CN103866345B - Sterilizing water generation apparatus - Google Patents
Sterilizing water generation apparatus Download PDFInfo
- Publication number
- CN103866345B CN103866345B CN201310656236.6A CN201310656236A CN103866345B CN 103866345 B CN103866345 B CN 103866345B CN 201310656236 A CN201310656236 A CN 201310656236A CN 103866345 B CN103866345 B CN 103866345B
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- Prior art keywords
- electrode
- oxide
- water
- electrolytic cell
- sterilized water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 230000001954 sterilising effect Effects 0.000 title abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 12
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 230000008859 change Effects 0.000 claims description 44
- 238000005868 electrolysis reaction Methods 0.000 claims description 38
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 241000370738 Chlorion Species 0.000 claims description 11
- 230000008520 organization Effects 0.000 claims description 10
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 241000894007 species Species 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 230000007246 mechanism Effects 0.000 abstract description 6
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract 1
- 229910000457 iridium oxide Inorganic materials 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 238000005245 sintering Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 238000010926 purge Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000005611 electricity Effects 0.000 description 9
- 150000003284 rhodium compounds Chemical class 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 150000003058 platinum compounds Chemical class 0.000 description 7
- 150000003482 tantalum compounds Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910018967 Pt—Rh Inorganic materials 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 platinum-yttrium oxide-rhodium oxide-tantalum oxide Chemical compound 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 241000628997 Flos Species 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JVOQKOIQWNPOMI-UHFFFAOYSA-N ethanol;tantalum Chemical compound [Ta].CCO JVOQKOIQWNPOMI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 2
- 229910001630 radium chloride Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000194370 Cyclocephala pan Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 229910010977 Ti—Pd Inorganic materials 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- GWZHWRVINLCSIC-UHFFFAOYSA-N [Ir].[N+](=O)(O)[O-] Chemical compound [Ir].[N+](=O)(O)[O-] GWZHWRVINLCSIC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000001217 buttock Anatomy 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- IMTFPWYLPOWRGG-UHFFFAOYSA-N platinum yttrium Chemical compound [Y].[Pt].[Pt].[Pt].[Pt].[Pt] IMTFPWYLPOWRGG-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/4613—Inversing polarity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/4614—Current
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/4615—Time
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The present invention provides a sterilizing water generation apparatus which realizes miniaturization and has strong sterilizing water generation capability on a high level and long electrode service life used for generating sterilizing water. Chlorine is generated on the positive electrode by directly electrolyzing chloridion-containing water, and thus sterilizing water of hypochlorous acid is generated through reaction of chlorine and water. The apparatus is provided with electrodes arranged in an electrolytic cell where the chloridion-containing water passes through, a catalyst layer being arranged on electrode base body formed by titanium or titanium alloy; a control mechanism used for electrifying the electrodes so as to generate hypochlorous acid in the electrolytic cell. The control mechanism electrifies the electrodes with the ampere density within 7A/dm<2> to 20 7A/dm<2> and carries out electrode switching operations of switching of a positive electrode and a negative electrode. The catalyst layer of the electrode contains at least iridium oxide and tantalum oxide and is composed of the mixture of metal and/or metallic oxide, wherein in the mixture, the molar ratio of the concentration of the platinum element is below 4%.
Description
Technical field
The present invention relates to a kind of sterilized water generating device, the device can Direct Electrolysis contain chlorion（Clˉ）Water and
The electrolysis water with high bactericidal property is generated, it is specially a kind of that chlorine is produced to the water Direct Electrolysis containing chlorion
（Cl2）, so as to generate the sterilized water generating device of hypochloric acid water.
Background technology
It is known in the prior art：Water containing chlorion generation chlorine at anode by electrode Direct Electrolysis,
And hypochlorous acid is generated by the chlorine and water reaction, using the hypochlorous bactericidal properties, such as in the equipment machine of general family
Upper to attach the function, opponent, humidification cleans nozzle of toilet seat etc. with water, water for bathing, closet, warm water carries out sterilization.Above-mentioned electricity
Solution is due to mainly using running water, and the calcium substance in running water can be with calcium carbonate（Hereinafter referred to as " incrustation scale "）Form it is attached
On cathode surface, so as to exist by between narrow and small electrode and cleaning spray nozzle clogging situation.In order to prevent above-mentioned feelings
Condition occurs, and generally known settling mode is：The polarity of negative electrode and anode is regularly switched（Change poles）Attachment is removed to reach
The purpose of the incrustation scale on negative electrode.
In addition, in order to the stable and efficient characteristic for producing chlorine can be obtained in the low saline solution of concentration, it is general,
Formed using the electrode catalyst layer being made up of the complex of platinum, yttrium oxide, rhodium oxide, tantalum oxide on conductive base
Electrode（Reference Japanese invention Patent Publication No 2009-052069）.
Patent document 1：Japanese invention Patent Publication No 2009-052069
However, in the electrode of described composition in the JP 2009-052069 publication of patent document 1, in order to suppress
The blocking of incrustation scale is produced on the stream of the path towards washer jet etc. and in the case of carrying out frequently change poles, electricity can be caused
The service life of pole is remarkably decreased, so as to need to provide a kind of sterilized water generating device of high life.
The content of the invention
In view of this, it is an object of the invention to provide a kind of sterilized water generating device, in higher level, not only may be used
Realize equipment miniaturization, and sterilized water generative capacity is improved, for generate sterilized water electrode can the high life, especially
It is to realize higher in current density and carried out with high-frequency the electrode high life under conditions of change poles operation.
