CN103781731A - Electrolysis system and electrolysis method for the same - Google Patents
Electrolysis system and electrolysis method for the same Download PDFInfo
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- CN103781731A CN103781731A CN201280043774.1A CN201280043774A CN103781731A CN 103781731 A CN103781731 A CN 103781731A CN 201280043774 A CN201280043774 A CN 201280043774A CN 103781731 A CN103781731 A CN 103781731A
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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
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- 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
- C02F2001/46119—Cleaning the electrodes
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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
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- C02F2001/46138—Electrodes comprising a substrate and a coating
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- 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
- 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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- C02F2001/46147—Diamond 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
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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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
- C02F2201/46195—Cells containing solid electrolyte
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Abstract
The present invention provides an electrolysis system and an electrolysis method for the same in which non-purified water containing a trace amount of alkali earth metal ions, such as calcium ion and magnesium ion is applied as raw material, having a configuration in which the raw material water is supplied to the cathode compartment (1), featuring that scale of the alkali earth metals including hydroxide can be prevented from depositing on the surface of the cathode (2) provided in the cathode compartment (1). The present invention prevents scales of hydroxide and others of the alkali earth metal from depositing on the cathode surface (2), by covering the substantially entire surface of the cathode (2) with the cation exchange resin-contained, alkali earth metal scale-preventive film in the electrolysis system having a configuration comprising a diaphragm (5), an anode compartment (3) separated by the diaphragm (5), a cathode compartment (1) separated by the diaphragm (5), an anode (4) provided in the anode compartment (3), a cathode (2) provided in the cathode compartment (1), and raw material water containing alkali earth metal ions supplied to the cathode compartment.
Description
Technical field
The present invention relates to electrolyzer and electrolysis process thereof, wherein will comprise trace alkaline-earth metal ion if the non-purified water of calcium ion and magnesium ion is as raw material, there is the structure that wherein raw water is supplied to cathode compartment, be characterised in that the dirt deposition that can prevent oxyhydroxide of alkaline-earth metal etc. is on cathode surface.
Background technology
Utilize the water treatment of electrolytic reaction be widely used in by electrolysis production function water, production ozone water and produce brine electrolysis, sterilizing, and decompose and remove the objects such as objectionable impurities.Have and conventionally there is anode, negative electrode and be arranged on the ion-exchange membrane between the two or be contained in the structure of the porous diaphragm in framework for the reactor of these processing, be called electrolyzer or tank room.Anolyte compartment, the cathode compartment of being separated by barrier film that this electrolyzer or tank room comprise barrier film, separated by barrier film, be arranged on the anode in anolyte compartment and be arranged on the negative electrode in cathode compartment, and knownly having two chamber-type electrolyzer and three Room type electrolyzers.Two chamber-type electrolyzer comprises diaphragm electrolysis device, cationic exchange embrane method electrolyzer and the solid polymer electrolyte method electrolyzer as the special methods of the type.
Diaphragm electrolysis device uses porous diaphragm as barrier film, cationic exchange embrane method electrolyzer uses cationic exchange membrane as barrier film, solid polymer electrolyte method electrolyzer uses cationic exchange membrane as solid polymer electrolyte (solid polymer electrolysis), its Anodic and negative electrode close attachment on two surfaces of cationic exchange membrane, thereby form the electrolyzer of even can electrolytic conduction little pure water.
Three Room type electrolyzers are provided with cationic exchange membrane and anion-exchange membrane is separated anolyte compartment and cathode compartment as barrier film, thereby form intermediate chamber between cationic exchange membrane and anion-exchange membrane.Produce various function water and ozone water by these electrolyzers.
The present invention relates to electrolyzer and electrolysis process thereof, wherein comprise trace alkaline-earth metal ion if the non-purified water of calcium ion and magnesium ion is as the raw material for the treatment of electrolysis; In more detail, the present invention proposes in the ozone water production equipment that passes through electrolysis and ozone water production method, function water production equipment and function water production method and brine electrolysis production equipment and the brine electrolysis production method that use non-purified water as raw water, sterilization, in waste water treatment process etc., can improve the devices and methods therefor of the problem that oxyhydroxide etc. deposits on negative electrode.In addition, electrolyzer of the present invention and electrolysis process thereof can contribute to solve similar problem in other Application Areas.
In general, adopt and comprise alkaline-earth metal ion if the non-purified water of calcium ion and magnesium ion is as raw material in liquid waste disposal method or in comprising the production method of function water of alkali ion water.Use in the electrolysis process of non-purified water at these, first increase with electrolysis time from the pH value of the catholyte of cathode surface, alkaline-earth metal ion using trace amount calcium as principal element is deposited on cathode surface as dielectric dirt (scale) (incrustation scale) using the form of its oxyhydroxide, oxide compound and carbonate, causes electrolytic functional obstacle.
In order to address these problems, patent documentation 1 and patent documentation 2 have proposed the method for cathode compartment liquid by acid; But structure becomes complexity and safety operation becomes difficulty.Patent documentation 3 proposes to suppress cathodic deposition by be used alternatingly the auxiliary tank and the multiple electrode that arrange in the production equipment of brine electrolysis with predetermined time interval.But this device design needs main equipment, causes cost to increase.Patent documentation 4 is described the method for removing deposition by carrying out pickling etc. when normally the closing of device operation in detail, and this causes complicated operation steps.Patent documentation 5 is advised by preventing the deposition on negative electrode with the non-diaphragm electrolysis of hcl acidifying chamber.The method is used and comprises the strong acid chemical solution of hydrochloric acid, and this is not only unfavorable on processing safety or cost, and may depend on application and do not accept strong acid.
