CN103300061B

CN103300061B - Sterilization solution and preparation method thereof

Info

Publication number: CN103300061B
Application number: CN201310215489.XA
Authority: CN
Inventors: 邵鹏飞
Original assignee: Individual
Current assignee: Shao Pengfei
Priority date: 2013-05-31
Filing date: 2013-05-31
Publication date: 2014-12-03
Anticipated expiration: 2033-05-31
Also published as: CN103300061A

Abstract

The invention relates to the field of sterilization and disinfection and particularly relates to a sterilization solution and a preparation method thereof. The preparation method of the sterilization solution, disclosed by the invention, comprises the following steps of: (1) providing an effective bromine providing unit containing effective bromine or being capable of producing the effective bromine; (2) providing a pH value regulating unit; and (3) mixing the pH value regulating unit with the effective bromine providing unit to obtain the sterilization solution, wherein the pH value of the sterilization solution is 2-9, the content of the effective bromine in the sterilization solution is not lower than 1mg/L, and the electric conductivity is not higher than 120S/m. Compared with the existing sterilization solution containing the effective bromine, the sterilization solution prepared by the preparation method of the sterilization solution containing the effective bromine can reduce the corrosion against metal and further expand the range of applications.

Description

A kind of germicidal solution and preparation method thereof

Technical field

The present invention relates to sterilizing field, particularly a kind of germicidal solution and preparation method thereof.

Background technology

Effectively bromine has strong oxidizing property, and the redox potential value of its aqueous solution is not less than 500mV conventionally, therefore, shows the effect of extremely strong killing microorganisms.

Due to the distribution difference inside and outside microbial biofilm such as hydrogen ion, potassium ion, sodium ion, while making the inside and outside current potential of film reach dynamic equilibrium, there is certain potential difference, be generally about-700～+ 900mV.Containing factors such as oxidation, reduction material and pH in the germicidal solution of effective bromine, making it have high ORP(is ORP>500mV).After this strong oxidizing property germicidal solution contact microorganism, capture rapidly electronics, disturb biomembrane balance, change biological transmembrane potential difference, the inside and outside osmotic pressure of film, cause the destruction of the enhancing of biomembrane permeability, cellular swelling and biotransferase, make material in film overflow, dissolve, thus quick killing microorganisms.

Under microcosmic, show, effectively bromine can make the permeability of cell change, or biomembrane generation mechanicalness is broken, and impels material in film outwards to ooze out, thus quick killing microorganisms.

But the existing germicidal solution containing effective bromine, has general metal protection.

Summary of the invention

The first object of the present invention is to provide a kind of preparation method of germicidal solution, has the technical matters of general metal protection to solve brominated germicidal solution of the prior art.

The second object of the present invention is to provide a kind of germicidal solution, has the technical matters of general metal protection to solve brominated germicidal solution of the prior art.

The object of the invention is achieved through the following technical solutions:

A preparation method for germicidal solution, comprises the following steps:

(1) provide the effective bromine that contains effective bromine or can produce effective bromine that unit is provided;

(2) provide pH value regulon;

(3) provide unit to mix with described effective bromine described pH value regulon, obtain germicidal solution, the pH value of described germicidal solution is between 2-9, and its effective bromine content is not less than 1mg/L, and its electrical conductivity is not higher than 120S/m.

Preferably, the pH value of described germicidal solution is between 4-9, and its redox potential is 500-1300mV, and its effective bromine content is 1-20000mg/L, and its electrical conductivity is not higher than 60S/m.

Preferably, the pH value of described germicidal solution is between 6-8, and its redox potential is 500-1200mV, and its effective bromine content is 1-2000mg/L, and its electrical conductivity is 10 ^-4-20S/m.

Preferably, in step (1), also comprise: provide unit to reduce the pretreatment of electrical conductivity to described effective bromine.

Preferably, in step (2), also comprise: described pH value regulon is reduced to the pretreatment of electrical conductivity.

Preferably, in step (3), also comprise: provide the mixed mixed liquor in unit to reduce the post processing of electrical conductivity to described pH value regulon and described effective bromine.

Preferably, the processing method of described reduction electrical conductivity can be selected from crystallisation, membrane separation process, electrochemical process, chromatography, absorption method, ion-exchange or add can suppress ionization material in one or several.

Preferably, the described material that suppresses ionization comprises can be with water miscible or in water, have an organic solvent of certain solubility.

Preferably, described can be with water miscible or have a certain solubility in water organic solvent is selected from methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, ethylene glycol, 1,2-propane diols, 1,3-PD, glycerine, acetone wherein one or more.

Preferably, described germicidal solution comprise ammonium ion, lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, barium ions, chlorion, sulfate ion, nitrate ion, methanesulfonate ion, benzene sulfonic acid radical ion, phosphate anion, acetate ion, succinic ion, tartrate anion ion, citrate ion wherein one or several.

A kind of germicidal solution, the pH value of described germicidal solution is between 2-9, and its effective bromine content is not less than 1mg/L, and its electrical conductivity is not higher than 120S/m.

Containing compared with the germicidal solution of effective bromine, the present invention has following advantage with existing:

1, the germicidal solution that prepared by the preparation method of the germicidal solution containing effective bromine of the present invention can reduce corrosion of metal, thereby has expanded range of application;

2, before using, the pH value regulon of the germicidal solution containing effective bromine of the present invention and effectively bromine provide unit to deposit separately, in the time will using, then provide unit to mix pH value regulon and effective bromine, solve the storage problem containing the germicidal solution of effective bromine, very easy to use;

3, in the process of the preparation germicidal solution containing effective bromine of the present invention, strengthen artificial controllability, can regulate according to the actual requirements the pH value of germicidal solution, effective bromine content.

Brief description of the drawings

Fig. 1, Fig. 2 are in pH=2,9 oxidative environment, electrical conductivity and the effective schematic diagram of the corrosive effect of bromine to copper;

Fig. 3, Fig. 4 are in the oxidative environment of pH=2-9, the schematic diagram of electrical conductivity and the pH corrosive effect to copper;

Fig. 5 is in the oxidative environment of the effective bromine=100000mg/L of pH=2.0/, the schematic diagram of the corrosive effect of the electrical conductivity of different cation regulation system to copper;

Fig. 6 is in the oxidative environment of the effective bromine=100000mg/L of pH=2.0/, the schematic diagram of the corrosive effect of the electrical conductivity of different anion regulation system to copper;

Fig. 7 is in the oxidative environment of the effective bromine=1mg/L of pH=2.0/, the schematic diagram of the corrosive effect of the electrical conductivity of different ion regulation system to copper;

Fig. 8 is in the oxidative environment of the effective bromine=100000mg/L of pH=9.0/, the schematic diagram of the corrosive effect of the electrical conductivity of different cation regulation system to copper;

Fig. 9 is in the oxidative environment of the effective bromine=100000mg/L of pH=9.0/, the schematic diagram of the corrosive effect of the electrical conductivity of different anion regulation system to copper;

Figure 10 is in the oxidative environment of the effective bromine=1mg/L of pH=9.0/, the schematic diagram of the corrosive effect of the electrical conductivity of different ion regulation system to copper;

Figure 11, Figure 12 are in the oxidative environment of pH=2-9, the schematic diagram of electrical conductivity and the pH corrosive effect to carbon steel;

Figure 13, Figure 14 are in the oxidative environment of pH=2-9, the schematic diagram of electrical conductivity and the pH corrosive effect to aluminium.

Embodiment

Below describe the present invention.

At present, containing the sterilized water of effective bromine, corrosion of metal has been launched to Primary Study, the result of having announced shows containing the sterilized water of effective bromine to have general metal protection.But the research of its corrosive mechanism is not carried out.The result announced shows the sterilized water containing effective bromine, substantially corrosion-free to mild corrosion to stainless steel, to carbon steel, copper, aluminium moderate to heavy corrosion, its conclusion widely different.

Be to cause due to oxidisability and hydrionic comprehensive effect containing the sterilized water of effective bromine to the generality of metal erosion, according to different mechanism, in its metal-effective bromo-aqueous systems, have chemical attack and electrochemical corrosion simultaneously.

Described chemical attack refers to the corrosion effect that metal and corrosion factor direct effect cause.Metal has the trend (as shown in Equation 1) by effectively bromine is oxidized in sterilized water, oxidation product has the trend (as shown in Equation 2) that is converted into water soluble ion under hydrogen ion effect, thereby complete the transformation to water-soluble metal ion by metal simple-substance, macro manifestations is metal be generally corroded (corrosion approach 1).

The formation of oxidation product has two-way function, can change water soluble ion into, causes corrosion, forms oxidative horizon simultaneously, has protective effect, can stop contacting of corrosion factor and metal inside, thereby stops further corrosion; Free hydrionic concentration affects the oxidisability of effective bromine, affected the dissolution velocity of oxidative horizon simultaneously.The generation of oxidative horizon forms dynamic balance with dissolving, and macro manifestations is that metal is corroded with given pace.

M+[O] → M ⁿ⁺formula 1

2H ⁺+ MO=M ²⁺+ H ₂o formula 2

Described electrochemical corrosion refers to that metal contacts generation electrochemical reaction with electrolyte solution, makes metal ion, or generates oxide, hydroxide, causes material to go bad and changes.We know, metal in reality has the defect on all microcosmic conventionally, as chemical constituent inhomogeneity, or metal structure structure inhomogeneity, or metal physics state inhomogeneity, or skin covering of the surface imperfection, these defects have caused the physics and chemistry performance of metal to exist microcosmic difference, make metal generally have electrochemical inhomogeneities, there is potential difference E (M in tiny area or regional area in metal ⁿ⁺/ M), form some microelectrodes, what wherein current potential was lower is anode, what current potential was higher is negative electrode, this potential difference (1) makes to exist between different microelectrodes the trend of electronics and the directed transfer of ion, after metal contacts with containing the solution that can move freely charged particle, metal forms electronic conductor (2), solution forms ion conductor (3), (1) (2) (3) factor makes the ion generation directed movement in electronics and the solution in metal, formed current loop, macro manifestations is that anode is corroded, and transfers ion (corrosion approach 2) to certain speed.Current loop is the necessary condition that corrosion approach 2 occurs, and wherein the conductive capability of solution has affected the speed of corrosion.The conductive capability of solution is subject to various factors, as aquation, the migration rate of ion and viscosity, the temperature etc. of solution of the characteristic of ion (ionic radius, electrically charged), the concentration of ion, interionic interaction, ion.

In sum, in metal-effective bromo-aqueous systems, exist the different electrode electricity of several electrode potentials right simultaneously, comprise that electrode electricity that metal in corrosion approach 1 and its ion form is right to, electrode electricity that effectively bromine forms, and some small E (M in corrosion approach 2 ⁿ⁺/ M).As E θ (Al ³⁺/ Al)=-1.66v, E θ (Fe ²⁺/ Fe)=-0.45v, E θ (Cu ²⁺/ Cu)=0.34v, E θ (Br ₂/ Br ^-)=1.07v, E θ (HBrO/Br ^-)=1.33v.The metal because the strong oxidizing property of effective bromine and directly contact are corroded, so the corrosion of the chemical oxidation of corrosion approach 1 has decisive influence.

What emphasis was considered in the present invention is impact or the impact of corrosion approach 2 on corrosion approach 1 on metal protection of the conductive capability of system.The present invention is not confined to merely the single characteristic such as the kind, concentration, unit charge number, transfer ability of ion, but introduce electrical conductivity (Κ, unit: Siemens/rice, symbol S/m) or resistivity (ρ, unit: ohm meter, symbol Ω is m) as conductive capability or the contained effectively measurement index of the ion of free migration containing the solution of effective bromine, because electrical conductivity (Κ) is the macroscopic properties of comprehensive conductive capability or the system intermediate ion of system with resistivity (ρ) evaluation, is also the key factor of corrosion approach 2.Because electrical conductivity and resistivity are reciprocal each other, can quantitatively convert again, so select the measurement index of one of them parameter as the conductive capability of reflection system, can quantitatively be scaled equally another parameter, the conductive capability of reflection system.

