CN103866345A - Sterilizing water generation apparatus - Google Patents
Sterilizing water generation apparatus Download PDFInfo
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- CN103866345A CN103866345A CN201310656236.6A CN201310656236A CN103866345A CN 103866345 A CN103866345 A CN 103866345A CN 201310656236 A CN201310656236 A CN 201310656236A CN 103866345 A CN103866345 A CN 103866345A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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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 apparatus, this device can contain chlorion (Cl by Direct Electrolysis
--) water and generate the brine electrolysis with high bactericidal property, be specially and a kind of the water Direct Electrolysis that contains chlorion produced to chlorine (Cl
2), thereby the sterilized water generating apparatus of generation hypochloric acid water.
Background technology
Be known in the prior art: the water that contains chlorion generates chlorine at anode place by electrode Direct Electrolysis, and react with water and generate hypochlorous acid by this chlorine, utilize this hypochlorous bactericidal properties, for example subsidiary this function on the equipment machine of general family, the nozzle of opponent, humidification water, bath water, closet, warm water cleaning toilet seat etc. carries out sterilization.What use is tap water due to main in above-mentioned electrolysis, and calcium substance in tap water can be attached on cathode surface with the form of calcium carbonate (hereinafter referred to as " incrustation scale "), thereby exists between narrow and small electrode and clean the situation of the spray nozzle clogging of use.In order to prevent that above-mentioned situation from occurring, general known settling mode is: the switching regular polarity of negative electrode and anode (change poles) is removed to the object that is attached to the incrustation scale on negative electrode to reach.
In addition, in order to obtain the characteristic of stablizing and producing efficiently chlorine in the low salt solution of concentration, general, on conductive base, use the electrode catalyst layer being formed by the complex body of platinum, iridium oxide, rhodium oxide, tantalum oxide and the electrode forming (No. 2009-052069, the Japanese patent of invention Publication JP of reference).
Patent documentation 1: No. 2009-052069, Japanese patent of invention Publication JP
But, in the electrode of the composition of recording in patent documentation 1 JP 2009-052069 communique, on the stream of the path of washing nozzle etc., to produce the obstruction of incrustation scale and carry out in the situation of change poles frequently in order to be suppressed at, can cause significantly decline the work-ing life of electrode, thereby the sterilized water generating apparatus of a kind of high life need to be provided.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of sterilized water generating apparatus, in higher level, not only can implement device miniaturization, and sterilized water generative capacity is improved, can the high life for the electrode that generates sterilized water, especially realize higher in current density and carry out with high frequency the electrode high life under the condition of change poles operation.
In order to achieve the above object, sterilized water generating apparatus of the present invention, on anode, produce chlorine by the water Direct Electrolysis to containing chlorion, react with water by described chlorine and generate hypochlorous sterilized water, described sterilized water generating apparatus has: electrode, it is arranged in the electrolyzer that the water that contains chlorion passes through, and on the electrode matrix being formed by titanium or titanium alloy, is provided with catalyst layer; Controlling organization, it generates hypochlorous acid for making described electrifying electrodes in described electrolyzer, and described controlling organization makes described electrode with 7A/dm
2～20A/dm
2current density energising, and the change poles that the polarity of electrode is carried out to the switching of anode and negative electrode operates, the catalyst layer of described electrode is at least made up of the complex body of the metal that comprises iridium oxide, rhodium oxide and tantalum oxide and/or person's metal oxide, and the shared mol ratio of the concentration of the platinum element in described complex body is below 4%.
In electrode more than the concentration that contains platinum element is specific concentration, carry out electrode while switching platinum dissolve from catalyst layer, along with the in poor quality of catalyst layer has been accelerated in the dissolving of platinum, thus, reduced hypochlorous generative capacity.If according to formation of the present invention, can be below specified quantitative by making the amount of the platinum element in electrode, can extend the life-span of electrode.In described complex body, preferably do not contain platinum element.
In addition, preferred described controlling organization is to carry out the change poles operation of the switching the polarity of electrode is carried out with interior interval anode and negative electrode for 30 seconds to the control of electrode.Thus, be formed as the problem of stronger acid atmosphere for the iridium oxide periphery place of the cathode side after change poles, can suppress by this simple structure.Expand the timed interval of change poles with the state of higher current density, form stronger acid atmosphere at the iridium oxide periphery of anode side.Therefore,, by the electrode reaction of the cathode side after change poles, accelerated the decline of the bonding force of iridium oxide.In the present invention, by carried out change poles operation in 30 seconds, can suppress acid atmosphere and form, thus the problem that the bonding force of the iridium oxide after inhibition change poles declines.
