CN103004869A - Low-corrosiveness oxidation potential sterilization water and preparation method thereof - Google Patents
Low-corrosiveness oxidation potential sterilization water and preparation method thereof Download PDFInfo
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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 3-3000 mg/L, and the total iron content is not higher than 1500 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
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, its available chlorine content 3-3000mg/L, and the content of its total iron is not higher than 1500mg/L.
Preferably, total iron of described strong oxidizing property solution comprises one or several in ferric iron, ferrous iron and the Zero-valent Iron.
Preferably, in step (1), also comprise: the preliminary treatment that part iron is removed in described A unit.
Preferably, in step (2), also comprise: the preliminary treatment that part iron 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 iron.
Preferably, the pretreated method of part iron 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 iron 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 iron 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 iron is the fast processing mode, or processes under the cryogenic conditions, or transfers B unit ionic available chlorine to molecule-type available chlorine, makes it to distinguish with ionic iron; Or transfer ionic iron to nonionic derivative, make it and ionic active ingredient is distinguished, remove purpose foreign ion iron 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 3-3000mg/L, the content of its total iron is not higher than 1500mg/L.
Preferably, total iron of described strong oxidizing property solution comprises one or several in ferric iron, ferrous iron and the Zero-valent Iron.
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, its available chlorine content 3-3000mg/L, the content of its total iron is not higher than 1500mg/L.
Preferably, total iron of described sterilized water comprises one or several in ferric iron, ferrous iron and the Zero-valent Iron.
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, available chlorine content and the redox potential of sterilized water.
Description of drawings
Fig. 1-2 is in the environment of pH=2.0-8.0, and the pH/ ferric iron changes the corrosive effect schematic diagram to carbon steel;
Fig. 3-4 is in the oxidative environment of pH=2.0-8.0, and available chlorine and ferric iron synergy are to the schematic diagram of the corrosive effect of carbon steel;
Fig. 5-6 is in the oxidative environment of pH=2.0-8.0, and pH and ferric iron synergy are to the schematic diagram of the corrosive effect of carbon steel;
Fig. 7-10 is in the oxidative environment of pH=2.0-8.0, and the iron of different valence state is to the schematic diagram of the corrosive effect of carbon steel;
Figure 11-14 is in the oxidative environment of pH=2.0-8.0, and the different total iron that form are to the schematic diagram of the corrosive effect of carbon steel;
Figure 15 is in the oxidative environment of pH=2.0-8.0, and the hybrid mode of different A, B unit is to corrosive schematic diagram that concerns of carbon steel.
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 the acidity of system, 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 metal protection 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 ferric iron and the corrosivity of total iron in the pH=2-8 oxidative environment.
Described ferric iron refers to that chemical valence state is the summation of iron of all forms of positive 3 valencys.Described total iron refers to the content summation of iron of all forms of various chemical valence states.
Chemical method prepares oxidizing potential solution, and the introducing of iron mainly contains three kinds of approach in the system, and one itself contains in employed acid-base modifier and the available chlorine or produces ferro element, such as iron chloride or hypochlorous acid iron or iron hydroxide etc.; Its two, use and carry ferrous contaminants in the raw material secretly; Its three, the component of other effects of iron content is such as thickener, stabilizing agent, hardening agent etc.
The equipment of iron content material and container (such as fiberglass, carbon steel and the stainless steel) extensive use in reality makes the raw materials such as acid, alkali, available chlorine inevitably pollute certain iron in production, transportation, storage process.As, the industrial burning in hydrogen with chlorine generates hydrogen chloride, and employed steel combustion tube and high-temperature chlorine solid/liquid/gas reactions generate ferric iron.As, during the industrial production high amount of acids, concentrated acid contacts with iron content equipment.That carry secretly in the raw materials for production or itself be exactly the raw material of iron content, increased especially iron-holder.As, (running water, well water, river or the above-mentioned water that simply purified) contains impurity iron in the employed water.As, production of sulfur from pyrite acid contains iron ore dust is dissolved in has increased iron in the acid content.
Because generality, multi-source (approach 1-3) and the inevitable property (approach 2) in iron source so the iron-holder in the single a certain source of restriction has little significance, also are unscientific simultaneously.Therefore be total iron and the ferric iron content that defines under the end-state among the present invention, i.e. A, the mixed iron-holder in B unit.Because what finally produce effect (such as bactericidal property, metal protection) is A, B unit mixed liquor, but not A unit or B unit.
Ferric iron is undertaken by following basic mode corrosion of metal,
Fe+2Fe
3+＝3Fe
2+ ——1
Cu+2Fe
3+＝Cu
2++2Fe
2+ ——2
Al+3Fe
3+＝Al
3++3Fe
2+ ——3
Fe
2++[O]＝Fe
3++e ——4
In normal temperature, neutrality and non-oxidizable solution, reaction 4 be slowly, above-mentioned serial reaction can be understood as simple ferric corrosive effect, depends on ferric initial content ( reaction 1,2,3), when ferric iron ran out, corrosion process finished.When ferric content was relatively stable, its corrosive effect changed little, and perhaps the corrosive effect that slowly carries out along with reaction 4 slowly strengthens.
In the oxidizing potential sterilized water, the environment of the introducing of available chlorine and low pH, accelerated to react 4 carrying out, promoted metal and ferric direct product ferrous iron again to change ferric iron into, reduced ferric reduction, ferric content remains on certain high level or continue to increase state to iron rot the time in the system in to copper, aluminium corrosion process thereby make, and then has aggravated reaction 1,2,3 and carried out.
As from the foregoing, contain ferric oxidizing potential sterilized water, ferric iron and hydrogen ion and available chlorine interact, and the system that affected greatly is to corrosion of metal.
Simultaneously, ferrous iron or Zero-valent Iron (perhaps ferrous iron, the Zero-valent Iron in total iron) in stable environment be do not have corrosive, but in the oxidative environment of pH=2-8, ferrous iron constantly changes ferric iron (reaction 4) into, and form dynamically with ferric iron, the coexisting body of balance; Also there is the ferric trend that is oxidized to simultaneously in Zero-valent Iron.Therefore, the actual ferric amount that generates, the speed that namely changes and the amount of conversion of depending on of the corrosivity of ferrous iron and Zero-valent Iron.