The negative electrode of film (reduction preventive film) introduced application and is coated with the reduction being coated on the low hydrogen overvoltage layer being formed on conductive base and prevents by patent documentation 7, utilize diaphragm-free electrolysis method, the method for electrolysis parity in the next life oxymuriate by the muriatic aqueous solution.Organic cation exchange membrane material or inorganic cation exchange membrane material or their compounding substances are prevented to film as reduction.But in diaphragm-free electrolysis method, this reduction prevents that film from preventing that hypochlorite ion is in cathodic reduction, the direct Contact cathod of product at its Anodic place, and do not prevent it being mainly the cathodic deposition of alkaline-earth metal oxyhydroxide.On the other hand, in the electrolysis process and electrolyzer of barrier film used according to the invention, different from patent documentation 7, prevent that without any need for reduction film from preventing hypochlorite ion (product at anode place) reduction.
In the conventional electrolysis method and electrolyzer of use barrier film, in the time that the non-purified water that contains alkaline-earth metal ion is used as raw material, ion turns to cationic metal ion to be assembled on cathode surface, and pH raises, and is formed as cathodic deposition material as the dirt of the oxyhydroxide of main raw.The dirt forming thus hinders electrolysis procedure.The technology that the conventional inhibition dirt proposing forms is disadvantageous, needs cost and manpower or sacrificial section performance.Need further to improve.
Reference listing
Patent documentation
Patent documentation 1:JP2002-173789A
Patent documentation 2:JP2005-177671A
Patent documentation 3:JP2011-050807A
Patent documentation 4:JP10-130876A
Patent documentation 5:JP2008-200667A
Patent documentation 6:JP2008-150665A
Patent documentation 7:JP08-104991A
Summary of the invention
the problem that invention will solve
In order to solve the shortcoming of ordinary method, the present invention aims to provide electrolyzer and the electrolysis process thereof on cathode surface such as the dirt deposition of oxyhydroxide etc. that the non-purified water that contains alkaline-earth metal ion in use can prevent alkaline-earth metal when using the electrolysis process of barrier film and the raw material of electrolyzer.
for the scheme of dealing with problems
As the 1st scheme addressing the above problem, the present invention is by having the barrier film of comprising, the anolyte compartment of being separated by barrier film, the cathode compartment of being separated by barrier film, be arranged on the anode in anolyte compartment, be arranged on the negative electrode in cathode compartment and be supplied in the electrolyzer of structure of the raw water containing alkaline-earth metal ion of cathode compartment, the dirt deposition that prevents oxyhydroxide of alkaline-earth metal etc. with the whole in fact surface of alkaline-earth metal antiscale film (the alkali earth metal scale-preventive film) covered cathode of cation exchange resin is on cathode surface.
As the 2nd scheme addressing the above problem, the present invention has constructed and has used the diaphragm electrolysis device of porous diaphragm as barrier film.
As the 3rd scheme addressing the above problem, the present invention has constructed and has used the cationic exchange embrane method electrolyzer of cationic exchange membrane as barrier film.
As the 4th scheme addressing the above problem, the present invention has constructed its Anodic and negative electrode and has been attached to respectively the solid polymer electrolyte type electrolyzer on two surfaces of cationic exchange membrane.
As the 5th scheme addressing the above problem, the present invention has constructed three Room type electrolyzers, described three Room type electrolyzers comprise that the cationic exchange membrane and the anion-exchange membrane that are arranged between anolyte compartment and cathode compartment separate anolyte compartment and cathode compartment as barrier film, thereby form intermediate chamber between cationic exchange membrane and anion-exchange membrane.
As the 6th scheme addressing the above problem, the present invention uses conductive diamond, plumbic oxide, precious metal or the metal oxide containing precious metals anode catalyst as anode.
As the 7th scheme addressing the above problem, the invention provides the energized components of anode and negative electrode.
As the 8th scheme addressing the above problem, the filler that comprises inorganic or organic materials of the present invention blend fiber or powder type in the alkaline-earth metal antiscale film of cation exchange resin is as the supporting material of film.
As the 9th scheme addressing the above problem, the present invention mixes the ceramic particle with cationic exchange function in the alkaline-earth metal antiscale film of cation exchange resin.
As the 10th scheme addressing the above problem, the present invention by least one of ceramic particle that is selected from phosphatic rock, perofskite type oxide and zeolite as thering is the ceramic particle of cationic exchange function.
As the 11st scheme addressing the above problem, the present invention uses sheet material, porous metal, fibrous metal molding, screen cloth or punch metal as cathode substrate.
As the 12nd scheme addressing the above problem, the invention provides the electrolysis process by carry out the raw water that electrolysis contains the alkaline-earth metal ion that comprises calcium ion and magnesium ion with described electrolyzer.
the effect of invention
According to the present invention, can suppress to comprise by the whole in fact surface of the alkaline-earth metal antiscale film covered cathode with cation exchange resin the deposition of oxyhydroxide with the electrolyzer of barrier film and electrolysis process thereof, and do not rely on the various means of routine techniques, and the rising of the electrolysis voltage of following can be suppressed at the non-purified water that contains alkaline-earth metal ion as raw material time.As a result, and not according to compared with situation of the present invention, can obtain electrolysis procedure steady in a long-term.
