CN104909436B - A kind of electrolysis-type sterilization and disinfection device, preparation method and application - Google Patents
A kind of electrolysis-type sterilization and disinfection device, preparation method and application Download PDFInfo
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- CN104909436B CN104909436B CN201510315154.4A CN201510315154A CN104909436B CN 104909436 B CN104909436 B CN 104909436B CN 201510315154 A CN201510315154 A CN 201510315154A CN 104909436 B CN104909436 B CN 104909436B
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- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000001954 sterilising effect Effects 0.000 claims abstract description 28
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002114 nanocomposite Substances 0.000 claims abstract description 12
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 9
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- 239000010935 stainless steel Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 230000000873 masking effect Effects 0.000 claims description 10
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- 239000002131 composite material Substances 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 5
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of electrolysis-type sterilization and disinfection device, preparation method and application, and in particular to a kind of swimming pool sterilization and disinfection device and application method based on coating functions nano composite ceramic electrode material.By chloro-iridic acid, cobalt chloride, cobalt oxide, citric acid and ethylene glycol in molar ratio 0.1~0.5：0.01~0.2：0.01~0.2：0.3~0.7：12~20 are well mixed, it is coated on the surface of metal electrode board, toasted again, sintering processes, obtain a kind of with nano composite ceramic coating, the functional electrode for electrolysis-type sterilization and disinfection device, assemble them into the functional module of sterilizing, it is put into swimming pool, functional module is connected with energy supply control module.Substantial amounts of hydroxyl radical free radical is produced by the effect of the electrolysis water of functional module, and under the circulative convection of water, sterilized, sterilization and purified treatment is carried out to swimming-pool water.The electrolysis-type sterilization and disinfection device structure that the present invention is provided is exquisite, has no toxic side effect, and the effect of sterilized, sterilization and purification is good, easy to install, the conventional sterilization method of alternative current swimming pool.
Description
Technical field
The invention belongs to water treatment technology field, sterilization is carried out to water body using electrolysis mode more particularly, to one kind
The functional module disinfected, preparation method and use.
Background technology
Swimming body-building is a kind of motion mode that people are liked, however, the health of swimming pool is but frequently subjected to the humiliation of people
Disease, it is primarily due to dissolve in a large amount of dusts of swimming pool, secretion and substantial amounts of bacterial reproduction and causes swimming pool water quality
Drastically decline, if purifying sterilizing not in time, most likely result in swimmer's skin, eyes, digestive system etc. and catch an illness.Existing side
Method is mainly utilized in the circulation filter put into outside chlorine class disinfectant and swimming pool in swimming pool.Using circulating filtration method cost
High, area occupied is big, and sterilization, filtering consuming time are long.Liquid chlorine disinfection method is advantageous in that easy, expense is low, can kill such as
Pathogen, virus and parasitic ovum etc..However, liquid chlorine belongs to high-risk violent in toxicity, liquid chlorine can produce many harmful in water
Material, such as chloroform, the liquid chlorine of surplus also can be to the skin of visitor, and the healthy aspect such as hair, eyes, respiratory tract is produced
Raw detrimental effect.It is always a developing direction of swimming pool industry without chlorine or less with chlorine.In addition, the manager of swimming pool
For the color for making pool inner water seems as clear as crystal, often using algicide (copper sulphate), this measure not only increased management
Cost, also easy influence people's is healthy, and the discharge of copper-containing wastewater also pollutes environment.Ozone is introduced in running water
Sterilization method, is the more popular another sterilization method in current market.The disinfection principle of ozone is the Strong oxdiative based on ozone
Performance, but solubility of the ozone in running water is limited, and ozone equally has greatly injury to human body, is chronically at ozone
In environment, dizziness is easily caused, more serious meeting causes the oxidation and perforation of lung's epidermal cell, so as to cause the diseases such as pneumothorax
Shape.Also one kind is disinfection by ultraviolet light mode, and this mode is difficult to be applied to inside water body, and has ultraviolet to irradiate human body
Injury.
In electrochemical field, hydroxyl radical free radical has extremely strong oxidability, and its ability for obtaining electronics is only second to fluorine gas.
The organic matters such as hydroxyl radical free radical and microorganism, bacterium react, and can be oxidized to harmless stability material
Such as CO2, H2O, inorganic salts etc., therefore, hydroxyl radical free radical can be used for purification, sterilization and sterilization of running water etc..By hydroxyl free
Effect of base is applied to swimming pool purification techniques field, the water consumption that can overcome prior art is big, purification not thoroughly, do not save
The deficiencies such as energy environmental protection, realize the convenience of swimming pool purification, efficiently and thoroughly.