Can know also that thus the corrosivity of total iron is actual to be determined by ferric iron.So in the identical situation of total iron content, the corrosion activity descending order of total iron is total iron that the Zero-valent Iron of total iron 〉=different proportion that 100% ferric iron forms, ferrous iron, ferric iron form; Again because ferrous iron is converted into the conversion trend that ferric trend is far longer than Zero-valent Iron, so total iron that total iron that total iron that 100% ferric iron forms＞100% ferrous iron forms＞100% Zero-valent Iron forms; Total iron that total iron that the ferrous iron of total iron 〉=different proportion that 100% ferrous iron forms and Zero-valent Iron form 〉=100% Zero-valent Iron forms.Because ferrous iron, Zero-valent Iron itself do not have corrosivity, and ferrous iron constantly decay in oxidative environment, therefore with the content of ferric content or total iron represent to have the iron of catalyzed corrosion more convenient with accurately.
See also Fig. 1-Fig. 2, 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, ferric adding and content increase have increased system to corrosion of metal.Simultaneously as seen, hydrogen ion and ferric iron synergy have strengthened system to corrosion of metal.
See also Fig. 3-Fig. 4, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, ferric iron and available chlorine synergy, the system that affected makes system produce hop to metal protection to corrosion of metal.Wherein, different available chlorine content (3-3000ppm) during ferric concentration＞1500ppm, 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. 5-Fig. 6, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, ferric iron 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 ferric concentration＞1500ppm, 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. 6 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 the control ferric iron content at 3-3000ppm, at 0-1500ppm and available chlorine content.
Chemical method preparation oxidizing potential sterilized water, relating to the form of iron and valence state has multiplely, as with typoiogical classification, then comprises iron oxide, free iron ion, slightly solubility molysite, with the chemical valence classification, then comprises Zero-valent Iron, ferrous iron, ferric iron.
See also Fig. 7-Figure 10, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, available chlorine (3-3000ppm) acts synergistically with the iron of different valence state, to the similar characteristic of the active generation of corrosion of metal.The increase of iron content makes system produce hop to metal protection.Its corrosion activity is ferric iron＞ferrous iron＞Zero-valent Iron from large extremely little order.Wherein, ferric corrosion activity is the strongest, and it produces the concentration minimum (1500ppm) of corrosivity hop.The iron of other valence state, along with activity decreased, the concentration increase that corrosion activity reduces or hop is required (＞1500ppm).
See also Figure 11-Figure 14, show among the figure: in the oxidisability of pH=2-8 (the containing ACC) system, available chlorine (3-3000ppm) acts synergistically with total iron of different proportion, to the similar characteristic of the active generation of corrosion of metal.The increase of total iron content makes system produce hop to metal protection.The different total iron that form have different corrosion activities, wherein, ferric corrosion activity is the strongest, the concentration minimum (1500ppm) of the corrosivity hop of the total iron that therefore fully is comprised of ferric iron, under the same amount, its corrosivity is greater than total iron of the iron that contains other valence states.
Comparison diagram 1-Fig. 6 as can be known, when the metal protection of oxidizing potential sterilized water be controlled or be reduced to control ferric iron content (0-1500ppm) and available chlorine content (3-3000ppm) can, comparison diagram 7-Figure 14 so, the control total iron content at 3-3000ppm, can control or reduce the metal protection of oxidizing potential sterilized water at 0-1500ppm and available chlorine content equally.
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 15, 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, contain the electrolyzed oxidizing water of ferric iron or total iron, ferric iron (perhaps the ferric iron in total iron and can be converted into ferric ferrous iron and Zero-valent Iron) 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, its available chlorine content 3-3000mg/L, and the content of its total iron is not higher than 1500mg/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 3-3000mg/L, the content of its total iron is not higher than 1500mg/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, acid iodide, periodic 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, metaphosphoric 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 3-3000mg/L in the B unit.
Available chlorine content is 3-3000mg/L in A unit and the B unit mixed liquor, wherein is preferably 3-2000mg/L, is preferably 30-1000mg/L again, also is preferably 30-500mg/L, most preferably is 30-250mg/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 iron content is not higher than 1500mg/L in A unit and the B unit mixed liquor, wherein is preferably not to be higher than 1250mg/L, is preferably not to be higher than 1000mg/L again, is preferably again not to be higher than 750mg/L, also is preferably not to be higher than 500mg/L, most preferably is not to be higher than 250mg/L.
Control the method for total iron and ferric iron content, one is controlled total iron and ferric 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 iron of part and ferric iron; Its three, by the post processing of AB unit mixed liquor, remove the total iron of part and ferric iron.
The total iron of described removal and ferric method can be selected one or several of following method, to remove or the total iron of masked segment and ferric iron.Can add the Fe deactivator, such as precipitating reagent and Fe
3+Form precipitation-OH
-Ion is such as chelating agent and Fe
3+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 iron and ferric iron 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 ionic iron to nonionic derivative, make it with ionic active ingredient (as, hydrogen ion, clorox) distinguish.After removing purpose impurity (total iron and ferric iron), 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, its available chlorine content 3-3000mg/L, and its total iron content is not higher than 1500mg/L.
Its pH value is 2-8, wherein is preferably between 3-8, is preferably again between 4-8, most preferably is between 5-8.
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.; The optional nitrogen substance of organic base is 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 3-3000mg/L wherein is preferably 3-2500mg/L, is preferably 3-2000mg/L again, is preferably again 3-1500mg/L, also is preferably 3-1000mg/L, and more preferably 3-500mg/L most preferably is 30-250mg/L.
Its total iron content is not higher than 1500mg/L, wherein is preferably not to be higher than 1250mg/L, is preferably not to be higher than 1000mg/L again, is preferably again not to be higher than 750mg/L, also is preferably not to be higher than 500mg/L, most preferably is not to be higher than 250mg/L.
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1: preparation 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 ferric iron 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 iron 5mg/L, wherein ferric iron 5mg/L).At this moment, contain organic monoacid, strong base-weak acid salt in the solution.
Embodiment 2: preparation 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 ferric iron 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 ferric iron 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 iron 25mg/L, wherein ferric iron 25mg/L).At this moment, the pH of solution is by acidic materials and alkaline matter co-controlling.