Reason is that, if do not use the alkaline-earth metal antiscale film of cation exchange resin, the alkalimetal ion of raw material underwater trace is as Na
+be attracted to the surface of cathod catalyst, herein, cathode surface is by cathodic reaction Na
++ H
2o+e
-naOH+ (1/2) H
2become alkalescence, and the like Na of alkaline-earth metal ion
+the same Ca comprising as impurity
2+cause on the surface of cathod catalyst as Ca (OH)
2alkali deposition, be deposited as the dirt of covered cathode catalyzer.
On the other hand, if negative electrode is covered by the alkaline-earth metal antiscale film of cation exchange resin of the present invention, be formed at NaOH and H on cathod catalyst
2gas dispersion, in the alkaline-earth metal antiscale film of cation exchange resin, filters from the surface of film, and is further dispersed in raw water.Now, as N
a +the same alkaline-earth metal ion comprising as impurity is as C
a 2+cause near the alkali deposition of alkaline-earth metal antiscale film of cation exchange resin, and became Ca (OH) before arriving the cathod catalyst surface contrary with anode
2, because Ca
2+operational throughput in Zeo-karb is less than Na
+.Comprise Ca (OH)
2cathode deposit not Direct precipitation on the surface of cathod catalyst.In addition, after long-term electrolysis procedure, range estimation or magnifying glass observation negative electrode confirm, cathode deposit not only precipitates near the alkaline-earth metal antiscale film of cation exchange resin, but also precipitate, and be deposited on almost evenly the whole surface of the negative electrode that comprises the back side near the cathod catalyst contrary with anode.Therefore, prevent that cathod catalyst surface is directly by Ca (OH)
2sedimental layer is preferential to be covered, and continues electrolysis.The hydrogen producing from cathode surface is distributed to outside by the microgap the alkaline-earth metal antiscale film of cation exchange resin.
Except suppressing (the Ca (OH) such as oxyhydroxide of alkaline-earth metal
2deng) the deposition of settling on cathode surface, the invention is characterized in the time that negative electrode is covered by the alkaline-earth metal antiscale film of cation exchange resin, settling anticathode surface adhere to a little less than, thereby observe Billy and more naturally come off when uncovered cathod catalyst carries out electrolysis with being directly exposed to solution.The microgap of the alkaline-earth metal antiscale film of cation exchange resin, as the discharge approach of hydrogen molecule that is formed on cathode surface, narrow gradually, cell voltage finally raises, but obviously mild compared with the device of rising speed and the alkaline-earth metal antiscale film covered cathode by cation exchange resin not.
In the time only using the film of the porous resin that there is no ion-exchange capacity including fluoro-resin to replace the alkaline-earth metal antiscale film of cation exchange resin to cover whole cathode surface, the area that exposes of cathode surface reduces, Faradaic current concentrates on few remaining exposed portions serve, and pH value sharply increases.As a result, the dirt of dielectric oxyhydroxide etc. forms, and cell voltage increases sharply, and shows disadvantageous effect.
Accompanying drawing explanation
Fig. 1 is the longitdinal cross-section diagram as SPE (registered trademark) the type electrolyzer of an example of two chamber-type electrolyzer according to an embodiment of the invention.
Fig. 2 (a) is the sectional view of example of the anode that uses in the present invention.
Fig. 2 (b) is the sectional view of example of the negative electrode that uses in the present invention.
Fig. 3 is the longitdinal cross-section diagram as diaphragm electrolysis device according to another embodiment of the invention.
Fig. 4 is the longitdinal cross-section diagram as the example of three Room type electrolyzers of other embodiment according to the present invention.
Fig. 5 is the figure that the electrolysis time vs cell voltage of the embodiment of the present invention 1 and comparative example 1 is shown.
Fig. 6 is the figure that the electrolysis time vs cell voltage of the embodiment of the present invention 2 and comparative example 2 is shown.
Fig. 7 is the figure that the electrolysis time vs cell voltage of the embodiment of the present invention 3 and comparative example 3 is shown.
Embodiment
The present invention by thering is the anolyte compartment, the cathode compartment of being separated by barrier film that comprise barrier film, separated by barrier film, be arranged on anode in anolyte compartment, be arranged on the negative electrode in cathode compartment and be supplied in the electrolyzer of structure of the raw water that comprises the alkaline-earth metal such as calcium ion and magnesium ion ion of cathode compartment, the dirt deposition that prevents oxyhydroxide of alkaline-earth metal etc. with the whole in fact surface of the alkaline-earth metal antiscale film covered cathode of cation exchange resin is on cathode surface.
Electrolyzer of the present invention is applied to installs septate electrolyzer, for example two chamber-type electrolyzer or three Room type electrolyzers.Two chamber-type electrolyzer comprises diaphragm electrolysis device, cationic exchange embrane method electrolyzer and the solid polymer electrolyte method electrolyzer as the special methods of the type.
Diaphragm electrolysis device uses porous diaphragm as barrier film, cationic exchange embrane method electrolyzer uses cationic exchange membrane as barrier film, use cationic exchange membrane as solid polymer electrolyte with solid polymer electrolyte method electrolyzer, its Anodic and negative electrode close attachment on two surfaces of cationic exchange membrane, thereby form the electrolyzer of even can electrolytic conduction little pure water.Three Room type electrolyzers are provided with cationic exchange membrane and anion-exchange membrane is separated anolyte compartment and cathode compartment as barrier film, thereby form intermediate chamber between cationic exchange membrane and anion-exchange membrane.
Fig. 1 is the longitdinal cross-section diagram as the solid polymer electrolyte type electrolyzer of the energized components 6 that comprises cathode compartment 1, negative electrode 2, anolyte compartment 3, anode 4, cationic exchange membrane 5, negative electrode 2 of an example of two chamber-type electrolyzer and the energized components 7 of anode 4.
