CN105813984B - The method for not adding electrolyte production sterilization oxidation water - Google Patents
The method for not adding electrolyte production sterilization oxidation water Download PDFInfo
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- CN105813984B CN105813984B CN201480067502.4A CN201480067502A CN105813984B CN 105813984 B CN105813984 B CN 105813984B CN 201480067502 A CN201480067502 A CN 201480067502A CN 105813984 B CN105813984 B CN 105813984B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 49
- 230000001954 sterilising Effects 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 41
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003792 electrolyte Substances 0.000 title description 2
- 239000012528 membrane Substances 0.000 claims abstract description 67
- 241000370738 Chlorion Species 0.000 claims abstract description 39
- OSVXSBDYLRYLIG-UHFFFAOYSA-N Chlorine dioxide Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 238000005341 cation exchange Methods 0.000 claims abstract description 28
- 239000011737 fluorine Substances 0.000 claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 18
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 13
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 3
- 230000037242 Cmax Effects 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 2
- DFGWJCZWKBGVOX-UHFFFAOYSA-N [Cl+].[O-2].[O-2].[Ti+4] Chemical compound [Cl+].[O-2].[O-2].[Ti+4] DFGWJCZWKBGVOX-UHFFFAOYSA-N 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- -1 halogen ion Chemical class 0.000 abstract description 23
- 229910052736 halogen Inorganic materials 0.000 abstract description 16
- 230000001264 neutralization Effects 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 description 36
- 229910052801 chlorine Inorganic materials 0.000 description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 33
- 239000002253 acid Substances 0.000 description 12
- 239000012266 salt solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- WQYVRQLZKVEZGA-UHFFFAOYSA-N Hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000844 anti-bacterial Effects 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N Hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Chemical compound Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000012476 oxidizable substance Substances 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000012492 regenerant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-N,4-N-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene (PE) Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 101710012506 METAP2 Proteins 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GCTOSMYFALESJI-UHFFFAOYSA-O [NH4+].CC(C)(C)O Chemical compound [NH4+].CC(C)(C)O GCTOSMYFALESJI-UHFFFAOYSA-O 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 235000021271 drinking Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004634 feeding behavior Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 101710031899 moon Proteins 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 125000000621 oxo-lambda(3)-chloranyloxy group Chemical group *OCl=O 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
To provide a kind of electrolytic method, become able to, by anodic oxidation raw water, such as running water, effectively using halogen ion contained in the raw water, such as chlorion, produce sterilization/sterilization oxidation water in neutral pH range whereby.A kind of method of the sterilization oxidation water produced containing chlorine dioxide, methods described include：Using the running water of three Room type electrolytic vessels electrolysis chloride ion-containings, then capture is dissolved in the chlorion in the running water, and the chlorion then captured on the anode electrode described in electrolytic oxidation.The three Room type electrolytic vessel is made up of anode chamber, cathode chamber and medial compartment, and the medial compartment is between the anode chamber and the cathode chamber and is formed by setting separation membrane between the anode chamber and the cathode chamber.In the three Room type electrolytic vessel, the separation membrane that the anode chamber separates with the medial compartment is made up of fluorine-containing cation exchange membrane and anion-exchange membrane, wherein porous anode electrode is adhered on the fluorine-containing cation exchange membrane in the separation membrane, the separation membrane that the cathode chamber separates with the medial compartment is made up of cation-exchange membrane or anion-exchange membrane, wherein porous cathode electrode is adhered on the separation membrane；And anion exchange resin fills the medial compartment.
Description
Technical field
The present invention relates to a kind of electrolysis by running water etc., does not substantially add chlorion and produces with suitable for sterilization
Concentration of residual chlorine and sterilized water containing chlorine dioxide method.
Background technology
By convention, it is two chamber-type electrolytic vessel or Fig. 2 shown in Fig. 1 for producing sterilization with the electrolytic vessel of water is aoxidized
Three shown Room type electrolytic vessels.In two chamber-type electrolytic vessel, by adding halogen such as salt into raw water come to anode chamber
Supply chlorion dissolving water.For example, when supplying salt solution, chlorion oxidation generation hypochlorite ion.