Embodiment 3: preparation 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 ferric iron 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 iron 50mg/L, wherein ferric iron 50mg/L).At this moment, contain inorganic acid, strong base-weak acid salt in the solution.
Embodiment 4: preparation 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 ferrous iron 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 iron 75mg/L, wherein ferrous iron≤75mg/L).At this moment, contain strong acid, strong acid and strong base salt in the solution.
Embodiment 5: preparation 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 ferrous iron 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 ferrous iron 10g).
During use, the A unit is added the B unit in batches, make B unit dissolving, every crowd of addition 100L makes 1000L subacidity oxidizing potential sterilized water (pH5-7, ORP1100-1200mV, ACC2000mg/L, total iron 100mg/L, wherein ferrous iron≤100mg/L).At this moment, contain strong acid, weak acid, weak acid strong alkali salt, strong acid and strong base salt in the solution.
Embodiment 6: preparation 1000L subacidity oxidizing potential sterilized water (available chlorine content is 3000mg/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 15Kg, add 17g sodium carbonate, mix packing, get B unit (the about 3Kg of available chlorine wherein contains ferrous iron 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, ACC3000mg/L, total iron 150mg/L, wherein ferrous iron≤150mg/L).At this moment, contain strong acid, weak acid, weak acid strong alkali salt, strong acid and strong base salt in the solution.
Embodiment 7: preparation 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 Zero-valent Iron 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 iron 200mg/L, wherein Zero-valent Iron 200mg/L).At this moment, contain strong acid, strong acid and strong base salt in the solution.
Embodiment 8: preparation 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 the A unit.
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 wherein contains Zero-valent Iron 2.5g).
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 iron 250mg/L, wherein Zero-valent Iron 250mg/L).
Embodiment 9: preparation 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 A unit (containing Zero-valent Iron 2g).
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 Zero-valent Iron 1g).
During use, the B unit is added the A unit, make 10L subacidity oxidizing potential sterilized water (pH5-7, ORP1000-1100mV, ACC1000mg/L, total iron 300mg/L, wherein Zero-valent Iron 300mg/L).At this moment, contain strong acid, weak acid, strong acid and strong base salt in the solution.
Embodiment 10: preparation 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 ferric iron 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 ferrous iron 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 iron 350mg/L, wherein ferric iron 300mg/L, ferrous iron 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: preparation 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 ferrous iron 3g).
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 ferric iron 1g).
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 iron 400mg/L, wherein ferric iron 100mg/L, ferrous iron 300mg/L).
Embodiment 12: preparation 10L subacidity oxidizing potential sterilized water (available chlorine content is 2500mg/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 ferric iron 4g, ferrous iron 0.5g).
Raw material B: liquor natrii hypochloritis (available chlorine 50mg/ml, sodium carbonate 0.11M), measure 500ml, 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 iron 450mg/L, wherein ferric iron 400mg/L, ferrous iron 50mg/L).
Embodiment 13: preparation 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 ferric iron 4g, ferrous iron 1g).
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 iron 500mg/L, wherein ferric iron 400mg/L, ferrous iron 100mg/L).
Embodiment 14: preparation 10L faintly acid oxidizing potential sterilized water (available chlorine content is 1000mg/L)
Raw material A: acetic acid aqueous solution (pH3-4), measure 9.8L, add 0.001mol aluminium chloride, after the dissolving, packing gets A unit (containing ferrous iron 5g).
Raw material B: the hypochlorite generator prepares liquor natrii hypochloritis's (sodium carbonate is regulated for available chlorine 50mg/ml, pH=8.5), measures 200ml, can, and sealing gets B unit (available chlorine 10g contains ferric iron 0.8g, ferrous iron 0.2g).
During use, the spraying of A unit is added the B unit, make 10L faintly acid oxidizing potential sterilized water (pH3-5, ORP1000-1200mV, ACC1000mg/L, total iron 600mg/L, wherein ferric iron 80mg/L, ferrous iron 520mg/L).At this moment, contain weak acid-weak acid strong alkali salt buffer system in the solution.
Embodiment 15: preparation 10L subacidity oxidizing potential sterilized water (available chlorine content is 1500mg/L)
Raw material A: acetic acid-sodium acetate solution (pH5.0-5.5), measure 9.85L, can, sealing gets A unit (containing ferric iron 5g, ferrous iron 1g).
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 150ml, can, and sealing gets B unit (available chlorine 15g contains ferric iron 0.8g, ferrous iron 0.2g).
During use, the A unit is added dropwise to the B unit, makes 10L subacidity oxidizing potential sterilized water (pH5-7, ORP1000-1200mV, ACC1500mg/L, total iron 700mg/L, wherein ferric iron 580mg/L, ferrous iron 120mg/L).At this moment, contain acetic acid-sodium acetate buffer system in the solution.
Embodiment 16: preparation 10L oxidizing potential sterilized water (available chlorine content is 3mg/L)
Raw material A: acid solution (0.06M acetic acid, 0.01M hydrochloric acid), measure 9.7L, can, sealing gets A unit (containing ferric iron 7.9g).
Raw material B: liquor natrii hypochloritis's (available chlorine 0.1mg/ml contains sodium carbonate 1.5M), measure 300ml, filling and sealing gets B unit (available chlorine 30mg contains Zero-valent Iron 0.1g).
During use, the A unit is added the B unit, make 10L oxidizing potential sterilized water (pH6.97, ORP700mV, ACC3mg/L, total iron 800mg/L, wherein ferric iron 790mg/L, Zero-valent Iron 10mg/L).At this moment, contain acetic acid-sodium acetate buffer system in the solution.
Embodiment 17: preparation 10L faintly acid oxidizing potential sterilized water (available chlorine content is 150mg/L)
Raw material A: citric acid solution (0.07M), measure 9L, can, sealing gets A unit (containing Zero-valent Iron 8.8g).
Raw material B: liquor natrii hypochloritis (available chlorine 1.5g/L, diisopropylamine transfers to pH=14), measure 1L, filling and sealing gets B unit (available chlorine 1.5g contains ferric iron 0.2g).