In addition, preferred described controlling organization makes described electrode with 12A/dm
2～17A/dm
2current density energising.Such sterilized water generating apparatus has good practicality, not only can guarantee fully bactericidal property, and can reach good balance aspect miniaturization, high life.
In addition,, to the water that contains chlorion of supplying with in described electrolyzer, be preferably the continuous-flow type of non-water cycle.Periphery at the iridium oxide of anode side is formed as strongly-acid atmosphere, in the time being changed to negative electrode by anode under the state of strongly-acid atmosphere, it is generally acknowledged that the valence mumber of iridium oxide reduces, and causes the bonding force of this iridium oxide and catalyzer significantly to decline.By making electrolyzer adopt continuous-flow type, owing to being supplied with to electrode by the water that approaches neutrality before electrolysis, can be suppressed at the strongly-acid atmosphere that the iridium oxide periphery of the electrode side that is formed as negative electrode after change poles forms, with the decline of the bonding force of inhibited oxidation iridium and catalyzer, thereby can depart from from catalyst layer by inhibited oxidation iridium.In other words, in the situation that electrolyzer is the stored water memory-type of water, easily produce strongly-acid atmosphere in the electrode perimeter of cathode side, cause thus decline electrode life.
In addition, preferred described controlling organization to the control of described electrode is, carries out the change poles operation of with 4～15 seconds intervals, the polarity of electrode being carried out the switching of anode and negative electrode.Thus, can further suppress effectively the problem of the bonding force decline of the iridium oxide after change poles, the sterilized water generating apparatus with following performance can be provided,, it has good practicality, sufficient bactericidal property not only can be guaranteed, and good balance can be reached aspect miniaturization, high life.
The effect of invention
According to sterilized water generating apparatus provided by the invention, in higher level, not only realized equipment miniaturization, and sterilized water generative capacity is improved, also can the high life for the electrode that generates sterilized water.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that represents the explanation use of electrolyzer, and this electrolyzer is for the clean washing apparatus with sterilized water generating apparatus of an embodiment of the invention;
Fig. 2 is the chart of the relation between the water discharge time of electrolyzer shown in presentation graphs 1 after change poles and the adhesion amount that is attached to the calcium carbonate (incrustation scale) on battery lead plate;
Fig. 3 is the stereographic map that represents the flush toilet stool arranging on the clean washing apparatus of an embodiment of the invention;
Fig. 4 is the system diagram of stream of the sterilization of the clean washing apparatus shown in presentation graphs 3 while cleaning;
Fig. 5 is the explanatory view of the action of the each key element during the sterilization of the clean washing apparatus shown in presentation graphs 3 is cleaned, (A) be illustrated in the chart of voltage additional between the battery lead plate of electrolyzer, (B) chart of the accumulation electrolysis time of the electrolyzer that expression is measured by control part, (C) be illustrated in the chart of the water yield mobile in drain flow path, (D) be illustrated in the chart of discharging the moving water yield in stream upper reaches;
Fig. 6 is the schematic diagram of the sectional view of battery lead plate 2,4;
The photo of initial stage (electrolysis 0 hour), electrolysis that Fig. 7 is respectively the electrode of embodiment 2 and comparing embodiment 2 after 27 hours, electrolysis after 82 hours, electrolysis after 162 hours, electrolysis after 257 hours, 377 hours rear surfaces of electrolysis;
Fig. 8 is the result representing by the x-ray fluorescence analysis device analysis of embodiment 2 and comparing embodiment 2.
[nomenclature]
1 electrolyzer; 2,4 battery lead plates; 10 flow path systems; 12 water-supply sources; 14 washing nozzles; 16 streams; 18 drain flow path; 20 furcations; 22 discharge stream; 24 control parts; 26 pumps; 28 cleaning valves; 30 outlet valves; 32 output mechanisms; 41 titanium matrixes (electrode matrix); 42 catalyst layers; 100 clean washing apparatus; 110 Western water closets; 120 closets.
Embodiment
Below with reference to drawing, the clean washing apparatus with sterilized water generating apparatus of an embodiment of the invention is described.
First,, for the clean washing apparatus of present embodiment, inventor of the present invention describes for found problem.
Fig. 1 is the schematic diagram that represents the explanation use of electrolyzer, and this electrolyzer is for the clean washing apparatus with sterilized water generating apparatus of an embodiment of the invention.As shown in the drawing, electrolyzer 1 has a pair of battery lead plate 2,4, by apply impressed voltage between this battery lead plate 2,4, water power is separated to solution.The state that represents impressed voltage in Fig. 1 (A), in this state, battery lead plate 2 is formed as negative electrode, and battery lead plate 4 is formed as anode.