In order to achieve the above object, sterilized water generating device of the invention, by the water Direct Electrolysis containing chlorion
And chlorine is produced on anode, hypochlorous sterilized water, the sterilized water generating device are generated by the chlorine and water reaction
Have：Electrode, it is arranged in the electrolytic cell that the water containing chlorion passes through, in the electrode base formed by titanium or titanium alloy
Catalyst layer is provided with body；Controlling organization, it is used to make the electrode be powered and generate hypochlorous acid in the electrolytic cell, institute
Stating controlling organization makes the electrode with 7A/dm2～20A/dm2Current density be powered, and the polarity to electrode carries out anode and the moon
The change poles operation of the switching of pole, the catalyst layer of the electrode at least by the metal comprising yttrium oxide, rhodium oxide and tantalum oxide and/
Or the complex of metal oxide is constituted, the mol ratio shared by the concentration of the platinum element in the complex is below 4%.
In the electrode that the concentration containing platinum element is more than specific concentration, platinum is being carried out when electrode switches from urging
Agent layer dissolves, and as the dissolving of platinum accelerates the in poor quality of catalyst layer, thus, reduces hypochlorous generative capacity.
If according to the present invention composition, can by making electrode in platinum element amount be specified quantitative below, electricity can be extended
The life-span of pole.Platinum element is not preferably contained in the complex.
Additionally, it is preferred that the controlling organization is controlled to electrode, the polarity with the interval within 30 seconds to electrode is carried out
Carry out the change poles operation of the switching of anode and negative electrode.Accordingly, for be formed as at the yttrium oxide periphery of the cathode side after change poles compared with
The problem of strong acidic atmosphere, can be suppressed by the simple structure.Expanded with the state of higher current density and changed
The time interval of pole, then in the acidic atmosphere that the yttrium oxide periphery formation of anode-side is stronger.Therefore, the cathode side after change poles
Electrode reaction, accelerate the decline of the adhesion of yttrium oxide.In the present invention, by carrying out change poles operation within 30 seconds,
Acidic atmosphere can be suppressed to be formed, so as to suppress change poles after yttrium oxide adhesion decline problem.
Additionally, it is preferred that the controlling organization makes the electrode with 12A/dm2～17A/dm2Current density be powered.It is such
Sterilized water generating device has good practicality, can not only sufficiently ensure bactericidal property, and in miniaturization, high life
Aspect can reach good balance.
Additionally, it is preferred that the water containing chlorion supplied in the electrolytic cell, is the continuous-flow type of non-water circulation.In anode
The periphery of the yttrium oxide of side is formed as highly acid atmosphere, when being changed to negative electrode from anode in the state of highly acid atmosphere, one
As think yttrium oxide valence mumber reduce, cause the yttrium oxide to be remarkably decreased with the adhesion of catalyst.Adopted by making electrolytic cell
Continuous-flow type, due to being electrolysed before close neutral water supply to electrode, the electricity for being formed as negative electrode after change poles can be suppressed
The highly acid atmosphere that the yttrium oxide periphery of pole side is formed, to suppress the decline of yttrium oxide and the adhesion of catalyst such that it is able to
Yttrium oxide is suppressed to depart from from catalyst layer.In other words, in the case where electrolytic cell is the stored water memory-type of water, in negative electrode
The electrode perimeter of side easily produces highly acid atmosphere, thus causes electrode life to decline.
Additionally, it is preferred that the controlling organization is controlled to the electrode, the polarity being spaced to electrode with 4～15 seconds is carried out
Carry out the change poles operation of the switching of anode and negative electrode.Thereby, it is possible to the combination for further effectively suppressing the yttrium oxide after change poles
The problem that power declines, it is possible to provide the sterilized water generating device with following performance, i.e. it has good practicality, can not only
Enough ensure sufficient bactericidal property, and good balance can be reached in terms of miniaturization, high life.
The effect of invention
According to the sterilized water generating device that the present invention is provided, in higher level, equipment miniaturization is not only realized, and
And sterilized water generative capacity is improved, the electrode for generating sterilized water also can the high life.
Description of the drawings
Fig. 1 is the schematic diagram of the explanation for representing electrolytic cell, and the electrolytic cell is used for the tool of an embodiment of the invention
There are the clean washing apparatus of sterilized water generating device；
Fig. 2 is to represent water discharge time of the electrolytic cell Jing after change poles shown in Fig. 1 and the calcium carbonate being attached on battery lead plate（Water
Dirt）Adhesion amount between relation chart；
Fig. 3 is the solid of the flush toilet stool arranged on the clean washing apparatus for represent an embodiment of the invention
Figure；
Fig. 4 is the system diagram of stream when representing the sterilized cleaning of the clean washing apparatus shown in Fig. 3；
Fig. 5 is the explanatory diagram of the action of each key element in the sterilized cleaning for represent the clean washing apparatus shown in Fig. 3,
(A) chart of additional voltage between the battery lead plate of electrolytic cell is represented, tiring out for the electrolytic cell measured by control unit (B) is represented
The chart of product electrolysis time, (C) represents the chart of the water yield flowed in drain flow path, (D) represents and is flowed in discharge duct
The water yield chart；
Fig. 6 is the schematic diagram of the sectional view of battery lead plate 2,4；
Fig. 7 is respectively after the initial stage of the electrode of embodiment 2 and comparing embodiment 2 (electrolysis 0 hour), electrolysis 27 hours, electricity
The photo on solution surface after 82 hours, after being electrolysed 162 hours, after being electrolysed 257 hours, after being electrolysed 377 hours；
Fig. 8 is the result for representing the x-ray fluorescence analysis device analysis by embodiment 2 and comparing embodiment 2.