Fig. 2 (a) is for using expanded mesh (expanded mesh) to be also coated with from the teeth outwards the example of the anode 4 of anode catalyst 4b as anode base material 4a.
Fig. 2 (b) is the same with the situation of anode base material 4a, use expanded mesh (expanded mesh) as cathode substrate 2a, and on substantially whole surface, be coated with the sectional view of the example of the negative electrode 2 of the alkaline-earth metal antiscale film 8 of cation exchange resin.
Can and comprise for the material of the cathode substrate 2a of negative electrode 2 of the present invention that at iron stainless its alloy, nickel and alloy, copper and alloy thereof, aluminium and alloy thereof, titanium, zirconium, molybdenum, tungsten, silicon and their alloy and carbide, carbon and allotropic substance thereof suitably select.In addition, according to purposes, precious metal or metal oxide containing precious metals can be used as the coating material of electrode catalyst.
The shape and the form that are used for the cathode substrate 2a of negative electrode 2 of the present invention comprise sheet material, punch metal, screen cloth, porous metal, Fiber metal (for example bibili fiber sintering body).In addition, for the base material of other shape and form, if the effective surface of cathode substrate 2a is coated with the anti-adhesion film for alkaline-earth metal dirt of cation exchange resin, can expect effect of the present invention and no problem.
Can select as tantalum, niobium, titanium, zirconium and silicon and alloy thereof at metal for the material of the anode base material 4a of anode 4, in treatment solution, form stable passive film, and depend on purposes, according to according to catalytic reaction material active and that suitably select, conductive diamond, plumbic oxide, precious metal or metal oxide containing precious metals can be coated with to the anode catalyst 4b for anode base material 4a.As the anode base material 4a of anode 4, the ferrite that can be used alone, decolorizing carbon or graphite.
In order to form the alkaline-earth metal antiscale film 8 of cation exchange resin on the whole in fact surface of cathode substrate 2a, the dispersion liquid of Zeo-karb is coated on the surface of cathode substrate 2a, subsequently baking.The cation exchange group of the dispersion liquid of Zeo-karb comprises sulfonic acid group, hydroxy-acid group, phosphonyl group and phosphate group.Wherein, applicable dispersion liquid is the perfluorinated sulfonic acid type Zeo-karb with the sulfonic acid group of chemical stability excellence.Perfluorinated sulfonic acid type Zeo-karb is not exclusively dissolved in solvent, and is considered to be present in solvent as relatively large-sized colloid with about 10nm.
Prepared resin dispersion liquid is coated on by spraying, roller, brush or sponge on the surface of cathode substrate 2a, leaves standstill subsequently predetermined time dry solvent under room temperature.Now, be the wetting level that extends from the level of nozzle or the most advanced and sophisticated dispersion liquid dripping.The electrode base material with the dispersion liquid coating of desciccator diaphragm state heats under 120-350 degree Celsius.Heating can be undertaken by drying machine, retort furnace or heat gun, or can on hot plate, carry out.Heat not only for evaporating solvent, but also for the colloid of sintering aggegation.If excess Temperature used, polymer molecule can go bad.Preferred scope will be 150-250 degree Celsius.During this period, can form microgap.
Also can use powder coated method, wherein be coated with the powder of Zeo-karb, be heat-treated to subsequently semi-melting to be closely coated with.
As the strengthening agent of the alkaline-earth metal antiscale film of cation exchange resin, the linking agent of fluoro-resin, fluoro-resin or ion exchange resin filler are added in dispersion liquid.Then,, after thermal treatment, the alkaline-earth metal antiscale film of cation exchange resin can be by reinforcement.
If the ceramic particle that comprises phosphatic rock, perofskite type oxide and zeolite with cation exchange capacity (CEC) is added into the film of cation exchange resin, physical strength can strengthen and not hinder the movement of positively charged ion in this film.
In addition, also the alkaline-earth metal antiscale film of cation exchange resin can be arranged on the two sides of electrode base material, form the bag shaped structure of periphery and multiple intermediate point close attachment as required.This class formation can be manufactured by hot pressing.Now, must provide minute opening to be released in the gas that comprises hydrogen that cathode surface produces.In this case, preferably only there is the structure of opening at top.
Fig. 3 illustrates the example of the energized components 6, the energized components 7 of anode 4 and the diaphragm electrolysis device of hydrophilic porous barrier film 9 that comprise cathode compartment 1, negative electrode 2, anolyte compartment 3, anode 4, negative electrode 2.Expanded mesh is used for the anode base material 4a of anode 4, and is coated with in its surface anode catalyst 4b.4a is similar with anode base material, and expanded mesh is used for the cathode substrate 2a of negative electrode 2, and on its whole in fact surface, is coated with the alkaline-earth metal antiscale film 8 of cation exchange resin.
Fig. 4 illustrates the example of three Room type electrolyzers of the energized components 6, the energized components 7 of anode 4 and alkaline-earth metal antiscale film 8, anion-exchange membrane 10, cationic exchange membrane 11 and the intermediate chamber 12 of cation exchange resin that comprise cathode compartment 1, negative electrode 2, anolyte compartment 3, anode 4, negative electrode 2.Expanded mesh is used for the anode base material 4a of anode 4, and is coated with in its surface anode catalyst 4b.4a is similar with anode substrate, and expanded mesh is used for the cathode substrate 2a of negative electrode 2, and on its whole in fact surface, is coated with the alkaline-earth metal antiscale film 8 of cation exchange resin.