Owing to including chlorion (Cl in tap water
--), by tap water ionization is decomposed, produce chlorine (Cl at electrode 4 places of anode side
2).The chlorine leach of above-mentioned generation, in water, generates hypochlorous acid.Therefore, can in electrolyzer 1, generate and contain hypochlorous sterilized water.
In addition, now, at battery lead plate 2 places of cathode side, the calcium ion containing in tap water is attached on battery lead plate 2 with the form of calcium carbonate (incrustation scale).Because the calcium carbonate in above-mentioned is attached on battery lead plate 2, cause the generative capacity of sterilized water to decline.
Therefore, the electrolyzer 1 of the clean washing apparatus of present embodiment, for example, reach the time point of the defined of time of defined etc. with the accumulation rise time of sterilized water, impressed voltage between battery lead plate 2,4 in state shown in Fig. 1 (A) is reversed to be formed as the state shown in Fig. 1 (B), namely change poles operation.By being transformed to the operation of change poles of the state shown in Fig. 1 (B), make to be formed as anode as the battery lead plate 2 of cathode function, make to be formed as negative electrode as the battery lead plate 4 of anode function.Thus, generate acid on the battery lead plate 2 being adhered to by calcium carbonate, the dissolving by this acid to calcium carbonate, can peel off the calcium carbonate being attached on battery lead plate 2.
The inventor has studied the relation between the adhesion amount of the calcium (incrustation scale) adhering on the water discharge time after change poles and electrode in above-mentioned electrolyzer 1, is explained below.In research process, be respectively the state of 10V and 5V based on interelectrode impressed voltage, the relation between the water discharge time after change poles and the adhesion amount of calcium (incrustation scale) is investigated.
Fig. 2 is the chart of the relation between the amount that is attached to the incrustation scale on electrode after elapsed time and this elapsed time of electrolyzer shown in presentation graphs 1 after change poles.As shown in the drawing, after change poles, through the time of defined, significantly reduced by the calcium amount of stripping electrode.Hence one can see that, the incrustation scale adhering on electrode, most of can coming off after change poles.
In addition, as shown in Figure 2, the situation that the impressed voltage on electrode is 10V, compares with the situation that the impressed voltage on electrode is 5V, and the amount of the incrustation scale adhering on electrode after change poles is roughly reduced to half left and right.Hence one can see that, is applied to impressed voltage on electrode larger, after change poles, just has at short notice more substantial incrustation scale and peel off.
According to above-mentioned result, in the clean washing apparatus of an embodiment of the invention of following explanation, make electrolyzer action and while carrying out sterilization, after change poles, the sterilized water generating within the time of defined is discharged by the upstream of nozzle.Below, the clean washing apparatus of present embodiment is described in detail.
Fig. 3 is the stereographic map that represents the flush toilet stool of the clean washing apparatus that is provided with an embodiment of the invention.As shown in the drawing, clean washing apparatus 100 is arranged on the closet 120 of Western-style w.c.pan 110 of water washing type.By operation control, make washing nozzle 14 in the interior turnover of closet 120, by rinse water is sprayed to body local (buttocks etc.) by the head end of washing nozzle 14, can clean body local.
Fig. 4 be represent an embodiment of the invention clean washing apparatus sterilization clean time flow path system figure.Omit in the figure and clean with sterilization and unconnected unit, the clean washing apparatus of present embodiment has known necessary structure of cleaning for body local.
As shown in Figure 4, the flow path system 10 of the clean washing apparatus when sterilization in present embodiment is cleaned, the water-supply source 12 of such as water pipe etc. is connected by stream 16,18 with washing nozzle 14, on this stream 16, is provided with above-mentioned electrolyzer 1.On the downstream of the electrolyzer 1 of stream 16, be provided with furcation 20, stream is split into the drain flow path 18 of being extended to washing nozzle 14 directions by furcation 20 and the discharge stream 22 being extended by furcation 20 downwards by this furcation 20.
On the downstream of the furcation 20 of drain flow path 18, be provided with the pump 26 that the mode can communicate by letter with control part 24 is connected.The instruction of pump 26 based on control part 24 pressurizeed to the flowing water in drain flow path 18.
On the downstream side of the pump 26 of drain flow path 18, be provided with the cleaning valve 28 that the mode can communicate by letter with control part 24 is connected.The instruction of cleaning valve 28 based on control part 24 opens and closes, and flows into drain flow path 18 to control water.
On the downstream side of the cleaning valve 28 of drain flow path 18, be connected with washing nozzle 14, the sterilized water of supplying with by drain flow path 18 is sprayed by the discharge outlet of this washing nozzle 14.Thus, can carry out sterilization cleaning to the main body of washing nozzle 14.
