Raw material A: tartaric acid powder and succinic acid powder, respectively take by weighing 0.5mol, hybrid packed, get A unit (containing cupric 7g, zerovalent copper 0.5g).
Raw material B: sodium chlorite solution (available chlorine 1mg/ml, barium hydroxide is adjusted to pH=13), measure 10L, filling and sealing gets B unit (available chlorine 10g).
During use, the A unit is mixed with the B unit, make 10L acid oxidation potential sterilized water (pH3-5, ORP1100-1200mV, ACC1000mg/L, total copper 750mg/L, wherein cupric 700mg/L, zerovalent copper 50mg/L).At this moment, solution contains buffer solution.
Embodiment 19: configuration 10L highly acid oxidizing potential sterilized water (available chlorine content is 2000mg/L)
Raw material A: succinic acid solution (1M), measure 10L, can, sealing gets the A unit.
Raw material B: sodium dichloro cyanurate (available chlorine 0.25g/g), take by weighing 80g, get B unit (the about 20g of available chlorine contains cupric 3g, zerovalent copper 5g).
During use, the A unit is mixed with the B unit, make 10L acid oxidation potential sterilized water (pH2-3, ORP1200-1400mV, ACC2000mg/L, total copper 800mg/L, wherein cupric 300mg/L, zerovalent copper 500mg/L).
Embodiment 20: configuration 1L oxidizing potential sterilized water (available chlorine content is 4500mg/L)
Raw material A: the citric acid powder, take by weighing 0.04mol, the zinc chloride powder takes by weighing 0.02mol, and the succinyl chloride solid takes by weighing 0.01mol, and the three mixes (containing cupric 10mg, zerovalent copper 20mg).
Raw material B: calcium hypochlorite powder (available chlorine 0.2g/g) takes by weighing 22.5g (the about 4.5g of available chlorine contains cupric 10mg).
A raw material and B raw material and 0.2mol calcium chloride (desiccant contains cupric 10mg) are mixed the monobasic packing.
During use, above-mentioned composition is dissolved in the 1L water (containing cupric 0.8g), behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP1000-1400mV, ACC4500mg/L, total copper 850mg/L, wherein cupric 830mg/L, zerovalent copper 20mg/L).
Embodiment 21: configuration 1L acid oxidation potential sterilized water (available chlorine content is 5000mg/L)
Raw material A: liquor zinci chloridi (0.05M), measure 0.95L, can, sealing gets A unit (containing zerovalent copper 0.7g).
Raw material B: liquor natrii hypochloritis (pH=9), measure 50ml (available chlorine 5g), can, sealing gets B unit (available chlorine 5g contains cupric 0.1g, zerovalent copper 0.1g).
During use, the A unit is mixed with the B unit, make 1L acid oxidation potential sterilized water (pH3-5, ORP1100-1300mV, ACC5000mg/L, total copper 900mg/L, wherein cupric 100mg/L, zerovalent copper 800mg/L).
Embodiment 22: configuration 1L oxidizing potential sterilized water (available chlorine content is 400mg/L)
Raw material A: aluminum chloride solids, take by weighing 0.01mol, the zinc chloride powder takes by weighing 0.001mol, and both are hybrid packed, get A unit (containing cupric 5mg, zerovalent copper 5mg).
Raw material B: sodium chlorite solution (pH=9), measure 1L (available chlorine 400mg), can, sealing gets B unit (available chlorine 400mg wherein contains cupric 0.9g, zerovalent copper 40mg).
During use, the A unit is mixed with the B unit, behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP900-1200mV, ACC400mg/L, total copper 950mg/L, wherein cupric 905mg/L, zerovalent copper 45mg/L).
Embodiment 23: configuration 1L acid oxidation potential sterilized water (available chlorine content is 600mg/L)
Raw material A: liquor zinci chloridi (0.05M), measure 1L, can, sealing gets A unit (containing monovalence copper 990mg).
Raw material B: the Efficacious Disinfeitant solid, take by weighing 6g, packing gets B unit (available chlorine 0.6g contains zerovalent copper 10mg).
During use, the A unit is mixed with the B unit, make 1L acid oxidation potential sterilized water (pH2-3, ORP1100-1300mV, ACC600mg/L, total copper 1000mg/L, wherein monovalence copper 990mg/L, zerovalent copper 10mg/L).
Embodiment 24: configuration 1L oxidizing potential sterilized water (available chlorine content is 700mg/L)
Raw material A: the iron sulfate solid, take by weighing 0.03mol, succinyl chloride takes by weighing 0.02mol, and both mix (containing cupric 10mg).
Raw material B: calcium hypochlorite powder (available chlorine 0.25g/g) takes by weighing 2.8g (the about 700mg of available chlorine contains zerovalent copper 10mg).
The A raw material is mixed the monobasic packing with B raw material and 5g sodium acetate (containing monovalence copper 50mg).
During use, the AB composition is dissolved in the 1L water (containing cupric 1.18g), behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP900-1300mV, ACC700mg/L, total copper 1250mg/L, wherein cupric 1190mg/L, monovalence copper 50mg/L, zerovalent copper 10mg/L).Because calcium sulphate is poorly soluble, thus insoluble matter is arranged in the system, but do not affect the characteristic of its available chlorine, pH, ORP.
Embodiment 25: configuration 1L oxidizing potential sterilized water (available chlorine content is 800mg/L)
Raw material A: succinyl chloride, take by weighing 0.05mol, packing, sealing gets A unit (containing cupric 10mg, monovalence copper 10mg).
Raw material B: liquor natrii hypochloritis (pH=11, sodium hydroxide-sodium carbonate is regulated), measure 1L (available chlorine 800mg), can, sealing gets B unit (available chlorine 800mg contains zerovalent copper 1480mg).
During use, the A unit is added the B unit, dissolving, behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP900-1300mV, ACC800mg/L, total copper 1500mg/L, wherein cupric 10mg/L, monovalence copper 10mg/L, zerovalent copper 1480mg/L).
Embodiment 26: configuration 1L oxidizing potential sterilized water (available chlorine content is 4000mg/L)
Raw material A: the succinyl chloride powder, take by weighing 0.02mol, the citric acid powder takes by weighing 0.01mol, and both mix (containing cupric 5mg, monovalence copper 5mg, zerovalent copper 5mg).