Discuss in the present invention electrical conductivity (Κ) corrupting influence to metal (to the inactive metal of hydrogen ion) in oxidative environment between pH=2-9.As, using copper as research object, because copper does not react with simple hydrogen ion, so can more effectively embody pH/[Br ⁺the comprehensive corrosive effect of]/Κ, has also embodied pH/[Br ⁺the etching characteristic of]/Κ for torpescence metal (to hydrogen ion).Represent the electrical conductivity of system with Κ, with [Br ⁺] represent the content of effective bromine.

We know, the conductive capability of germicidal solution is to be caused by contained ion that can free migration wherein, and the introducing of ion mainly contains four kinds of approach, and one has the material of pH regulating action, as sulfuric acid, sodium hydroxide; Its two, can provide the material of effective bromine, as sodium hypobromite, bromo glycolylurea; Its three, the ionic impurity of carrying secretly in raw material that uses; Its four, there is the ionic component of other effects, as thickener, stabilizing agent, hardening agent, desiccant, nutritional agents, pH buffer, chelating agent, corrosion inhibiter, surfactant etc.

Refer to Fig. 1, Fig. 2, in figure, show: in the system of pH=2,9 oxidisability (containing effective bromine), effectively the chemical attack of bromine is main corrosion factor (corrosion approach 1), and etching characteristic depends on the content of effective bromine, the effectively reduction of bromine, reduces the metal protection of system.Simultaneously known, the electrical conductivity of system mainly by corrosion approach 1, produces more stable corrosion rate to metal in the time of 0-120S/m, and this corrosion rate depends on the content of effective bromine.Simultaneously known, within the scope of > 120S/m, there is corrosion approach 1 and corrosion approach 2 in system simultaneously, oxidisability (corrosion approach 1) and conductive capability (corrosion approach 2) synergy, the system that affected, to corrosion of metal, makes system produce hop to corrosion of metal.Be in the system of pH=2.0 or 9.0, effective bromine (>=1mg/L) of variable concentrations is collaborative with Κ (> 120S/m), the hop that all can produce metal protection.

Refer to Fig. 3, Fig. 4, in figure, show: in the system of pH=2-9 oxidisability (containing effective bromine), effectively the chemical attack of bromine is main corrosion factor (corrosion approach 1), it is the environment (acid) that etching characteristic depends on effective bromine, acid reduction, oxidisability is reduced, thereby the metal protection of system is reduced.Simultaneously known, the electrical conductivity of system mainly by corrosion approach 1, produces more stable corrosion rate to metal in the time of 0-120S/m, and this corrosion rate depends on the environment (acid) of effective bromine.Simultaneously known, within the scope of > 120S/m, there is corrosion approach 1 and corrosion approach 2 in system simultaneously, oxidisability (corrosion approach 1) and conductive capability (corrosion approach 2) synergy, the system that affected, to corrosion of metal, makes system produce hop to corrosion of metal.,, containing the system (>=1mg/L) of effective bromine, pH, between 2-9, when Κ > 120S/m, all can produce the hop to corrosion of metal.

Comparison diagram 1-Fig. 4 is known, controls Κ≤120S/m, can control or reduce the metal protection containing the germicidal solution of effective bromine.

Refer to Fig. 5-Figure 10, in figure, show: pH=2,9 oxidisability are (containing [Br ⁺]>=1mg/L) system in, different ions form electrical conductivity corrosion of metal is had to similar characteristic.That is, the electrical conductivity of system mainly by corrosion approach 1, makes metal with more stable speed corrosion in the time of 0-120S/m, and this corrosion rate depends on the pH/[Br of system ⁺]; The electrical conductivity of system in the time of > 120S/m, pH/[Br ⁺] (corrosion approach 1) and conductive capability (corrosion approach 2) synergy, the system that affected, to corrosion of metal, makes system produce hop to corrosion of metal.

Comparison diagram 5-Figure 10 is known, and to corrosion of metal, the impact of electrical conductivity is greater than the impact of the difference of the ion that forms electrical conductivity.Be that the electrical conductivity that different ions produces has similar characteristic to corrosion of metal.

Secondly electrical conductivity (Κ) corrupting influence to metal (to the active metal of hydrogen ion) in oxidative environment between pH=2-9 is discussed in the present invention.As, using carbon steel and aluminium as research object, because itself and simple hydrogen ion have certain reactivity, so can embody pH/[Br ⁺the comprehensive corrosive effect of]/Κ, has also embodied the reactivity of hydrogen ion and metal to the impact of metal protection.

Refer to Figure 11-Figure 12, the etching characteristic of the system that shows pH=2-9 oxidisability (containing effective bromine) in figure to carbon steel.Effectively the chemical attack of bromine is main corrosion factor (corrosion approach 1), and etching characteristic depends on content and the environment (acid) of effective bromine.Simultaneously known, the electrical conductivity of system mainly by corrosion approach 1, produces more stable corrosion rate to metal in the time of 0-60S/m, and this corrosion rate depends on the oxidisability of effective bromine.Simultaneously known, within the scope of > 60S/m, can there is the synergy of corrosion approach 1 and corrosion approach 2 in system, be oxidisability (corrosion approach 1) with conductive capability (the corrosion approach 2) system that affected to corrosion of metal, make system produce hop to corrosion of metal.,, containing the system (>=1mg/L) of effective bromine, pH, between 2-9, when Κ > 60S/m, all can produce the corrosive hop to carbon steel.

Refer to Figure 13-Figure 14, the etching characteristic of the system that shows pH=2-9 oxidisability (containing effective bromine) in figure to aluminium.Effectively the chemical attack of bromine is main corrosion factor (corrosion approach 1), and etching characteristic depends on content and the environment (acid) of effective bromine.Simultaneously known, the electrical conductivity of system mainly by corrosion approach 1, produces more stable corrosion rate to metal in the time of 0-20S/m, and this corrosion rate depends on the oxidisability of effective bromine.Simultaneously known, within the scope of > 20S/m, can there is the synergy of corrosion approach 1 and corrosion approach 2 in system, be oxidisability (corrosion approach 1) with conductive capability (the corrosion approach 2) system that affected to corrosion of metal, make system produce hop to corrosion of metal.

The known pH/[Br of comparison diagram 11-Figure 14 ⁺]/Κ has similar comprehensive corrosive effect to copper or carbon steel or aluminium, corrodes approach 1 and be the collaborative stage of main stage and corrosion approach 1 and corrosion approach 2.The reactivity of its hydrogen ion and metal has been accelerated the impact of electrical conductivity on metal protection.

Therefore, the invention provides a kind of preparation method of germicidal solution, comprise the following steps:

(2) provide pH value regulon;

PH value regulon is acid or weakly alkaline solid or liquid, and wherein the pH value of liquid is preferably between 0-9, is preferably between 1-8 again, then is preferably between 1-7, is also preferably between 1-5, most preferably is between 2-3.

The combination that pH value regulon comprises acidic materials, alkaline matter or acidic materials and alkaline matter.Optional one or several in the precursor of inorganic acid, organic acid, strong acid weak base salt, weak acid and 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, as aluminium chloride, iron chloride, aluminum sulfate, iron sulfate, copper nitrate or ammonium chloride.Common be acid weak acid and weak base salt, as ammonium formate, zinc acetate, Schweinfurt green.The precursor of acidic materials refers to the material that can be converted into acidic materials in solution, as sour chloride derivative, as succinyl chloride.Wherein alkaline matter can be selected from one or several in 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, as sodium hydroxide, potassium hydroxide etc., also can be selected from the hydroxide of alkaline earth metal, as slaked lime, barium hydroxide, magnesium hydroxide etc., also can be selected from the hydroxide of transition metal, as zinc hydroxide, iron hydroxide etc.Organic base is optional from nitrogen substance, as ammoniacal liquor, diethanol amine, triethylamine, natural alkaloid etc.Common strong base-weak acid salt, as sodium carbonate, sodium acetate, tertiary sodium phosphate, sodium citrate etc.Common be alkaline weak acid and weak base salt, as carbonic hydroammonium, ammonium sulfite, triammonium phosphate.The combined optional of its middle acid substance and alkaline matter from weak acid and weak base salt as the combination of the combination of ammonium citrate, strong acid weak base salt and strong base-weak acid salt, weak acid and its conjugate base.

Effectively bromine provides unit can contain one or more in bromide ion, bromine, hypobromite, bromite or effective bromine precursor substance.Hypobromite can be selected from one or more of sodium hypobromite, hypobromous acid calcium.Bromite can be selected from sodium bromite, bromous acid calcium.Effectively bromine precursor substance refers to acid or water and reacts the bromo-containing substance that can generate the effective bromine of activated state, and it provides stability in unit higher than providing in the mixed liquor of unit at pH value regulon, effective bromine at effective bromine, effectively bromine precursor substance can be selected from bromo glycolylurea, as one or more of C5H6Br2N2O2, BCDMH.

Bromide ion (as bromine salt or hydrobromic acid) can generate effective bromine from different oxidants.

As being oxidized by available chlorine

2Br ^-+Cl ₂=2Cl ^-+Br ₂

2Br ^-+ClO ^-+H ₂O=Br ₂+Cl ^-+2OH ^-

Br ₂+H ₂O=HBr+HBrO

As being oxidized by hydracid

BrO ₃ ^-+5Br ^-+6H ⁺=3Br ₂+3H ₂O

Br ₂+H ₂O=HBr+HBrO

Effective bromine that effectively bromine provides unit to contain stable form.Effective bromine of stable form refers in effective bromine provides unit to have better stability, reacts the bromo-containing substance that can generate the effective bromine of activated state with acid or water.Effectively bromine provides effective bromine content in unit should ensure that pH value regulon and effective bromine provide the effective bromine content in unit mixed liquor to be not less than 1mg/L.

PH value regulon provides effective bromine content in unit mixed liquor to be not less than 1mg/L with effective bromine, wherein be preferably 1-100000mg/L, be preferably again 1-50000mg/L, more preferably 1-20000mg/L, be preferably again 1-10000mg/L, also be preferably 1-5000mg/L, most preferably be 1-2000mg/L.

PH value regulates single and effective bromine to provide the pH value of unit mixed liquor between 2-9, is wherein preferably between 3-9, then is preferably between 4-9, most preferably is between 6-8.

PH value regulon provides the redox potential value of unit mixed liquor to be not less than 500mV with effective bromine, is wherein preferably 500-1500mV, then is preferably 500-1400mV, is preferably again 500-1300mV, most preferably is 500-1200mV.

PH value regulon provides the electrical conductivity of unit mixed liquor not higher than 120S/m with effective bromine.Wherein be preferably not higher than 100S/m, be preferably again not higher than 80S/m, be also preferably not higher than 60S/m, then be preferably not higher than 40S/m, most preferably be 10 ^-4-20S/m.

Control the method for electrical conductivity, one, by adjusting pH value regulon, effectively bromine provides the volume of unit and inherent component control pH value regulon, effective bromine that the content of the conductive materials in unit mixed liquor is provided, thus reduction electrical conductivity; Its two, by pH value regulon or (and) effectively bromine the pretreatment of unit is provided, reduce the content of mixed liquor conductive materials, thereby reduce electrical conductivity; Its three, by pH value regulon, effectively bromine provides the post processing of unit mixed liquor, reduces the content of mixed liquor conductive materials, thereby reduce electrical conductivity.

The method of described reduction electrical conductivity can be selected one or several of following method, to remove or to shield ionic species.Can add the material that can suppress ionization, the described material that suppresses ionization comprises can be with water miscible or in water, have an organic solvent of certain solubility, its principle is to utilize the difference of substance dielectric constant, add a certain amount of organic solvent, form mixed solvent system, suppress the ionization of ion, electrical conductivity of solution is declined, as add methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, ethylene glycol, 1,2-propane diols, 1,3-PD, glycerine, acetone etc. are can be with water miscible or in water, have an organic solvent of certain solubility.Also can adopt crystallisation, described crystallisation is the characteristic of utilizing Solubility of Substances, forms crystallization or precipitation, reduces the content of water soluble ion, as changed temperature or adding different solvents to change the polarity of system.Also can utilize membrane separation process, as filtration, ultrafiltration, nanofiltration, reverse osmosis membrane, ion-selective membrane, reduce the content of conductive materials, thereby reduce electrical conductivity.Also can utilize electrochemical process, as electroosmose process, electrolysis.Also can utilize chromatography, absorption method or ion-exchange, reduce the content of conductive materials, thereby reduce electrical conductivity.Described electroosmose process refers to and under electric field action, carries out dialysis, utilizes the otherness of the charged solute particles (as ion) in solution to make the method for content of predetermined substance enrichment or reduction by film.