On the downstream side of furcation 20 of discharging stream 22, be provided with the outlet valve 30 that the mode can communicate by letter with control part 24 is connected.The instruction of outlet valve 30 based on control part 24 opens and closes, and flows into discharge stream 22 to control water.Form output mechanism 32 by above-mentioned discharge stream 22 and outlet valve 30.In the present embodiment, be provided with the discharge stream 22 that stream 16 is shunted, but be not limited to this, also can only on the lower surface of stream 16, opening be set.In addition, in the present embodiment, be provided with outlet valve 30 discharging on stream 22, control thus current and discharging flowing on stream 22, but be not limited to this, use pump etc. also can control current and discharging flowing on stream 22.
When electrolyzer 1 is driven, control part 24 instrumentation accumulative total electrolysis time T, this accumulative total electrolysis time T is the cumulative time that electrolyzer 1 carries out electrolysis treatment.In addition, on control part 24, preset the cumulative time set(ting)value T of the defined for determining the time point of implementing change poles
pC, when accumulative total electrolysis time, T reaches this cumulative time set(ting)value T
pCtime, implement the change poles operation of electrolyzer 1.Therefore, by making cumulative time set(ting)value T
pCshorter, can reduce the adhesion amount of incrustation scale on battery lead plate.From the viewpoint of the adhesion amount of incrustation scale, for example, in the situation that impressed voltage between battery lead plate is 5V, can make this cumulative time set(ting)value T
pCbe about 60 seconds.
In addition, on control part 24, set in advance, after change poles by cleaning valve 28 lockings by the efflux time set(ting)value T of defined open outlet valve 30
oP.By this efflux time set(ting)value T open outlet valve 30
oP, as illustrated with reference to Fig. 1, between battery lead plate 2,4 when additional larger voltage, in the short period of time of cause after change poles, incrustation scale is peelable, so can be set as shorter, when additional less voltage, can be set to long between battery lead plate 2,4.
Action in below the sterilization of clean washing apparatus being cleaned describes.
Fig. 5 is the explanatory view of the action of the each key element during the sterilization of the clean washing apparatus shown in presentation graphs 3 is cleaned, (A) be illustrated in the chart of impressed voltage between the battery lead plate 2,4 of electrolyzer 1, (B) chart of the accumulation electrolysis time of the electrolyzer 1 that expression is measured by control part 24, (C) be illustrated in the chart of the water yield mobile in drain flow path, (D) be illustrated in the chart of discharging the moving water yield in stream upper reaches.The transverse axis (time shaft) that the chart of (A) in Fig. 5～(D) is recorded is consistent.
Do not reach cumulative time set(ting)value T by the accumulation electrolysis time of control part 24 computation and measurements
pCstate under, the instruction (, t1, t3 in Fig. 5) that sterilization is cleaned is implemented in the input of operating portion (not shown) by user to clean washing apparatus, drives electrolyzer 1, is controlled open cleaning valve 28, is closed outlet valve 30 simultaneously by control part 24.Thus, as shown in (C) in Fig. 5, the sterilized water generating in electrolyzer 1 flows into drain flow path 18, is then discharged by the discharge outlet of washing nozzle 14, thereby can carry out sterilization cleaning to washing nozzle 14.Then,, after completing the sufficient sterilization cleaning of washing nozzle 14, complete sterilization cleaning operation at t2, t4 place.Between this t1～t2 and t3～t4, as shown in (B) in Fig. 5, the accumulative total electrolysis time T of the electrolyzer 1 of measuring by control part 24 increases to some extent.
In the time that control part 24 carries out above-mentioned sterilization cleaning, when accumulation electrolysis time T reaches cumulative time set(ting)value T
pCwhen (, the t5 in Fig. 5 in (A)), implement the change poles operation of electrolyzer 1.Meanwhile, control part 24 after by change poles (t=t5) to efflux time set(ting)value T
oPbetween, close cleaning valve 28, open outlet valve 30 simultaneously.In addition, meanwhile, control part 24 quits work the force (forcing) pump 26 arranging in drain flow path 18.
By implement change poles operation in electrolyzer 1, as shown in (A) in Fig. 5, by the impressed voltage reversion being applied on battery lead plate 2,4.Thus, the incrustation scale that makes to be up to the present attached on the battery lead plate 2 of negative electrode one side is peeled off.To this, outlet valve 30 is opened due to cleaning valve 28 is closed when, thereby sterilization electrolytic water is discharged to the pond of closet by discharging stream 22.Thus, because the sterilized water that contains incrustation scale is discharged to the pond of closet, and do not flow to washing nozzle 14, thereby can prevent that the water outlet of washing nozzle 14 from being stopped up by incrustation scale.