Raw material B: calcium hypochlorite powder (available chlorine 0.25g/g), take by weighing 8g, toluene-sodium-sulfonchloramide (available chlorine 0.25g/g) takes by weighing 8g, hybrid packed (total available chlorine 4g contains cupric 10mg).
A, B raw material and 5g calcium chloride (desiccant contains cupric 5mg) are mixed the monobasic packing.
During use, above-mentioned composition is dissolved in the 1L water (containing cupric 1.72g), behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP1000-1400mV, ACC4000mg/L, total copper 1750mg/L, wherein cupric 1740mg/L, monovalence copper 5mg/L, zerovalent copper 5mg/L).
Embodiment 27: configuration 1000L highly acid oxidizing potential sterilized water (available chlorine content is 5000mg/L)
Raw material A: electrolysis produces acidic oxidized electric potential water (pH2-3, ACC decomposes rapidly), measures 1000L, can, and sealing gets A unit (containing cupric 800g, monovalence copper 70g, zerovalent copper 530g).
Raw material B: Efficacious Disinfeitant powder (available chlorine 0.1g/g) takes by weighing 25Kg, sodium dichloro cyanurate (available chlorine 0.25g/g), take by weighing 10Kg, mix, packing, get B unit (total available chlorine 5000g contains cupric 300g, zerovalent copper 300g).
During use, the A unit is mixed with the B unit, make 1000L acid oxidation potential sterilized water (pH2-3, ORP1200-1400mV, ACC5000mg/L, total copper 2000mg/L, wherein cupric 1100mg/L, monovalence copper 70mg/L, zerovalent copper 830mg/L).
Embodiment 28: configuration 1L acid oxidation potential sterilized water (available chlorine content is 50mg/L)
Raw material A: hydrochloric acid solution (pH2-3), measure 1L, independent packaging (containing total copper 2g).
Raw material B: chlorine/nitrogen mixture, can amount 5ml, available chlorine 50mg, independent high sealing packing.
During use, under the airtight condition, the A unit is added the B unit mix, make 1L acid oxidation potential sterilized water (pH2-3, ORP1100-1200mV, ACC50mg/L, total copper 2000mg/L).
Embodiment 29: configuration 10L acid oxidation potential sterilized water (available chlorine content is 500mg/L)
Raw material A: hydrochloric acid solution (3M), measure 15ml (containing total copper 50mg), independent corrosion-proof packing.
Raw material B: sodium chlorate solution's (sodium carbonate is regulated for 2.5M, pH=8), measure 10ml (containing total copper 50mg), independent corrosion-proof packing.
During use, the A unit with after the B unit mixes, again with the water dilution of 9.975L, is made 10L acid oxidation potential sterilized water (pH2.5-3.5, ORP1100-1300mV, ACC500mg/L, total copper 10mg/L).
Embodiment 30: configuration 10L acid oxidation potential sterilized water (available chlorine content is 150mg/L)
Raw material A: hydrochloric acid solution (4M), measure 10ml, independent corrosion-proof packing.
Raw material B: sodium perchlorate solution (sodium carbonate is regulated for 0.5M, pH=8), measure 10ml (containing total copper 0.2g), independent corrosion-proof packing.
During use, the A unit with after the B unit mixes, again with the water dilution of 9.98L, is made 10L acid oxidation potential sterilized water (pH5-7, ORP900-1000mV, ACC150mg/L, total copper 20mg/L).
Embodiment 31: configuration 1L acid oxidation potential sterilized water (available chlorine content is 200mg/L)
Raw material A: hydrochloric acid solution (pH=0), measure 10ml (containing cupric 0.1g, monovalence copper 0.1g, zerovalent copper 0.1g), independent packaging.
Raw material B: liquor natrii hypochloritis (pH=12.5, potassium hydroxide is regulated), measure 10ml (available chlorine 200mg contains cupric 0.1g, monovalence copper 0.1g, zerovalent copper 0.1g), independent packaging.
During use, A unit and B unit are placed 0.98L water (containing cupric 0.8g, monovalence copper 0.4g, zerovalent copper 0.2g), make 1L acid oxidation potential sterilized water (pH2-3, ORP1100-1200mV, ACC200mg/L, total copper 2000mg/L, wherein cupric 1000mg/L, monovalence copper 600mg/L, zerovalent copper 400mg/L).
Embodiment 32: configuration 10L subacidity oxidizing potential sterilized water (available chlorine content is 5000mg/L)
Raw material A: aqueous hydrochloric acid solution (pH=2.76), measure 9.5L, add 0.01mol citric acid and 0.0035mol zinc chloride, after the dissolving, packing gets A unit (containing cupric 15g).
Raw material B: liquor natrii hypochloritis (available chlorine 100mg/ml, sodium carbonate 0.11M), measure 500ml, can, sealing gets B unit (available chlorine 50g contains cupric 5g).
During use, the A unit is mixed with the B unit, make 10L acid oxidation potential sterilized water (pH5-7, ORP1000-1200mV, ACC5000mg/L, total copper 2000mg/L, wherein cupric 2000mg/L).
Embodiment 33: configuration 1000L highly acid oxidizing potential sterilized water (available chlorine content is 1000mg/L)
Raw material A: acidic aqueous solution 2000L (pH2-3 contains total copper 100mol).
The raw material A preliminary treatment
Method 1, raw material A add EDTA (100mol), form the macromolecular complex thing, and filtrate is got in ultrafiltration, adjust pH, obtain raw material A 1 (pH2-3, total copper＜1000mg/L).
Method 2, raw material A add water-soluble sulphion (100mol), form precipitation, and filtrate is got in ultrafiltration, adjust pH, obtain raw material A 2 (pH2-3, total copper＜200mg/L).
Method 3, raw material A is analysed post by sodium type resinbed, removes part ion copper; Efflux adds enough water dissolubility sulphion, makes S 2+: the mol ratio of ion copper 1: 1; Ultrafiltration, the filtering insoluble matter is adjusted pH, obtains raw material A 3 (pH2-3, total copper＜10mg/L).
Method 4, raw material A are by NF membrane, and controlled condition is removed the large molecule of part cupric, adjusts pH, obtain raw material A 4 (pH2-3, total copper＜1900mg/L).