Contain the solution of effective bromine in the time reducing electrical conductivity by said method, effectively bromine has certain loss conventionally, and its content need to redeterminate.In order to reduce the loss of effective bromine, can select fast processing mode; Also can select to process under cryogenic conditions; Also can transfer effective ionic bromine to the effective bromine of molecule-type (acidity), make it to distinguish with conductive ion; Also conductive ion can be transferred to water-insoluble derivative, make it and ionic active ingredient (BrO ^-) distinguish.Remove after purpose impurity (conductive ion), then return to stable form or the activation form of effective bromine.

Equally, the effectively bromine of post processing meeting loss part of germicidal solution, but as long as suitably increase the amount of effective bromine and control percent of loss, ensure that the germicidal solution of processing is at pH2-9, ORP>=500mV, [Br ⁺in the scope of]>=1mg/L, all can produce enough bactericidal effects.

The present invention also provides a kind of germicidal solution, and the pH value of described germicidal solution is between 2-9, and its effective bromine content is not less than 1mg/L, and its electrical conductivity is not higher than 120S/m.

The pH value of germicidal solution is between 2-9, is wherein preferably between 3-9, then is preferably between 4-9, most preferably is between 6-8.

The control of its pH value, can be separately by acidic materials, alkaline matter control or by acidic materials and alkaline matter co-controlling, make to 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 containing the germicidal solution of effective bromine.

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, 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, 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, as aluminium chloride, iron chloride, aluminum sulfate, iron sulfate, copper nitrate or ammonium chloride.Common be acid weak acid and weak base salt, as ammonium formate, zinc acetate, Schweinfurt green.The precursor of acidic materials refers to the material that can be converted into acidic materials in solution, as sour chloride derivative, as succinyl chloride.

Described alkaline matter can be one or several of highly basic, middle highly basic, weak base, strong base-weak acid salt or weak acid and weak base salt.Described alkaline matter can be selected from alkali-metal hydroxide, as sodium hydroxide, potassium hydroxide etc., also can be selected from the hydroxide of alkaline earth metal, as slaked lime, barium hydroxide, magnesium hydroxide etc., also can be selected from the hydroxide of transition metal, as zinc hydroxide, iron hydroxide etc., also optional from nitrogen substance, as ammoniacal liquor, diethanol amine, triethylamine, natural alkaloid etc., also optional from strong base-weak acid salt, as sodium carbonate, sodium acetate, tertiary sodium phosphate, sodium citrate etc.Also can be selected from the weak acid and weak base salt that is alkaline, as carbonic hydroammonium, ammonium sulfite, triammonium phosphate.

Contained effective bromine can be by bromide ion, bromine simple substance, hypobromite, bromite or effectively one or more generations of bromine precursor substance.As hypobromite and free hydrogen ion generation hypobromous acid, as sodium hypobromite, hypobromous acid calcium.As bromite and free hydrogen ion generation bromous acid, as sodium bromite, bromous acid calcium.Effectively bromine precursor substance refers to acid or water and react the bromo-containing substance that can generate the effective bromine of activated state, and effective bromine precursor substance can be selected from bromo glycolylurea, as one or more of C5H6Br2N2O2, BCDMH.The effective bromine of generation as oxidized in bromide ion (as shown in the formula).

As being oxidized by available chlorine

2Br ^-+Cl ₂=2Cl ^-+Br ₂

2Br ^-+ClO ^-+H ₂O=Br ₂+Cl ^-+2OH ^-

Br ₂+H ₂O=HBr+HBrO

As being oxidized by hydracid

BrO ₃ ^-+5Br ^-+6H ⁺=3Br ₂+3H ₂O

Br ₂+H ₂O=HBr+HBrO

Effective bromine content of germicidal solution is not less than 1mg/L, is wherein preferably 1-100000mg/L, then is preferably 1-50000mg/L, and more preferably 1-20000mg/L is preferably again 1-10000mg/L, is also preferably 1-5000mg/L, most preferably is 1-2000mg/L.

The redox potential value of germicidal solution is not less than 500mV, is wherein preferably 500-1500mV, then is preferably 500-1400mV, is preferably again 500-1300mV, most preferably is 500-1200mV.

The electrical conductivity of germicidal solution is not higher than 120S/m.Wherein be preferably not higher than 100S/m, be preferably again not higher than 80S/m, be also preferably not higher than 60S/m, then be preferably not higher than 40S/m, most preferably be 10 ^-4-20S/m.

Below in conjunction with embodiment, the present invention is described, Κ represents electrical conductivity, [Br ⁺] represent effective bromine content.

Embodiment 1: configuration 10L is containing the germicidal solution of effective bromine

Prepare different pH value regulons, A1-A8 unit:

Configuration maleic acid two potassium solutions (0.6M), hydrochloric acid is adjusted to pH=2.0, measures 10L, filling, makes A1 unit (pH2.0);

Configuration di-potassium tartrate solution (1.4M), hydrochloric acid is adjusted to pH=3.0, measures 10L, filling, makes A2 unit (pH3.0);

Configuration glutaric acid two potassium solutions (1.4M), hydrochloric acid is adjusted to pH=4.0, measures 10L, filling, makes A3 unit (pH4.0);

Configuration hydroxysuccinic acid two potassium solutions (1.6M), hydrochloric acid is adjusted to pH=5.0, measures 10L, filling, makes A4 unit (pH5.0);

Configuration glutaric acid two potassium solutions (1.7M), hydrochloric acid is adjusted to pH=6.0, measures 10L, filling, makes A5 unit (pH6.0);

Configuration citric acid tri potassium solution (2.2M), hydrochloric acid is adjusted to pH=7.0, measures 10L, filling, makes A6 unit (pH7.0);

Configuration tripotassium phosphate solution (0.3M), hydrochloric acid is adjusted to pH=8.0, measures 10L, filling, makes A7 unit (pH8.0);

Configuration trisodium phosphate solution (0.01M), is adjusted to pH=9.0, measures 10L, filling, makes A8 unit (pH9.0).

Prepare different effective bromines and provide unit, B1-B8 unit:

C5H6Br2N2O2, weighs 30mg, and packing makes B1 unit (containing effective bromine 10mg);

C5H6Br2N2O2, weighs 150g, and packing makes B2 unit (containing effective bromine 50g);

C5H6Br2N2O2 300g, anhydrous sodium sulfate 4mol, potassium hyperchlorate 3mol, hybrid packed, make B3 unit (containing effective bromine 100g);

C5H6Br2N2O2 600g, anhydrous sodium sulfate 6mol, potassium hyperchlorate 4mol, potassium nitrate 4mol, hybrid packed, make B4 unit (containing effective bromine 200g);

C5H6Br2N2O2 1500g, anhydrous sodium sulfate 6mol, potassium hyperchlorate 4mol, potassium nitrate 4mol, hybrid packed, make B5 unit (containing effective bromine 500g);

C5H6Br2N2O2 3000g, anhydrous sodium sulfate 6mol, potassium hyperchlorate 5mol, hybrid packed, make B6 unit (containing effective bromine 1000g);

C5H6Br2N2O2 60g, hyperbromic acid potassium 2mol, hybrid packed, make B7 unit (containing effective bromine 20g);

C5H6Br2N2O2 30mg, packing, makes B8 unit (containing effective bromine 10mg).

When use, provide unit to mix with effective bromine pH value regulon, make effective bromine provide unit to dissolve, make the following germicidal solution containing effective bromine:

Germicidal solution	pH	ORP（mV）	[Br ⁺](mg/L)	Κ（S/m）
					A1+B1	2.0	1000	1	20
A2+B2	3.0	1060	5000	40
					A3+B3	4.0	1110	10000	60
A4+B4	5.0	1120	20000	80
					A5+B5	6.0	1090	50000	100
A6+B6	7.0	1140	100000	120
					A7+B7	8.0	800	2000	10
A8+B8	9.0	500	1	1

Embodiment 2: configuration 10L is containing the germicidal solution of effective bromine

Prepare different pH value regulons, A1-A8 unit:

Configuration tripotassium phosphate solution (2M), hydrochloric acid is adjusted to pH=2.0, measures 10L, filling, makes A1 unit (pH2.0).

Configuration citric acid tri potassium solution (1.5M), hydrochloric acid is adjusted to pH=3.0, measures 10L, filling, makes A2 unit (pH3.0);

Configuration potassium lactate solution (2M), hydrochloric acid is adjusted to pH=4.0, measures 10L, filling, makes A3 unit (pH4.0);

Configuration n-butyric acie solution (0.2M), sodium hydroxide is adjusted to pH=5.0, measures 10L, filling, makes A4 unit (pH5.0);

Configuration hydrochloric acid solution (pH=6.0, containing 5% ethanol), measures 10L, filling, makes A5 unit (pH6.0);

The configuration aqueous solution (containing 10% ethanol), measures 10L, filling, makes A6 unit (pH7.0);

Configuration tripotassium phosphate solution (0.5M), hydrochloric acid is adjusted to pH=8.0, measures 10L, filling, makes A7 unit (pH8.0);

Configuration ethanolamine solutions (1M), hydrochloric acid is adjusted to pH=9.0, measures 10L, filling, makes A8 unit (pH9.0).

Prepare different effective bromines and provide unit, B1-B8 unit:

C5H6Br2N2O2 3000g, anhydrous sodium sulfate 6mol, ammonium nitrate 6mol, hybrid packed, make B1 unit (containing effective bromine 1000g);

C5H6Br2N2O2 1500g, anhydrous sodium sulfate 3mol, ammonium nitrate 3mol, hybrid packed, make B2 unit (containing effective bromine 500g);

C5H6Br2N2O2 600g, anhydrous sodium sulfate 6mol, ammonium nitrate 6mol, hybrid packed, make B3 unit (containing effective bromine 200g);

C5H6Br2N2O2, weighs 300g, and packing makes B4 unit (containing effective bromine 100g);

C5H6Br2N2O2, weighs 60g, and packing makes B5 unit (containing effective bromine 20g);

C5H6Br2N2O2, weighs 30g, and packing makes B6 unit (containing effective bromine 10g);

C5H6Br2N2O2, weighs 15g, and packing makes B7 unit (containing effective bromine 5g);

C5H6Br2N2O2, weighs 30mg, and packing makes B8 unit (containing effective bromine 10mg).

Germicidal solution	pH	ORP（mV）	[Br ⁺](mg/L)	Κ（S/m）
					A1+B1	2.0	1500	100000	120
A2+B2	3.0	1400	50000	80
					A3+B3	4.0	1300	20000	60
A4+B4	5.0	1200	10000	1
					A5+B5	6.0	1000	2000	10 ^-2
A6+B6	7.0	800	1000	10 ^-4
					A7+B7	8.0	600	500	20
A8+B8	9.0	500	1	10

Embodiment 3: configuration 10L is containing the germicidal solution of effective bromine

Tartaric acid 13.5mol, packing, makes pH value regulon A1;

The effective bromine 10mg of C5H6Br2N2O2 30mg(), disodium tartrate 4.5mol, hybrid packed, making effective bromine provides unit B 1(total effectively bromine 10mg);

When use, provide unit to be dissolved in 10L water pH value regulon and effective bromine, make germicidal solution (pH2-4, the ORP900-1050mV, [Br of 10L containing effective bromine ⁺]=1mg/L, Κ=8S/m).

Embodiment 4: configuration 10L is containing the germicidal solution of effective bromine

Configuration hydrochloric acid solution (0.1M), gets 10L, filling, makes pH value regulon A1.

The effective bromine 50g of C5H6Br2N2O2 150g(), sodium acetate 2mol, anhydrous sodium sulfate 1mol, hybrid packed, making effective bromine provides unit B 1(total effectively bromine 50g);

When use, provide unit to mix with effective bromine pH value regulon, make effective bromine provide unit to dissolve, make germicidal solution (pH4-6, the ORP900-1000mV, [Br of 10L containing effective bromine ⁺]=5000mg/L, Κ=5.8S/m).