In addition, started through efflux time set(ting)value T by change poles
oP(, t=t6) afterwards, control part 24 is closed outlet valve 30, cleaning valve 28 is opened simultaneously, makes again pump 26 start action.Thus, again in washing nozzle 14, supply with sterilized water, thereby can carry out sterilization cleaning to washing nozzle 14.
Thus, according to present embodiment, by after change poles to passing through the defined time, because the sterilized water of the upstream of the washing nozzle 14 of stream 16 is discharged to closet, thereby can suppress to contain after change poles by the sterilized water of a large amount of incrustation scale of stripping electrode and flow to washing nozzle 14, the water outlet that, can suppress washing nozzle 14 is stopped up by incrustation scale.
Thus, change poles operation can be in electrolyzer 1, carried out frequently, sterilized water can be supplied with for a long time and stably.In addition, because the abstergent sterilized water of tool is discharged in closet, thereby can save the rinse water for cleaning closet, can play sterilization effect to closet self simultaneously.
In addition, according to present embodiment, in drain flow path 18, be provided with cleaning valve 28, due to after by change poles to efflux time set(ting)value T
oPbetween, this cleaning valve 28 is closed, and the brine electrolysis of being supplied with by electrolyzer 1 after change poles that prevents that therefore can be practical flow in drain flow path 18.
In addition, according to present embodiment, the structure that is set to extend upward due to drain flow path 18, comparing with drain flow path 18, it is less to discharge the pressure-losses of stream 22, be present in water in drain flow path 18 towards furcation 20 adverse currents simultaneously, thereby the incrustation scale flowing in drain flow path 18 can be discharged.
More have, according to present embodiment, by the discharge stream 22 being extended downwards by furcation 20 is set, the brine electrolysis that contains incrustation scale of flow direction discharge stream 22 can be accelerated it and flow under the effect of self gravitation, thereby the sterilized water that can suppress to contain incrustation scale flows into drain flow path 18.
In the above-described embodiment, by after change poles to efflux time set(ting)value T
oPbetween, by cleaning valve 28, the drain flow path 18 being communicated with washing nozzle 14 is closed, but also might not drain flow path 18 need to be closed.As mentioned above, in the clean washing apparatus of present embodiment, compare with drain flow path 18, the minimum flowing path section of discharging stream 22 is larger, thereby compares with drain flow path 18, and the pressure-losses of discharging stream 22 is less.Therefore, drain flow path 18 also can not closed, and in the time that outlet valve 30 is opened, sterilized water flow into drain flow path 18 and discharges in stream 22.
More have, in the clean washing apparatus of present embodiment, owing to being provided with force (forcing) pump 26 in drain flow path 18, by after by change poles to efflux time set(ting)value T
oPbetween, force (forcing) pump 26 is stopped, thus, comparing with drain flow path 18, the pressure-losses of discharging stream 22 is less.Therefore, outlet valve 30 is opened, discharging in stream 22, be compared to drain flow path 18 and have a large amount of sterilized water inflows, thereby can reduce the sterilized water that contains incrustation scale flowing in drain flow path 18.
In addition, in the above-described embodiment, when carrying out the change poles operation of electrolyzer 1 by control part 24, close cleaning valve 28, and open outlet valve 30, but be not limited to this, also can, after change poles within the defined time, the sterilized water generating in electrolyzer 1 be discharged by output mechanism 32.,, in the situation that 1 point, output mechanism 32 and electrolyzer is arranged, after the time of defined, cleaning valve 28 closed by starting after change poles, and outlet valve 30 is opened and also can.
Fig. 6 is the mode chart of the sectional view of battery lead plate 2,4.The material of the electrode matrix 41 of battery lead plate 2,4 can be for example titanium or titanium base alloy.Titanium alloy is the conduction alloy of the erosion resistance of having take titanium as main body.As the titanium base alloy of electrode materials, for example, generally formed by compositions such as Ti-Ta-Nb, Ti-Pd, Ti-Zr, Ti-Al.Such electrode materials can be processed according to desired shape, and this shape is for example, and tabular, porose tabular, bar-shaped, web plate shape etc., to use as electrode matrix 41.
To electrode matrix 41 as above, according to common mode, carry out in advance pre-treatment.This pre-treating process, for example make its grit-blasting treatment process that is mechanical surface roughening for removing material is sprayed, this electrode matrix 41 is immersed in the flow or static liquid of the acid solutions such as oxalic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, so that the engraving method of the chemical of the surface dissolution of this electrode matrix, make electrode matrix surface electrolytic oxidation in electrolyte solution, so that the surface of matrix is formed as the electrolytic oxidation treatment process of porous materialization etc.In addition, also can use above-mentioned pre-treating process of more than two kinds simultaneously.