Method 5 by ion-selective membrane, is removed part ion copper under the certain electric current of raw material A, by NF membrane, removes large molecule copper again, adjusts pH, obtains raw material A 5 (pH2-3, total copper＜400mg/L).
Measure respectively each 1000L of raw material A 1-A5, can, sealing gets A unit 1-5: 1000L acidulous water (pH2-3, total copper 10-1900mg/L).
Raw material B: calcium hypochlorite powder (available chlorine 200mg/g), take by weighing 5kg, packing gets the B unit: 5kg powder (available chlorine 1000g contains total copper 100g).
Prepare each 5 parts of above-mentioned identical B unit.
During use, A unit A1-A5 is mixed with a B unit respectively, make following 1000L oxidizing potential sterilized water, see the following form 1.
Table 1
Electrolyzed oxidizing water pH ORP：mV ACC(mg/L) Total copper
A1+B 2-3 1150-1250 1000 1100mg/L
A2+B 2-3 1150-1250 1000 300mg/L
A3+B 2-3 1150-1250 1000 110mg/L
A4+B 2-3 1150-1250 1000 2000mg/L
A5+B 2-3 1150-1250 1000 500mg/L
Above-mentioned acid oxidation potential sterilized water (A4+B) continues post processing
Method 1, sterilized water (A4+B) add gauge water dissolubility sulphion, make S 2+: Cu 2+Mol ratio 1: 1, form precipitation, the leaching supernatant obtains sterilized water 6 (pH2-3, ORP1150-1250mV, ACC1000mg/L, total copper＜200mg/L).
Method 2, sterilized water (A4+B) is analysed post by resinbed first fast, removes part ion copper, large molecule copper is removed in the more lower ultrafiltration of low temperature (5-10 ℃), obtains sterilized water 7 (pH2-3, ORP1150-1250mV, ACC700mg/L, total copper＜200mg/L).
Method 3, under the low temperature (5-10 ℃), sterilized water (A4+B) passes through first NF membrane fast, remove the large molecule pattern of copper, filtrate is analysed post by resinbed more fast, obtains sterilized water 8 (pH2-3, ORP1150-1250mV, ACC600mg/L, total copper＜100mg/L).
Method 4, sterilized water (A4+B) fast by ion-selective membrane, are removed part ion copper under certain electric current, again with the total copper of charcoal absorption part, obtain sterilized water 9 (pH2-3, ORP1150-1250mV, ACC600mg/L, total copper＜400mg/L).
The post processing meeting of sterilized water makes the available chlorine partial loss, but at pH2-8, ORP 〉=600mV in the scope of ACC 〉=3mg/L, all can produce enough bactericidal effects.
Embodiment 34: configuration 10L highly acid oxidizing potential sterilized water (available chlorine 500-1000mg/L)
Raw material A: the citric acid powder, weighing 1mol, packing gets the A unit.Prepare identical 5 parts.
Raw material B: available chlorine solution 100L (pH8.5 contains total copper 6.35g/L).
Raw material B preliminary treatment
Method 1, raw material B quantitatively adds water-soluble CO 3 2-(10mol), form precipitation, low temperature (5-10 ℃) is got filtrate by NF membrane, adjusts pH, gets raw material B1 (pH8.5, ACC800mg/L, total copper＜10mg/L).
Method 2, raw material B alkalizes to pH12, forms the Kocide SD precipitation, adds charcoal absorption, after the filtration, adjusts pH, gets raw material B2 (pH8.5, ACC900mg/L, total copper＜200mg/L).
Method 3, raw material B analyses post by sodium type resinbed fast, removes ion copper, adjusts pH, obtains raw material B3 (pH8.5, ACC900mg/L, total copper＜500mg/L).
Method 4, raw material B removes the total copper of part fast by NF membrane, and low temperature (5-10 ℃) is analysed post by resinbed, removes part ion copper, adjusts pH, obtains raw material B4 (pH8.5, ACC600mg/L, total copper＜100mg/L).
Method 5 under the low temperature (5-10 ℃), after raw material B is acidified to 6.5-7.0, fast by ion-selective membrane, is removed part ion copper under certain electric current, recover pH, obtains raw material B5 (pH8.5, ACC700mg/L, total copper＜2000mg/L).
Through above-mentioned processing, available chlorine has certain loss, and its content need to redeterminate.
Raw material B1-B5 is respectively measured 10L, can, and sealing makes the B1-B5 unit.
During use, the B1-B5 unit is mixed with a A unit respectively, make following 10L acid oxidation potential sterilized water, see the following form 2.
Table 2
Electrolyzed oxidizing water pH ORP：mV ACC(mg/L) Total iron
A+B1 2-3 1150-1250 800 10mg/L
A+B2 2-3 1150-1250 900 200mg/L
A+B3 2-3 1150-1250 900 500mg/L
A+B4 2-3 1150-1250 600 100mg/L
A+B5 2-3 1150-1250 700 2000mg/L
Above-mentioned acid oxidation potential sterilized water (A+B5) continues post processing
Method 1, sterilized water (A+B5) quantitatively adds water-soluble S 2-, make S 2-: Cu 2+Mol ratio 1: 1, form precipitation, quick filtering precipitation obtains sterilized water 6 (pH2-3, ORP1150-1250mV, ACC700mg/L, total copper＜200mg/L).
Method 2, sterilized water (A+B5) low temperature (5-10 ℃) is analysed post by resinbed, removes part ion copper, obtains sterilized water 7 (pH2-3, ORP1150-1250mV, ACC500mg/L, total copper＜800mg/L).
Method 3, sterilized water (A+B5) are fast by NF membrane, and controlled condition makes the amount of the total copper that is trapped greater than other material, obtain sterilized water 8 (pH2-3, ORP1150-1250mV, ACC500mg/L, total copper＜1000mg/L).
Method 4, sterilized water (A+B5) fast by ion-selective membrane, are removed part ion copper under certain electric current, obtain sterilized water 9 (pH2-3, ORP1150-1250mV, ACC600mg/L, total copper＜500mg/L).
The post processing meeting of sterilized water makes the available chlorine partial loss, but at pH2-8, ORP 〉=600mV in the scope of ACC 〉=3mg/L, all can produce enough bactericidal effects.