Embodiment 5: configuration 10L is containing the germicidal solution of effective bromine

Prepare different pH value regulons, A1-A8 unit:

Configuration sodium hydrate aqueous solution (pH8-8.5), measures 9.999L, obtains A1 unit (pH8-9);

The configuration aqueous solution (pH=7.2), measures 9.999L, obtains A2 unit (pH=7-8);

Configuration aqueous hydrochloric acid solution (pH=6), measures 9L, and configuration aqueous citric acid solution (pH=7), measures 0.995L, and two kinds of acid solutions are mixed, and obtain A3 unit (pH6-7);

Configuration aqueous sulfuric acid (pH=5), measures 5L, and configuration zinc sulfate solution (pH=6), measures 4.99L, and two kinds of acid solutions are mixed, and obtain A4 unit (pH5-6);

Configuration acetic acid aqueous solution (pH=4), measures 5L, and the configuration succinic acid aqueous solution (pH=4), measures 4.98L, and two kinds of acid solutions are mixed, and obtain A5 unit (pH4-5);

Configuration aqueous citric acid solution (pH=3.5), measures 5L, and configuration aluminum nitrate aqueous solution (pH=3.5), measures 4.97L, and two kinds of acid solutions are mixed, and obtain A6 unit (pH3-4);

Configuration zinc sulfate solution (pH=3), measures 5L, and aluminum chloride aqueous solution (pH=3), measures 4.96L, and two kinds of acid solutions are mixed, and obtain A7 unit (pH2-3);

Configuration aqueous hydrochloric acid solution (pH2), measures 7L, and configuration aqueous tartaric acid solution (pH3), measures 1.95L, and configuration solder(ing)acid (pH3), measures 1L, and three kinds of acid solutions are mixed, and obtain A8 unit (pH2-3).

Prepare different effective bromines and provide unit, B1-B8 unit:

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 10mg/ml), measures 1ml, makes B1 unit;

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 100mg/ml), measures 1ml, makes B2 unit;

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 100mg/ml), measures 5ml, makes B3 unit;

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 100mg/ml), measures 10ml, makes B4 unit;

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 100mg/ml), measures 20ml, makes B5 unit;

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 100mg/ml), measures 30ml, makes B6 unit;

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 100mg/ml), measures 40ml, makes B7 unit;

The sodium hypobromite aqueous solution (pH9.1, effectively bromine 100mg/ml), measures 50ml, makes B8 unit.

Provide unit to mix with effective bromine pH value regulon, make the following bactericidal liquid containing effective bromine:

Germicidal solution	pH	ORP：mV	[Br ⁺](mg/L)	Κ（S/m）
					A1+B1	8-9	500-600	1	15
A2+B2	7-8	600-700	10	10 ^-4
					A3+B3	6-7	600-700	50	10 ^-3
A4+B4	5-6	700-800	100	10 ^-2
					A5+B5	4-5	800-900	200	10 ^-1
A6+B6	3-4	900-1000	300	1
					A7+B7	2-3	1050-1150	400	5
A8+B8	2-3	1050-1150	500	10

Embodiment 6: configuration 100L is containing the germicidal solution of effective bromine

Configuration aqueous hydrochloric acid solution (0.01M), gets 100L, makes pH value regulon; Configure 2 parts of identical pH value regulons, A1-A2.

Configuration aqueous hydrochloric acid solution (3M), gets 100L, makes pH value regulon; Configure 2 parts of identical pH value regulons, A3-A4.

C5H6Br2N2O2 0.3g, packing, making effective bromine provides unit B 1(total effectively bromine 0.1g);

C5H6Br2N2O2 15Kg, packing, making effective bromine provides unit B 2(total effectively bromine 5000g);

The effective bromine 0.1g of C5H6Br2N2O2 0.3g(), potassium hydroxide 299mol, anhydrous sodium sulfate 160mol, mixes, packaging, making effective bromine provides unit B 3(total effectively bromine 0.1g);

The effective bromine 3Kg of C5H6Br2N2O2 9Kg(), potash 149.5mol, anhydrous sodium sulfate 180mol, mixes, packaging, making effective bromine provides unit B 4(total effectively bromine 3000g).

Germicidal solution	pH	ORP（mV）	[Br ⁺]（mg/L）	Κ（S/m）
					A1+B1	2.0	1020	1	0.5
A2+B2	2.0	1480	50000	15
					A3+B3	2.0	1020	1	90
A4+B4	2.0	1450	30000	110

Embodiment 7: configuration 100L is containing the germicidal solution of effective bromine

Configuration aqueous hydrochloric acid solution (pH=0), gets 100L, makes pH value regulon A1;

Configuration chloric acid aqueous solution (pH=1), gets 100L, makes pH value regulon A2;

The configuration bromic acid aqueous solution (pH=2), gets 100L, makes pH value regulon A3;

The configuration acid iodide aqueous solution (pH=3), gets 100L, makes pH value regulon A4;

Configuration aqueous sulfuric acid (pH=4), gets 100L, makes pH value regulon A5.

The effective bromine 60g of BCDMH 180g(), sodium hydroxide 99.9mol, hybrid packed, making effective bromine provides unit B 1(total effectively bromine 60g);

The effective bromine 70g of BCDMH 210g(), sodium hydroxide 9.99mol, hybrid packed, making effective bromine provides unit B 2(total effectively bromine 70g);

The effective bromine 80g of BCDMH 240g(), sodium carbonate 0.571mol, hybrid packed, making effective bromine provides unit B 3(total effectively bromine 80g);

The effective bromine 90g of BCDMH 270g(), trisodium citrate 1mol, hybrid packed, making effective bromine provides unit B 4(total effectively bromine 90g);

The effective bromine 100g of BCDMH 300g(), tertiary sodium phosphate 0.009mol, hybrid packed, making effective bromine provides unit B 5(total effectively bromine 100g).

Germicidal solution	pH	ORP（mV）	[Br ⁺]（mg/L）	Κ（S/m）
					A1+B1	3.0	1110	600	1.5
A2+B2	4.0	1050	700	0.95
					A3+B3	5-7	900-1000	800	0.63
A4+B4	6-8	800-1000	900	0.85
					A5+B5	7-9	700-900	1000	1.2

Embodiment 8: configuration 100L alkalescence is containing the germicidal solution of effective bromine

Configuration aqueous sulfuric acid (0.4062M), gets 100L, makes pH value regulon A1.

Configuration aqueous methane sulfonic acid (0.8125M), gets 100L, makes pH value regulon A2.

Configuration aqueous sulfuric acid (0.1M), gets 100L, makes pH value regulon A3.

The configuration benzene sulfonic acid aqueous solution (0.2M), gets 100L, makes pH value regulon A4.

The effective bromine 0.1g of C5H6Br2N2O2 0.3g(), tripotassium phosphate 80mol, anhydrous sodium sulfate 80mol, hybrid packed, making effective bromine provides unit B 1(total effectively bromine 0.1g).

The effective bromine 2Kg of C5H6Br2N2O2 6Kg(), tripotassium phosphate 80mol, anhydrous sodium sulfate 125mol, hybrid packed, making effective bromine provides unit B 2(total effectively bromine 2Kg).

The effective bromine 0.1g of C5H6Br2N2O2 0.3g(), sodium carbonate 15mol, hybrid packed, making effective bromine provides unit B 3(total effectively bromine 0.1g).

The effective bromine 2Kg of C5H6Br2N2O2 6Kg(), sodium carbonate 15mol, hybrid packed, make effective bromine and provide unit B 4(containing effective bromine 2Kg).

Germicidal solution	pH	ORP（mV）	[Br ⁺]（mg/L）	Κ（S/m）
					A1+B1	9.0	500	1	50
A2+B2	9.0	1050	20000	70
					A3+B3	9.0	500	1	3
A4+B4	9.0	1050	20000	8

Embodiment 9: configuration 10L is containing the germicidal solution of effective bromine

Configuration aqueous hydrochloric acid solution (0.02M), measures 5L, makes pH value regulon A1;

Configuration aqueous hydrochloric acid solution (1.09M), measures 9L, makes pH value regulon A2;

The configuration 2-hydroxysuccinic acid aqueous solution (3.6M), measures 5L, makes pH value regulon A3;

Configuration aqueous hydrochloric acid solution (pH=0), measures 5L, makes pH value regulon A4.

Sodium hypobromite solution, gets 5L, and making effective bromine provides unit B 1(effective bromine 6g/L);

Sodium hypobromite solution, measures 1L, adds 2-hydroxysuccinic acid disodium 5mol, makes effective bromine unit B 2 is provided, containing effective bromine 40g/L;

Sodium hypobromite solution, measures 5L, adds sodium hydroxide 0.69228mol(pH ≈ 13.14), make effective bromine unit B 3 is provided, containing effective bromine 12g/L;

Sodium hypobromite solution, measures 5L, adds potassium hydroxide 4.9mol(pH ≈ 13.99), make effective bromine unit B 4 is provided, containing effective bromine 14g/L.

Provide unit to mix with effective bromine pH value regulon, make following effectively bromine solutions:

Germicidal solution	pH	ORP（mV）	[Br ⁺]（mg/L）	Κ（S/m）
					A1+B1	2.0	1100	3000	1
A2+B2	2.0	1110	4000	15

A3+B3	2.0	1115	6000	5
					A4+B4	2.0	1130	7000	20

Embodiment 10: configuration 10L alkalescence is containing the germicidal solution (pH=7.0-9.0) of effective bromine

Configuration sodium hydroxide solution (pH=7-7.1), gets 5L, and configuration potassium hydroxide solution (pH=7-7.1), gets 4.999L, and two kinds of alkali lye mix, and obtain pH value regulon A1(pH=7-7.1);

Configuration sodium hydroxide solution (pH=7-7.1), gets 9L, and configuration diethylamine solution (pH=7-7.1), gets 0.999L, and two kinds of alkali lye mix, and obtain pH value regulon A2(pH=7-7.1);

Configuration sodium hydroxide solution (pH=7-7.1), gets 9L, and configuration sodium acetate solution (pH=7-7.1), gets 0.995L, and two kinds of alkali lye mix, and obtain pH value regulon A3(pH=7-7.1);

Configuration triethylamine solution (pH=7-7.1), gets 5L, and configuration triethanolamine solution (pH=7-7.1), gets 4.995L, and two kinds of alkali lye mix, and obtain pH value regulon A4(pH=7-7.1);

Configuration triethylamine solution (pH=8-8.1), gets 9L, and configuration sodium carbonate liquor (pH=8-8.1), gets 0.985L, and two kinds of alkali lye mix, and obtain pH value regulon A5(pH=8-8.1);

Configuration sodium carbonate liquor (pH=8-8.1), gets 5L, and configuration sodium propionate solution (pH=8-8.1), gets 4.2L, and two kinds of alkali lye mix, and obtain pH value regulon A6(pH=8-8.5);

Sodium hydroxide solution (pH8-8.5), gets 4L, and triethylamine solution (pH8-8.5), gets 3L, and sodium butyrate solution (pH8-8.5), gets 2.1L, and three kinds of alkali lye mix, and obtain pH value regulon A7(pH=8-8.5).

Prepare different effective bromines and provide unit, B1-B7 unit:

Sodium hypobromite solution (pH9.1), measures 1ml, makes B1 unit, containing effective bromine 10mg/ml;

Sodium hypobromite solution (pH9.1), measures 1ml, makes B2 unit, containing effective bromine 100mg/ml;

Sodium hypobromite solution (pH9.1), measures 5ml, makes B3 unit, containing effective bromine 50mg/ml;

Sodium hypobromite solution (pH9.1), measures 5ml, makes B4 unit, containing effective bromine 100mg/ml;

Sodium hypobromite solution (pH9.1), measures 15ml, makes B5 unit, containing effective bromine 50mg/ml;

Sodium hypobromite solution (pH9.1), measures 800ml, makes B6 unit, containing effective bromine 100mg/ml;

Sodium hypobromite solution (pH9.1), measures 900ml, makes B7 unit, containing effective bromine 100mg/ml.