Then, the surface of titanium matrix 41 is covered by the catalyst layer 42 as complex body that includes platinum, iridium oxide, rhodium oxide and tantalum oxide.Here, the shared mol ratio of the concentration of the platinum element in described complex body, below 4%, does not preferably contain platinum element.In addition, catalyst layer 42 also can be between layer be formed on titanium matrix 41.By middle layer is set, occur although exist because life-time service etc. causes the problem that catalyst layer peels off, can prevent contacting of matrix and electrolytic solution, thereby can not cause due to impressed voltage the damage of matrix.Owing to need to making middle layer contact closely with catalyst layer and not hindering the electrical conductivity between matrix and catalyst layer, therefore can consider that this middle layer is by including the metal of metal tantalum or metal tantalum alloy or the composite oxides of tantalum oxide or tantalum oxide form.
Platinum compound used herein, iridic compound, rhodium compound and tantalum compound comprise, decomposition and inversion is the compound of platinum, iridium oxide, rhodium oxide and tantalum oxide respectively under the following conditions, be specially, platinum compound is for example Platinic chloride, platinum chloride etc., especially take Platinic chloride as best.In addition, iridic compound is for example chloro-iridic acid, iridium chloride, nitric acid iridium etc., wherein take chloro-iridic acid as best.Have again, rhodium compound is for example rhodium chloride, rhodium nitrate etc., wherein take rhodium chloride as best.Tantalum compound is for example tantalum chloride, ethanol tantalum etc., wherein take ethanol tantalum as best.
Have again, the solvent that the solution dissolving as the platinum compound for to above-mentioned, iridic compound, rhodium compound and tantalum compound is adjusted, take lower alcohol as best.Be for example methyl alcohol, ethanol, propyl alcohol, butanols etc., or be above-mentioned mixture.
The concentration of the total of platinum compound, iridic compound, rhodium compound and tantalum compound in low-alcohol solution, to add up to metal concentration to convert, is generally 20～200g/L, wherein take the concentration range at 40～150g/L as best.If this metal concentration is lower than 20g/L, the deposit efficiency of catalyzer is low, in addition, if this metal concentration higher than 200g/L, can produce the problem of activity, the adhesion strength of catalyzer, unhomogeneity of adhesion amount etc.
In addition, the relative usage ratio of platinum compound, iridic compound, rhodium compound and tantalum compound, convert with metal, be preferably, the shared mol ratio of platinum compound is below 4%, the shared mol ratio of iridic compound is 24.6～80%, and the shared mol ratio of tantalum compound is 0.25 times～1.5 times of the shared mol ratio of iridic compound.In addition, the shared mol ratio of rhodium compound is preferably 3～30%.When the shared mol ratio of platinum compound is 4% when above, in the time that the polarity of electrode is switched, can make the dissolving ratio of catalyst layer increase, thereby accelerate the overall in poor quality of catalyst layer and shorten life-span of electrode.Preferably, do not contain platinum compound.Iridic compound, during as the function of catalyzer, in order to make the function of its performance catalyzer, preferred shared mol ratio is 24.6～80%.In addition, general, can be poor at the situation stability inferior that only has iridic compound, and can shorten electrode life, therefore, preferably it is mixed with tantalum compound in order to improve stability.If calculated with shared mol ratio, the shared ratio of tantalum compound is iridic compound 0.25 times～1.5 times, in this case, can obtain good electrode life and bring into play preferably catalyst function.Rhodium compound, considers when produce the function of catalyzer of hydrogen as negative electrode place, can improve the generation efficiency of chlorine, and therefore, making the shared mol ratio of this rhodium compound is 3～30%, can obtain good electrode life and bring into play preferably catalyst function.
On the surface of titanium matrix 41, be coated with the matrix of this solution, as required, after being dried with the temperature in the scope of approximately 20～150 ℃, (for example, in air) sintering in the atmosphere that contains oxygen.This sintering, for example, carry out in the suitable process furnace of electric stove, gas furnace, infrared heating heating furnace etc., generally in the scope of approximately 450 ℃～600 ℃, heats, wherein take the temperature within the scope of approximately 500～550 ℃ as best.Heat-up time is corresponding with size that should sintering matrix etc., roughly between 5～30 minutes.By this sintering, make the surface of this matrix can adhere to platinum-iridium oxide-rhodium oxide-tantalum oxide complex body.Can not adhere to enough platinum-iridium oxide-rhodium oxides-tantalum oxide complex body in the case of an attach operation, the operation that can repeatedly carry out the coating of above-mentioned solution-dry-sintering by the number of times with desired realizes.
Herein, " platinum-iridium oxide-rhodium oxide-tantalum oxide complex body " is the mixing of 4 kinds of interaction between component impacts of platinum, iridium oxide, rhodium oxide and tantalum oxide or the composition of the state of close contact.The state of the crystallization of platinum-iridium oxide-rhodium oxide-tantalum oxide complex body can be noncrystalline or crystalline state.