Embodiment 35: configuration 100L acid oxidation potential sterilized water (available chlorine content 1000mg/L)
Raw material A: sulfuric acid solution 100L (pH2-3 contains monovalence copper 10mol).
Raw material A quantitatively adds water-soluble EDTA (10mol), forms complex compound, and under the low temperature (5-10 ℃), filtrate is got in ultrafiltration, adjusts pH, obtains raw material A 1 (pH2-3, monovalence copper 600mg/L).Measure 99L, can, sealing makes the A1 unit.
Raw material B: liquor natrii hypochloritis 10L (pH8.5, cupric 1mol).
Raw material B quantitatively adds water-soluble CO 3 2-(1mol), form precipitation, under the low temperature (5-10 ℃), filtrate is got in ultrafiltration, adjusts pH, obtains raw material B1 (pH8.5, ACC100mg/ml, cupric 200mg/L).Measure 1L raw material B1, can, sealing makes the B1 unit.
During use, the A1 unit is mixed with the B1 unit, make 100L acid oxidation potential sterilized water (pH2-3, ORP1150-1250mV, ACC1000mg/L, total copper 596mg/L, monovalence copper≤594mg/L wherein, cupric 〉=2mg/L).
Embodiment 36: configuration 10L acid oxidation potential sterilized water (available chlorine content 800mg/L)
Raw material A: aqueous acid (pH5-6 contains monovalence copper 3g/L), measure 9L, can, sealing makes the A unit.
Raw material B: liquor natrii hypochloritis's (pH8.5, ACC10g/L contain zerovalent copper 1.5g/L), take by weighing 1L, can, sealing makes the B unit.
During use, the A unit is mixed with the B unit, make the acid oxidation potential sterilized water (pH5-7, ACC1000mg/L, ORP1000-1100mV, total copper 2.85g/L, wherein monovalence copper 2.7g/L, zerovalent copper 150mg/L) of the high cupric of 10L.Fast ion exchange adsorption column and NF membrane under the above-mentioned sterilized water low temperature, remove part copper ion and large molecule copper, adjust again pH, make the sterilized water (pH5-7 of low copper ion, ACC800mg/L, ORP1000-1100mV, total copper 200mg/L, wherein monovalence copper 170mg/L, zerovalent copper 30mg/L).
Embodiment 37: preparation 100L alkalescence oxidizing potential sterilized water (pH=7-8)
Prepare the aqueous solution of different pH, prepare different A1-A11 unit:
Configuration aqueous hydrochloric acid solution (pH=0) is got 100L, makes A1 unit (containing cupric 200g);
Configuration aqueous hydrochloric acid solution (pH=2) is got 100L, makes A2 unit (containing monovalence copper 200g);
Configuration aqueous hydrochloric acid solution (pH=4) is got 100L, makes A3 unit (containing zerovalent copper 200g);
Configuration aqueous hydrochloric acid solution (pH=6) is got 100L, makes A4 unit (containing total copper 200g);
Configuration diethylamine aqueous solution (pH=7-8) is got 100L, makes A5 unit (containing total copper 0g);
Configuration diethylamine aqueous solution (pH=7-8) is got 30L, and configuration triethylamine aqueous solution (pH=7-8) is got 70L, and two kinds of alkali lye mix, and make A6 unit (containing cupric 200g);
Configuration diethylamine aqueous solution (pH=7-8) is got 50L, and configuration potassium hydroxide aqueous solution (pH=7-8) is got 50L, and two kinds of alkali lye mix, and make A7 unit (containing monovalence copper 200g);
Configuration diethylamine aqueous solution (pH=7-7.5) is got 80L, and configuration aqueous sodium acetate solution (pH=7-7.5) is got 20L, and two kinds of alkali lye mix, and make A8 unit (containing zerovalent copper 200g);
Configuration sodium hydrate aqueous solution (pH=7-7.5) is got 50L, and configuration aqueous sodium acetate solution (pH=7-7.5) is got 50L, and two kinds of alkali lye mix, and make A9 unit (containing total copper 0g);
Configuration sodium hydrate aqueous solution (pH=7-8) is got 50L, and configuration baryta water (pH=7-8) is got 50L, and two kinds of alkali lye mix, and make A10 unit (containing total copper 100g);
Configuration aqueous sodium acetate solution (pH=7-7.5) is got 50L, and configuration sodium lactate aqueous solution (pH=7-7.5) is got 50L, and two kinds of alkali lye mix, and make A11 unit (containing total copper 50g).
Different solid available chlorine preparations prepares different B1-B11 unit:
Sodium dichloro cyanurate, weighing 1.2g, the sodium carbonate of interpolation 60mo l, packing makes B1 unit (available chlorine 0.3g contains total copper 0mg);
The calcium chlorite, weighing 1.5g, the sodium carbonate of interpolation 0.6mol, packing makes the B2 unit, (available chlorine 0.3g contains total copper 0mg);
Dichlord isocyanurice acid, weighing 1.5g, the sodium carbonate of interpolation 0.006mol, packing makes B3 unit (available chlorine 0.3g contains total copper 0mg);
Efficacious Disinfeitant, weighing 3g, the sodium carbonate of interpolation 0.00006mol, packing makes B4 unit (available chlorine 0.3g contains total copper 0mg);
Toluene-sodium-sulfonchloramide, weighing 1.2g, packing makes B5 unit (available chlorine 0.3g contains total copper 0mg);
Toluene-sodium-sulfonchloramide, weighing 2Kg, packing makes B6 unit (available chlorine 500g contains total copper 0mg);
Toluene-sodium-sulfonchloramide, weighing 2Kg, packing makes B7 unit (available chlorine 500g contains total copper 0mg);
Toluene-sodium-sulfonchloramide, weighing 2Kg, packing makes B8 unit (available chlorine 500g contains total copper 0mg);
Toluene-sodium-sulfonchloramide, weighing 2Kg, packing makes B9 unit (available chlorine 500g contains total copper 0mg);
Toluene-sodium-sulfonchloramide, weighing 40g, packing makes B10 unit (available chlorine 10g contains total copper 0mg);
Toluene-sodium-sulfonchloramide, weighing 80g, packing makes B11 unit (available chlorine 20g contains total copper 0mg).