【Symbol description】
1 electrolytic cell；2nd, 4 battery lead plate；10 flow path systems；12 waterings；14 washer jets；16 streams；18 drain flow paths；20
Furcation；22 discharge duct；24 control units；26 pumps；28 purge valves；30 dump valves；32 output mechanisms；41 Titanium bases (electrode base
Body)；42 catalyst layers；100 clean washing apparatus；110 Western-style w.c.pans；120 closets.
Specific embodiment
Referring to clean washing apparatus with sterilized water generating device of the drawing to an embodiment of the invention
Illustrate.
Firstly, for the clean washing apparatus of present embodiment, the inventor of the present invention is carried out for found problem
Explanation.
Fig. 1 is the schematic diagram of the explanation for representing electrolytic cell, and the electrolytic cell is used for the tool of an embodiment of the invention
There are the clean washing apparatus of sterilized water generating device.As shown in the drawing, electrolytic cell 1 has a pair of battery lead plate 2,4, by this
Apply applied voltage between battery lead plate 2,4, by water power from decomposition.The state of applied voltage is represented in Fig. 1 (A), in the state
In, battery lead plate 2 is formed as negative electrode, and battery lead plate 4 is formed as anode.
Due to including chlorion (Cl in running water-), by the way that running water ionization is decomposed, in the battery lead plate 4 of anode-side
Place produces chlorine (Cl2).The chlorine leach of above-mentioned generation generates hypochlorous acid in water.Therefore, it is possible to generate in electrolytic cell 1
Containing hypochlorous sterilized water.
In addition, now, at the battery lead plate 2 of cathode side, the calcium ion contained in running water is with the shape of calcium carbonate (incrustation scale)
Formula is attached on battery lead plate 2.Because the calcium carbonate in above-mentioned is attached on battery lead plate 2, the generative capacity for causing sterilized water declines.
Therefore, the electrolytic cell 1 of the clean washing apparatus of present embodiment, for example, is reached with the accumulation generation time of sterilized water
The time point of the defined of the time to defined etc., by the outer power-up between the battery lead plate 2,4 in the state shown in Fig. 1 (A)
Pressure inverts to be formed as the state shown in Fig. 1 (B), that is, change poles operation.By changing for the state that is transformed to shown in Fig. 1 (B)
The operation of pole, makes to be formed as anode as the battery lead plate 2 of cathode function, makes to be formed as negative electrode as the battery lead plate 4 of anode function.
Thus, acid is generated on the battery lead plate 2 adhered to by calcium carbonate, by dissolving of the acid to calcium carbonate, electrode can be will be attached to
Calcium carbonate on plate 2 is peeled off.
Present inventors studied the calcium (incrustation scale) adhered on the water discharge time in above-mentioned electrolytic cell 1 after change poles and electrode is attached
Relation between the amount of wearing, is explained below.In research process, based on interelectrode applied voltage be respectively 10V and
The state of 5V, investigates the relation between the adhesion amount of water discharge time and calcium (incrustation scale) after change poles.
Fig. 2 is to represent be attached to electrode after elapsed time of the electrolytic cell Jing after change poles and the elapsed time shown in Fig. 1
On incrustation scale amount between relation chart.As shown in the drawing, after change poles, through the time of defined, by stripping electrode
Calcium amount is greatly reduced.It follows that the incrustation scale adhered on electrode, major part can fall off Jing after change poles.
In addition, as shown in Fig. 2 the applied voltage on electrode for 10V situation, with the applied voltage on electrode for 5V
Situation compares, and the amount of the incrustation scale adhered on electrode after change poles is substantially reduced to half or so.It follows that being applied to electrode
On applied voltage it is bigger, after change poles, more substantial incrustation scale is just had at short notice and is peeled off.
According to above-mentioned result, in the clean washing apparatus of an embodiment of invention described below, electricity is made
When solving groove action and carrying out sterilization, after change poles, the sterilized water generated within the time of defined is set to be discharged by the upstream of nozzle.With
Under, the clean washing apparatus of present embodiment are described in detail.
Fig. 3 is the solid of the flush toilet stool for representing the clean washing apparatus for being provided with an embodiment of the invention
Figure.As shown in the drawing, clean washing apparatus 100 are arranged on the closet 120 of the Western-style w.c.pan 110 of rinsing type.By behaviour
Make controller, make the turnover in the closet 120 of washer jet 14, by by rinse water from washer jet 14 head end to body local
（Buttocks etc.）Spray, body local can be cleaned.
Flow path system figure when Fig. 4 is the sterilized cleaning of the clean washing apparatus for representing an embodiment of the invention.
Omit in the figure to sterilized cleaning and unconnected unit, the clean washing apparatus of present embodiment have known being used for
The necessary structure of body local cleaning.
As shown in figure 4, the flow path system 10 of the clean washing apparatus when sterilization in present embodiment is cleaned, such as water channel
The watering 12 and washer jet 14 of pipe etc. is connected by stream 16,18, and above-mentioned electrolytic cell 1 is provided with the stream 16.