During use, the A unit is added the B unit in batches, every crowd of 400ml makes 10L faintly acid oxidizing potential sterilized water (pH3-5, ORP1000-1100mV, available chlorine content are 150mg/L, total iron 900mg/L, wherein ferric iron 20mg/L, Zero-valent Iron 880mg/L).At this moment, solution contains citric acid-citrate buffer solution.
Embodiment 18: preparation 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, sealing gets A unit (containing ferric iron 9.5g, Zero-valent Iron 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 faintly acid oxidizing potential sterilized water (pH3-5, ORP1100-1200mV, ACC1000mg/L, total iron 1000mg/L, wherein ferric iron 950mg/L, Zero-valent Iron 50mg/L).At this moment, solution contains buffer solution.
Embodiment 19: preparation 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 ferric iron 6g, Zero-valent Iron 5g).
During use, the A unit is mixed with the B unit, make 10L highly acid oxidizing potential sterilized water (pH2-3, ORP1200-1400mV, ACC2000mg/L, total iron 1100mg/L, wherein ferric iron 600mg/L, Zero-valent Iron 500mg/L).
Embodiment 20: preparation 1L oxidizing potential sterilized water (available chlorine content is 3000mg/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 ferric iron 0.1g, Zero-valent Iron 0.1g).
Raw material B: calcium hypochlorite powder (available chlorine 0.2g/g) takes by weighing 15g (the about 3g of available chlorine contains ferric iron 0.1g).
A raw material and B raw material and 0.2mol calcium chloride (desiccant contains ferric iron 0.1g) are mixed the monobasic packing.
During use, above-mentioned composition is dissolved in the 1L water (containing ferric iron 0.8g), behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP900-1400mV, ACC3000mg/L, total iron 1200mg/L, wherein ferric iron 1100mg/L, Zero-valent Iron 100mg/L).
Embodiment 21: preparation 1L acid oxidation potential sterilized water (available chlorine content is 300mg/L)
Raw material A: ferric chloride solution (0.015M), measure 0.98L, can, sealing gets A unit (containing ferric iron 0.83g).
Raw material B: liquor natrii hypochloritis (pH=9), measure 20ml (available chlorine 300mg), can, sealing gets B unit (available chlorine 300mg contains ferric iron 0.4g, Zero-valent Iron 0.07g).
During use, the A unit is mixed with the B unit, make 1L acid oxidation potential sterilized water (pH3-5, ORP1000-1100mV, ACC300mg/L, total iron 1300mg/L, wherein ferric iron 1230mg/L, Zero-valent Iron 70mg/L).
Embodiment 22: preparation 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 ferric iron 10mg, Zero-valent Iron 10mg).
Raw material B: sodium chlorite solution (pH=9), measure 1L (available chlorine 400mg), can, sealing gets B unit (available chlorine 400mg contains ferric iron 0.89g, Zero-valent Iron 0.49g).
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 iron 1400mg/L, wherein ferric iron 900mg/L, Zero-valent Iron 500mg/L).
Embodiment 23: preparation 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 ferrous iron 1.45g).
Raw material B: the Efficacious Disinfeitant solid, take by weighing 6g, packing gets B unit (available chlorine 0.6g contains Zero-valent Iron 50mg).
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 iron 1500mg/L, wherein ferrous iron 1450mg/L, Zero-valent Iron 50mg/L).
Embodiment 24: preparation 1L oxidizing potential sterilized water (available chlorine content is 700mg/L)
Raw material A: the iron sulfate solid, take by weighing 0.008mol, succinyl chloride takes by weighing 0.045mol, and both mix (wherein containing ferric iron 0.9g).
Raw material B: calcium hypochlorite powder (available chlorine 0.25g/g) takes by weighing 2.8g (the about 700mg of available chlorine contains Zero-valent Iron 10mg).
The A raw material is mixed the monobasic packing with B raw material and 5g sodium acetate (wherein containing ferrous iron 10mg).
During use, the AB composition is dissolved in the 1L water (containing ferric iron 0.53g), behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP900-1300mV, ACC700mg/L, total iron 1450mg/L, wherein ferric iron 1430mg/L, ferrous iron 10mg/L, Zero-valent Iron 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: preparation 1L oxidizing potential sterilized water (available chlorine content is 800mg/L)
Raw material A: succinyl chloride, take by weighing 0.05mol, packing gets A unit (containing ferric iron 10mg, ferrous iron 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 Zero-valent Iron 1330mg).
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 iron 1350mg/L, wherein ferric iron 10mg/L, ferrous iron 10mg/L, Zero-valent Iron 1330mg/L).
Embodiment 26: preparation 1L oxidizing potential sterilized water (available chlorine content is 1000mg/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 ferric iron 5mg, ferrous iron 5mg, Zero-valent Iron 5mg).
Raw material B: calcium hypochlorite powder (available chlorine 0.25g/g), take by weighing 3g, toluene-sodium-sulfonchloramide (available chlorine 0.25g/g) takes by weighing 1g, hybrid packed (total available chlorine 1000mg contains ferric iron 50mg).
A, B raw material and 5g calcium chloride (desiccant contains ferric iron 5mg) are mixed the monobasic packing.
During use, above-mentioned composition is dissolved in the 1L water (containing ferric iron 1180mg), behind the pH of solution≤8.0, make 1L oxidizing potential sterilized water (pH2-8, ORP1000-1300mV, ACC1000mg/L, total iron 1250mg/L, wherein ferric iron 1240mg/L, ferrous iron 5mg/L, Zero-valent Iron 5mg/L).
Embodiment 27: preparation 1000L highly acid oxidizing potential sterilized water (available chlorine content is 1500mg/L)
Raw material A: electrolysis produces acidic oxidized electric potential water (pH2-3, ACC decomposes rapidly), measures 1000L, and packing gets A unit (containing ferric iron 300g, ferrous iron 300g, Zero-valent Iron 300g).
Raw material B: Efficacious Disinfeitant powder 7.5Kg (available chlorine 0.1g/g), sodium dichloro cyanurate 3Kg (available chlorine 0.25g/g) mixes, and packing gets B unit (total available chlorine 1.5Kg contains ferric iron 150g, Zero-valent Iron 100g).