In these electrolyzers, produce various function water and ozone water.
For the present invention, function water means " the useful function water solution with the regeneration obtaining by manual handling, the scientific basis of described processing and function have been illustrated maybe and will have been illustrated ".Existence comprises the various function water of brine electrolysis and ozone water.
Brine electrolysis in the homepage of Japanese function water foundation (Functional Water Foundation) by as give a definition and classify.
Brine electrolysis is by the popular name of the aqueous solution of electrolysis tap water under little volts DS or the acquisition of weak salt solution.Various brine electrolysis are produced by distinct device with under different condition.Based on application purpose, brine electrolysis is roughly divided into two classes: as the sterilization electrolytic water of cleaning and sterilizing etc. (comprise strongly-acid and subacidity brine electrolysis and be considered to the electrolysis javelwater of the clorox of dilution), and by continuing to drink, gastrointestinal symptoms is had the electrolyzed alkaline water (alkali ion water) of clear and definite effect for sanitary inspection.
Acidic electrolytic water is the popular name of the brine electrolysis below pH6.5, and it shows strong sterilizing character widely to various pathogenic bacterias and those resistant organisms (MRSA etc.), and for various fields as medical treatment, dentistry, food or agriculture etc.Main sterilization factors is the hypochlorite that electrolysis produces.In the time that strong acidic electrolyzed water in 2002 and subacidity brine electrolysis are defined as foodstuff additive to the harmless character of human health in Japan because of it, provide title " hypochloric acid water ".
The hypochlorous acid that strong acidic electrolyzed water (strongly-acid hypochloric acid water) produces at anode for having below pH2.7 is as the brine electrolysis of major constituent (available chlorine density is 20-60ppm), its by electrolysis in the two chamber-type electrolyzer that is separated into anode and negative electrode by barrier film the salt solution (NaCl) below 0.1% prepare.The brine electrolysis of the strong basicity (pH11-11.5) simultaneously producing at cathode side is called strong basicity brine electrolysis.
Subacidity brine electrolysis is the hypochlorous aqueous solution of pH5-6.5, and there is the available chlorine of 10-30ppm, prepared by the hydrochloric acid water by electrolysis 2-6% in the single chamber type electrolyzer that is not separated into anode and negative electrode by barrier film, the water that is characterised in that all generations is sterilized water.
Alkali ion water is the another name with the electrolysis tap water of weak base degree (pH9-10), prepared by the family expenses device for producing electrolytic water electrolysis tap water that is commonly referred to alkali ion water purifier by use.Family expenses device for producing electrolytic water is the title that classifies as the medical facilities of family's use of " the medical material maker of utensil apparatus 83 " in medicine thing method-writ of execution (Pharmaceutical Affairs Act-Enforcement Order).As the result of strict control clinical trial, confirm the following effect of the alkali ion water that is approved as medicine equipment.Be, effective for " abnormal fermentation in chronic diarrhoea, maldigestion, stomach and intestine, press down acid and hyperchlorhydria ".Recognize equally the reinforced effects for constipation.At present, in the revised edition of medicine thing method (2005), upgraded existence " gastrointestinal syndrome improve effect ".
In the present invention, the electrolysate that mainly comprises ozone gas of the acquisitions such as the sterilized solution of the tank room electrolysis pure water that ozone water is the application of the invention or tap water, processing, waste water, waste liquid.Ozone water also means to comprise OH free radical beyond deozonize gas, oxyradical as the water containing ozone gas of superoxide anion, hydrogen peroxide and other oxygenant.As the effect of this ozone water, under low pH (acidity), ozone gas becomes oxidation object, under high pH (alkalescence), ozone gas decomposes, then carry out by the oxidation of the OH that is formed free radical, even total in the case of oxidation chemistry equivalent also show stronger oxygenizement identical.
The present invention can be used for producing the electrolyzer of hydrogen, oxygen, ozone water, alkali ion water, sour water and subacidity water and for wastewater treatment.
As operator scheme, for the mobile method of catholyte that regularly makes to comprise alkaline-earth metal ion, realize described effect but also comprise for regular replacement that the method for the non-purifying catholyte of alkaline-earth metal ion is best suited for.
Embodiment
Be below embodiments of the invention; But the present invention should be not limited to this.
[embodiment 1]
In embodiment 1, SPE type electrolyzer (SPE is the registered trademark of Permelec Electrode Ltd.) is as solid polymer electrolyte type electrolyzer, as an example of the electrolyzer of two chamber-type shown in Fig. 1.For anode base material 4a and cathode substrate 2a, use SUS304 screen cloth (the screen cloth specification: sheet metal thickness 1mm, SW3.5mm, and specific surface area 1.1m that size is 30mm × 30mm expanding metal
2/ m
2).
By the Zeo-karb being obtained commercially 5% dispersion liquid (trade(brand)name: Nafion (registered trademark) DE520 – Nafion is the registered trademark of E.I.du Pont de Nemours and Company) be coated on except with the connection portion of energized components 6 the whole in fact surface of negative electrode 2, baking under 170 degrees Celsius subsequently, the whole in fact surface coated of negative electrode 2 has the alkaline-earth metal antiscale film 8 of cation exchange resin thus.In addition, anode 4 is by being coated with the Ti screen cloth preparation of same shape of Pt.Between anode 4 and negative electrode 2, insert cationic exchange membrane 5 (trade(brand)name: Nafion117, the registered trademark of E.I.du Pont de Nemours and Company).With 300mL/min, tap water is supplied to anolyte compartment 3 and the cathode compartment 1 of this electrolyzer, and under the supply current of 1.8A, carries out electrolytic trial.Duration of test, monitors as the voltage between anode and the negative electrode of electrolytic cell voltage using certain interval.The results are shown in Fig. 5.In embodiment 1, before reaching 20V, cell voltage needs 26 hours, prove the inhibition that the Zeo-karb by being coated on negative electrode raises to voltage.