Specifically, in the oxidation reaction, chlorion generates chlorine molecule through electrolytic oxidation.Chlorine molecule is changed into hypochlorous acid in water
Radical ion and hydrogen ion.Therefore, highly acid oxidation water is formed.
[chemical formula 1]
When using two chamber-type electrolytic vessel, ion concentration deficiency.In order to promote electrolytic oxidation reaction, it is necessary to improve electrolysis
Voltage adds halogen such as salt into raw water.When adding halogen, generation highly acid oxidation water.Therefore, in the maintenance of device
The problem of highly acid be present with control aspect.
Fig. 2 shows three Room type electrolytic vessels, wherein being provided with medial compartment between anode chamber and cathode chamber.In separation membrane
In, provided with amberplex, and the porous electrode shown in Fig. 3 is used as electrode.By the supply such as salt solution to medial compartment.In
Indoor chlorion is transferred to anode chamber.Chlorine molecule is formed according to chemical formula (1) part chlorion to ultimately form highly acid
Hypochlorous acid.When the medial compartment addition aqueous solution such as salt solution to three Room type electrolytic vessels and produce the sterilization containing residual chlorine
During water, problems be present.
(i) solution for filling medial compartment is highly acid, i.e. pH is up to 1 or lower, and the maintenance of device is highly difficult.
(ii) oxidation water is highly acid, and pH is 2 to 3, and produces sterilization regular oxidation water.
(iii) when using common three Room type electrolytic vessel, main oxidizable substance is hypochlorite ion.Go out occurrence chlorine
Acid ion has the problem of defect, wherein losing bactericidal effect and the bactericidal effect when organic substance coexists because of alkaline pH
Reduce.
The three Room type electrolytic vessels provided with medial compartment have above mentioned problem.For example, to medial compartment add salt solution when, chlorine
Ion-transfer is to anode chamber, and sodium ion is transferred to cathode chamber.PH in known medial compartment due between separation membrane ion ooze
The difference of permeability and become acid.It is electrolysed by long-time, the pH of middle indoor liquid becomes highly acid so that pH is reduced to 1
It is or lower.
Such strong acidic liquid has corrosivity, and equipment is adversely affected.
As described above, produced by convention using haloid liquid (such as salt solution) by electrolytic oxidation containing residual
Stay the oxidation water of chlorine.Maintenance and control aspect in device, there is the problems such as such as corrosion for being attributed to hydrochloric acid.In order to solve
The problems such as such as corroding, first purpose are by electrolytic oxidation natural water (such as typical running water), do not add halogen acids
(halogen acid) produces sterilized water.
Have been reported and claim hypochlorite ion to show sterilizing power and cause concentration of residual chlorine.Hypochlorite ion has
Following shortcoming.
(1) the sterilizing power highest in 4 to 6 neutral pH range, 8 or the sterilizing power more in the range of high alkalinity pH significantly
Reduce, and the sterilizing power under 10 or higher pH substantially eliminates.
(2) when hypochlorite ion and bacterium and organic substance coexist, sterilizing power has notified reduction.
Second purpose is to strengthen sterilizing power and be maintained at the sterilizing power of alkaline range, and further by electrolytically generated
When organic substance coexists, the oxidizable substance of sterilizing power will not be also substantially reduced.
Can be chlorine dioxide by electrolytically generated oxidable chlorine compound in addition to hypochlorite ion.The following files are
Sterilizing power through report chlorine dioxide is constant and stronger than hypochlorous sterilizing power in the range of 6.0 to 10.0 pH.
(Masahiko Takayama etc., J.Antibact, Antifung, Agent the 7th phase of volume 23, page 401)
The content of the invention
Technical problem
The purpose that the present invention wants to reach is to provide a kind of electrolytic method, and it can be by anodic oxidation raw water as originally
Water, effectively using halogen ion such as chlorion contained in the raw water, produce sterilization/sterilization oxidation in neutral pH range
Water.