The content of the invention
The present invention is directed to the sterilizing treatment technology of existing water, and the sterilization in particular for indoor and outdoor swimming pool water body disappears
It is not enough present in malicious technology, there is provided a kind of functional electrode and preparation method thereof, and be applied to prepare a kind of electrolysis-type sterilization and disappear
Malicious device, satisfaction is processed the microorganism and bacterium in swimming pool water, with efficient sterilization function, and nontoxic pair
Effect.
To achieve the above object, the technical scheme of use of the invention is to provide a kind of electrolysis-type sterilization and disinfection device, it
Including several disinfection function modules, described disinfection function module includes dc source and disinfection function electricity
Pole combiner；Described disinfection function electrode combination part includes anode electrode and cathode electrode, described anode electricity
Extremely functional electrode, described negative electrode is electrode function electrode or stainless steel mesh electrode, and described functional electrode is surface tool
The thickness for having the metal electrode of nano composite ceramic coating, nano composite ceramic coating is more than 2 μm.
Disinfection function module of the present invention, its disinfection function electrode combination part is by hollow out outer cover and side
Lid is fixed.Described disinfection function electrode combination part includes base plate, stainless steel anode screw rod and negative electrode screw rod；Direct current
The positive and negative output end in source is connected with anode tap and cathode terminal on base plate respectively, and the anode tap and cathode terminal on base plate lead to respectively
Stainless steel anode screw rod and negative electrode screw rod is crossed to be connected with anode electrode and cathode electrode；It is provided between anode electrode and cathode electrode
The dielectric isolation layer of one hollow out.
In technical solution of the present invention, the installation of functional electrode combiner, a specific scheme is：In anode electrode
With the axis holes at two electrical connection circular holes and an axle center are opened up on cathode electrode respectively, two electrical connection circular holes are by screw point
Anode electrode and cathode electrode are not fixed with stainless steel anode screw rod and negative electrode screw rod；Insulation locating dowel passes through axis hole.
Technical solution of the present invention also includes a kind of preparation method of the functional electrode of electrolysis-type sterilization and disinfection device, including such as
Lower step：
1st, by chloro-iridic acid, cobalt chloride, cobalt oxide, citric acid and ethylene glycol in molar ratio 0.1~0.5：0.01~0.2：
0.01~0.2：0.3~0.7：12~20 are well mixed, and obtain compound solution；
2nd, the compound solution obtained with step 1 is masking liquid, is evenly applied to the surface of metal electrode board, then dried
It is roasting；
3rd, the coating of the masking liquid of repeat step 2, baking procedure 15~20 times, then sintered treatment, obtain a kind of multiple with nanometer
Close ceramic coating, the functional electrode for electrolysis-type sterilization and disinfection device.
A preferred scheme of the invention is that the mol ratio of chloro-iridic acid, cobalt chloride, cobalt oxide, citric acid and ethylene glycol is：
0.12 : 0.01：0.02 : 0.5 : 16.Described metal electrode board is titanium net electrode, and the mesh physical dimension of electrode is less than
3mm × 6mm, mesh number is 20~100 mesh.Baking process temperature is 100~200 DEG C, and the time is 10~15 minutes.Sintering process temperature
It is 500~650 DEG C to spend, and the time is 10~120 minutes.
The present invention provide electrolysis-type sterilization and disinfection device, be applied to carry out sterilizing to the water body of swimming pool, using when
Several disinfection function electrode combination parts are immersed directly in the water of swimming pool, work can be carried out after connecting direct current
Make.
The present invention is to provide a kind of sterilization and disinfection device, by special functional electrode electrolytic method, can directly exist
The hydroxyl radical free radical of electrolytically generated strong oxidizing property in swimming-pool water, these hydroxyl radical free radicals are applied to microorganism and bacterium in water quality
Surface, can play sterilizing effect, and hydroxyl radical free radical has certain life-span in itself, and automatic reduction is water again after a period of time
Molecule, therefore, this sterilizing method has no toxic side effect, and the effect of sterilized, sterilization and purification is good, easy to install, complete
The conventional sterilization method of current swimming pool can be substituted entirely.
Be coated in for composite nano materials masking liquid rush net electrode surface by the present invention, and it is sintered after, in titanium net electrode surface
Form the thick about several microns nano-composite coating compared with high adhesion force.Citric acid and ethylene glycol in coating are as solvent in height
Vapored away under temperature, chloro-iridic acid, cobalt chloride and cobalt oxide are formd and combined closely with matrix material under conditions of high temperature sintering
Oxidate nano ceramic composite, material surface has cascade connection type micro-nano nested structure.