Furcation 20 is provided with the downstream of the electrolytic cell 1 of stream 16, the furcation 20 splits into stream from furcation 20 to clear
The drain flow path 18 for washing the extension of the direction of nozzle 14 and the discharge duct 22 extended downwards by furcation 20.
Drain flow path 18, the sectional area of the delivery port of its washer jet 14（That is, the minimum flowing path section of drain flow path 18
Product）Less than the minimum flow path cross sectional area of discharge duct 22.Thus, compared with drain flow path 18, the pressure of discharge duct 22 is damaged
Lose less.
On the downstream of the furcation 20 of drain flow path 18, the pump being connected in the way of it can communicate with control unit 24 is provided with
26.Pump 26 is pressurizeed based on the instruction of control unit 24 to the circulating water in drain flow path 18.
On the downstream of the pump 26 of drain flow path 18, the cleaning being connected in the way of it can communicate with control unit 24 is provided with
Valve 28.Purge valve 28 is opened and closed based on the instruction of control unit 24, and to control water drain flow path 18 is flowed into.
On the downstream of the purge valve 28 of drain flow path 18, washer jet 14 is connected with, is supplied by drain flow path 18
Sterilized water by the washer jet 14 floss hole spray.Thereby, it is possible to carry out sterilized cleaning to the main body of washer jet 14.
On the downstream of the furcation 20 of discharge duct 22, it is provided with what is be connected in the way of it can communicate with control unit 24
Dump valve 30.Dump valve 30 is opened and closed based on the instruction of control unit 24, and to control water discharge duct 22 is flowed into.By above-mentioned row
Go out stream 22 and dump valve 30 constitutes output mechanism 32.In the present embodiment, it is provided with the discharge stream for shunting stream 16
Road 22, but be not limited thereto, opening also only can be set on the lower surface of stream 16.In addition, in the present embodiment, in row
Go out on stream 22 and be provided with dump valve 30, thus control flowing of the current in discharge duct 22, but be not limited thereto, use
Pump etc. can also control flowing of the current in discharge duct 22.
When electrolytic cell 1 is driven, control unit 24 measures accumulative electrolysis time T, and the accumulative electrolysis time T enters for electrolytic cell 1
The cumulative time that row electrolysis is processed.In addition, presetting on control unit 24 for determining being advised for the time point for implementing change poles
Fixed accumulated time setting value TPC, when accumulative electrolysis time T reaches accumulated time setting value TPCWhen, implement changing for electrolytic cell 1
Pole operates.Therefore, by making accumulated time setting value TPCIt is shorter, adhesion amount of the incrustation scale on battery lead plate can be reduced.From incrustation scale
Adhesion amount from the viewpoint of, such as between battery lead plate applied voltage be 5V in the case of, the accumulated time setting value can be made
TPCFor 60 seconds or so.
In addition, pre-setting on control unit 24, dump valve 30 is opened while after change poles by 28 locking of purge valve
Defined efflux time setting value TOP.Efflux time setting value T that dump valve 30 is openedOP, such as with reference to Fig. 1 explanations
As, between battery lead plate 2,4 during additional larger voltage, because incrustation scale is peelable in the short time after change poles, so
Can set it to shorter, between battery lead plate 2,4 during additional less voltage, can be set to longer.
The action in the sterilized cleaning of clean washing apparatus is illustrated below.
Fig. 5 is the explanatory diagram of the action of each key element in the sterilized cleaning for represent the clean washing apparatus shown in Fig. 3,
（A）The chart of the applied voltage between the battery lead plate 2,4 of electrolytic cell 1 is represented,（B）Represent the electrolytic cell measured by control unit 24
The chart of 1 accumulation electrolysis time,（C）The chart of the water yield flowed in drain flow path is represented,（D）Represent in discharge duct
The chart of the water yield of flowing.In Fig. 5（A）~（D）Chart described in transverse axis（Time shaft）Unanimously.
Accumulated time setting value T is not reaching to by the accumulation electrolysis time of the computation and measurement of control unit 24PCIn the state of, lead to
Cross operating portion of the user to clean washing apparatus（It is not shown）The instruction of sterilized cleaning is implemented in input（T1 i.e., in Fig. 5,
t3）, electrolytic cell 1 is driven, while by the open purge valve 28 of the control of control unit 24, closing dump valve 30.Thus, as in Fig. 5
（C）Shown, the sterilized water generated in electrolytic cell 1 flows into drain flow path 18, is discharged by the floss hole of washer jet 14 then, from
And sterilized cleaning can be carried out to washer jet 14.Then, after the sufficient sterilized cleaning to washer jet 14 is completed,
Sterilized cleaning operation is completed at t2, t4.Between the t1～t2 and t3～t4, in such as Fig. 5（B）It is shown, by control unit 24
The accumulative electrolysis time T of the electrolytic cell 1 of measure increased.
When control unit 24 carries out above-mentioned sterilized cleaning, when accumulation electrolysis time T reaches accumulated time setting value TPC
（That is, in Fig. 5（A）In t5）When, implement the change poles operation of electrolytic cell 1.At the same time, control unit 24 is after by change poles（t=t5）
To efflux time setting value TOPBetween, purge valve 28 is closed, while opening dump valve 30.In addition, at the same time, control unit 24 makes
The force (forcing) pump 26 arranged in drain flow path 18 quits work.
By implementing change poles operation in electrolytic cell 1, in such as Fig. 5（A）It is shown, it is additional on battery lead plate 2,4 by being applied to
Voltage reversal.Thus, peel off the incrustation scale on the battery lead plate 2 for being up to the present attached to negative electrode side.In this regard, due to cleaning
Valve 28 opens dump valve 30 while closing, so that sterilization electrolytic water is discharged by discharge duct 22 to the pond of closet.