Germicidal solution	pH	ORP：mV	Effectively bromine (mg/L)	Κ（S/m）
					A1+B1	7-8	550-650	1	10 ^-4
A2+B2	7-8	550-650	10	10 ^-3
					A3+B3	7-8	550-650	25	10 ^-2

A4+B4	7-8	550-650	50	10 ^-1
					A5+B5	8-9	550-650	75	1
A6+B6	8-9	900-1000	8000	5
					A7+B7	8-9	900-1000	9000	10

Embodiment 11: configuration 10L is containing the germicidal solution of effective bromine

Citric acid powder 1mol, packing, makes pH value regulon;

Sodium hypobromite solution, measures 10L, adds sodium hydroxide 0.5mol, filling, and sealing, makes effective bromine unit is provided, containing effective bromine 25g/L;

When use, provide unit to mix with effective bromine pH value regulon, dissolve, make the germicidal solution (pH2-4, ORP1100-1200mV, effectively bromine 25000mg/L, Κ=2.5S/m) of 10L containing effective bromine.

Embodiment 12: configuration 10L is containing the germicidal solution of effective bromine

Citric acid powder 1mol, packing, makes pH value regulon A1;

Sodium hydroxide 2.5mol, packing, makes pH value regulon A2;

The effective bromine 15g of C5H6Br2N2O2 45g(), packing, making effective bromine provides unit B 1(total effectively bromine 15g).

Water, measures 10L, and packing makes C unit.

When use, A1 unit is placed in to C unit and dissolves, form acid unit C1; Again A2 unit is placed in to C1 unit and dissolves, form acid unit C2; Then B1 unit is placed in to C2 unit and dissolves, form the germicidal solution (pH6-8, ORP800-900mV, effectively bromine 1500mg/L, Κ=7.5S/m) containing effective bromine.

Embodiment 13: preparation 10L is containing the germicidal solution of effective bromine

Zinc citrate pressed powder, weighs 0.2mol, makes pH value regulon;

C5H6Br2N2O2, weighs 30mg, makes effective bromine unit (containing effective bromine 10mg) is provided;

PH value regulon provides unit mixing monobasic packaging or independent binary packing with effective bromine.

Before use, above-mentioned substance is dissolved in to 10L water, makes the germicidal solution (pH3-5, ORP800-900mV, effectively bromine 1mg/L, Κ=2S/m) containing effective bromine.

Embodiment 14: preparation 10L is containing the germicidal solution of effective bromine

Zinc chloride powder, weighs 10mol, and independent packing, makes pH value regulon A1;

Potassium acetate powder, weighs 20mol, and independent packing, makes pH value regulon A2;

C5H6Br2N2O2 600g, independent packing, making effective bromine provides unit B 1(effective bromine 200g);

Water, measures 10L, and packing makes C unit.

When use, the disposable A1/A2 unit C of being placed in unit is dissolved, form acid unit C1; Then B1 unit is placed in to C1 unit and dissolves, form the germicidal solution (pH4-6, ORP1100-1300mV, effectively bromine 20000mg/L, Κ=60S/m) containing effective bromine.

Embodiment 15: preparation 10L is containing the germicidal solution of effective bromine

Zinc nitrate powder, weighs 5mol, and independent packing, makes pH value regulon A1;

Sodium acetate powder, weighs 5mol, and independent packing, makes pH value regulon A2;

Sodium lactate powder, weighs 5mol, and independent packing, makes pH value regulon A3;

C5H6Br2N2O2 60g, independent packing, making effective bromine provides unit B 1(effective bromine 20g);

Water, measures 10L, and packing makes C unit.

When use, B1 unit is placed in to C unit and dissolves, form brominated unit C1; Then by A1/A2/A3 unit successively or the disposable C1 of being placed in unit dissolve, form containing the germicidal solution of effective bromine (pH6-8, ORP800-900mV, effectively bromine 2000mg/L, Κ=20S/m).

Embodiment 16: configuration 10L is containing the germicidal solution of effective bromine

Raw material A, niter cake powder, takes 7mol.

Raw material B, citric acid tri potassium, weighs 14mol.

Raw material C, C5H6Br2N2O2, weighs 1650g, containing effective bromine 550g.

Raw material D, anhydrous sodium sulfate (desiccant), weighs 10mol.

Raw material E, sodium perchlorate (hardening agent), weighs 5mol.

After A-E raw material is mixed, monobasic packaging.

Above-mentioned mixed material is placed in to 10L water and dissolves, behind pH≤9.0 of solution, make the germicidal solution (pH5-8, ORP1000-1100mV, effectively bromine 55000mg/L, Κ=120S/m) containing effective bromine.

Embodiment 17: configuration 10L is containing the germicidal solution of effective bromine

Sodium radio-phosphate,P-32 solution (0.01M, containing ethanol 30%, pH=7.0), measure 10L, make pH value regulon.

C5H6Br2N2O2 100mg, anhydrous sodium sulfate 100mg, hybrid packed, make effective bromine unit (total effectively bromine 10mg) is provided.

Provide unit to mix with effective bromine pH value regulon, dissolve, make germicidal solution (pH6-8, ORP500-700mV, effectively bromine 1mg/L, Κ=10 of 10L containing effective bromine ^-4s/m).

Embodiment 18: configuration 1000L is containing the germicidal solution of effective bromine

Electrolysis produces acidic oxidized electric potential water (pH5-7, available chlorine decomposes rapidly), measures 1000L, filling, and sealing, makes pH value regulon.

C5H6Br2N2O2 24Kg, anhydrous calcium chloride 650mol, hybrid packed, make effective bromine unit (total effectively bromine 8Kg) is provided.

When use, provide unit to mix with effective bromine pH value regulon, make the germicidal solution (pH5-7, ORP900-1000mV, effectively bromine 8000mg/L, Κ=20S/m) containing effective bromine.

Embodiment 19: configuration 1L is containing the germicidal solution of effective bromine

Sodium hydroxide solution (pH8.0), measures 1L, and independent packaging makes pH value regulon.

Bromine, filling 1ml, effectively bromine 50mg, independent high sealing packaging, makes pH value regulon.

When use, under airtight condition, provide unit to mix with effective bromine pH value regulon, make 1L germicidal solution (pH7-9, ORP500-700mV, effectively bromine 50mg/L, Κ=1S/m).

Implement 20: configuration 10L is containing the germicidal solution of effective bromine

Raw material A: hydrobromic acid solution (1M), measures 100ml, independent packaging.

Raw material B: liquor natrii hypochloritis (0.5M), measure 100ml, add 0.05mol sodium hydroxide (pH=13.70), independent corrosion-proof packing.

After A, B raw material are mixed, leave standstill 1 hour, then with the dilution of 9.8L water, make the germicidal solution (pH6-8, ORP800-900mV, effectively bromine 400mg/L, Κ=15S/m) of 10L containing effective bromine.

Embodiment 21: configuration 1L is containing the germicidal solution of effective bromine

Raw material A: sodium bromide, 0.2mol, independent packaging.

Raw material B: sodium dichloro cyanurate 10g (available chlorine 2.5g), independent packaging.

Raw material C: aqueous acid 1L(pH5.0), independent packaging.

After A, B, C raw material are mixed, dissolve, leave standstill 1 hour, make 1L germicidal solution (pH4-6, ORP900-1000mV, effectively bromine 1000mg/L, available chlorine 500mg/L, Κ=30S/m).

Embodiment 22: configuration 1L is containing the germicidal solution of effective bromine

Raw material A: sodium bromide, 1mol, independent packaging.

Raw material B: sodium bromate 1mol, independent packaging.

Raw material C: salpeter solution (1M), get 1L, independent corrosion-proof packing.

After A, B, C raw material are mixed, dissolve, leave standstill 30 minutes, be diluted to 100L, make 10L germicidal solution (pH2-3, ORP1000-1100mV, effectively bromine 500mg/L, Κ=10S/m).

Embodiment 23: configuration 1L is containing the germicidal solution of effective bromine

Raw material A: hydrochloric acid solution (pH=0), measures 10ml, independent packaging.

Raw material B: sodium hypobromite solution (potassium hydroxide is adjusted to pH=14.0), measures the effective bromine 30g/L of 10ml(), independent packaging.

Above-mentioned substance is placed in to 0.98L water and dilutes, make the germicidal solution (pH6-8, ORP800-900mV, effectively bromine 300mg/L, Κ=2S/m) of 1L containing effective bromine.

Embodiment 24: configuration 1000L is containing the germicidal solution of effective bromine

Raw material A: acidic aqueous solution 2000L(pH2-3, Κ=150S/m).Raw material A is carried out following pretreatment, removes conductive ion, reduces electrical conductivity:

Method 1, under raw material A low temperature, (3 DEG C) leave standstill 24 hours, crystallization, filtration, ultrafiltration, remove after insoluble matter, obtains raw material A 1(pH2-3).

Method 2, raw material A is analysed post by charcoal absorption chromatography post and resinbed, efflux is adjusted pH, obtains raw material A 2(pH2-3).

Method 3, raw material A, by NF membrane and ion-selective membrane, is removed conductive ion, filtrate is adjusted pH, obtains raw material A 3(pH2-3).

Method 4, raw material A, through electrodialysis, by ion permeable membrane, reduces electrical conductivity under certain electric field, adjusts pH, obtains raw material A 4(pH2-3).

Measure respectively the each 1000L of raw material A 1-A4, filling, make pH value regulon A1-A4.

Raw material B: C5H6Br2N2O2 powder (effectively bromine 0.4g/g), take 2.5Kg, packing, obtains effective bromine unit B (effectively bromine 1000g) is provided.Prepare 4 parts of identical B unit.

A1-A4 is mixed with a B unit respectively, makes the following germicidal solution 1-4 containing effective bromine:

Germicidal solution	pH	ORP：mV	Effectively bromine (mg/L)	Κ（S/m）
					A1+B	2-3	1000-1100	1000	10
A2+B	2-3	1000-1100	1000	2
					A3+B	2-3	1000-1100	1000	5
A4+B	2-3	1000-1100	1000	40

The above-mentioned germicidal solution 4 containing effective bromine continues post processing, removes conductive ion, reduces electrical conductivity

Method 1, germicidal solution 4, fast by charcoal absorption chromatography post, obtains germicidal solution 5(pH2-3, ORP1000-1100mV, effectively bromine 900mg/L, Κ=10S/m).

Method 2, under germicidal solution 4 low temperature (5-10 DEG C), successively by amberplex, NF membrane and charcoal absorption chromatography post, obtains germicidal solution 6(pH2-3 fast, ORP1000-1100mV, effectively bromine 800mg/L, Κ=1S/m).

Method 3, germicidal solution 4 mixes (volume ratio 99:1) with absolute ethyl alcohol, and 0 DEG C of lucifuge leaves standstill 2 hours, and quick-hyperfiltration, nanofiltration, obtain germicidal solution 7(pH2-3, ORP1000-1100mV, effectively bromine 700mg/L, Κ=0.1S/m, containing ethanol 1%).

Method 4, germicidal solution 4 mixes (volume ratio 4:1) with absolute ethyl alcohol, and 0 DEG C of lucifuge leaves standstill 2 hours, and crystallization fast by conventional filtration film, milipore filter, NF membrane, obtains germicidal solution 8(pH2-3 successively, ORP1000-1100mV, effectively bromine 600mg/L, Κ=10 ^-2s/m, containing ethanol 20%).

Method 5, germicidal solution 4 mixes (volume ratio 3:7) with absolute ethyl alcohol, and 0 DEG C of lucifuge leaves standstill 2 hours, crystallization, conventional filtration, ultrafiltration, nanofiltration fast, obtains germicidal solution 9(pH3-5 successively, ORP900-1000mV, effectively bromine 200mg/L, Κ=10 ^-3s/m, containing ethanol 70%).

Method 6, germicidal solution 4 mixes (volume ratio 5:2:3) with absolute ethyl alcohol and acetone, and 0 DEG C of lucifuge leaves standstill 2 hours, crystallization, fast by conventional filtration film, milipore filter, NF membrane, obtains germicidal solution 10(pH3-5 successively, ORP900-1000mV, effectively bromine 400mg/L, Κ=10 ^-4s/m, containing ethanol 20%, containing acetone 30%).

The post processing meeting of germicidal solution makes effective bromine partial loss, but at pH2-9, ORP >=500mV, effectively, in the scope of bromine >=1mg/L, all can produce enough bactericidal effects.