During use, the A unit is mixed with the B unit, make 1000L acid oxidation potential sterilized water (pH2-3, ORP1200-1300mV, ACC1500mg/L, total iron 1150mg/L, wherein ferric iron 450mg/L, ferrous iron 300mg/L, Zero-valent Iron 400mg/L).
Embodiment 28: preparation 1L acid oxidation potential sterilized water (available chlorine content is 50mg/L)
Raw material A: hydrochloric acid solution (pH2-3), measure 1L (containing total iron 950mg), independent packaging.
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 iron 950mg/L).
Embodiment 29: preparation 10L acid oxidation potential sterilized water (available chlorine content is 500mg/L)
Raw material A: hydrochloric acid solution (3M), measure 15ml (containing total iron 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 iron 50mg), independent corrosion-proof packing.
During use, water (wherein the containing total iron 8.4g) dilution of 9.975L with after the B unit mixes, is used again in the A unit, make 10L acid oxidation potential sterilized water (pH2.5-3.5, ORP1100-1300mV, ACC500mg/L, total iron 850mg/L).At this moment, solution contains strong acid, strong acid and strong base salt.
Embodiment 30: preparation 10L acid oxidation potential sterilized water (available chlorine content is 150mg/L)
Raw material A: hydrochloric acid solution (4M), measure 10ml (containing total iron 0.25g), independent corrosion-proof packing.
Raw material B: sodium perchlorate solution (sodium carbonate is regulated for 0.5M, pH=8), measure 10ml (containing total iron 0.25g), independent corrosion-proof packing.
During use, water (wherein the containing total iron 7g) dilution of 9.98L with after the B unit mixes, is used again in the A unit, make 10L acid oxidation potential sterilized water (pH5-7, ORP900-1000mV, ACC150mg/L, total iron 750mg/L).
Embodiment 31: preparation 1L acid oxidation potential sterilized water (available chlorine content is 200mg/L)
Raw material A: hydrochloric acid solution (pH=0), measure 10ml (containing ferric iron 70mg, ferrous iron 20mg, Zero-valent Iron 10mg), independent packaging.
Raw material B: liquor natrii hypochloritis (pH=12.5, potassium hydroxide is regulated), measure 10ml (available chlorine 200mg contains ferric iron 80mg, ferrous iron 10mg, Zero-valent Iron 10mg), independent packaging.
During use, A unit and B unit are placed 0.98L water (containing ferric iron 0.3g, ferrous iron 0.05g, Zero-valent Iron 0.1g), make 1L acid oxidation potential sterilized water (pH2-3, ORP1150-1200mV, ACC200mg/L, total iron 650mg/L, wherein ferric iron 450mg/L, ferrous iron 80mg/L, Zero-valent Iron 120mg/L).
Embodiment 32: preparation 1000L highly acid oxidizing potential sterilized water (available chlorine content is 1000mg/L)
Raw material A: acidic aqueous solution 2000L (pH2-3 contains total iron 100mol).
The raw material A preliminary treatment
Measure respectively each 1000L of raw material A 1-A5, can, sealing gets the A1-A5 unit.
Raw material B: calcium hypochlorite powder (available chlorine 200mg/g), take by weighing 5kg, packing gets B unit (available chlorine 1000g contains total iron 100g).
Prepare each 5 parts of identical B unit.
During use, the A1-A5 unit is mixed with a B unit respectively, make following 1000L oxidizing potential sterilized water 1-5, see Table 1.
Table 1
| Electrolyzed oxidizing water | pH | ORP：mV | ACC(mg/L) | Total iron |
| A1+B | 2-3 | 1150-1250 | 1000 | 1100mg/L |
| A2+B | 2-3 | 1150-1250 | 1000 | 150mg/L |
| A3+B | 2-3 | 1150-1250 | 1000 | 400mg/L |
| A4+B | 2-3 | 1150-1250 | 1000 | 1500mg/L |
| A5+B | 2-3 | 1150-1250 | 1000 | 700mg/L |
Above-mentioned acid oxidation potential sterilized water (A4+B) continues post processing
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 33: preparation 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 respectively identical 6 parts.
Raw material B: (pH8.5 contains total iron=5.6g/L) to available chlorine solution 100L.
Raw material B preliminary treatment
Through above-mentioned processing, available chlorine has certain loss, and its content need to redeterminate.
Raw material B1-B6 is respectively measured 10L, can, and sealing makes the B1-B6 unit.
During use, the B1-B6 unit is mixed with a A unit respectively, make following 10L acid oxidation potential sterilized water 1-6, see Table 2.
Table 2
| Electrolyzed oxidizing water | pH | ORP：mV | ACC(mg/L) | Total iron |
| A+B1 | 2-3 | 1150-1250 | 900 | 100mg/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 | 700 | 50mg/L |
| A+B5 | 2-3 | 1150-1250 | 700 | 1500mg/L |
| A+B6 | 2-3 | 1150-1250 | 700 | 400mg/L |
Above-mentioned acid oxidation potential sterilized water (A+B5) continues post processing
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: preparation 100L acid oxidation potential sterilized water (available chlorine content 1000mg/L)
Raw material A: hydrochloric acid solution 100L (pH2-3 contains ferrous iron 5.6g/L).
Raw material A adds EDTA (10mol), forms complex compound, and under the low temperature (5-10 ℃), ultrafiltration behind the large molecule of filtering, is adjusted pH, obtains raw material A 1 (pH2-3, ferrous iron 600mg/L).Measure 99L, can, sealing makes the A1 unit.
Raw material B: liquor natrii hypochloritis 10L (pH8.5 contains ferric iron 10g/L).
Raw material B is fast by manganese sand adsorption column, and the absorbed portion ferric iron is adjusted pH, obtains raw material B1 (pH8.0, ACC100mg/ml, ferric iron 200mg/L).Take by weighing 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 iron 596mg/L, ferrous iron 594mg/L wherein, ferric iron 2mg/L).
Embodiment 35: preparation 10L acid oxidation potential sterilized water (available chlorine content 800mg/L)
Raw material A: aqueous acid (pH5-6 contains ferrous iron 3g/L), measure 9L, can, sealing makes the A unit.
Raw material B: liquor natrii hypochloritis's (pH8.5, ACC10g/L contain Zero-valent Iron 1.5g/L), take by weighing 1L, can, sealing makes the B1 unit.