Thus, because the sterilized water containing incrustation scale is discharged to the pond of closet, and washer jet 14 is not flowed to such that it is able to prevent cleaning
The delivery port of nozzle 14 is blocked by incrustation scale.
In addition, by change poles Jing efflux times setting value TOPAfterwards（That is, t=t6）, control unit 24 closes dump valve 30,
Purge valve 28 is opened simultaneously, the beginning action of pump 26 is made again.Thus, in washer jet 14 sterilized water is supplied again, so as to
It is enough that sterilized cleaning is carried out to washer jet 14.
Thus, according to present embodiment, by after change poles to through the defined time, due to the washer jet 14 of stream 16
Upstream sterilized water to closet discharge such that it is able to suppress after change poles containing by stripping electrode substantial amounts of incrustation scale sterilized water
Flow to washer jet 14, i.e. the delivery port that can suppress washer jet 14 is blocked by incrustation scale.
Thus, change poles operation can be frequently carried out in electrolytic cell 1, for a long time and sterilized water can be stably supplied.In addition,
It is discharged in closet due to having abstergent sterilized water such that it is able to the rinse water for cleaning closet is saved, while energy
It is enough that bactericidal effect is played to closet itself.
In addition, according to present embodiment, purge valve 28 is provided with drain flow path 18, due to after by change poles to row
Go out time setting value TOPBetween, the purge valve 28 is closed, therefore, it is possible to the practical electrolysis for preventing from being supplied by electrolytic cell 1 after change poles
Water is flowed in drain flow path 18.
In addition, according to present embodiment, because drain flow path 18 is provided towards the structure that top extends, with drain flow path
18 compare discharge duct 22 the pressure loss it is less, while the water being present in drain flow path 18 is towards the adverse current of furcation 20,
So as to the incrustation scale flowed in drain flow path 18 is discharged.
More have, according to present embodiment, by arranging the discharge duct 22 extended downwards by furcation 20, flow direction is discharged
The electrolysis water containing incrustation scale of stream 22 can accelerate its flowing in the presence of self gravitation such that it is able to which suppression contains incrustation scale
Sterilized water flow into drain flow path 18.
In the above-described embodiment, by after change poles to efflux time setting value TOPBetween, by purge valve 28 will with it is clear
The drain flow path 18 for washing the connection of nozzle 14 is closed, but is also not necessarily required to need to close drain flow path 18.As described above,
In the clean washing apparatus of present embodiment, compared with drain flow path 18, the minimum flowing path section of discharge duct 22 is larger,
So as to compared with drain flow path 18, the pressure loss of discharge duct 22 is less.Therefore, drain flow path 18 can not also be closed,
When dump valve 30 is opened, sterilized water is flowed in drain flow path 18 and discharge duct 22.
More have, in the clean washing apparatus of present embodiment, due to being provided with force (forcing) pump 26 in drain flow path 18, lead to
Cross after by change poles to efflux time setting value TOPBetween, stop force (forcing) pump 26, thus, compared with drain flow path 18, row
The pressure loss for going out stream 22 is less.Therefore, dump valve 30 is opened, in discharge duct 22, is compared to drain flow path 18
Have substantial amounts of sterilized water to flow into such that it is able to which reduction is flowed into the sterilized water containing incrustation scale in drain flow path 18.
In addition, in the above-described embodiment, the change poles for carrying out electrolytic cell 1 by control unit 24 is closed clear while operation
Valve 28 is washed, and opens dump valve 30, but be not limited thereto, also can be after change poles within the defined time, will be in electrolytic cell 1
The sterilized water of middle generation is discharged by output mechanism 32.That is, in the case where output mechanism 32 and electrolytic cell 1 are provided separately, by
After beginning to pass through the time of defined after change poles, purge valve 28 is closed, and dump valve 30 is opened also may be used.
Fig. 6 is the ideograph of the sectional view of battery lead plate 2,4.The material of the electrode matrix 41 of battery lead plate 2,4, for example can be
Titanium or titanium-base alloy.Titanium alloy is the conduction alloy with corrosion resistance based on titanium.As the titanium of electrode material
Based alloy, for example, is typically made up of compositions such as Ti-Ta-Nb, Ti-Pd, Ti-Zr, Ti-Al.Such electrode material can be by
It is processed according to desired shape, the shape is, for example, tabular, abacus shape, bar-shaped, web plate shape etc., using as electrode base
Body 41 is used.
To electrode matrix as above 41, in usual way, pre-treatment is carried out in advance.The pre-treating method, example
Such as it is set to be in the grit-blasting treatment process of mechanical rough surface, make the electrode matrix 41 to be sprayed removing material
In being immersed in the flow fluid of the acid solutions such as oxalic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid or static liquid, so that the electrode matrix
Surface dissolving engraving method chemically, electrode matrix surface electrolytic oxidation in electrolyte solution is made, so that the table of matrix
Face is formed as electrolytic oxidation process method of porous materialization etc..In addition, also can simultaneously use above-mentioned pre-treatment side of more than two kinds
Method.
Titanium base 41 after premenstrual process, by sintering in an atmosphere, can make the surface oxidation of the matrix and be formed as
TiO2, also can enter directly into without sintering processes in next operation.