Embodiment 25: configuration 10L is containing the germicidal solution of effective bromine

Raw material A: citric acid powder, weigh 1mol, packing, makes pH value regulon A.Prepare 3 parts of identical pH value regulon A.

Raw material B: effectively bromine solutions 100L(pH8.0, Κ=130S/m).Raw material B carries out following pretreatment, reduces electrical conductivity:

Method 1, under raw material B low temperature, (0 DEG C) lucifuge leaves standstill 2 hours, and crystallization, precipitates through milipore filter filtering, mother liquor, fast by NF membrane and active carbon adsorption column, is removed part ion, and efflux is adjusted pH, obtain raw material B1(pH8.0, effectively bromine 800mg/L, Κ=0.5S/m).

Method 2, raw material B, fast by NF membrane, removes water soluble ion, adjusts pH, obtains raw material B2(pH8.0, effectively bromine 950mg/L, Κ=10S/m).

Method 3, the pH of raw material B is adjusted to 6.0, makes effective bromine be converted into molecular conformation, through electrodialysis, under certain electric field, fast by ion permeable membrane, deionization liquid recovers pH again, obtains raw material B3(pH8.0, effectively bromine 800mg/L, Κ=20S/m).

Through above-mentioned processing, effectively bromine has certain loss, and its content need to redeterminate.

Raw material B1-B3 respectively measures 10L, filling, makes effective bromine unit B 1-B3 unit is provided.

B1-B3 unit is mixed with a A unit respectively, makes following germicidal solution 1-3:

Germicidal solution	pH	ORP：mV	Effectively bromine (mg/L)	Κ（S/m）
					A+B1	2-3	1000-1100	800	5
A+B2	2-3	1000-1100	950	15
					A+B3	2-3	1000-1100	800	25

The above-mentioned germicidal solution 3 containing effective bromine continues post processing, removes conductive ion, reduces electrical conductivity

Method 1, under germicidal solution 3 low temperature, (5-10 DEG C) is fast by charcoal absorption chromatography post and ion-selective membrane, efflux adds 1,2-propane diols (volume ratio 1:4), 0 DEG C of lucifuge leaves standstill 2 hours, through milipore filter filtering insoluble matter, obtain germicidal solution 4(pH3-5, ORP900-1000mV, effectively bromine 100mg/L, Κ=10 ^-4s/m, containing 1,2-PD 80%).

Method 2, germicidal solution 3 mixes (volume ratio 7:2:1) with 1-propyl alcohol, 1,3-PD, and 0 DEG C of lucifuge leaves standstill 1 hour, filters insoluble matter through milipore filter, NF membrane, obtains germicidal solution 5(pH3-5, ORP900-1000mV, effectively bromine 450mg/L, Κ=10 ^-3s/m, containing 1-propyl alcohol 20%, 1,3-PD 10%).

Method 3, germicidal solution 3 mixes (volume ratio 60:25:14:1) with methyl alcohol, 2-propyl alcohol, n-butyl alcohol, and 0 DEG C of lucifuge leaves standstill 5 hours, and NF membrane is filtered, and obtains germicidal solution 6(pH3-5, ORP900-1000mV, effectively bromine 300mg/L, Κ=10 ^-2s/m, containing methyl alcohol 25%, 2-propyl alcohol 14%, n-butyl alcohol 1%).

Method 4, germicidal solution 3 mixes (volume ratio 9:1) with 2-butanols, obtains germicidal solution 7(pH2-3, ORP1000-1100mV, effectively bromine 720mg/L, Κ=10 ^-1s/m, containing 2-butanols 10%).

Embodiment 26: configuration 100L is containing the germicidal solution (effectively bromine content 1000mg/L) of effective bromine

Acid solution (pH3-5, Κ=130S/m), by reverse osmosis membrane, obtains raw material A (pH3-5, Κ=10S/m).Raw material A is got 99L, filling, makes pH value regulon A.

Sodium hypobromite solution (pH8.5, Κ=100S/m), adjust pH to 6.0, make effective bromine be converted into molecular conformation, under low temperature, (3 DEG C), through electrodialysis, pass through fast ion-selective membrane under certain electric field, deionization liquid recovers pH again, obtain raw material B(pH8.5, effectively bromine 0.1g/ml, Κ=10S/m).Raw material B takes 1L, filling, makes effective bromine unit B is provided.

When use, A unit is mixed with B unit, make the germicidal solution (pH3-5, ORP900-1000mV, effectively bromine 1000mg/L, Κ=10S/m) of 100L containing effective bromine.

Embodiment 27: configuration 10L is containing the germicidal solution of effective bromine

Aqueous acid (pH5-6), measures 9.5L, makes pH value regulon A(Κ=40S/m).

Sodium hypobromite solution (pH8.1, effectively bromine 100g/L, Κ=40S/m), takes 0.5L, makes effective bromine unit B is provided.

When use, A unit is mixed with B unit, make the germicidal solution (pH5-8, effectively bromine 5000mg/L, ORP800-900mV, Κ=40S/m) of 10L containing effective bromine.Under above-mentioned germicidal solution low temperature, (0 DEG C) lucifuge leaves standstill 2 hours, crystallization, and filtering-depositing, mother liquor mixes (volume ratio 1:9) with glycerine, 0 DEG C of lucifuge leaves standstill 1 hour, filters insoluble matter, makes germicidal solution (pH5-8, effectively bromine 400mg/L, ORP700-900mV, Κ=10 ^-4s/m, containing glycerine 90%).

Embodiment 28: configuration 10L is containing the germicidal solution of effective bromine

Aqueous acid (pH3-5, Κ=120S/m), 5 DEG C leave standstill 24 hours, crystallization, ultrafiltration, mother liquor, after NF membrane is filtered, measures 9.5L, makes pH value regulon A(pH3-5, Κ=5S/m).

Sodium hypobromite solution (pH8.1, Κ=40S/m), is acidified to after pH5.0, and under low temperature, (5-10 DEG C) is through electrodialysis process, remove water soluble ion, the liquid that desalts returns to pH8.1, takes 0.5L, make effective bromine unit B (pH8.1, effectively bromine 100g/L, Κ=1S/m) is provided.

When use, A unit is mixed to (volume ratio 2:3) with the mixed mixed solution in B unit with ethylene glycol, 0 DEG C of lucifuge of mixed liquor leaves standstill 60 minutes, and quick-hyperfiltration makes germicidal solution (pH5-7, effectively bromine 1900mg/L, ORP700-800mV, Κ=10 ^-4s/m, containing ethylene glycol 60%).

Embodiment 29: the effective bromine solutions of configuration 1L

Citric acid, weighs 0.01mol, and independent packing, makes pH value regulon.

C5H6Br2N2O2, weighs 30g, and independent packing makes effective bromine unit (containing effective bromine 10g) is provided.

Water (electrical conductivity 60S/m), 3 DEG C leave standstill 48 hours, crystallization, ultrafiltration, mother liquor, again through ion exchange resin post, activated-charcoal column and reverse osmosis membrane, is removed ion, measures 1L, and independent packing, makes lytic agent unit (Κ=5S/m).

After providing unit to mix with lytic agent unit pH value regulon, effective bromine, make effective bromine solutions (pH2-3, effectively bromine 10000mg/L, Κ=15S/m).

Disinfection effect test: note, below experiment all (adds 0.3% organic chaff interference) and carries out under clean conditions.

Represent pyococcus in bacterial propagule with staphylococcus aureus; Escherichia coli represent enteron aisle bacterium in bacterial propagule; Pseudomonas aeruginosa represents the bacterial propagule the most often separating in hospital infection; Staphylococcus albus represents airborne bacterium; Mycobacterium chelonei abscess subspecies representative Much's bacillus; Bacillus subtilis black variety gemma represents bacterial spore; Candida albicans and black-koji mould represent pathogenic fungus; Polyovirus-I type vaccine strain (Poliovirus-I) represents virus; Staphylococcus aureus (MRSA) and vancomycin-resistant enterococcus (VRE) with methicillin-resistant represent drug-fast bacteria; Vibrio parahemolyticus, Listeria monocytogenes represent the pathogenic bacteria in aquatic products; White diarrhea salmonella represents bird pathogenic bacteria; Wheat stripe rust represents agriculture pathogenic bacteria.

Bactericidal assay 1 (suspension is quantitative), kills logarithm and time containing the germicidal solution of effective bromine

Trial target 1, pH10.0, ORP450mV, effective bromine 1mg/L, Κ=120S/m

Trial target 2, pH10.0, ORP450mV, effective bromine 1mg/L, Κ=0.1S/m

Trial target 3, pH9.0, ORP500mV, effective bromine 1mg/L, Κ=120S/m

Trial target 4, pH9.0, ORP500mV, effective bromine 1mg/L, Κ=0.1S/m

Trial target 5, pH7.0, ORP700mV, effective bromine 1mg/L, Κ=120S/m

Trial target 6, pH7.0, ORP700mV, effective bromine 1mg/L, Κ=0.1S/m

Trial target 7, pH4.0, ORP900mV, effective bromine 1mg/L, Κ=120S/m

Trial target 8, pH4.0, ORP900mV, effective bromine 1mg/L, Κ=0.1S/m

Trial target 9, pH2.0, ORP1000mV, effective bromine 1mg/L, Κ=120S/m

Trial target 10, pH2.0, ORP1000mV, effective bromine 1mg/L, Κ=0.5S/m

After trial target 1-10 effect 15min, kill logarithm referring to table 1.

After table 1 15min action time, kill logarithm

Test organisms	Trial target 1	Trial target 3	Trial target 5	Trial target 7	Trial target 9
						Staphylococcus aureus	＜1.00	>5.00	>5.00	>5.00	>5.00
Escherichia coli	＜1.00	>5.00	>5.00	>5.00	>5.00
						Pseudomonas aeruginosa	＜1.00	>5.00	>5.00	>5.00	>5.00
Candida albicans	＜1.00	>5.00	>5.00	>5.00	>5.00
						Black-koji mould	＜1.00	>5.00	>5.00	>5.00	>5.00
Staphylococcus albus	＜1.00	>5.00	>5.00	>5.00	>5.00
						Poliovirus-Ⅰ	＜1.00	>5.00	>5.00	>5.00	>5.00
Mycobacterium chelonei abscess subspecies	＜1.00	>5.00	>5.00	>5.00	>5.00
						Test organisms	Trial target 2	Trial target 4	Trial target 6	Trial target 8	Trial target 10
Staphylococcus aureus	＜1.00	>5.00	>5.00	>5.00	>5.00

Escherichia coli	＜1.00	>5.00	>5.00	>5.00	>5.00
						Pseudomonas aeruginosa	＜1.00	>5.00	>5.00	>5.00	>5.00
Candida albicans	＜1.00	>5.00	>5.00	>5.00	>5.00
						Black-koji mould	＜1.00	>5.00	>5.00	>5.00	>5.00
Staphylococcus albus	＜1.00	>5.00	>5.00	>5.00	>5.00
						Poliovirus-Ⅰ	＜1.00	>5.00	>5.00	>5.00	>5.00
Mycobacterium chelonei abscess subspecies	＜1.00	>5.00	>5.00	>5.00	>5.00

Bactericidal assay 2 (suspension is quantitative), kills logarithm and time containing the germicidal solution of effective bromine

Trial target 1, pH10.0, ORP950mV, effective bromine 20g/L, Κ=120S/m

Trial target 2, pH10.0, ORP950mV, effective bromine 20g/L, Κ=1S/m

Trial target 3, pH9.0, ORP1000mV, effective bromine 20g/L, Κ=120S/m

Trial target 4, pH9.0, ORP1000mV, effective bromine 20g/L, Κ=1S/m

Trial target 5, pH7.0, ORP1050mV, effective bromine 20g/L, Κ=120S/m

Trial target 6, pH7.0, ORP1050mV, effective bromine 20g/L, Κ=1S/m

Trial target 7, pH4.0, ORP1150mV, effective bromine 20g/L, Κ=120S/m

Trial target 8, pH4.0, ORP1150mV, effective bromine 20g/L, Κ=1S/m

Trial target 9, pH2.0, ORP1350mV, effective bromine 20g/L, Κ=120S/m

Trial target 10, pH2.0, ORP1350mV, effective bromine 20g/L, Κ=1S/m

After trial target 1-10 effect 0.5min, kill logarithm referring to table 2.