During use, the A1 unit is mixed with the B1 unit, make the acid oxidation potential sterilized water (pH6-7, ACC1000mg/L, ORP1000-1100mV, total iron 2.85g/L, wherein ferrous iron≤2.7g/L, Zero-valent Iron 150mg/L) of the high iron content of 10L.Fast by manganese sand adsorption column and NF membrane, part is adsorbed the Fe element, adjusts pH again under the above-mentioned sterilized water low temperature, make low iron content sterilized water (pH5-7, ACC800mg/ml, ORP1000-1100mV, total iron 100mg/L, ferrous iron 90mg/L wherein, Zero-valent Iron 10mg/L).
Embodiment 36: 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 ferrous iron 150g);
Configuration aqueous hydrochloric acid solution (pH=2) is got 100L, makes A2 unit (containing ferric iron 150g);
Configuration aqueous hydrochloric acid solution (pH=4) is got 100L, makes A3 unit (containing Zero-valent Iron 150g);
Configuration aqueous hydrochloric acid solution (pH=6) is got 100L, makes A4 unit (containing total iron 150g);
Configuration diethylamine aqueous solution (pH=7-8) is got 100L, makes A5 unit (containing total iron 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 ferrous iron 150g);
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 ferric iron 150g);
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 Zero-valent Iron 150g);
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 iron 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 iron 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 iron 50g).
Different solid available chlorine preparations prepares different B1-B11 unit:
Sodium dichloro cyanurate, weighing 1.2g, the sodium carbonate of interpolation 60mol, packing makes B1 unit (available chlorine 0.3g contains total iron 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 iron 0mg);
Dichlord isocyanurice acid, weighing 1.5g, the sodium carbonate of interpolation 0.006mol, packing makes B3 unit (available chlorine 0.3g contains total iron 0mg);
Efficacious Disinfeitant, weighing 3g, the sodium carbonate of interpolation 0.00006mol, packing makes B4 unit (available chlorine 0.3g contains total iron 0mg);
Toluene-sodium-sulfonchloramide, weighing 1.2g, packing makes B5 unit (available chlorine 0.3g contains total iron 0mg);
Toluene-sodium-sulfonchloramide, weighing 1.2Kg, packing makes B6 unit (available chlorine 300g, total iron 0mg);
Toluene-sodium-sulfonchloramide, weighing 1.2Kg, packing makes B7 unit (available chlorine 300g, total iron 0mg);
Toluene-sodium-sulfonchloramide, weighing 1.2Kg, packing makes B8 unit (available chlorine 300g, total iron 0mg);
Toluene-sodium-sulfonchloramide, weighing 1.2Kg, packing makes B9 unit (available chlorine 300g, total iron 0mg);
Toluene-sodium-sulfonchloramide, weighing 40g, packing makes B10 unit (available chlorine 10g, total iron 0mg);
Toluene-sodium-sulfonchloramide, weighing 80g, packing makes B11 unit (available chlorine 20g, total iron 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 iron 1500mg/L, wherein ferrous iron 1500mg/L;
A2+B2, pH7-8, ORP600-700mV, ACC3mg/L, total iron 1500mg/L, wherein ferric iron 1500mg/L;
A3+B3, pH7-8, ORP600-700mV, ACC3mg/L, total iron 1500mg/L, wherein Zero-valent Iron 1500mg/L;
A4+B4, pH7-8, ORP600-700mV, ACC3mg/L, total iron 1500mg/L;
A5+B5, pH7-8, ORP600-700mV, ACC3mg/L, total iron 0mg/L;
A6+B6, pH7-8, ORP1000-1100mV, ACC3000mg/L, total iron 1500mg/L, wherein ferrous iron 1500mg/L;
A7+B7, pH7-8, ORP1000-1100mV, ACC3000mg/L, total iron 1500mg/L, wherein ferric iron 1500mg/L;
A8+B8, pH7-8, ORP1000-1100mV, ACC3000mg/L, total iron 1500mg/L, wherein Zero-valent Iron 1500mg/L;
A9+B9, pH7-8, ORP1000-1100mV, ACC3000mg/L, total iron 0mg/L;
A10+B10, pH7-8, ORP800-900mV, ACC100mg/L, total iron 1000mg/L;
A11+B11, pH7-8, ORP800-900mV, ACC200mg/L, total iron 500mg/L.
Embodiment 37: 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 iron 0mg);
Configuration sodium acetate solution (pH=7-7.5) is got 9L, makes A2 unit (containing total iron 0mg);
Configuration aqueous hydrochloric acid solution (pH=4) is measured 5L, makes A3 unit (containing total iron 0mg);
Configuration aqueous hydrochloric acid solution (pH=2) is measured 5L, makes A4 unit (containing total iron 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 30g, total iron 6g);
The liquor natrii hypochloritis, pH8.5 is measured 1L, and packing makes B2 unit (available chlorine 15g, total iron 8g);
The liquor natrii hypochloritis is measured 5L, adds sodium carbonate 0.0003mol, and packing makes B3 unit (available chlorine 7.5g, total iron 10g);
The liquor natrii hypochloritis is measured 5L, adds sodium carbonate 0.03mol, and packing makes B4 unit (available chlorine 2.5, total iron 12g).
During use, the A unit is mixed with the B unit, make following 10L oxidizing potential sterilized water, see Table 3.
Table 3
| Electrolyzed oxidizing water | pH | ORP：mV | ACC(mg/L) | Total iron |
| A1+B1 | 7-8 | 1000-1100 | 3000 | 600mg/L |
| A2+B2 | 7-8 | 950-1050 | 1500 | 800mg/L |
| A3+B3 | 7-8 | 900-1000 | 750 | 1000mg/L |
| A4+B4 | 7-8 | 800-900 | 250 | 1200mg/L |
Embodiment 38: preparation 100L alkalescence oxidizing potential sterilized water (pH=8.0)
Aqueous sulfuric acid (0.1M), the identical A1-A2 unit (containing total iron 140g) of preparation 100L.