In order to produce sterilization oxidation water by electrolysis procedure, halogen ion is added conventionally milled as from outside, it is special
It is not chlorion, and aoxidizes chlorion and produce sterilization water solution to produce residual chlorine such as hypochlorous acid and chlorine dioxide.
In this case, there is the problem of pH is in highly acid.It is contemplated that by greatly reduce halogen ion such as chlorine used from
Son concentration and prevent pH reduce and produce sterilization weak oxide water.
In general, running water chloride ion-containing etc..Specifically, when chlorion etc. is used efficiently, producing sterilization has
The oxidation water of effect.In the case of for running water, originally water quality standard usually requires that concentration of residual chlorine caused by hypochlorous acid etc. is
0.1ppm or higher.In the present invention, water is aoxidized to can be used for sterilizing for hand and pin, equipment etc..When concentration of residual chlorine is higher, effect
Fruit is improved.However, because it is restricted by the use of running water as raw material, concentration.In the present invention, concentration target 0.5ppm
Or it is higher, it is 5 times of originally water quality standard, and preferably 1.0ppm or higher.
The solution of problem
The present invention relates to a kind of method of the sterilization oxidation water produced containing chlorine dioxide, methods described includes：Use
The running water of three Room type electrolytic vessel electrolysis chloride ion-containings, wherein medial compartment between anode chamber and cathode chamber and is to pass through
Separation membrane is set between the anode chamber and the cathode chamber and formed；
Capture is dissolved in the chlorion in the running water；And
The chlorion captured on the anode electrode described in electrolytic oxidation；
The separation membrane that the anode chamber and the medial compartment separate wherein had into fluorine-containing cation exchange membrane and anion
Exchange membrane and porous anode electrode are adhered on the fluorine-containing cation exchange membrane in the separation membrane,
The separation membrane that the cathode chamber and the medial compartment separate wherein had into cation-exchange membrane or anion exchange
Film and porous cathode electrode is adhered on the separation membrane, and
Wherein described medial compartment is filled with anion exchange resin.
The beneficial effect of invention
According to the present invention it is possible to produce sterilization/sterilization oxidation water in neutral range.
Brief description of the drawings
Fig. 1 shows the schematic diagram of two chamber-type electrolytic vessel.
Fig. 2 shows the schematic diagram of three Room type electrolytic vessels.
Fig. 3 is the plan of porous electrode.
Fig. 4 shows the schematic diagram of the three Room type electrolytic vessels used in embodiment 1.
Fig. 5 (a) shows the schematic diagram of the three Room type electrolytic vessels used in embodiment 2.
Fig. 5 (b) shows the schematic diagram of the three Room type electrolytic vessels used in embodiment 2.
Fig. 6 shows the schematic diagram of the three Room type electrolytic vessels used in embodiment 3.
Fig. 7 is the flow chart in embodiment 4 and 5.
Fig. 8 is the flow chart in embodiment 6.
Fig. 9 is the flow chart according to another embodiment of embodiment 6.
Figure 10 shows the schematic diagram of the three Room type electrolytic vessels used in embodiment 7.
Embodiment
In running water etc., chlorion is dissolved with 200ppm Cmax.In the two chamber-type electrolytic vessel shown in Fig. 1 or
In simple three Room type electrolytic vessel shown in Fig. 2, when being electrolysed using the chlorion in such running water, concentration of residual chlorine is
0.1ppm or lower, and it is so low so that undesirable bactericidal effect.When using electrolytic vessel electrolysis running water, originally
The electrical conductance of water is not enough to obtain target bactericidal effect by being electrolysed.Therefore, electricity is electrolysed under about 10mA/cm2 current density
Pressure is up to 100V or higher.Therefore, it is actually still problematic.For actual use, preferably in about 30V or lower electrolysis
Voltage is issued to target cl concn.