After table 2 0.5Min action time, kill logarithm

Skin irritatin test

Test according to the repeatedly intact skin irritant test method in " version disinfection technology standard in 2008 ".

Trial target 1-6, effective bromine solutions of the effective bromine/Κ of different pH/ORP/.

Wherein trial target 1, regulates electrical conductivity with ammonium chloride, lithium chloride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, barium chloride, sodium sulphate, sodium nitrate, methanesulfonic sodium, benzene sulfonic acid sodium salt, sodium phosphate, sodium acetate, sodium succinate, sodium tartrate, sodium citrate respectively.Make the trial target that 16 different ions regulate, numbering 1-1 to 1-16, its difference is only to regulate the material difference of electrical conductivity, tries to achieve the mean value of the primary stimulation index of 16 samples, as the skin irritation value of trial target 1.The like, make the mean value of trial target 2-1 to 2-16, the mean value of 3-1 to 3-16, the mean value of 4-1 to 4-16, the mean value of 5-1 to 5-16, the mean value of 6-1 to 6-16.

Table 3 irritation test data

As shown in Table 3, the effective bromine 2000mg/L/ of pH=6-8/ORP≤1200mV/ Κ=20S/m containing bromine solutions, to the excitant minimum of skin; The effective bromine 2000mg/L/ of pH=4-9/ORP≤1300mV/ Κ=20S/m containing bromine solutions, to the stimulation index of skin at 0-1; The effective bromine 2000mg/L/ of pH=2-10/ORP≤1400mV/ Κ=20S/m containing bromine solutions, to the stimulation index of skin at 1-2.Simultaneously known in the time there is ammonium ion, lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, barium ions, chlorion, sulfate ion, nitrate ion, methanesulfonate ion, benzene sulfonic acid radical ion, phosphate anion, acetate ion, succinic ion, tartrate anion ion, citrate ion in solution, there is reliable safety.

Metal protection test, with reference to " version disinfection technology standard in 2008 "

Test material 1, copper; Test material 2, carbon steel; Test material 3, aluminium.

Test material 1-3, makes circle, diameter 24.00mm, and thick 1.0mm, wearing a diameter is 2.0mm aperture, surface area total value is about 9.80cm ².Fineness is 6.

Test material 4, thimerosal, the germicidal solution containing effective bromine of different electrical conductivity.

Experimental group, test material 1 or 2 or 3 is removed attachment (fully deoil, fully deoxidation layer, cleans); Measure diameter, thickness, the aperture of sheet; 50 DEG C of dry 1h, weigh (as weight before test); Hang in 200ml test material 4, continue 72 hours, keep the fresh of test material 4; Take out sheet metal, remove corrosion product, clean, 50 DEG C of dry 1h, weigh.

Blank group, test material 1 or 2 or 3 repeats by above-mentioned steps, but soaks without disinfectant.And calculate its average weightless value.

R = \frac{8.76 \times 10^{7} \times (m - m_{t} - m_{k})}{S \times t \times d}

Calculate rate of corrosion according to above formula.Wherein, R is corrosion rate, mm/a(millimeter/year); M is the front sheet metal weight of test, g; m _tfor testing rear sheet metal weight, g; m _kremove the weightless value of corrosion product print for chemical treatment, g, does not carry out chemical scavenging processor in test, leave out m when calculating in formula _kvalue; S is the surface area total value of sheet metal, cm ²; T is test period, h; D is metal material density, kg/m ³.

Corrosion test 1, carries out corrosion test according to above-mentioned steps, and rate of corrosion data as shown in Figure 1, can be learnt by Fig. 1 data: when pH=2.0, with the solution comparison that does not contain effective bromine (effectively bromine=0mg/L), introduce effective bromine, with Κ synergy, affect the metal erosion characteristic of solution.Simultaneously known, in the effective bromine/Κ of pH/ system, when pH=2.0, effective bromine/Κ of different content, metal is had to similar etching characteristic, and when pH=2.0/ Κ > 120S/m, effective bromine system of different content all produces hop to corrosion of metal.

Corrosion test 2, carries out corrosion test according to above-mentioned steps, and rate of corrosion data as shown in Figure 2, can be learnt by Fig. 2 data: when pH=9.0, with the solution comparison that does not contain effective bromine (effectively bromine=0mg/L), introduce effective bromine, with Κ synergy, affect the metal erosion characteristic of solution.Simultaneously known, in the effective bromine/Κ of pH/ system, when pH=9.0, effective bromine/Κ of different content, metal is had to similar etching characteristic, and when pH=9.0/ Κ > 120S/m, effective bromine system of different content all produces hop to corrosion of metal.

Comparison diagram 1, Fig. 2 are known, in the effective bromine/Κ of pH/ system, and pH=2.0,9.0 o'clock, effectively bromine reduces, and the corrosivity of system is reduced, and reduced the significance of hop.

Corrosion test 3, carry out corrosion test according to above-mentioned steps, rate of corrosion data as shown in Figure 3, can be learnt by Fig. 3 data: in the effective bromine/Κ of pH/ system, when effective bromine=100000mg/L, pH has similar etching characteristic at 2.0-9.0 to metal, and effectively when bromine=100000mg/L and Κ > 120S/m, pH all produces hop in the system of 2.0-9.0 to corrosion of metal.

Corrosion test 4, carry out corrosion test according to above-mentioned steps, rate of corrosion data as shown in Figure 4, can be learnt by Fig. 4 data: in the effective bromine/Κ of pH/ system, when effective bromine=1mg/L, pH has similar etching characteristic to metal equally at 2.0-9.0, and effectively when bromine=1mg/L and Κ > 120S/m, pH all produces hop in the system of 2.0-9.0 to corrosion of metal.

Comparison diagram 3, Fig. 4 are known, and in the effective bromine/Κ of pH/ system, effectively when bromine >=1mg/L, acid reduction, reduces the corrosivity of system, and reduced the significance of hop.

Corrosion test 5, prepares the germicidal solution of the effective bromine=100000mg/L of multiple pH=2.0/, and the anionic group of each germicidal solution is fixed, and gets different cations.Cation is respectively: solution 1 (NH ₄ ⁺), solution 2 (Li ⁺), solution 3 (Na ⁺), solution 4 (K ⁺), solution 5 (Rb ⁺), solution 6 (Cs ⁺), solution 7 (NH ₄ ⁺and Li ⁺/ Na ⁺/ K ⁺/ Rb ⁺/ Cs ⁺), solution 8 (Ba ²⁺), solution 9 (Sr ²⁺), solution 10 (Ca ²⁺), solution 11 (Mg ²⁺), solution 12 (Be ²⁺), solution 13 (Ba ²⁺/ Sr ²⁺/ Ca ²⁺/ Mg ²⁺/ Be ²⁺), solution 14 (Zn ²⁺), solution 15 (Ni ²⁺), solution 16 (Mn ²⁺), solution 17 (Cu ²⁺), solution 18 (Zn ²⁺/ Ni ²⁺/ Mn ²⁺/ Cu ²⁺), solution 19 (Al ³⁺), solution 20 (Cr ³⁺), solution 21 (V ³⁺), solution 22 (Co ³⁺), solution 23 (Fe ³⁺), solution 24 (Al ³⁺and Cr ³⁺/ V ³⁺/ Co ³⁺/ Fe ³⁺), solution 25 (Sn ⁴⁺), solution 26 (Ti ⁴⁺), solution 27 (Zr ⁴⁺), solution 28 (Sn ⁴⁺and Ti ⁴⁺/ Zr ⁴⁺), solution 29 (NH ₄ ⁺and Li ⁺/ Na ⁺/ K ⁺/ Rb ⁺/ Cs ⁺and Zn ²⁺/ Ni ²⁺/ Mn ²⁺and Cu ²⁺/ Ba ²⁺/ Sr ²⁺/ Ca ²⁺/ Mg ²⁺/ Be ²⁺), solution 30 (NH ₄ ⁺and Li ⁺/ Na ⁺/ K ⁺/ Rb ⁺/ Cs ⁺/ Al ³⁺/ Cr ³⁺and V ³⁺/ Co ³⁺and Fe ³⁺), solution 31 (NH ₄ ⁺and Li ⁺/ Na ⁺/ K ⁺/ Rb ⁺/ Cs ⁺and Sn ⁴⁺/ Ti ⁴⁺/ Zr ⁴⁺), solution 32 (Ba ²⁺/ Sr ²⁺/ Ca ²⁺and Mg ²⁺/ Be ²⁺and Zn ²⁺/ Ni ²⁺/ Mn ²⁺/ Cu ²⁺and Al ³⁺/ Cr ³⁺/ V ³⁺/ Co ³⁺and Fe ³⁺), solution 33 (Ba ²⁺/ Sr ²⁺/ Ca ²⁺and Mg ²⁺/ Be ²⁺and Zn ²⁺/ Ni ²⁺/ Mn ²⁺/ Cu ²⁺/ Sn ⁴⁺/ Ti ⁴⁺and Zr ⁴⁺), solution 34 (Al ³⁺/ Cr ³⁺/ V ³⁺/ Co ³⁺and Fe ³⁺/ Sn ⁴⁺/ Ti ⁴⁺/ Zr ⁴⁺), solution 35 (NH ₄ ⁺/ Li ⁺/ Na ⁺/ K ⁺and Rb ⁺/ Cs ⁺and Ba ²⁺/ Sr ²⁺/ Ca ²⁺/ Mg ²⁺/ Be ²⁺and Zn ²⁺/ Ni ²⁺/ Mn ²⁺/ Cu ²⁺and Al ³⁺/ Cr ³⁺/ V ³⁺and Co ³⁺/ Fe ³⁺/ Sn ⁴⁺/ Ti ⁴⁺/ Zr ⁴⁺), wherein, combining cationic ratio is equimolar ratio example.Carry out corrosion test according to above-mentioned steps.As shown in Figure 5, when pH2.0 and effectively bromine 100000mg/L, the electrical conductivity of different cation regulation system produces similar etching characteristic to metal to rate of corrosion data.Can be learnt by Fig. 5 data: the strong and weak order of the impact on metal protection is: the difference of cationic property in the electrical conductivity > system of the effective bromine > of the pH/ system of system.

Corrosion test 6, prepares the germicidal solution of the effective bromine=100000mg/L of multiple pH=2.0/, and the cationic components of each germicidal solution is fixed, and gets different anion.Anion is respectively: solution 1 (Cl ^-), solution 2 (Br ^-), solution 3 (I ^-), solution 4 (NO ₃ ^-), solution 5 (methanesulfonate ion), solution 6 (SO ₄ ^2-), solution 7 (chloroacetic acid radical ion), solution 8 (dichloroacetic acid radical ion), solution 9 (trichloroacetic acid ion), solution 10 (chloroacetic acid radical ion/dichloroacetic acid radical ion/trichloroacetic acid ion), solution 11 (trifluoroacetic acid radical ion), solution 12 (Cl ^-/ Br ^-/ I ^-and NO ₃ ^-/ chloroacetic acid radical ion/dichloroacetic acid radical ion/trichloroacetic acid ion/ClO ₃ ^-/ BrO ₃ ^-/ IO ₃ ^-/ trifluoroacetic acid radical ion/SO ₄ ^2-and ClO ₄ ^-/ BrO ₄ ^-/ IO ₄ ^-/ methanesulfonate ion), the ratio that wherein combines anion is equimolar ratio example.Carry out corrosion test according to above-mentioned steps.As shown in Figure 6, when pH2.0 and effectively bromine 100000mg/L, the electrical conductivity of different anion regulation system produces similar etching characteristic to metal to rate of corrosion data.Can be learnt by Fig. 6 data: the strong and weak order of the impact on metal protection is: the difference of anionic nature in the electrical conductivity > system of the effective bromine > of the pH/ system of system.