Aqueous hydrochloric acid solution (0.2M), the identical A3-A4 unit (containing total iron 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 iron 10g);
Calcium hypochlorite, weighing 1.5Kg, the sodium carbonate of interpolation 13mol, packing makes B2 unit (containing available chlorine 300g, total iron 10g);
Sym-closene, weighing 0.75g, the sodium carbonate of interpolation 13mol, packing makes B3 unit (containing available chlorine 0.3g, total iron 0g);
Toluene-sodium-sulfonchloramide, weighing 1.2Kg, the sodium carbonate of interpolation 13mol, packing makes B4 unit (containing available chlorine 0.3Kg, total iron 0g).
The A unit is mixed with the B unit, make the dissolving of B unit, make following oxidizing potential sterilized water, see Table 4.
Table 4
| Electrolyzed oxidizing water | pH | ORP：mV | ACC(mg/L) | Total iron |
| A1+B1 | 8.0 | 600 | 3 | 1500mg/L |
| A2+B2 | 8.0 | 1050 | 3000 | 1500mg/L |
| A3+B3 | 8.0 | 600 | 3 | 0mg/L |
| A4+B4 | 8.0 | 1050 | 3000 | 0mg/L |
Embodiment 39: 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 iron 150g);
Configuration aqueous hydrochloric acid solution (pH=1) is got 100L, makes A2 unit (containing total iron 150g);
Configuration aqueous hydrochloric acid solution (pH=2) is got 100L, makes A3 unit (containing total iron 0g);
Configuration aqueous hydrochloric acid solution (pH=2) is got 100L, makes A4 unit (containing total iron 0g).
Different solid available chlorine preparations prepares different B1-B4 unit:
Sodium dichloro cyanurate, weighing 1.2g, the sodium hydroxide of interpolation 99mol mixes, and packing makes B1 unit (containing available chlorine 0.3g);
Toluene-sodium-sulfonchloramide, weighing 1.2Kg, the sodium hydroxide of interpolation 9mol mixes, and packing makes B2 unit (containing available chlorine 300g);
Sym-closene, weighing 0.75g, packing makes B3 unit (containing available chlorine 0.3g);
Efficacious Disinfeitant, weighing 3Kg, packing makes B4 unit (containing available chlorine 300g).
The AB unit is mixed, make the dissolving of B unit, make following oxidizing potential sterilized water, see Table 5.
Table 5
| Electrolyzed oxidizing water | pH | ORP：mV | ACC(mg/L) | Total iron (mg/L) |
| A1+B1 | 2.0 | 1050 | 3 | 1500 |
| A2+B2 | 2.0 | 1350 | 3000 | 1500 |
| A3+B3 | 2.0 | 1050 | 3 | 0 |
| A4+B4 | 2.0 | 1350 | 3000 | 0 |
Embodiment 40: preparation 10L oxidizing potential sterilized water
The zinc citrate pressed powder, weighing 1mol makes A unit (containing total iron 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 iron 10mg/L).
Embodiment 41: preparation 10L oxidizing potential sterilized water
The zinc chloride powder, weighing 0.5mol makes A unit (containing total iron 1g).
The magnesium hypochlorite powder, weighing 100g (containing available chlorine 20g), Efficacious Disinfeitant, weighing 100g (containing available chlorine 10g) adds sodium acetate 1mol, mixes, and makes B unit (total available chlorine 30g contains total iron 14g).
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, ACC3000mg/L, total iron 1500mg/L).
Embodiment 42: 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 iron 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 〉=600mV, ACC1000mg/L, total iron 1000mg/L).
Disinfection effect test:
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 9, ACC3mg/L, pH2.0, ORP1050mV, total iron 0mg/L
Kill logarithm behind table 6 15min action time
| Test organisms | Trial target 1-3 | |
|
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 |
Annotate: above experiment (adds 0.3% organic chaff interference) and carries out under clean conditions
Bactericidal assay 2 (suspension is quantitative), the oxidizing potential sterilized water is killed logarithm and time
Trial target 9, ACC3000mg/L, pH2.0, ORP1350mV, total iron 0mg/L
Kill logarithm behind table 7 0.5min action time
Annotate: above experiment (adds 0.3% organic chaff interference) and carries out under clean conditions
Stability test
" disinfection technology standard (version in 2008) " middle three kinds of term of validity detection methods stipulating that product among the embodiment 7,8,17,18,19,20,23,24,25,26 is promulgated according to the Ministry of Public Health, the result shows that the term of validity surpasses 2 years.
The corrosion of carbon steel test is with reference to " version disinfection technology standard in 2008 "
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.
Relatively Fig. 1-2 data can be learnt: the non-oxide system of pH=2-8, the pH/ ferric iron has corrosivity to carbon steel.
Comparison diagram 3 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 ferric iron synergy, has affected the etching characteristic of solution to carbon steel.
Simultaneously as can be known, in pH/ACC/ ferric iron system, the ACC/ ferric iron of different content has similar etching characteristic to metal during pH=2.0, when being pH=2.0/ ferric iron＞1500mg/L, the ACC of different content (3-3000ppm) system all produces hop to corrosion of metal.
Comparison diagram 4 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 ferric iron synergy, has affected the etching characteristic of solution to carbon steel.
Simultaneously as can be known, in pH/ACC/ ferric iron system, the ACC/ ferric iron of different content during pH=8.0 has similar etching characteristic to metal equally, when being pH=8.0/ ferric iron＞1500mg/L, the ACC of different content (3-3000ppm) system all produces hop to corrosion of metal.
Compare corrosion test 2,3, in pH/ACC/ ferric iron system, during pH=2.0-8.0, available chlorine reduces, and the corrosivity of system is reduced, and reduced the significance of hop.Available chlorine content (for example, in the time of 3500mg/L), with different content ferric iron synergy, sharply rises to the corrosivity of carbon steel more than 3000mg/L.
Comparison diagram 5 data can be learnt: in pH/ACC/ ferric iron system, during ACC=3000ppm, pH has similar etching characteristic at 2.0-8.0 to metal, when being ACC=3000ppm/ ferric iron＞1500mg/L, pH all produces hop in the system of 2.0-8.0 to corrosion of metal.
Comparison diagram 6 data can be learnt: in pH/ACC/ ferric iron system, during ACC=3ppm, pH has similar etching characteristic to metal equally at 2.0-8.0, when being ACC=3ppm/ ferric iron＞1500mg/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/ ferric iron system, during ACC=3000-3ppm, acid reduction reduces the corrosivity of system, and has reduced the significance of hop.