Compared with embodiment 3, embodiment 1 shows that voltage raises more rapidly with aftermentioned embodiment 2.Reason is, think that applied current value is larger, and there is cation exchange resin membrane between anode and negative electrode, its compared with Zeo-karb coating in embodiment 2 tack a little less than, cause the deposition of oxyhydroxide of the alkaline-earth metal ion in small electrode inside clearance and the alkaline-earth metal ion in film etc.
In embodiment 1, suppose that common water electrolysis produces oxygen and hydrogen, the anode by use with Pt coating carries out electrolysis under relatively low current density.Any material that has hyperoxia generation overvoltage by electrolysis under high current density or by use, as conductive diamond, can produce ozone water by following reaction.
Form ozone by following reaction formula.
Ozone generation reaction (anode): 3H
2o=O
3+ 6H
++ 6e
-
E
0=+1.51V
Oxygen produces reaction (anode): 2H
2o=O
2+ 4H
++ 4e
-
E
0=+
1.23V
Hydrogen produces reaction (negative electrode): 2H
++ 2e
-=H
2
Ozone generation is reacted and is and the aitiogenic competing reaction of oxygen, will preferentially emit the oxygen of low generation current potential in the case, causes low current efficiency.If use the anode with over-pressure, for example plumbous oxide or conductive diamond electrode suppress the generation of oxygen, if or the electrode that uses platinum to be coated with, electrolysis is under high pressure carried out by high current density electrolysis.
[comparative example 1]
In comparative example 1, except using the SUS304 screen cloth of coating of the alkaline-earth metal antiscale film 8 that there is no cation exchange resin as negative electrode, use as in Example 1 electrolyzer to test.In addition, in comparative example 1, carry out SPE electrolysis by the existence at cation exchange resin membrane.As shown in Figure 5, wherein the voltage of comparative example 1 just starts to raise result after electrolysis procedure, and reaches 20V in approximately 8 hours.This shows, uses common tank room under condition used, to be difficult to long-term ongoing operation in tap water electrolysis.
[embodiment 2]
In embodiment 2, use diaphragm electrolysis device as shown in Figure 3.For negative electrode 2 and anode 4, use Ti screen cloth (the screen cloth specification: sheet metal thickness 1mm, SW3.5mm and specific surface area 1.1m that size is 16mm × 16mm
2/ m
2).The Zeo-karb being obtained commercially 5% dispersion liquid (trade(brand)name: Nafion (registered trademark) DE520 – Nafion is the registered trademark of E.I.du Pont de Nemours and Company) is coated on to the whole in fact surface of negative electrode 2, under 150 degrees Celsius, toast subsequently, form thus the alkaline-earth metal antiscale film 8 of cation exchange resin.Negative electrode 2 and anode 4 be with the spaced and parallel setting of about 1.5mm, and separated by the hydrophilic porous barrier film 9 of 20mm × 20mm (neutral film).These are arranged on to the cathode compartment 1 of diaphragm electrolysis device and the central authorities of anolyte compartment 3.
With the flow velocity of 12mL/min, tap water is supplied to respectively to anolyte compartment 3 and the cathode compartment 1 of electrolyzer, and at room temperature under the supply current of 0.03A, carries out electrolytic trial.Duration of test, monitors as the voltage between anode and the negative electrode of electrolytic cell voltage using the intervals of 30 seconds.
The results are shown in Fig. 6.In embodiment 2, voltage is continual and steady in the scope of 20-26V, and clearly illustrates the inhibition that the voltage of the alkaline-earth metal antiscale film 8 of the cation exchange resin by negative electrode raises.
Meanwhile, the structure of the diaphragm electrolysis device in embodiment 2 is identical with the structure of alkali ion water purifier.In the alkali ion water purifier being obtained commercially, electrode base material is sheet material, and electrolytic solution is the gap of the approximately 1mm through negative electrode and porous diaphragm rapidly, suppresses whereby by the catholyte of porous diaphragm and mixing of anolyte.Referring to, in embodiment 2, the mean ph value of monitoring the catholyte in the cathode compartment exit of 3 times at approximately every 24 hours is 8.75, in comparative example 2, the mean ph value of similar monitoring is 8.98.
[comparative example 2]
In comparative example 2, Ti screen cloth (the screen cloth specification: sheet metal thickness 1mm, SW3.5mm and specific surface area 1.1m that to use in the size of coating of alkaline-earth metal antiscale film 8 that there is no cation exchange resin be 16mm × 16mm
2/ m
2) on be coated with the negative electrode 2 of Pt.Except negative electrode, use to have as the electrolyzer of the structure of embodiment 2 and test, result provides in Fig. 6.Cell voltage just starts raise and reached 42V in 100 hours after electrolysis procedure.