As described in example 4 above, the method for reducing decomposition voltage is to use three Room types in cationic ion-exchange resin blank map 2
The method of the medial compartment of electrolytic vessel.The cationic ion-exchange resin of filling allows to the decomposition voltage drop under about 10mA/cm2
As little as 20V or lower.However, even if in this case, concentration of residual chlorine also as little as about 0.1ppm.
In order to increase concentration of residual chlorine, electrolytic vessel is improved as shown in Figs. 4-6.
In Fig. 4, the medial compartment separated in Fig. 2 by amberplex is filled with anion exchange resin.Use anion
Exchange membrane is as the separation membrane on anode chamber side.When allowing running water to pass through medial compartment, halogen ion such as chlorion stay in it is cloudy from
On sub-exchange resin and it is enriched with.When being electrolysed in this state, concentration of residual chlorine can be increased.
The anion exchange resin and fluorine-containing cation exchange membrane used in the present invention is described below.Amino is as function
Group is bonded with anion exchange resin.
Such anion exchange resin includes strong basicity and weakly alkaline two kinds of exchanger resins.In order to efficiently collect running water
In chlorion etc., strong basic ion exchange resin is suitable.Basic resin includes two kinds, is bonded with trimethyl ammonium
I types and the II types being bonded with dimethyl ethanol ammonium.I types basic resin is effective for the efficiency for capturing chlorion etc.
's.And specifically, it is preferable to can be from the strong basicity I type anion exchange trees that Mitsubishi Chemical Corporation are obtained
Fat.
On the other hand, in fluorine-containing cation exchange membrane, sulfate ion group is bonded as functional group with fluororesin.
In the environment of fluororesin, the H with sulfate ion group bonding+Ion is easy to dissociate, and H+Ion can rise during electrolysis
To the effect of carrier.Therefore, it has been reported that pure water can be also electrolysed., can be from DuPont as such cation-exchange membrane
Co. Nafion 117 obtained etc. is useful.It has been reported that be adhered on fluorine-containing cation exchange membrane when anode electrode and
When carrying out anode electrolysis, ozone is produced (based on aromatic hydrocarbon and poly- (aryl oxide) (poly (Arlene of two partially fluorinated sulfonation
Ether the)) proton exchange film fuel battery system of copolymer).Because fluorine-containing cation exchange membrane is swelled in water, chlorine
There is a strong possibility that property can pass through the film for ion.
In order to increase the concentration of the residual chlorine containing chlorine dioxide, the membrane permeability of chlorion may be critically important.In this feelings
Under condition, when 1 to 1,000 micron of hole is produced in fluorine-containing cation exchange membrane, the reactivity of ozone and chlorion can be strengthened.
In Fig. 4, when setting fluorine-containing cationic friendship on the anode chamber side between anion-exchange membrane and anode electrode
When changing film as separation membrane, concentration of residual chlorine can further improve.
It is known when anode electrode is especially adhered on fluorine-containing cation exchange membrane and is electrolysed, the generation of ozone effect
Rate increase.Ozone caused by making is subjected to being shown below to generate high price chlorine monoxid with the oxidation reaction of chlorion.(JPH08-
134677 and JP2000-234191)
[chemical formula 2]
Cl-+O3→ClO3 - (3)
By high price chlorine monoxid, chlorine dioxide is generated.
[chemical formula 3]
2ClO2 -+O2 -+4H+→2ClO2+3H2O (4)
ClO3 -+OH·+3H+→ClO2+2H2O (5)
2ClO3 -+2Cl-+4H+→2ClO2+2H2O+Cl2 (6)
Cl2、ClO-And ClO2With oxidability, and kill the effect of microorganism.The material causes concentration of residual chlorine,
And show sterilizing power.
Therefore, chlorion is directly appended in the residual chlorine by electrolytic oxidation reaction generation, because ozone causes chlorine
During the oxidation reaction of ion, concentration of residual chlorine can be increased.Specifically, as shown in Figure 6, it is intended to by making porous mass positioned at sun
The reaction efficiency of ozone caused by anode electrode and chlorion is improved at anode electrode on the side of pole room inner anode room.