Then, the surface of Titanium base 41 is by the urging as complex for including platinum, yttrium oxide, rhodium oxide and tantalum oxide
Agent layer 42 is covered.Here, the shared mol ratio of the concentration of the platinum element in the complex is not preferably contained below 4%
Platinum element.In addition, catalyst layer 42 also layer can be formed on Titanium base 41 between.By arranging intermediate layer, although deposit
Occur in the problem for causing catalyst layer to be peeled off due to Long-Time Service etc., but be prevented from contact of the matrix with electrolyte, from
Damage without causing matrix due to applied voltage.Due to needing to make intermediate layer tight with catalyst layer contacts and do not hinder
Electrical conductance between matrix and catalyst layer, therefore it is contemplated that the intermediate layer by including metal tantalum or metal tantalum alloy
Metal or tantalum oxide or tantalum oxide composite oxides constitute.
Platinum compound used herein, iridic compound, rhodium compound and tantalum compound are included, and under the following conditions can
Respectively decomposition and inversion is the compound of platinum, yttrium oxide, rhodium oxide and tantalum oxide, specifically, platinum compound is, for example, chlorine platinum
Acid, platinum chloride etc., are especially optimal with chloroplatinic acid.In addition, iridic compound is, for example, chloro-iridic acid, iridium chloride, nitric acid iridium etc., its
In with chloro-iridic acid be optimal.Have again, rhodium compound is, for example, radium chloride, rhodium nitrate etc., wherein being optimal with radium chloride.Tantalum
Compound is, for example, tantalic chloride, ethanol tantalum etc., wherein being optimal with ethanol tantalum.
Have again, as the molten of above-mentioned platinum compound, iridic compound, rhodium compound and tantalum compound dissolving
The solvent that liquid is adjusted, is optimal with lower alcohol.For example, methyl alcohol, ethanol, propyl alcohol, butanol etc., or for above-mentioned mixing
Thing.
Total concentration of platinum compound, iridic compound, rhodium compound and tantalum compound in low-alcohol solution, with
Total metal concentration conversion, generally 20～200g/L, wherein being optimal with the concentration range in 40～150g/L.If the gold
Category concentration is less than 20g/L, then the deposit efficiency of catalyst is low, in addition, if the metal concentration is higher than 200g/L, can produce and urge
The problem of activity, adhesive strength, the inhomogeneity of adhesion amount of agent etc..
In addition, the relative use ratio of platinum compound, iridic compound, rhodium compound and tantalum compound, with metal
Conversion, preferably, below 4%, mol ratio shared by iridic compound is 24.6～80% to mol ratio shared by platinum compound, tantalum chemical combination
Mol ratio shared by thing is 0.25 times～1.5 times of mol ratio shared by iridic compound.In addition, mol ratio is preferably shared by rhodium compound
3～30%.When mol ratio shared by platinum compound is more than 4%, the molten of catalyst layer can be made in the polarity switching by electrode
Solution ratio increases, and so as to accelerate the overall in poor quality of catalyst layer the life-span of electrode is shortened.It is preferred that, do not contain platinum chemical combination
Thing.Iridic compound, as catalyst function when, in order that it plays the function of catalyst, preferably shared mol ratio is 24.6
～80%.In addition, general, stability can be poor in the case of only iridic compound, and electrode life can shorten, therefore, it is
Raising stability preferably mixes it with tantalum compound.If with the calculating of shared mol ratio, the ratio shared by tantalum compound is
0.25 times of iridic compound～1.5 times, in this case, can obtain preferable electrode life and preferably play catalysis
Agent function.Rhodium compound, it is contemplated that in the function as the catalyst that hydrogen is produced at negative electrode, the generation efficiency of chlorine can be improved,
Therefore, make mol ratio shared by the rhodium compound be 3～30%, preferable electrode life can be obtained and catalysis is preferably played
Agent function.
The matrix of the solution is coated with the surface of Titanium base 41, as needed, with the temperature in the range of about 20～150 DEG C
After degree is dried, in the atmosphere containing oxygen（For example in atmosphere）Sintering.The sintering, for example electric furnace, gas burner,
Carry out in the appropriate heating furnace of infrared heating heating furnace etc., typically heated in the range of about 450 DEG C～600 DEG C, wherein with about
Temperature in the range of 500～550 DEG C is optimal.Heat time is corresponding with the size that should sinter matrix etc., substantially 5～30
Between minute.By the sintering, platinum-yttrium oxide-rhodium oxide-tantalum oxide complex is adhered on the surface for enabling the matrix.
In the case that once attachment operation can not adhere to enough platinum-yttrium oxide-rhodium oxide-tantalum oxide complexs, can pass through
The operation of coating-drying-sintering of above-mentioned solution is repeated with desired number of times realizing.
Herein, " platinum-yttrium oxide-rhodium oxide-tantalum oxide complex " is the 4 of platinum, yttrium oxide, rhodium oxide and tantalum oxide
Plant the composition of the mixing of interaction between component impact or the state of close contact.Platinum-yttrium oxide-rhodium oxide-tantalum oxide
The state of the crystallization of complex can be noncrystalline or crystalline state.
In an embodiment of the present invention, the sterilized water generating device of illustration applies the situation in clean washing apparatus, but
Be not limited thereto, such as in being also applicable in any commodity for needing clean environment, such as bathroom, kitchen, medicine equipment
And the water containing chlorion can be carried out ionizing and decomposed in the environment for generating sterilized water by automatic vending machine etc..