The A unit is mixed with the B unit, makes the dissolving of B unit, make following oxidizing potential sterilized water:
A1+B1, pH7-8, ORP600-700mV, ACC3mg/L, total copper 2000mg/L, wherein cupric 2000mg/L;
A2+B2, pH7-8, ORP600-700mV, ACC3mg/L, total copper 2000mg/L, wherein monovalence copper 2000mg/L;
A3+B3, pH7-8, ORP600-700mV, ACC3mg/L, total copper 2000mg/L, wherein zerovalent copper 2000mg/L;
A4+B4, pH7-8, ORP600-700mV, ACC3mg/L, total copper 2000mg/L;
A5+B5, pH7-8, ORP600-700mV, ACC3mg/L, total copper 0mg/L;
A6+B6, pH7-8, ORP1050-1150mV, ACC5000mg/L, total copper 2000mg/L, wherein cupric 2000mg/L;
A7+B7, pH7-8, ORP1050-1150mV, ACC5000mg/L, total copper 2000mg/L, wherein monovalence copper 2000mg/L;
A8+B8, pH7-8, ORP1050-1150mV, ACC5000mg/L, total copper 2000mg/L, wherein zerovalent copper 2000mg/L;
A9+B9, pH7-8, ORP1050-1150mV, ACC5000mg/L, total copper 0mg/L;
A10+B10, pH7-8, ORP800-900mV, ACC100mg/L, total copper 1000mg/L;
A11+B11, pH7-8, ORP800-900mV, ACC200mg/L, total copper 500mg/L.
Embodiment 38: preparation 10L alkalescence oxidizing potential sterilized water (pH=7.0-8.0)
Prepare the aqueous solution of different pH, prepare different A1-A4 unit:
Configuration sodium hydroxide solution (pH=7-7.5) is got 9L, makes A1 unit (containing total copper 0mg);
Configuration sodium acetate solution (pH=7-7.5) is got 9L, makes A2 unit (containing total copper 0mg);
Configuration aqueous hydrochloric acid solution (pH=4) is measured 5L, makes A3 unit (containing total copper 0mg);
Configuration aqueous hydrochloric acid solution (pH=2) is measured 5L, makes A4 unit (containing total copper 0mg).
Prepare the liquor natrii hypochloritis of different available chlorine contents, prepare different B1-B4 unit,
The liquor natrii hypochloritis, pH8.5 is measured 1L, and packing makes B1 unit (available chlorine 50g, total copper 6g);
The liquor natrii hypochloritis, pH8.5 is measured 1L, and packing makes B2 unit (available chlorine 30g, total copper 8g);
The liquor natrii hypochloritis is measured 5L, adds sodium carbonate 0.0003mol, and packing makes B3 unit (available chlorine 15g, total copper 10g);
The liquor natrii hypochloritis is measured 5L, adds sodium carbonate 0.03mol, and packing makes B4 unit (available chlorine 1g, total copper 15g).
During use, the A unit is mixed with the B unit, make following 10L oxidizing potential sterilized water, see the following form 3.
Table 3
Electrolyzed oxidizing water pH ORP：mV ACC(mg/L) Total copper
A1+B1 7-8 1000-1100 5000 600mg/L
A2+B2 7-8 950-1050 3000 800mg/L
A3+B3 7-8 900-1000 1500 1000mg/L
A4+B4 7-8 800-900 100 1500mg/L
Embodiment 39: preparation 100L alkalescence oxidizing potential sterilized water (pH=8.0)
Aqueous sulfuric acid (0.1M), the identical A1-A2 unit (containing total copper 195g) of preparation 100L.
Aqueous hydrochloric acid solution (0.2M), the identical A3-A4 unit (containing total copper 0) of preparation 100L.
Different solid available chlorine preparations prepares different B1-B4 unit:
Sodium dichloro cyanurate, weighing 1.2g, the sodium carbonate of interpolation 13mol, packing makes B1 unit (containing available chlorine 0.3g, total copper 5g);
Calcium hypochlorite, weighing 2.5Kg, the sodium carbonate of interpolation 13mol, packing makes B2 unit (containing available chlorine 500g, total copper 5g);
Sym-closene, weighing 0.75g, the sodium carbonate of interpolation 13mol, packing makes B3 unit (containing available chlorine 0.3g, total copper 0g);
Toluene-sodium-sulfonchloramide, weighing 2Kg, the sodium carbonate of interpolation 13mol, packing makes B4 unit (containing available chlorine 0.5Kg, total copper 0g).
The A unit is mixed with the B unit, make the dissolving of B unit, make following oxidizing potential sterilized water, see the following form 4.
Table 4
Electrolyzed oxidizing water pH ORP：mV ACC(mg/L) Total copper
A1+B1 8.0 600 3 2000mg/L
A2+B2 8.0 1100 5000 2000mg/L
A3+B3 8.0 600 3 0mg/L
A4+B4 8.0 1100 5000 0mg/L
Embodiment 40: configuration 100L acid oxidation potential sterilized water (pH=2.0)
Dispose the aqueous hydrochloric acid solution of different pH, prepare different A1-A4 unit:
Configuration aqueous hydrochloric acid solution (pH=0) is got 100L, makes A1 unit (containing total copper 200g);
Configuration aqueous hydrochloric acid solution (pH=1) is got 100L, makes A2 unit (containing total copper 200g);
Configuration aqueous hydrochloric acid solution (pH=2) is got 100L, makes A3 unit (containing total copper 0g);
Configuration aqueous hydrochloric acid solution (pH=2) is got 100L, makes A4 unit (containing total copper 0g).
Different solid available chlorine preparations prepares different B1-B4 unit:
Sodium dichloro cyanurate, weighing 1.2g, the sodium hydroxide of interpolation 99mo l mixes, and packing makes B1 unit (containing available chlorine 0.3g);
Toluene-sodium-sulfonchloramide, weighing 2Kg, the sodium hydroxide of interpolation 9mol mixes, and packing makes B2 unit (containing available chlorine 500g);
Sym-closene, weighing 0.75g, packing makes B3 unit (containing available chlorine 0.3g);
Efficacious Disinfeitant, weighing 5Kg, packing makes B4 unit (containing available chlorine 500g).
The AB unit is mixed, make the dissolving of B unit, make following oxidizing potential sterilized water, see the following form 5.