In the present invention, the cobalt oxide ceramic material that high temperature sintering is formed plays a part of to stabilize and solidify, and not only strengthens
Adhesive force with matrix material, meanwhile, mixed phase is formed with the yttrium oxide after sintering, the mixed phase is after high temperature sintering
The nanometer rod structure with high specific surface area is showed on surface, rather than a relatively flat plane.In addition, sintering institute
The cobalt oxide material of formation enable to the relatively low main reaction current potential that yttrium oxide cobalt oxide nano ceramic composite coating has and
Side reaction current potential higher, beneficial to hydroxyl radical free radical electrode surface generation, it is suppressed that generation of the oxygen in electrode surface.This
One nanometer cascade surface texture of sample greatly strengthen the contact area with water, particular, it is important that these surfaces are abundant receiving
Meter level joins surface texture in input safe voltage（24~36V）And after being interacted with water, the hydroxyl of more horn of plenty can be produced
Free radical, so as to accelerate the efficiency of sterilizing.
, with water as main media, the function nano composite ceramic material with the coating of anode both sides is as work(for the sterilization and disinfection device
The generator of the energy factor, in the presence of low-voltage, generates the hydroxyl radical free radical with strong oxidizing property, and reach by decomposition water
Purify water, residual and disinfection the effect of agriculture of degrading.After generator is stopped, aseptic hydroxyl radical free radical due to
With certain life-span（About 60 seconds）Water is then reduced into, there will not be any residual in water.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of the functional electrode material surface that the present invention is provided；
Fig. 2 is the structural representation of disinfection function electrode combination part provided in an embodiment of the present invention；
Fig. 3 be functional module provided in an embodiment of the present invention to methyl orange solution under different time effects, its degraded
During ultraviolet-visible spectrogram.
In figure：1st, outer cover；2nd, stainless steel cathode screw rod；3rd, side cover；4th, stainless steel anode screw rod；5th, insulate hollow out dividing plate；
6th, functional coating titanium net anode；7th, negative electrode；8th, insulate locating dowel.
Specific embodiment
With reference to the accompanying drawings and examples, technical solution of the present invention is further elaborated.
Embodiment 1：
The compound solution of certain mol proportion mixing composition is pressed with chloro-iridic acid, cobalt chloride, cobalt oxide, citric acid and ethylene glycol
It is the masking liquid of nano-composite coating, preferably mol ratio is：0.12：0.01：0.02：0.5：16.In this ratio, hairbrush is used
Masking liquid is coated uniformly on two surfaces of titanium net, the mesh physical dimension of titanium net is less than 3mm × 6mm, and mesh number is 20~100
Mesh.Place it in 150 DEG C of baking oven and toast 15 minutes, repeat said process 16 times.Titanium net is inserted again in 550 DEG C of high temperature
Baking 120 minutes.Taken out after cooling, obtain electrode material, the thickness of resulting nano composite ceramic coating is more than 2 μm.
Referring to accompanying drawing 1, it is the SEM photograph of the functional coating of the electrode material surface that the present embodiment is provided
Piece, figure a is the surface topography of 10,000 times of amplification, and figure b is the surface topography of 30,000 times of electric discharge.By Fig. 1 it can be seen that, its shape characteristic
With obvious cascade structure.In the present embodiment, the masking liquid of nano-composite coating is coated in titanium net electrode surface, and is passed through
After temperature is 500 DEG C of sintering, the thick about several microns nano-composite coating compared with high adhesion force is formed in titanium net electrode surface.
Citric acid and ethylene glycol in coating are vapored away at high temperature as solvent, and chloro-iridic acid, cobalt chloride and cobalt oxide are in high temperature sintering
Under conditions of, the oxidate nano ceramic composite combined closely with matrix material is formd, material surface has cascade connection type
Micro-nano nested structure.
In the present invention, the cobalt oxide ceramic material that high temperature sintering is formed plays a part of to stabilize and solidify, and not only strengthens
Adhesive force with matrix material, meanwhile, mixed phase is formed with the yttrium oxide after sintering, the mixed phase is after high temperature sintering
The nanometer rod structure with high specific surface area is showed on surface, rather than a relatively flat plane.The mixed phase
Scanning electron microscope diagram piece is as shown in figure 1, be clear that material surface has width about 30nm, is about 150nm or so
Nanometer column structure, these nanostructureds are randomly distributed on the body structure surface of the several micron dimensions of physical dimension again.Separately
Outward, the relatively low master for sintering that formed cobalt oxide material enables to that yttrium oxide cobalt oxide nano ceramic composite coating has is anti-
Answer current potential and side reaction current potential higher, beneficial to hydroxyl radical free radical electrode surface generation, it is suppressed that oxygen is in electrode surface
Generation.Such a nanometer of cascade surface texture greatly strengthen the contact area with water, particular, it is important that these surfaces
Abundant nanometer cascade surface texture is in input safe voltage（24~36V）And after being interacted with water, can produce more rich
Rich hydroxyl radical free radical, so as to accelerate the efficiency of sterilizing.