[embodiment 3]
In embodiment 3, use three Room type electrolyzers as shown in Figure 4.Three Room type electrolyzers comprise the anode 4 prepared as embodiment 1 and negative electrode 2, as the cationic exchange membrane 11 (trade(brand)name: the registered trademark of Nafion117-E.I.du Pont de Nemours and Company) between anion-exchange membrane 10 (trade(brand)name: the registered trademark of TOSFLEX SF48-Tosoh Corporation) and intermediate chamber 12 and the cathode compartment 1 of the barrier film of anolyte compartment 3 and intermediate chamber 12.This is configured to simulation, and to be provided with salt solution be raw material, produces the equipment that comprises hypochlorous so-called strong oxidized water and produce the production equipment of alkali ion water at cathode compartment in anolyte compartment 3.
The brine recycling that remains on the dilution of 30g/L is supplied to the intermediate chamber 12 of electrolyzer, and with the flow velocity of 500mL/min, tap water is supplied to respectively to anolyte compartment 3 and cathode compartment 1.Electrolytic trial carries out under the supply current of 0.5A.At duration of test, monitor as the voltage between anode and the negative electrode of electrolytic cell voltage using certain interval.
As a result, as shown in Figure 7, in embodiment 3, electrolytic cell voltage stops under about 12V, proves positive effect of the present invention.
[comparative example 3]
In comparative example 3, will there is no the SUS304 screen cloth of coating of alkaline-earth metal antiscale film 8 of cation exchange resin for negative electrode 2.Except negative electrode, test is by carrying out as the electrolyzer of the same configuration of embodiment 3.As a result, as shown in Figure 7, the electrolytic cell voltage that has been less than in the early stage 7V rose to 18V in 480 hours.
utilizability in industry
The present invention can be used for following field, but needn't be limited to this.
1. waste water and liquid waste disposal
1) containing the treatment facility of organic high BODCOD waste liquid
For example, in JP2006-281013A, record the treatment process containing organic waste liquid by electrolysis.In the disclosure, suppose to process and contain alkaline-earth metal ion if Ca ion is as sanitary wastewater and the trade effluent of impurity.But, even not clear mentioning of specification sheets, but be apparent that, unless special device is provided, the oxyhydroxide of these impurity etc. can be deposited on negative electrode.
2) decomposition of the hardly-degradable substance (dissolved persistent substance) dissolving
The hardly-degradable substance that JP2003-126860A has proposed to remove dissolving is as the electrolysis process of aromatic substance, PCB He dioxin.In view of operability and economy, produce the raw water of the waste liquid that comprises dioxin conventionally by supplying with for underground water or the town water of non-purified water.These raw waters contain alkaline-earth metal element if Ca ion is as impurity, and its oxyhydroxide is deposited on negative electrode, do not comprise the maintenance that regular acid is cleaned, and can hinder long-term ongoing operation.But electrolyzer of the present invention can be suppressed at the deposition on negative electrode, under significantly reduced maintenance cost, obtain long-term lasting operation.
2. the production of brine electrolysis
Propose hypothesis and by electrolysis production comprised the brine electrolysis of alkali ion water as the whole bag of tricks of raw material and device take non-purified water as tap water.In these devices, negative electrode comprises that the deposition of oxyhydroxide is common problem.JP2002-316155A also discloses the means of dissolving and removing the incrustation (scale deposit) of negative electrode.But, according to the present invention, comprise that the deposition of superoxide can reduce in essence.
3. ozone water is produced
Generally speaking, non-purified water comprises the negative electrode of conductive diamond electrode as the device for producing ozone water of anode and staggered cationic exchange membrane as tap water is supplied to.For example the deposition of superoxide on negative electrode is problem.But according to the present invention, deposition can significantly reduce.
description of reference numerals
1: cathode compartment
2: negative electrode
2a: cathode substrate
3: anolyte compartment
4: anode
4a: anode base material
4b: anode catalyst
5: cationic exchange membrane
6: the energized components of negative electrode 2
7: the energized components of anode 4
8: the alkaline-earth metal antiscale film of cation exchange resin
9: hydrophilic porous barrier film
10: anion-exchange membrane
11: cationic exchange membrane
12: intermediate chamber
Claims (12)
1. an electrolyzer, it has the anolyte compartment, the cathode compartment of being separated by described barrier film that comprise barrier film, separated by described barrier film, is arranged on the anode in described anolyte compartment, the structure that is arranged on the negative electrode in described cathode compartment and is supplied to the raw water containing alkaline-earth metal ion of described cathode compartment, the whole in fact surface coverage of wherein said negative electrode has the alkaline-earth metal antiscale film of cation exchange resin, thereby oxyhydroxide that prevents alkaline-earth metal etc. is deposited on described cathode surface.
2. electrolyzer according to claim 1, it forms diaphragm electrolysis device, wherein porous diaphragm is used as to described barrier film.
3. electrolyzer according to claim 1, it comprises cationic exchange embrane method electrolyzer, wherein cationic exchange membrane is used as to described barrier film.
4. according to the electrolyzer described in claim 1 or 3, it forms solid polymer electrolyte type electrolyzer, and wherein said anode and described negative electrode be extremely two surfaces of described cationic exchange membrane of close attachment respectively.
5. electrolyzer according to claim 1, it forms three Room type electrolyzers, described three Room type electrolyzers comprise that the cationic exchange membrane and the anion-exchange membrane that are arranged between described anolyte compartment and described cathode compartment separate described anolyte compartment and described cathode compartment as described barrier film, thereby are formed on the intermediate chamber between described cationic exchange membrane and described anion-exchange membrane.
6. according to the electrolyzer described in claim 1-5 any one, wherein conductive diamond, plumbic oxide, precious metal or metal oxide containing precious metals are used as to the anode catalyst of described anode.