In an embodiment of the present invention, illustrate the situation that sterilized water generating apparatus is applied in clean washing apparatus, but be not limited to this, for example also can be applicable in any commodity that need clean environment, the water that contains chlorion can being ionized of such as bathroom, kitchen, medicine equipment and vending machine etc. decomposed in the environment that generates sterilized water.
Embodiment
The titanium plate (t0.5mm × 20mm × 40mm) of the JIS1 of Japanese Industrial Standards class is used as titanium matrix after punch process.Be immersed in acetone, and carry out, after the ultrasonic cleaning degreasing of 10 minutes, implementing surface roughening processing.
Next, iridium concentration is adjusted into the ratio of components that the butanol solution of the butanol solution of the chloro-iridic acid of 100g/L, butanol solution that tantalum concentration is adjusted into the ethanol tantalum of 100g/L, butanol solution that platinum concentration is adjusted into the Platinic chloride of 200g/L, rhodium chloride that rhodium concentration is adjusted into 100g/L converts with the metal of Ir-Ta-Pt-Rh to be weighed respectively according to the molar percentage shown in following table 1, and diluted by butanols, with make each metal ingredient metal scaled value addition add up to concentration be weight percentage 8%, thus make form coating liquid.
Measure this solution 120 μ l by transfer pipet, and be coated on this titanium matrix, then use tweezers that titanium matrix is tilted, after solution applied expanding on the whole surface of titanium matrix, by drying at room temperature, then sintering 10 minutes in the atmosphere of 550 ℃.This coating of repetitive operation-dry-sintering circuit 5 times, is made into the electrode shown in embodiment 1 and embodiment 3 thus.
Embodiment 2 and embodiment 4～8
Repeat the operation 3 times of this coating-dry-sintering circuit, other are identical with embodiment 1 and embodiment 3, can be made into thus the electrode shown in embodiment 2 and embodiment 4～8.
Comparing embodiment 1
Weigh respectively above-mentioned butanol solution, to make ratio of components that the metal of Ir-Ta-Pt-Rh converts as according to the molar percentage shown in table 1, make like this coating liquid,, other are identical with embodiment 1, can be made into thus the electrode of comparing embodiment 1.
Comparing embodiment 2～7
Weigh respectively above-mentioned butanol solution, to make ratio of components that the metal of Ir-Ta-Pt-Rh converts as according to the molar percentage shown in table 1, make like this coating liquid, and repeat the operation 3 times of this coating-dry-sintering circuit, other are identical with embodiment 1, can be made into thus the electrode of comparing embodiment 2～7.
Table 1
Implement to generate as hypochlorous acid the durability test of electrode for the electrode of the embodiment 1～8 making and comparing embodiment 1～7.In this durability test, in electrolytic solution, use the tap water of 0.45L/min, interelectrode distance is 0.5mm, fixed current control is 14.7A/dm
2(electric current 1A, electrode area 680mm
2) current density, electrolysis time is once changed anode and negative electrode for every 5 seconds, and with the electrolysing period condition iterative cycles without electrolysis of the electrolysis of 5 second time, 1 second time.Record electrolysis voltage value and free cl concn over time, and using the free chloro concentration that produces by electrode for electrolysis lower than the time point of 0.3ppm as its life termination point.The concentration of free chlorine is by being used small-sized chlorine residue to detect meter (model: HACH2470 uses reagent: DPD(diethyl-p-PDA) 10ml) measure.
In table 2, represent the result of the durability test 1 of embodiment 1～4 and comparing embodiment 1～2.Embodiment 1 is compared known with the result of embodiment 3 and comparing embodiment 1, it is all the coating-sintering through 5 times, identical at the total amount of metal of Ir-Pt-Rh that is considered to have catalyst function, being 0.0268(g/ sheet) in situation, the less side of amount of platinum has the longer life-span.In addition, embodiment 2 is compared known with the result of embodiment 4 and comparing embodiment 2, it is all the coating-sintering through 3 times, identical at the total amount of metal of Ir-Pt-Rh that is considered to have catalyst function, be 0.0161(g/ sheet) situation under, the less side of amount of platinum has the longer life-span.
Table 2
* the proportion of solution is according to 0.81g/cm
3convert
In table 3, represent the result of embodiment 2,5～8 and comparing embodiment 3～7.Embodiment 2 and the result of embodiment 3 being compared known, is all the coating-sintering through 3 times, and the relative molar ratio of 3 kinds of compositions in moiety except platinum is identical in the situation that, and known do not have the longer life-span containing a side of platinum.Same, embodiment 5 and embodiment 4, embodiment 6 and embodiment 5, embodiment 7 and embodiment 6, embodiment 8 are compared respectively known with the result of embodiment 7, it is all the coating-sintering through 3 times, the relative molar ratio of 3 kinds of compositions in moiety except platinum, identical in the situation that, does not all have the longer life-span containing a side of platinum.