Corrosion test 7, prepares the germicidal solution of the effective bromine=1mg/L of multiple pH=2.0/, and wherein the anionic group of solution 1-35 is fixed, and gets different cations, and its cation is chosen the solution 1-35 in corresponding corrosion test 5; The cationic components of solution 36-47 is fixed, and gets different anion, and its anion is chosen the solution 1-12 in corresponding corrosion test 6.Carry out corrosion test according to above-mentioned steps.As shown in Figure 7, when the effective bromine 1mg/L of pH2.0/, the electrical conductivity of different ion regulation system produces similar etching characteristic to metal to rate of corrosion data.Can be learnt by Fig. 7 data: the strong and weak order of the impact on metal protection is: the difference of the electrical conductivity > system intermediate ion character of the effective bromine > of the pH/ system of system.

Corrosion test 8, prepares the germicidal solution of the effective bromine=100000mg/L of multiple pH=9.0/, and the anionic group of each germicidal solution is fixed, and gets different cations.Cation is respectively: solution 1 (NH ₄ ⁺), solution 2 (Li ⁺), solution 3 (Na ⁺), solution 4 (K ⁺), solution 5 (Rb ⁺), solution 6 (Cs ⁺), solution 7 (NH ₄ ⁺and Li ⁺/ Na ⁺/ K ⁺/ Rb ⁺/ Cs ⁺), solution 8 (Ba ²⁺), solution 9 (Sr ²⁺), solution 10 (Ca ²⁺), solution 11 (Ba ²⁺and Sr ²⁺/ Ca ²⁺), solution 12 (NH ₄ ⁺and Li ⁺/ Na ⁺/ K ⁺/ Rb ⁺/ Cs ⁺and Ba ²⁺/ Sr ²⁺/ Ca ²⁺), solution 13 is (containing NH ₄ ⁺/ Li ⁺/ Na ⁺/ K ⁺/ Rb ⁺/ Cs ⁺and Ba ²⁺/ Sr ²⁺/ Ca ²⁺and Mg ²⁺/ Cu ²⁺/ Zn ²⁺/ Sn ⁴⁺and Fe ³⁺/ Cr ³⁺and Al ³⁺), wherein, the cationic ratio of the combination of solution 1-12 is equimolar ratio example.Carry out corrosion test according to above-mentioned steps.As shown in Figure 8, when pH9.0 and effectively bromine 100000mg/L, the electrical conductivity of different cation regulation system produces similar etching characteristic to metal to rate of corrosion data.Can be learnt by Fig. 8 data: the strong and weak order of the impact on metal protection is: the difference of cationic property in the electrical conductivity > system of the effective bromine > of the pH/ system of system.

Corrosion test 9, prepares the germicidal solution of the effective bromine=100000mg/L of multiple pH=9.0/, and the cationic components of each germicidal solution is fixed, and gets different anion.Anion is respectively: solution 1 (Cl ^-), solution 2 (Br ^-), solution 3 (I ^-), solution 4 (NO ₃ ^-), solution 5 (methanesulfonate ion), solution 6 (SO ₄ ^2-), solution 7 (Cl ^-/ Br ^-/ I ^-/ NO ₃ ^-and ClO ₃ ^-/ BrO ₃ ^-/ IO ₃ ^-and ClO ₄ ^-/ BrO ₄ ^-/ IO ₄ ^-/ SO ₄ ^2-/ methanesulfonate ion), solution 8 (chloroacetic acid radical ion), solution 9 (dichloroacetic acid radical ion), solution 10 (trichloroacetic acid ion), solution 11 (trifluoroacetic acid radical ion), solution 12 (acetate ion/propionate ion/butyrate ion/valerate ion/caproate ion), solution 13 (acetate ion/glycolic acid radical ion/chloroacetic acid radical ion/dichloroacetic acid radical ion/trichloroacetic acid ion/trifluoroacetic acid radical ion), solution 14 (acrylic acid radical ion/butenoic acid radical ion/penetenoic acid radical ion), solution 15 (succinic ion/glutarate ion/adipic acid radical ion), solution 16 (succinic ion/malate ion/tartrate anion ion), solution 17 (maleic acid radical ion/fumaric acid radical ion), solution 18 (citrate ion), solution 19 (phosphate anion), solution 20 (Cl ^-/ NO ₃ ^-and ClO ₃ ^-/ ClO ₄ ^-/ SO ₄ ^2-/ methanesulfonate ion/acetate ion/trifluoroacetic acid radical ion/glycolic acid radical ion/acrylic acid radical ion/succinic ion/tartrate anion ion/butene dioic acid radical ion/citrate ion/phosphate anion), wherein, the ratio of combination anion is equimolar ratio example.Carry out corrosion test according to above-mentioned steps.As shown in Figure 9, when the effective bromine 100000mg/L of pH9.0/, the electrical conductivity of different anion regulation system produces similar etching characteristic to metal to rate of corrosion data.Can be learnt by Fig. 9 data: the strong and weak order of the impact on metal protection is: the difference of anionic nature in the electrical conductivity > system of the effective bromine > of the pH/ system of system.

Corrosion test 10, prepares the germicidal solution of the effective bromine=1mg/L of multiple pH=9.0/, and wherein the anionic group of solution 1-13 is fixed, and gets different cations, and its cation is chosen the solution 1-13 in corresponding corrosion test 8; The cationic components of solution 14-33 is fixed, and gets different anion, and its anion is chosen the solution 1-20 in corresponding corrosion test 9.Carry out corrosion test according to above-mentioned steps.As shown in figure 10, when the effective bromine 1mg/L of pH9.0/, the electrical conductivity of different ions regulation system produces similar etching characteristic to metal to rate of corrosion data.Can be learnt by Figure 10 data: the strong and weak order of the impact on metal protection is: the difference of the electrical conductivity > system intermediate ion character of the effective bromine > of the pH/ system of system.

Comparison diagram 5-Figure 10 is known, and in the effective bromine/Κ of pH/ system, the principal element that affects metal protection is the effective bromine of pH/, is secondly the impact of electrical conductivity, is the difference of ionic nature again.Simultaneously known, the electrical conductivity that different ions forms has similar impact to metal protection.

Corrosion test 11, carry out corrosion test according to above-mentioned steps, rate of corrosion data as shown in figure 11, can be learnt by Figure 11 data: in the effective bromine/Κ of pH/ system, when effective bromine=100000mg/L, pH has similar etching characteristic at 2.0-9.0 to carbon steel, corrodes approach 1 and be the collaborative stage of main stage and corrosion approach 1 and corrosion approach 2.The reactivity of its hydrogen ion and metal has been accelerated the impact of electrical conductivity on metal protection.

Corrosion test 12, carry out corrosion test according to above-mentioned steps, rate of corrosion data as shown in figure 12, can be learnt by Figure 12 data: in the effective bromine/Κ of pH/ system, when effective bromine=1mg/L, pH has similar etching characteristic to carbon steel equally at 2.0-9.0, corrodes approach 1 and be the collaborative stage of main stage and corrosion approach 1 and corrosion approach 2.The reactivity of its hydrogen ion and metal has been accelerated the impact of electrical conductivity on metal protection.

Corrosion test 13, carry out corrosion test according to above-mentioned steps, rate of corrosion data as shown in figure 13, can be learnt by Figure 13 data: in the effective bromine/Κ of pH/ system, when effective bromine=100000mg/L, pH has similar etching characteristic at 2.0-9.0 to aluminium, corrodes approach 1 and be the collaborative stage of main stage and corrosion approach 1 and corrosion approach 2.The reactivity of its hydrogen ion and metal has been accelerated the impact of electrical conductivity on metal protection.

Corrosion test 14, carry out corrosion test according to above-mentioned steps, rate of corrosion data as shown in figure 14, can be learnt by Figure 14 data: in the effective bromine/Κ of pH/ system, when effective bromine=1mg/L, pH has similar etching characteristic to aluminium equally at 2.0-9.0, corrodes approach 1 and be the collaborative stage of main stage and corrosion approach 1 and corrosion approach 2.The reactivity of its hydrogen ion and metal has been accelerated the impact of electrical conductivity on metal protection.

Comparison diagram 11-Figure 14 is known, and the effective bromine/Κ of pH/ system has similar comprehensive corrosive effect to the different metal such as copper or carbon steel or aluminium.

Germicidal solution prepared by the preparation method of the germicidal solution containing effective bromine of the present invention can reduce corrosion of metal, thereby has expanded range of application.Before use, the pH value regulon of the germicidal solution containing effective bromine of the present invention and effectively bromine provide unit to deposit separately, in the time will using, then provide unit to mix pH value regulon and effective bromine, solve the storage problem containing the germicidal solution of effective bromine, very easy to use.In the process of the preparation germicidal solution containing effective bromine of the present invention, strengthen artificial controllability, can regulate according to the actual requirements the pH value of germicidal solution, effective bromine content and ORP value.

Disclosed is above only several specific embodiments of the application, but the application is not limited thereto, and the changes that any person skilled in the art can think of, all should drop in the application's protection domain.

Claims

1. a preparation method for germicidal solution, is characterized in that, comprises the following steps:

(2) provide pH value regulon;

(3) provide unit to mix with described effective bromine described pH value regulon, make the pH value of mixed solution between 2-9, effectively bromine content is not less than 1mg/L, and redox potential is 500-1300mV, and electrical conductivity, not higher than 120S/m, obtains germicidal solution.

2. the preparation method of germicidal solution as claimed in claim 1, is characterized in that, the pH value of described germicidal solution is between 4-9, and its effective bromine content is 1-20000mg/L, and its electrical conductivity is not higher than 60S/m.

3. the preparation method of germicidal solution as claimed in claim 1, is characterized in that, the pH value of described germicidal solution is between 6-8, and its redox potential is 500-1200mV, and its effective bromine content is 1-2000mg/L, and its electrical conductivity is 10 ^-4-20S/m.

4. the preparation method of germicidal solution as claimed in claim 1, is characterized in that, in step (1), also comprises: provide unit to reduce the pretreatment of electrical conductivity to described effective bromine.

5. the preparation method of germicidal solution as claimed in claim 1, is characterized in that, in step (2), also comprises: described pH value regulon is reduced to the pretreatment of electrical conductivity.

6. the preparation method of germicidal solution as claimed in claim 1, is characterized in that, in step (3), also comprises: provide the mixed mixed liquor in unit to reduce the post processing of electrical conductivity to described pH value regulon and described effective bromine.

7. the preparation method of the germicidal solution as described in claim 4 or 5 or 6, it is characterized in that, the processing method of described reduction electrical conductivity be selected from crystallisation, membrane separation process, electrochemical process, chromatography, absorption method, ion-exchange or add can suppress ionization material in one or several.

8. the preparation method of germicidal solution as claimed in claim 7, is characterized in that, the described material that suppresses ionization comprises can be with water miscible or in water, have an organic solvent of certain solubility.

9. the preparation method of germicidal solution as claimed in claim 8, it is characterized in that, described can be with water miscible or have a certain solubility in water organic solvent is selected from methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, ethylene glycol, 1,2-propane diols, 1,3-PD, glycerine, acetone wherein one or more.

10. the preparation method of germicidal solution as claimed in claim 1, it is characterized in that, described germicidal solution comprise ammonium ion, lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, barium ions, chlorion, sulfate ion, nitrate ion, methanesulfonate ion, benzene sulfonic acid radical ion, phosphate anion, acetate ion, succinic ion, tartrate anion ion, citrate ion wherein one or several.

11. 1 kinds of germicidal solutions, is characterized in that, the pH value of described germicidal solution is between 2-9, and its effective bromine content is not less than 1mg/L, and its redox potential is 500-1300mV, and its electrical conductivity is not higher than 120S/m.

12. germicidal solutions as claimed in claim 11, is characterized in that, the pH value of described germicidal solution is between 4-9, and its effective bromine content is 1-20000mg/L, and its electrical conductivity is not higher than 60S/m.

13. germicidal solutions as claimed in claim 11, is characterized in that, the pH value of described germicidal solution is between 6-8, and its redox potential is 500-1200mV, and its effective bromine content is 1-2000mg/L, and its electrical conductivity is 10 ^-4-20S/m.

14. germicidal solutions as claimed in claim 11, it is characterized in that, described germicidal solution comprise ammonium ion, lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, barium ions, chlorion, sulfate ion, nitrate ion, methanesulfonate ion, benzene sulfonic acid radical ion, phosphate anion, acetate ion, succinic ion, tartrate anion ion, citrate ion wherein one or several.