[chemical formula 4]
Cl-+O3→ClO3 - (7)
In order to efficiently carry out the oxidation reaction of halogen ion, set plane can on the anode chamber side of porous anode electrode
Permeable member.This construction prevents the water of supply from directly being contacted with anode electrode, and improves the reaction of chlorion and ozone etc.
Efficiency.In addition, reactant is supplied to the side of anode water by the hole of adhesive-bonded fabric.
The example of the plane permeable members used in the present invention may include porous separator, porous membrane and on-woven
Thing.
Porous separator or porous membrane are that have perhaps multiporous plate or film.Porous separator may make up porous separation
Film.It is permeable in plane in order to prevent causing halide ion concentration to reduce due to directly feeding the raw water of anode chamber to anode electrode
In component, porous separator is set on the anode chamber side of anode electrode.Porous separator or porous membrane desirably by
Synthetic resin is formed such as polypropylene and polyethylene as material because the material would be less likely to cause deterioration, such as due to
Become rusty caused by electrolytic oxidation water.As the plate or film formed by resin, using wherein forming many diameter phis as 1mm or more
The plate or film in small hole.Kong Kejing is mechanically formed, or can be used with the porous thin of the hole that diameter phi is 100 μm or bigger
Film.
Adhesive-bonded fabric is the sheet fabric that wherein polymer fiber is wound without weaving.In general, using polyethylene,
The fibers such as polypropylene, polyethylene terephthalate.Because in the present invention, adhesive-bonded fabric is combined with anode electrode, so
Need inoxidizability.For this reason, polytetrafluoroethylene (PTFE) (PTFE) resin adhesive-bonded fabric is adapted to the present invention.The hole of adhesive-bonded fabric
Gap is dimensioned for as 10 to 1,000 μm.
In order to promote the ozone and unreacted chlorion as described above that are generated on oxidizable substance such as anode electrode surface
Deng reaction, anode chamber is separated with plane permeable members.
In table 1, anode electrode side is referred to as mixing chamber.The plane permeable members prevent raw water to be directly fed to anode
The surface of electrode and the reaction efficiency that ozone and chlorion etc. can be improved.
It is contemplated that the raw water (such as running water) that can be used for drinking by electrolytic oxidation aoxidizes water to produce sterilization.So
And raw water generally includes the bivalent metal ion of the alkaline-earth metal such as calcium and magnesium of dissolving.Known bivalent metal ion is attached to the moon
Pole electrode, and cathode electrode is contaminated and raises decomposition voltage.Therefore so that electrolysis procedure is difficult.In the present invention, confession is worked as
To in the raw water of the medial compartment to three Room type electrolytic vessels bivalent metal ion it is dense when, raw water to medial compartment supply
Allow raw water before by cationic ion-exchange resin tower to prevent cathode electrode from polluting.
Embodiment 1
As shown in figure 4, between anode chamber 2 and cathode chamber 4 in the three Room electrolytic vessels provided with medial compartment, porous anode electricity
Pole 1 is adhered on the separation membrane 1 (31) as anion-exchange membrane, and porous cathode electrode is adhered to as cation exchange
On the separation membrane 2 of film.Medial compartment 6 is located between separation membrane 1 and separation membrane 2 (32), and is filled with anion exchange resin 9.
In anion exchange resin 9, halogen ion such as chlorion, bromide ion and iodide ion in running water are captured.Because halogen ion has
Help be electrolysed, so the halogen ion of capture is used to carry out oxidation Decomposition.The use of capture ion, which improves, produces what can be sterilized
Cl2、Br2And I2Efficiency.