Table 5
Electrolyzed oxidizing water pH ORP：mV ACC(mg/L) Total copper (mg/L)
A1+B1 2.0 1050 3 2000
A2+B2 2.0 1370 5000 2000
A3+B3 2.0 1050 3 0
A4+B4 2.0 1370 5000 0
Embodiment 41: preparation 10L oxidizing potential sterilized water
The zinc citrate pressed powder, weighing 1mol makes A unit (containing total copper 0.1g).
The sodium dichloro cyanurate powder, weighing 40mg (containing available chlorine 10mg), sym-closene, weighing 50mg (containing available chlorine 20mg) mixes, and makes B unit (total available chlorine 30mg).
A unit and B unit mixing monobasic packing or independent binary packing.
Before the use, A unit and B unit are dissolved in 10L water, behind the pH of solution≤8.0, make oxidizing potential sterilized water (pH2-8, ORP 〉=600mV, ACC3mg/L, total copper 10mg/L).
Embodiment 42: preparation 10L oxidizing potential sterilized water
The zinc chloride powder, weighing 0.5mol makes A unit (containing total copper 1g).
The magnesium hypochlorite powder, weighing 100g (containing available chlorine 20g), Efficacious Disinfeitant, weighing 300g (containing available chlorine 30g) adds sodium acetate 1mol, mixes, and makes B unit (total available chlorine 50g contains total copper 19g).
A unit and B unit mixing monobasic packing or independent binary packing.
Before the use, A unit and B unit are dissolved in 10L water, behind the pH of solution≤8.0, make oxidizing potential sterilized water (pH2-8, ORP 〉=1000mV, ACC5000mg/L, total copper 2000mg/L).
Embodiment 43: preparation 10L oxidizing potential sterilized water
The zinc chloride powder, weighing 0.5mol adds sodium acetate 1mol, mixes, and makes the A unit.
Toluene-sodium-sulfonchloramide, weighing 40g makes B unit (containing available chlorine 10g, total copper 10g).
A unit and B unit mixing monobasic packing or independent binary packing.
Before the use, A unit and B unit are dissolved in 10L water, behind the pH of solution≤8.0, make oxidizing potential sterilized water (pH2-8, ORP 〉=900mV, ACC1000mg/L, total copper 1000mg/L).
Disinfection effect test: (annotating: under clean conditions, (add 0.3% organic chaff interference) and carry out)
With the representative of staphylococcus aureus ATCC 6538 as pyococcus in the bacterial propagule; Escherichia coli 8099 are as the representative of enteron aisle bacterium in the bacterial propagule; Pseudomonas aeruginosa ATCC 15442 is as the representative of the bacterial propagule of normal separation in the hospital infection; Staphylococcus albus 8032 is as the representative of bacterium in the air; Mycobacterium chelonei abscess subspecies ATCC 93326 is as bacillus tuberculosis typus humanus's representative; Bacillus subtilis black variety gemma ATCC 9372 is as the representative of bacterial spore; Candida albicans ATCC 10231 and black-koji mould ATCC 16404 are as the representative of pathogenic fungus; Polyovirus-I type vaccine strain (Poliovirus-I) is as the representative of virus; With the representative as drug-fast bacteria of the staphylococcus aureus (MRSA) of methicillin-resistant and vancomycin-resistant enterococcus (VRE); Represent pathogenic bacteria in the aquatic products with vibrio parahemolyticus, Listeria monocytogenes; Represent the bird pathogenic bacteria with the white diarrhea salmonella; Represent agriculture pathogenic bacteria with wheat stripe rust.
Bactericidal assay 1 (suspension is quantitative), the oxidizing potential sterilized water is killed logarithm and time
Trial target 1, ACC3mg/L, pH8.0, ORP600mV, cupric 2000mg/L
Trial target 2, ACC3mg/L, pH8.0, ORP600mV, monovalence copper 2000mg/L
Trial target 3, ACC3mg/L, pH8.0, ORP600mV, zerovalent copper 2000mg/L
Trial target 4, ACC3mg/L, pH8.0, ORP600mV, total copper 0mg/L
Trial target 5, ACC3mg/L, pH7.0, ORP700mV, total copper 0mg/L
Trial target 6, ACC3mg/L, pH2.0, ORP1050mV, cupric 2000mg/L
Trial target 7, ACC3mg/L, pH2.0, ORP1050mV, monovalence copper 2000mg/L
Trial target 8, ACC3mg/L, pH2.0, ORP1050mV, zerovalent copper 2000mg/L
Trial target 9, ACC3mg/L, pH2.0, ORP1050mV, total copper 0mg/L
Kill logarithm behind table 6 15min action time
Test organisms Trial target 1-3 Trial target 4 Trial target 5 Trial target 6-8 Trial target 9
Staphylococcus aureus ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Escherichia coli ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Pseudomonas aeruginosa ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Candida albicans ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Black-koji mould ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Staphylococcus albus ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Poliovirus-I ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Mycobacterium chelonei abscess subspecies ＞5.00 ＞5.00 ＞5.00 ＞5.00 ＞5.00
Bactericidal assay 2 (suspension is quantitative), the oxidizing potential sterilized water is killed logarithm and time
Trial target 1, ACC5000mg/L, pH8.0, ORP1100mV, cupric 2000mg/L
Trial target 2, ACC5000mg/L, pH8.0, ORP1100mV, monovalence copper 2000mg/L
Trial target 3, ACC5000mg/L, pH8.0, ORP1100mV, zerovalent copper 2000mg/L
Trial target 4, ACC5000mg/L, pH8.0, ORP1100mV, total copper 0mg/L
Trial target 5, ACC5000mg/L, pH6.99, ORP1050mV, total copper 0mg/L
Trial target 6, ACC5000mg/L, pH2.0, ORP1370mV, cupric 2000mg/L
Trial target 7, ACC5000mg/L, pH2.0, ORP1370mV, monovalence copper 2000mg/L
Trial target 8, ACC5000mg/L, pH2.0, ORP1370mV, zerovalent copper 2000mg/L
Trial target 9, ACC5000mg/L, pH2.0, ORP1370mV, total copper 0mg/L
Kill logarithm behind table 7 0.5min action time
Figure BDA00002564684100281
Stability test
" disinfection technology standard (version in 2008) " middle three kinds of term of validity detection methods stipulating that product among the embodiment 7,8,17,1,19,20,23,24,25,26 is promulgated according to the Ministry of Public Health, the result shows that the term of validity surpasses 2 years.