Table 3
* the proportion of solution is according to 0.81g/cm
3convert
Wearing quality evaluates 1
Initial stage (electrolysis 0 hour), electrolysis that represents the electrode of embodiment 2 and comparing embodiment 2 in Fig. 7 after 27 hours, electrolysis after 82 hours, electrolysis after 162 hours, electrolysis after 257 hours, the electrode of electrolysis after the 377 hours photo on surface separately.In this photo, the part of taking a fancy to de-black is complex body, and appearing as white part is not complex body, but the part of Ti matrix.As shown in Figure 7, even if the adhesion amount of complex body is identical, for not containing the embodiment 2 of platinum composition, can confirm that it is slow with the comparing embodiment 2 phase specific consumptions that contain platinum composition.
Wearing quality evaluates 2
For the electrode in embodiment 2 and comparing embodiment 2, use x-ray fluorescence analysis device (Rigaku (リ ガ Network) ZSX Primus II processed) to analyze, measure with the amount of the each element to Ir and Pt.For each electrode, with regard to initial stage (electrolysis time: 0 hour), electrolysis after 27 hours, electrolysis after 82 hours, electrolysis after 162 hours, electrolysis after 257 hours, electrolysis analyze respectively after 377 hours, peak strength value while setting initial stage of each element is 100, then according to the peak strength value of the each element after each electrolysis time, try to achieve the variation of the amount of each element.The mensuration region of the x-ray fluorescence analysis device using the centre portions of electrode as Φ 10.
Fig. 8 represents by the result of the x-ray fluorescence analysis device analysis of embodiment 2 and comparing embodiment 2.Peak strength value (Kcps) while setting initial stage (electrolysis time: 0 hour) of each element of Ir and Pt is 100%, according to electrolysis time, shows the variation of the peak strength value of each element.The Ir of comparing embodiment 2 compares known with the Pt of comparing embodiment 2, Pt is compared to Ir, starts easier in poor quality by the electrolysis initial stage.In addition, the Ir of the embodiment 2 of electrolysis after 82 hours and the Ir of comparing embodiment 2 compare known, even if the composition of Ir is identical, the comparing embodiment 2 that does not contain platinum composition containing a side of the embodiment 2 of platinum composition is not easy in poor quality.
Claims (6)
1. a sterilized water generating apparatus, it produces chlorine by the water Direct Electrolysis to containing chlorion on anode, reacts generate hypochlorous sterilized water by described chlorine with water, it is characterized in that, and described sterilized water generating apparatus has:
Electrode, it is arranged in the electrolyzer that the water that contains chlorion passes through, and on the electrode matrix being formed by titanium or titanium alloy, is provided with catalyst layer; Controlling organization, it generates hypochlorous acid for making described electrifying electrodes in described electrolyzer,
Described controlling organization makes described electrode with 7A/dm
2～20A/dm
2current density energising, and the polarity of electrode is carried out to the change poles operation of the switching of anode and negative electrode,
The catalyst layer of described electrode is configured to and at least comprises the metal of iridium oxide, rhodium oxide and tantalum oxide and/or the complex body of person's metal oxide,
The shared mol ratio of the concentration of the platinum element in described complex body is below 4%.
2. sterilized water generating apparatus according to claim 1, is characterized in that,
In described complex body, do not contain described platinum element.
3. sterilized water generating apparatus according to claim 1, is characterized in that,
Described controlling organization is to carry out the change poles operation of the switching the polarity of electrode is carried out with interior interval anode and negative electrode for 30 seconds to the control of electrode.
4. sterilized water generating apparatus according to claim 1, is characterized in that,
Described controlling organization makes described electrode with 12A/dm
2～17A/dm
2current density energising.
5. sterilized water generating apparatus according to claim 2, is characterized in that,
To the water that contains chlorion of supplying with in described electrolyzer, it is the continuous-flow type of non-water cycle.
6. according to the sterilized water generating apparatus described in any one in claim 1～3, it is characterized in that,
Described controlling organization to the control of described electrode is, carries out the change poles operation of with 4～15 seconds intervals, the polarity of electrode being carried out the switching of anode and negative electrode.
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| JP2013060536A JP5646677B2 (en) | 2012-12-07 | 2013-03-22 | Sterilization water generator |
| JP2013-060536 | 2013-03-22 |
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| KR20140074227A (en) | 2014-06-17 |
| CN103866345B (en) | 2017-04-12 |
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