Embodiment
Embodiment 1 and embodiment 3
By the titanium plate of Japanese Industrial Standards' JIS1 classes（t0.5mm×20mm×40mm）As Titanium base after stamped processing
Use.It is dipped in acetone, and carries out after the ultrasonic wave cleaning and degreasing of 10 minutes, implements rough surfaceization and process.
Next, the butanol solution of the chloro-iridic acid of 100g/L, tantalum concentration are adjusted to iridium concentration is adjusted to the second of 100g/L
The butanol solution of alcohol tantalum, platinum concentration are adjusted to the chlorine that the butanol solution of the chloroplatinic acid of 200g/L, rhodium concentration are adjusted to 100g/L
The butanol solution for changing rhodium is claimed respectively with the ratio of components that the metal of Ir-Ta-Pt-Rh converts according to the molar percentage shown in table 1 below
Amount, and is diluted by butanol, so that the total concentration of the addition of the metal scaled value of each metal ingredient is weight percentage 8%,
Thus make and form coating liquid.
The solution 120 μ l are measured by pipette, and is coated onto on the Titanium base, then using tweezers by Titanium base
Incline, after solution coating is expanded in the whole surface of Titanium base, by drying at room temperature, then in 550 DEG C of air
Sintering 10 minutes.The coating-drying-sintering circuit 5 times is repeated, embodiment 1 and the electricity shown in embodiment 3 is thus fabricated to
Pole.
Embodiment 2 and embodiment 4～8
The repeatedly operation of the coating-drying-sintering circuit 3 times, other are identical with embodiment 1 and embodiment 3, thus, it is possible to
It is fabricated to embodiment 2 and the electrode shown in embodiment 4～8.
Comparing embodiment 1
Above-mentioned butanol solution is weighed respectively, so that the ratio of components of the metal conversion of Ir-Ta-Pt-Rh is according to shown in table 1
Molar percentage, so make coating liquid, other are same as Example 1, the electricity thus, it is possible to be fabricated to comparing embodiment 1
Pole.
Comparing embodiment 2～7
Above-mentioned butanol solution is weighed respectively, so that the ratio of components of the metal conversion of Ir-Ta-Pt-Rh is according to shown in table 1
Molar percentage, so make coating liquid, and repeat the operation 3 times of the coating-drying-sintering circuit, other and enforcement
Example 1 is identical, the electrode thus, it is possible to be fabricated to comparing embodiment 2～7.
Table 1
Long duration test 1
For the electrode of the embodiment 1～8 and comparing embodiment 1～7 that make is implemented to generate electrode as hypochlorous acid
Durability test.In the durability test, the running water of 0.45L/min used in electrolyte, interelectrode distance is 0.5mm, Gu
Given current controller is 14.7A/dm2（Electric current 1A, electrode area 680mm2）Current density, electrolysis time every five seconds for example is by anode and the moon
Pole is once changed, and with the electrolysis of 5 second time, the electroless electrolysing period condition iterative cycles of 1 second time.Record electricity
Solution magnitude of voltage and free cl concn over time, and are less than with the free chloro concentration produced by electrode for electrolysis
The time point of 0.3ppm is used as its life termination point.The concentration of free chlorine is counted by using small-sized chlorine residue detection（Model：
HACH2470, using reagent：DPD（Diethyl-p-PDA）10ml）It is measured.
The result of the durability test 1 of embodiment 1～4 and comparing embodiment 1～2 is represented in table 2.By embodiment 1 and in fact
The result for applying example 3 and comparing embodiment 1 is compared and understands, is all the coating-sintering through 5 times, is being considered to have catalysis
Total amount of metal of the Ir-Pt-Rh of agent function is identical, is 0.0268（G/ pieces）In the case of, the amount of platinum it is less one
Side has the longer life-span.In addition, the result of embodiment 2 and embodiment 4 and comparing embodiment 2 is compared understanding, all it is
It is identical in total amount of metal of the Ir-Pt-Rh for being considered to have catalyst function through the coating-sintering of 3 times, it is
0.0161（G/ pieces）In the case of, the side that the amount of platinum is less has the longer life-span.
Table 2
* the proportion of solution is according to 0.81g/cm3Converted
The result of embodiment 2,5～8 and comparing embodiment 3～7 is represented in table 3.By embodiment 2 and embodiment 3
As a result it is compared and understands, be all the coating-sintering through 3 times, the relative of 3 kinds of compositions in constituent in addition to platinum is rubbed
That ratio is under identical circumstances, it is known that the side without platinum has the longer life-span.Likewise, by embodiment 5 and implementing
Example 4, embodiment 6 are compared respectively with the result of embodiment 7 and understand with embodiment 5, embodiment 7 and embodiment 6, embodiment 8,
All it is the coating-sintering through 3 times, the relative molar ratios of 3 kinds of compositions in constituent in addition to platinum are in identical feelings
Under condition, the side without platinum is respectively provided with the longer life-span.
Table 3
* the proportion of solution is according to 0.81g/cm3Converted
Durability evaluates 1
The initial stage of the electrode of embodiment 2 and comparing embodiment 2 is represented in the figure 7（Electrolysis 0 hour）, electrolysis 27 hours after,
The photo on the respective surface of electrode after electrolysis 82 hours, after electrolysis 162 hours, after electrolysis 257 hours, after electrolysis 377 hours.