Embodiment 2
In the anion-exchange membrane of separation membrane 1 (31) in Fig. 4 three Room type electrolytic vessels, it is known that oxidation generally promotes
Deterioration.Therefore, as shown in Fig. 5 (a), fluorine-containing cation exchange membrane 33 is placed in the separation membrane 1 (31) comprising anion-exchange membrane
Between porous anode electrode.The presence of fluorine-containing cation exchange membrane extends the life-span of anion-exchange membrane.Further, it is important
Be, it is known that fluorine-containing cation exchange membrane also can easily allow anion by and being generated with high ozone through water-swellable
Efficiency.The ozone of generation has bactericidal properties.Chlorion generates chlorine dioxide (ClO by ozone oxidation2)。
In addition, because the concentration of halogen ion such as chlorion is low, ion described in effective use is needed in the present invention.Such as Fig. 5
(b) it is more in being provided with porous partition wall 35 on the water connection side of porous anode electrode with three Room type electrolytic vessels of increase shown in
Halide ion concentration around the anode electrode of hole.In the present invention, the chamber separated by anode electrode 1 and porous separation membrane 35 is referred to as
Mixing chamber.When setting porous separation membrane, allow to prevent halogen ion around anode electrode to be fed to the water supply of anode water
The reduction of concentration.So as to improve electrolytic oxidation reaction efficiency, and improve concentration of residual chlorine.
Embodiment 3
In order to improve the reactivity of ozone and chlorion in the three Room type electrolytic vessels as shown in Fig. 5 (a) and 5 (b), such as
The surface of anode electrode 1 is covered in three Room type electrolytic vessels shown in Fig. 6 with porous membrane.Specifically, by fluorine-containing adhesive-bonded fabric
36 are used as covering.The offer of adhesive-bonded fabric allows to improve the ozone gas of generation and the reaction efficiency of chlorion.
Embodiment 4
As shown in figure 3, use 8 × 6cm2Platinized titanium porous anode and cathode electrode, and the thickness of medial compartment is
1cm.Relatively and research generates the efficiency of oxidizable substance in the electrolytic vessel shown in Fig. 2,4,5 and 6.System shown in Fig. 7
As experimental rig.In the system in fig. 7, the running water for initially allowing for chlorine ion concentration to be about 100ppm passes through cation exchange
Resin tower 10 can pollute the bivalent metal ion of cathode electrode significantly to remove.Will filter out bivalent metal ion water supply to
The medial compartment of each electrolytic vessel shown in Fig. 2,4,5 and 6.Tap water inlets 12 are installed so that running water is injected into cation exchange
Resin tower 10.It is used as salt of regenerant salt etc. by periodically being added from regenerant salt adding mouth 11 and is stirred using mixing pump 101
The aqueous solution of regenerant salt and make ion exchange resin highly efficient regeneration.
Faradaic current is 8A in each electrolytic vessel.The originally water-carrying capacity supplied to anode chamber is 0.5L/min, and
Supply to the originally water-carrying capacity of medial compartment is 2.0L/min.
When the simple three Room type electrolytic vessel using Fig. 2 is with comparison, decomposition voltage is raised and Faradaic current is down to
1A or lower, and concentration of residual chlorine is 0.01ppm or lower.When the medial compartment of Fig. 2 three Room type electrolytic vessels is filled with sun
During ion exchange resin, decomposition voltage is down to 20V or lower, but concentration of residual chlorine is about 0.1ppm.When using as shown in Figure 3
Wherein medial compartment is filled with three Room type electrolytic vessels of anion exchange resin, and concentration of residual chlorine is changed into about 1.5pm.By these values
Comparison, disclose and load anion exchange resin and caused influence for medial compartment.
In order to strengthen the durability of the anion-exchange membrane of separation membrane and ozone be efficiently used, using wherein such as Fig. 5
Shown fluorine-containing cation exchange membrane and anion-exchange membrane are overlapping to cause fluorine-containing cation exchange membrane to adhere on the anode electrode
Film is as separation membrane.During using this electrolytic vessel, concentration of residual chlorine is about 2.0ppm.In order to increase the transmitance of chlorion,
35 about 0.5 micron of hole is formed in this fluorine-containing cation exchange membrane.
When being covered with the electrolytic vessel of adhesive-bonded fabric using anode electrode surface wherein as shown in Figure 6, the oxidation of generation
Concentration of residual chlorine in water is changed into about 4.0ppm.From these data, effectiveness of the invention is shown.