Comparison diagram 7-10 data can be learnt: in the oxidisability system of pH=2-8, and ferric corrosivity＞ferrous iron＞Zero-valent Iron.So the corrosivity of the different total iron that consist of of same amount, total iron of total iron that total iron that 100% ferric iron consists of＞100% ferrous iron consists of＞100% Zero-valent Iron formation.
Comparison diagram 11-14 data can be learnt: in the oxidisability system of pH=2-8, and ferric corrosivity＞ferrous iron＞Zero-valent Iron.So the corrosivity of the different total iron that consist of of same amount, the ferrous iron of total iron＞different proportion of the ferric iron of total iron＞different proportion that 100% ferric iron consists of and ferrous iron combination＞100% ferrous iron formation and total iron that Zero-valent Iron combination＞100% Zero-valent Iron consists of.
The copper corrosion performance test is with reference to " version disinfection technology standard in 2008 "
The Calculation of corrosion rate is such as table 8.
Table 8 pair copper corrosion speed
| pH | ACC(mg/L) | Total iron (mg/L) | Corrosion rate (mm/a) |
| 2.0 | 0 | 100 | 0.0742 |
| 2.0 | 3 | 100 | 0.1238 |
| 2.0 | 3 | 750 | 0.2942 |
| 2.0 | 3 | 1500 | 0.3586 |
| 2.0 | 3 | 2000 | 0.8375 |
| 2.0 | 3000 | 100 | 0.2398 |
| 2.0 | 3000 | 750 | 0.3912 |
| 2.0 | 3000 | 1500 | 0.5678 |
| 2.0 | 3000 | 2000 | 1.6835 |
| 2.0 | 0 | 2000 | 0.1917 |
| 2.0 | 3500 | 100 | 0.5532 |
| 2.0 | 3500 | 1000 | 1.2115 |
Can learn from table 8: available chlorine and total iron synergy have increased solution to corrosion of metal.When available chlorine content is higher than 3mg/L, copper corrosion is significantly risen, and make total iron content when 1500mg/L is above, to impatient acute rising of copper corrosion.Available chlorine content (for example, in the time of 3500mg/L), with total iron synergy, significantly rises to copper corrosion more than 3000mg/L.
The aluminium corrosion test is with reference to " version disinfection technology standard in 2008 "
The Calculation of corrosion rate is such as table 9.
Table 9 pair Corrosion of Al speed
| pH | ACC(mg/L) | Ferric iron (mg/L) | Corrosion rate (mm/a) |
| 2.0 | 0 | 100 | 0.0798 |
| 2.0 | 3 | 100 | 0.1356 |
| 2.0 | 3 | 750 | 0.2825 |
| 2.0 | 3 | 1500 | 0.4759 |
| 2.0 | 3 | 2000 | 0.8932 |
| 2.0 | 3000 | 100 | 0.2198 |
| 2.0 | 3000 | 750 | 0.3878 |
| 2.0 | 3000 | 1500 | 0.5823 |
| 2.0 | 3000 | 2000 | 1.7145 |
| 2.0 | 0 | 2000 | 0.2156 |
| 2.0 | 3500 | 100 | 0.5539 |
| 2.0 | 3500 | 1000 | 1.4985 |
Can learn from table 9: available chlorine and total iron synergy have increased solution to corrosion of metal.When available chlorine content is higher than 3mg/L, Corrosion of Al is significantly risen, and make total iron content when 1500mg/L is above, to impatient acute rising of Corrosion of Al.Available chlorine content (for example, in the time of 3500mg/L), with total iron synergy, significantly rises to Corrosion of Al more than 3000mg/L.
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, its available chlorine content 3-3000mg/L, and the content of its total iron is not higher than 1500mg/L.
2. the preparation method of the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 1 is characterized in that, total iron of described strong oxidizing property solution comprises one or several in ferric iron, ferrous iron and the Zero-valent Iron.
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 iron 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 iron 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 iron.
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 iron 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 iron 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 iron 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 iron is the fast processing mode, or process under the cryogenic conditions, or transfer B unit ionic available chlorine to molecule-type available chlorine, make it to distinguish with ionic iron; Or transfer ionic iron to nonionic derivative, make it and ionic active ingredient is distinguished, remove purpose foreign ion iron 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 3-3000mg/L, the content of its total iron is not higher than 1500mg/L.
14. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 13 is characterized in that, total iron of described strong oxidizing property solution comprises one or several in ferric iron, ferrous iron and the Zero-valent Iron.
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, its available chlorine content 3-3000mg/L, and the content of its total iron is not higher than 1500mg/L.
18. the oxidizing potential sterilized water of low-corrosiveness as claimed in claim 17 is characterized in that, total iron of described sterilized water comprises one or several in ferric iron, ferrous iron and the Zero-valent Iron.
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.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453196A (en) * | 2018-11-08 | 2019-03-12 | 中国地质大学（北京） | A kind of bactericidal composition and its preparation method and application |
| CN109996567A (en) * | 2016-09-30 | 2019-07-09 | 东部科技公司 | Oxidative reductive potential water solution, preparation method and its application method |
| CN111248222A (en) * | 2020-04-15 | 2020-06-09 | 广东爱锝医药技术研究院有限公司 | Composition for removing formaldehyde, sterilizing and removing peculiar smell |
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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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| 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 |
| CN102659217A (en) * | 2011-12-31 | 2012-09-12 | 邵鹏飞 | Weakly acidic oxidation potential sterilizing water and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109996567A (en) * | 2016-09-30 | 2019-07-09 | 东部科技公司 | Oxidative reductive potential water solution, preparation method and its application method |
| CN109453196A (en) * | 2018-11-08 | 2019-03-12 | 中国地质大学（北京） | A kind of bactericidal composition and its preparation method and application |
| CN109453196B (en) * | 2018-11-08 | 2021-03-16 | 中国地质大学（北京） | Bactericidal composition and preparation method and application thereof |
| CN111248222A (en) * | 2020-04-15 | 2020-06-09 | 广东爱锝医药技术研究院有限公司 | Composition for removing formaldehyde, sterilizing and removing peculiar smell |
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