In the photo, it appears that black part is complex, it appears that the part for white is not complex, but the portion of Ti matrixes
Point.Even if as shown in fig. 7, the adhesion amount of complex is identical, for the embodiment 2 for not containing platinum composition, being able to confirm that
It is slow with the phase specific consumption of comparing embodiment 2 containing platinum composition.
Durability evaluates 2
For the electrode in embodiment 2 and comparing embodiment 2, using x-ray fluorescence analysis device（Rigaku（リガ
ク）ZSX Primus II processed）It is analyzed, is measured with the amount to Ir and each element of Pt.For each electrode, with regard to the initial stage
（Electrolysis time：0 hour）, electrolysis 27 hours after, electrolysis 82 hours after, electrolysis 162 hours after, electrolysis 257 hours after, electrolysis
Be analyzed respectively after 377 hours, peak intensities values when setting the initial stage of each element as 100, then according to each electrolysis time
The peak intensities values of each element afterwards, try to achieve the change of the amount of each element.The core of electrode is glimmering as the X-ray of Φ 10
The mensuration region of light analytical equipment.
Fig. 8 represents the result of the x-ray fluorescence analysis device analysis by embodiment 2 and comparing embodiment 2.Setting Ir and
The initial stage of each element of Pt（Electrolysis time：0 hour）When peak intensities values（Kcps）For 100%, according to electrolysis time, show
The change of the peak intensities values of each element.The Ir of comparing embodiment 2 compared with the Pt of comparing embodiment 2 understand, Pt compared to
Ir, the easily in poor quality by the electrolysis initial stage.In addition, the Ir and the Ir of comparing embodiment 2 of the embodiment 2 after being electrolysed 82 hours
Compare and understand, even if the composition of Ir is identical, a side of the embodiment 2 without platinum composition is compared with the comparison reality containing platinum composition
Apply example 2 and be not easy in poor quality.
Claims (5)
1. a kind of sterilized water generating device, it is led to by the way that chlorine is produced on anode to the water Direct Electrolysis containing chlorion
Cross the chlorine and generate hypochlorous sterilized water with water reaction, it is characterised in that the sterilized water generating device has：
Electrode, it is arranged in the electrolytic cell that the water containing chlorion passes through, in the electrode base formed by titanium or titanium alloy
Catalyst layer is provided with body；Controlling organization, it is used to make the electrode be powered and hypochlorous acid is generated in the electrolytic cell,
The controlling organization makes the electrode with 7A/dm2～20A/dm2Current density be powered, and the polarity to electrode carries out sun
The change poles operation of the switching of pole and negative electrode,
The catalyst layer of the electrode is configured to a species complex, and the complex is the complex of metal oxide or the gold
The complex of category oxide and metal, and including at least yttrium oxide, rhodium oxide and tantalum oxide,
The complex contains yttrium oxide, rhodium oxide and tantalum oxide, wherein, with metal conversion, mol ratio shared by yttrium oxide is
24.6～80%, mol ratio shared by rhodium oxide is 3～30%, and mol ratio shared by tantalum oxide is 0.25 of mol ratio shared by yttrium oxide
Times～1.5 times, the complex does not contain platinum element or mol ratio shared by platinum element is less than 4%.
2. sterilized water generating device according to claim 1, it is characterised in that
The controlling organization is controlled to electrode, and implementation carries out anode and negative electrode with the interval within 30 seconds to the polarity of electrode
Switching change poles operation.
3. sterilized water generating device according to claim 1, it is characterised in that
The controlling organization makes the electrode with 12A/dm2～17A/dm2Current density be powered.
4. sterilized water generating device according to claim 1, it is characterised in that
The water containing chlorion supplied in the electrolytic cell, is the continuous-flow type of non-water circulation.
5. sterilized water generating device according to claim 1 and 2, it is characterised in that
The controlling organization is controlled to the electrode, and carry out carries out anode and the moon with 4～15 seconds intervals to the polarity of electrode
The change poles operation of the switching of pole.
Applications Claiming Priority (4)
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| JP2012-268405 | 2012-12-07 | ||
| JP2012268405 | 2012-12-07 | ||
| JP2013060536A JP5646677B2 (en) | 2012-12-07 | 2013-03-22 | Sterilization water generator |
| JP2013-060536 | 2013-03-22 |
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| CN103866345A CN103866345A (en) | 2014-06-18 |
| CN103866345B true CN103866345B (en) | 2017-04-12 |
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| JP6209255B1 (en) * | 2016-07-21 | 2017-10-04 | 株式会社日本トリム | Electrolyzed water generator |
| CN109790635A (en) * | 2016-12-28 | 2019-05-21 | Toto株式会社 | Electrolytic water generating device |
| CN106932647B (en) * | 2017-01-24 | 2019-10-25 | 中国科学院计算技术研究所 | Conductivity sensor |
| CN111286747A (en) * | 2018-12-10 | 2020-06-16 | 彭志军 | Built-in ultrasonic electrolysis system oxyhydrogen device |
| KR102355824B1 (en) | 2018-12-27 | 2022-01-26 | 코웨이 주식회사 | Electrode catalyst layer composed of palladium, iridium, and tantalum, and sterilizing water generating module coated with the electrode catalyst |
| CN113529109A (en) * | 2021-08-03 | 2021-10-22 | 北京德义法正科技有限公司 | Hypochlorous acid molecule solution preparation facilities |
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| CN103866345A (en) | 2014-06-18 |
| KR101579154B1 (en) | 2015-12-21 |
| KR20140074227A (en) | 2014-06-17 |
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