[table 1]
Embodiment 5
Fig. 8, which is shown, can be such that both purification running water and salt solution suitably exchanges and supply to three Room type electrolysis to hold
One example of the system of the medial compartment of device.In this example, the electrolytic vessel shown in Fig. 5 (b) is built-in.In this electrolysis
In container, using the separation membrane structure with anion-exchange membrane 31 and fluorine-containing cation exchange membrane 33, and this structure
Separation membrane is adhered on anode electrode 1.In the side of anode chamber 2, that is, the offside for separating membrane structure is provided with porous separation membrane 35.It is right
For the medial compartment of electrolytic vessel, it can select to medial compartment supply by the running water of exchange resin tower 10
Method and the method for supplying the salt solution from salt solution groove 13 to medial compartment using measuring pump 150.
In the system of fig. 8, salt solution groove is filled with 15% salt solution, and by about 3mL/min that salt is molten
Liquid is supplied to medial compartment.The size for the electrode being built in electrolytic vessel is 6 × 8cm2, and Faradaic current is 10A.Supply
The flow of running water is 1L/min.The concentration of residual chlorine of the electrolytic oxidation water of generation is tested to be about 45ppm.Aoxidize dioxy in water
The ratio for changing chlorine is 72%.In the measurement of chlorine dioxide, the colorimetric of glycine and diethyl-p-phenylenediamine (DPD) is used
Method.
Embodiment 6
Shunt valve that is substantially the same with Fig. 8 system and being provided with the anode chamber for surrounding electrolytic vessel is shown in Fig. 9
The system of line.During using this system, the flow of the running water in anode chamber as raw water can substantially reduce, while keep aoxidizing
The overall flow of water.When under electrolytic condition same as Example 5, by the flow restriction in anode chamber be 0.2L/min and
When the overall flow of running water is 1L/min, concentration of residual chlorine increases to 85ppm.
Embodiment 7
Herein, in Figure 10 it is being shown in which that three Room type electrolytic vessels are improved to reduce the structure of the dosage of water.Such as
Shown in Figure 10, cathode chamber is eliminated, and air electrode is used as cathode electrode.When using fluorine-containing cation exchange membrane as negative electrode
During the separation membrane of side, the water in medial compartment is partly transferred to due to swellability, i.e. a kind of characteristic of fluorine-containing cation exchange membrane
Porous cathode electrode side.Therefore, electrolysis can be carried out continuously.
Industrial applicibility
According to the present invention it is possible to produce sterilization/sterilization oxidation water in neutral range.Therefore, the present invention is for food
Product processing or exceedingly useful in a clinical setting.
List of reference signs
1 porous anode electrode
2 anode chambers
21 anode compartment outlets
22 Anode chamber inlets
31 separation membranes 1
32 separation membranes 2
33 fluorine-containing cation exchange membranes
35 porous separators
36 adhesive-bonded fabrics
4 cathode chambers
41 cathode chamber outlets
42 negative electrode chamber inlets
5 porous cathode electrodes
6 medial compartments
61 middle chamber inlets
62 medial compartments export
9 anion exchange resin
Claims (9)
1. a kind of sterilization method of oxidation water produced containing chlorine dioxide, it includes：
Using three Room type electrolytic vessels, wherein in the three Room type electrolytic vessel, the separation of the separation membrane and negative electrode of anode is used
Film sets medial compartment between anode chamber and cathode chamber, the separation for the anode that the anode chamber and the medial compartment are separated
Film has the fluorine cation-exchange membrane and anion-exchange membrane for having opened many holes, and porous anode electrode is adhered to the anode
Separation membrane in the fluorine-containing cation exchange membrane on,
The separation membrane for the negative electrode for wherein separating the cathode chamber and the medial compartment have cation-exchange membrane or it is cloudy from
Proton exchange, and porous cathode electrode is adhered on the anion separation membrane, and
Wherein described medial compartment is filled with anion exchange resin,
The running water of chloride ion-containing is supplied to the medial compartment, and the running water by the medial compartment is supplied to described
Anode chamber, the Cmax of the chlorion is 200ppm,
The running water of the medial compartment is supplied to by electrolysis, by the chlorion being dissolved in the running water with the sun
Ion isolation film captures, and generates ozone on the porous anode,
By the chlorion captured on the separation membrane of the anode, electrolytic oxidation generates chlorine dioxide on the porous anode electrode,
Generate the oxidation water of the sterilization containing chlorine dioxide.