The metal protection test is with reference to " version disinfection technology standard in 2008 "
Test material 1, copper, circle, diameter 24.00mm, thick 1.0mm, wearing a diameter is the 2.0mm aperture, the surface area total value is about 9.80cm 2Fineness is 6.
Test material 2, thimerosal, the oxidizing potential sterilized water of different Cu content.
Experimental group, test material 1 are removed attachment (fully deoil, fully the deoxidation layer is cleaned); Measure diameter, thickness, the aperture of sheet; 50 ℃ of dry 1h, weigh (as weight before the test); Hang in the 200ml test material 2, continue 72 hours, and regularly change thimerosal; Take out sheet metal, remove corrosion product, clean, 50 ℃ of dry 1h weigh.
The blank group, test material 1 repeats by above-mentioned steps, but soaks without disinfectant.And calculate its average weightless value.
The Calculation of corrosion rate.
Corrosion test 1, (see Fig. 1, the pH/ cupric is to copper corrosion speed)
Can learn from Fig. 1 data: the non-oxide system of pH=2-8, the pH/ cupric has corrosivity to copper.
Corrosion test 2, (see Fig. 2, the pH/ACC/ cupric is to copper corrosion speed)
Comparison diagram 2 data can be learnt: during pH=2.0, compare with the solution that does not contain available chlorine (ACC=0ppm), the introducing of available chlorine with the cupric synergy, has affected solution to the copper corrosion characteristic.
Simultaneously as can be known, in pH/ACC/ cupric system, the ACC/ cupric of different content has similar etching characteristic to metal during pH=2.0, when being pH=2.0/ cupric＞2000mg/L, the ACC of different content (3-5000ppm) system all produces hop to corrosion of metal.
Corrosion test 3, (see Fig. 3, the pH/ACC/ cupric is to copper corrosion speed)
Comparison diagram 3 data can be learnt: during pH=8.0, compare with the solution that does not contain available chlorine (ACC=0ppm), the introducing of available chlorine with the cupric synergy, has affected solution to the copper corrosion characteristic.
Simultaneously as can be known, in pH/ACC/ cupric system, the ACC/ cupric of different content during pH=8.0 has similar etching characteristic to metal equally, when being pH=8.0/ cupric＞2000mg/L, the ACC of different content (3-5000ppm) system all produces hop to corrosion of metal.
Compare corrosion test 2,3, in pH/ACC/ cupric system, during pH=2.0-8.0, available chlorine reduces, and the corrosivity of system is reduced, and reduced the significance of hop.(for example, in the time of 5500mg/L), with different content cupric synergy, rise to copper corrosion by impatient play more than 5000mg/L for available chlorine content.
Corrosion test 4, (see Fig. 4, the pH/ACC/ cupric is to copper corrosion speed)
Comparison diagram 4 data can be learnt: in pH/ACC/ cupric system, during ACC=5000ppm, pH has similar etching characteristic at 2.0-8.0 to metal, when being ACC=5000ppm/ cupric＞2000mg/L, pH all produces hop in the system of 2.0-8.0 to corrosion of metal.
Corrosion test 5, (see Fig. 5, the pH/ACC/ cupric is to copper corrosion speed)
Comparison diagram 5 data can be learnt: in pH/ACC/ cupric system, during ACC=3ppm, pH has similar etching characteristic to metal equally at 2.0-8.0, when being ACC=3ppm/ cupric＞2000mg/L, pH all produces hop in the system of 2.0-8.0 to corrosion of metal.
Compare corrosion test 4,5, in pH/ACC/ cupric system, during ACC=5000-3ppm, acid reduction reduces the corrosivity of system, and has reduced the significance of hop.
Corrosion test 6, (see Fig. 6-9, the copper of pH/ACC/ different valence state is to copper corrosion)
Comparison diagram 6-9 data can be learnt: in the oxidisability system of pH=2-8, and cupric corrosivity＞monovalence copper＞zerovalent copper.So the different total copper corrosions that consist of of same amount, total copper of total copper that total copper that 100% cupric consists of＞100% monovalence copper consists of＞100% zerovalent copper formation.
Corrosion test 7, (see Figure 10-13, the different total copper that form of pH/ACC/ are to copper corrosion)
Comparison diagram 10-13 data can be learnt: in the oxidisability system of pH=2-8, and cupric corrosivity＞monovalence copper＞zerovalent copper.So the different total copper corrosions that consist of of same amount, the monovalence copper of total copper＞different proportion of the cupric of total copper＞different proportion that 100% cupric consists of, monovalence copper, zerovalent copper combination＞100% monovalence copper formation and total copper that zerovalent copper combination＞100% zerovalent copper consists of.
Oxidizing potential sterilized water of the present invention can reduce corrosion of metal, thereby has enlarged range of application.Before use, A unit and the B unit of oxidizing potential solution of the present invention are deposited separately, in the time will using, A unit and B unit are mixed again, and have solved the storage problem of oxidizing potential sterilized water, and be very easy to use.In the process of preparation oxidizing potential solution of the present invention, strengthened artificial controllability, can regulate according to the actual requirements pH value, available chlorine content and the redox potential of sterilized water.
More than disclosed only be several specific embodiments of the application, but the application is not limited thereto, the changes that any person skilled in the art can think of all should drop in the application's the protection domain.

Claims (20)

1. the preparation method of the oxidizing potential sterilized water of a low-corrosiveness is characterized in that, may further comprise the steps:
(1) provides pH adjusting agent A unit;
(2) provide available chlorine that the unit B unit is provided;
(3) described A unit is mixed with described B unit, obtain strong oxidizing property solution, the pH value of described strong oxidizing property solution is between 2-8, and its redox potential is not less than 600mV, and its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
2. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1 is characterized in that, the total copper in the described strong oxidizing property solution mainly comprises one or several in cupric, monovalence copper and the zerovalent copper.
3. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1 or 2 is characterized in that, also comprises in step (1): the preliminary treatment that part copper is removed in described A unit.
4. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1 or 2 is characterized in that, also comprises in step (2): the preliminary treatment that part copper is removed in described B unit.
5. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1 or 2 is characterized in that, also comprises in step (3): the post processing that the mixed mixed liquor in described A unit and described B unit is removed part copper.
6. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 3, it is characterized in that the pretreated method that part copper is removed in described A unit is selected from and adds in deactivator, membrane separation process, electrochemical process, chromatography, absorption method or the ion-exchange one or several.
7. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 4, it is characterized in that the pretreated method that part copper is removed in described B unit is selected from and adds in deactivator, membrane separation process, electrochemical process, chromatography, absorption method or the ion-exchange one or several.
8. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 5, it is characterized in that the described method that the mixed mixed liquor in A unit and B unit is removed the post processing of part copper is selected from and adds in deactivator, membrane separation process, electrochemical process, chromatography, absorption method or the ion-exchange one or several.
9. such as the preparation method of the oxidizing potential sterilized water of claim 6 or 7 or 8 described low-corrosiveness, it is characterized in that, the processing mode of described removal part copper is the fast processing mode, or processes under the cryogenic conditions, or transfers B unit ionic available chlorine to molecule-type available chlorine; Or transfer ion copper to nonionic derivative, make it and ionic active ingredient is distinguished, remove the purpose impurity copper after, return to again the stable form of available chlorine.
10. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1 is characterized in that, described A unit is acidity or alkalescent.
11. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1, it is characterized in that, described B contains the unit one or more in double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite, and described available chlorine precursor substance refers to can generate with acid or water reaction the chlorine-bearing compound of available chlorine.
12. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1 is characterized in that, described B unit is neutral or alkaline.
13. the oxidizing potential sterilized water of a low-corrosiveness is characterized in that, comprises A unit and the B unit of independent packing before using, described A unit is pH adjusting agent; Described B unit provides the unit for available chlorine, described A unit with obtain strong oxidizing property solution after described B unit mixes, the pH value of described strong oxidizing property solution is between 2-8, its redox potential is not less than 600mV, its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
14. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 13 is characterized in that, the total copper in the described strong oxidizing property solution mainly comprises one or several in cupric, monovalence copper and the zerovalent copper.
15. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 13, it is characterized in that, described B contains the unit one or more in double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite, and described available chlorine precursor substance refers to can generate with acid or water reaction the chlorine-bearing compound of available chlorine.
16. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 13 is characterized in that, described B unit is neutral or alkaline.
17. the oxidizing potential sterilized water of a low-corrosiveness is characterized in that, the pH value of described sterilized water is between 2-8, and its redox potential is not less than 600mV, and its available chlorine content is 3-5000mg/L, and the content of its total copper is not higher than 2000mg/L.
18. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 17 is characterized in that, the total copper in the described sterilized water mainly comprises one or several in cupric, monovalence copper and the zerovalent copper.
19. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 17, it is characterized in that, contain one or several of inorganic acid, organic acid, inorganic base, organic base, strong acid weak base salt, strong base-weak acid salt, weak acid and weak base salt or strong acid and strong base salt in the described sterilized water.
20. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 17, it is characterized in that, available chlorine in the described sterilized water is by one or more generations of double salt, chlorite or the available chlorine precursor substance of liquid chlorine, chlorine dioxide, hypochlorite, hypochlorite, and described available chlorine precursor substance refers to can generate with acid or water reaction the chlorine-bearing compound of available chlorine.
CN2012105332714A 2012-12-11 2012-12-11 Low-corrosiveness oxidation potential sterilization water and preparation method thereof Pending CN103004868A (en)

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CN103300059A (en) * 2013-05-31 2013-09-18 邵鹏飞 Low-corrosivity alkaline active chlorine solution and preparation method thereof
CN103299990A (en) * 2013-05-31 2013-09-18 邵鹏飞 Peracetic acid solution and preparation method thereof
CN103300061A (en) * 2013-05-31 2013-09-18 邵鹏飞 Sterilization solution and preparation method thereof
CN103300064A (en) * 2013-05-31 2013-09-18 邵鹏飞 Sterilization solution and preparation method thereof
CN103314995A (en) * 2013-04-18 2013-09-25 邵鹏飞 Low-corrosion oxidation potential sterilization solution and its preparation method
CN105581913A (en) * 2015-08-26 2016-05-18 北京建元天地环保科技有限公司 Manufacturing method for novel function liquid disinfectant wet wipes harmless to human body
CN106550941A (en) * 2016-11-08 2017-04-05 东北大学秦皇岛分校 A kind of stabilizing chlorine dioxide disinfectant solution

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CN1293540A (en) * 1999-02-26 2001-05-02 崔永成 Weak acidic disinfectant
CN101437754A (en) * 2006-02-28 2009-05-20 巴斯福催化剂公司 Chlorine dioxide based cleaner/sanitizer
CN102616895A (en) * 2011-12-31 2012-08-01 邵鹏飞 Electrolyzed oxidizing water and preparation method thereof
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CN103314995A (en) * 2013-04-18 2013-09-25 邵鹏飞 Low-corrosion oxidation potential sterilization solution and its preparation method
CN103300059A (en) * 2013-05-31 2013-09-18 邵鹏飞 Low-corrosivity alkaline active chlorine solution and preparation method thereof
CN103299990A (en) * 2013-05-31 2013-09-18 邵鹏飞 Peracetic acid solution and preparation method thereof
CN103300061A (en) * 2013-05-31 2013-09-18 邵鹏飞 Sterilization solution and preparation method thereof
CN103300064A (en) * 2013-05-31 2013-09-18 邵鹏飞 Sterilization solution and preparation method thereof
CN103300064B (en) * 2013-05-31 2014-11-05 邵鹏飞 Sterilization solution and preparation method thereof
CN105581913A (en) * 2015-08-26 2016-05-18 北京建元天地环保科技有限公司 Manufacturing method for novel function liquid disinfectant wet wipes harmless to human body
CN106550941A (en) * 2016-11-08 2017-04-05 东北大学秦皇岛分校 A kind of stabilizing chlorine dioxide disinfectant solution
CN106550941B (en) * 2016-11-08 2020-11-06 东北大学秦皇岛分校 Stable chlorine dioxide disinfectant

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