7. according to the electrolyzer described in claim 1-6 any one, wherein for described anode and described negative electrode arrange energized components.
8. according to the electrolyzer described in claim 1-7 any one, wherein in the alkaline-earth metal antiscale film of described cation exchange resin the filler that comprises inorganic or organic materials of blend fiber or powder type as the supporting material of described film.
9. according to the electrolyzer described in claim 1-8 any one, wherein in the alkaline-earth metal antiscale film of described cation exchange resin, mix the ceramic particle with cationic exchange function.
10. electrolyzer according to claim 9, has the ceramic particle of cationic exchange function described in wherein at least one of ceramic particle that is selected from phosphatic rock, perofskite type oxide and zeolite being used as.
11. according to the electrolyzer described in claim 1-10 any one, wherein sheet material, porous metal, fibrous metal molding, screen cloth or punch metal is used as to described cathode substrate.
12. 1 kinds of electrolysis processs, wherein, carry out by using according to the electrolyzer described in claim 1-11 any one the raw water that electrolysis contains the alkaline-earth metal ion that comprises calcium ion and magnesium ion.
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|---|---|---|---|
| JP2011-196356 | 2011-09-08 | ||
| JP2011196356 | 2011-09-08 | ||
| PCT/JP2012/072668 WO2013035762A1 (en) | 2011-09-08 | 2012-08-30 | Electrolysis system and electrolysis method for the same |
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| CN103781731A true CN103781731A (en) | 2014-05-07 |
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|---|---|---|---|
| CN201280043774.1A Pending CN103781731A (en) | 2011-09-08 | 2012-08-30 | Electrolysis system and electrolysis method for the same |
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| Country | Link |
|---|---|
| JP (1) | JP5716100B2 (en) |
| KR (1) | KR20140074927A (en) |
| CN (1) | CN103781731A (en) |
| TW (1) | TWI535894B (en) |
| WO (1) | WO2013035762A1 (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54147198A (en) * | 1978-05-11 | 1979-11-17 | Tokuyama Soda Co Ltd | Cathode |
| US5599437A (en) * | 1995-06-20 | 1997-02-04 | Faraday Technology, Inc. | Electrolysis of electroactive species using pulsed current |
| DE20315557U1 (en) * | 2003-10-07 | 2004-02-12 | Arneth, Borros | Seawater desalination plant has reactor chamber around an array of plastic-coated anode and cathode electrodes with continually reversed polarity |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4738904A (en) * | 1986-10-14 | 1988-04-19 | Hughes Aircraft Company | Low temperature thermoelectrochemical system and method |
| US5266421A (en) * | 1992-05-12 | 1993-11-30 | Hughes Aircraft Company | Enhanced membrane-electrode interface |
| JP3319887B2 (en) | 1994-10-05 | 2002-09-03 | クロリンエンジニアズ株式会社 | Method for producing hypochlorite |
| JPH10130876A (en) | 1996-11-01 | 1998-05-19 | Kobe Steel Ltd | Electrolytic ozonized water producing unit and its regenerating method |
| JP2002173789A (en) | 2000-12-04 | 2002-06-21 | Japan Storage Battery Co Ltd | Electrolyzer |
| JP2002316155A (en) | 2001-04-23 | 2002-10-29 | Matsushita Electric Ind Co Ltd | Electrolytic water making apparatus |
| JP4000508B2 (en) | 2001-10-22 | 2007-10-31 | 株式会社オメガ | Wastewater or wastewater treatment method |
| JP4394941B2 (en) | 2003-12-22 | 2010-01-06 | 株式会社Ｉｈｉシバウラ | Electrolytic ozonizer |
| JP2006281013A (en) | 2005-03-31 | 2006-10-19 | Mitsubishi Heavy Ind Ltd | Electrolyzing apparatus |
| JP4464387B2 (en) | 2006-12-18 | 2010-05-19 | 日科ミクロン株式会社 | Ozone water generation method |
| JP2008200667A (en) | 2007-02-22 | 2008-09-04 | Hokuetsu:Kk | Method and apparatus for deodorizing, decolorizing and sterilizing water |
| JP2011050807A (en) | 2009-08-31 | 2011-03-17 | Sanyo Electric Co Ltd | Electrolytic water generator and electrolytic water spray device provided with the same |
-
2012
- 2012-08-30 KR KR1020147009212A patent/KR20140074927A/en active Search and Examination
- 2012-08-30 WO PCT/JP2012/072668 patent/WO2013035762A1/en active Application Filing
- 2012-08-30 CN CN201280043774.1A patent/CN103781731A/en active Pending
- 2012-08-30 JP JP2013548687A patent/JP5716100B2/en active Active
- 2012-09-04 TW TW101132140A patent/TWI535894B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54147198A (en) * | 1978-05-11 | 1979-11-17 | Tokuyama Soda Co Ltd | Cathode |
| US5599437A (en) * | 1995-06-20 | 1997-02-04 | Faraday Technology, Inc. | Electrolysis of electroactive species using pulsed current |
| DE20315557U1 (en) * | 2003-10-07 | 2004-02-12 | Arneth, Borros | Seawater desalination plant has reactor chamber around an array of plastic-coated anode and cathode electrodes with continually reversed polarity |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5716100B2 (en) | 2015-05-13 |
| TW201319322A (en) | 2013-05-16 |
| KR20140074927A (en) | 2014-06-18 |
| TWI535894B (en) | 2016-06-01 |
| WO2013035762A1 (en) | 2013-03-14 |
| JP2014530291A (en) | 2014-11-17 |
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Application publication date: 20140507 |