2. the method for production sterilization oxidation water according to claim 1, wherein using the electricity with following structures
Container is solved to increase the concentration of the chlorine dioxide, is had in the structure described in the hole that diameter phi is 1 micron or bigger
Fluorine-containing cation exchange membrane is adhered on the porous anode electrode.
3. the method for production sterilization oxidation water according to claim 1 or 2, is provided with parallel to three Room wherein utilizing
The system of the by-pass line of supply pipeline in the anode chamber of type electrolytic vessel is to increase the concentration of the chlorine dioxide.
4. the method for production sterilization oxidation water according to claim 1 or 2, wherein utilizing by being handed over filled with cation
The raw water of water softening system purifying of resin is changed as the water to be fed to the medial compartment.
5. the method for production sterilization oxidation water according to claim 1 or 2, wherein, by using relative to described more
Hole anode electrode configures the plane permeable members on the anode chamber side, to be supplied from the medial compartment to the anode chamber
The mode that is not contacted directly with the porous anode of the running water, running water is supplied to the anode chamber.
6. the method for sterilization oxidation water of the production according to claim 5 containing chlorine dioxide, wherein the plane can
Permeable member is porous separator.
7. the method for sterilization oxidation water of the production according to claim 5 containing chlorine dioxide, wherein the plane can
Permeable member is adhesive-bonded fabric.
8. the production sterilization method of oxidation water according to claim 1 or 2, is provided with the water-soluble liquid bath of chlorion, and
And supplied chlorion saline solution to the medial compartment by measuring pump, if it is necessary, causing electrolytic oxidation, with described in increase
The concentration of chlorine dioxide.
9. the method for production sterilization oxidation water according to claim 1 or 2, wherein by making raw water be handed over by cation
The water for changing resin tower and obtaining is supplied to the medial compartment to maintain electrolytic efficiency for a long time, so that the water contains titanium dioxide
Chlorine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-253922 | 2013-12-09 | ||
| JP2013253922 | 2013-12-09 | ||
| PCT/JP2014/006119 WO2015087536A1 (en) | 2013-12-09 | 2014-12-08 | Method for producing oxidized water for sterilization use without adding electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105813984A CN105813984A (en) | 2016-07-27 |
| CN105813984B true CN105813984B (en) | 2018-02-09 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005058848A (en) * | 2003-08-08 | 2005-03-10 | Spring:Kk | Production method for water used for washing, disinfecting, and wound healing, its production apparatus, and water used for washing, disinfecting, and wound healing |
| WO2008072388A1 (en) * | 2006-12-11 | 2008-06-19 | Ideo Co., Ltd. | Aqueous solution and method of prolonging life of residual chlorine in aqueous solution |
| JP4722749B2 (en) * | 2006-03-30 | 2011-07-13 | 島崎電機株式会社 | Electrolyte tank water supply / drainage system in electrolyzer |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005058848A (en) * | 2003-08-08 | 2005-03-10 | Spring:Kk | Production method for water used for washing, disinfecting, and wound healing, its production apparatus, and water used for washing, disinfecting, and wound healing |
| JP4722749B2 (en) * | 2006-03-30 | 2011-07-13 | 島崎電機株式会社 | Electrolyte tank water supply / drainage system in electrolyzer |
| WO2008072388A1 (en) * | 2006-12-11 | 2008-06-19 | Ideo Co., Ltd. | Aqueous solution and method of prolonging life of residual chlorine in aqueous solution |
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