Referring to accompanying drawing 2, it is the structural representation of the disinfection function electrode combination part that the present embodiment is provided；It is sterilized
The base plate of sterilizing function electrode combination part is placed in side cover 3, is fixed by the outer cover 1 and side cover 3 of hollow out, dc source just,
Negative output terminal is connected with anode tap and cathode terminal on base plate respectively, and the anode tap and cathode terminal on base plate pass through stainless steel respectively
Anode screw rod 4 and negative electrode screw rod 2 are connected with anode electrode and cathode electrode；In the present embodiment, anode electrode is functional coating
Titanium net anode 6, cathode electrode is stainless (steel) wire negative electrode 7, and an insulation hollow out dividing plate 5 is provided between anode electrode and cathode electrode.
Open up the axis hole at two electrical connection circular holes and an axle center, two electrical connection circular holes respectively on anode electrode and cathode electrode
Anode electrode and cathode electrode are fixed with stainless steel anode screw rod and negative electrode screw rod respectively by screw；Insulation locating dowel 8 is worn
Cross axis hole.The present embodiment provides preferably electrode unit：Two pieces of left and right is stainless steel mesh electrode, and middle is active to coat
The titanium net anode of energy nanocomposite ceramic material, has insulation hollow out dividing plate to isolate between two plate electrodes, negative electrode is by screw and the moon
Pole screw rod fastening, anode is fastened by screw with stainless steel anode screw rod, using 25 groups of electrode units as described above, whole dress
The dc source for putting use is powered, and voltage is 24~36V, and power is 500W.
It is 50mg/L that the disinfection function electrode combination part that the present embodiment is provided is put into the concentration for preparing in advance
Methyl orange polymer solution in water in, the color of methyl orange aqueous solution is orange-yellow, and the volume of solution is 10L.Press dc source
Button, supply voltage is 36V, rated input power 500W or so, and the functional electrode of functional module plays a role immediately, largely
Micro-bubble from stainless steel electrode surface through outer cover escape, while invisible hydroxyl radical free radical also constantly by point
Xie Shui dissipates out from function Ti electrode surface, decomposites these hydroxyl radical free radicals for coming and is sent out with the methyl orange molecule in running water
Biochemical effect, the organic molecule with methyl orange carries out continuous oxidation Decomposition.
Referring to accompanying drawing 3, it is different action time Methyl Orange solution during disinfection function electrode degrading
Ultraviolet-visible spectrogram comparison diagram.It can be found that after 2 minutes, the methyl orange solution of higher concentration has been degraded, its concentration is several
It is zero, after 5 minutes, the complete orange-yellow aqueous solution becomes colorless, and percent of decolourization is almost 100%.As can be seen here, the water catalyst is killed
Bacterium sterilizer can be ideally degradable by the methyl orange organic matter containing organic molecule.
Embodiment 2：
Disinfection function module, disinfection function electrode combination part are made and installed by the technical scheme of embodiment 1
Structure be 25 groups of electrode units of configuration, disinfection function electrode combination part is put into the concentration for preparing in advance is respectively
The chlopyrifos of 1mg/L, 5mg/L and 20mg/L（A kind of moderately toxic organophosphorus insecticide）Originally in aqueous emulsion, volume is
10L.The dc source button that voltage is 24V is pressed, rated input power is in 500W or so.Discharged after functional electrode decomposition water
There is strong oxidative degradation, emulsion process time in the chlopyrifos organic molecule that the hydroxyl free for coming is based in emulsion
5 minutes.During filling liquid after treatment entered into sample cell, carry out liquid chromatography test and compare, in test process, sampling volume
It is 5 μ l, Detection wavelength is 230nm.Result shows that three kinds of chlopyrifos solution concentration after the treatment of water catalyst functional module have surpassed
The Monitoring lower-cut of instrument is gone out.As can be seen here, the water catalyst sterilizing sterilizer ideally can poison the similar of fruit and vegetable surfaces with poison
The Organic pesticide residues of tick are degradable.
Embodiment 3
Disinfection function module, disinfection function electrode combination part are made and installed by the technical scheme of embodiment 1
Structure be 25 groups of electrode units of configuration, put it into advance the large intestine clump count for preparing in 1.7*105CFU/mL, 3.1*
105CFU/mL, 5.4*105In three kinds of aqueous solution of CFU/mL, volume is respectively 10L.The dc source button that voltage is 24V is pressed,
Rated input power is in 500W or so.Large intestine bar in the hydroxyl radical free radical and the aqueous solution that are discharged after functional electrode decomposition water
The oxidation interaction that the cell membrane of bacterium is strong is acted on, and process time is 3 minutes.Filling liquid after treatment is entered into sample cell
In, and carry out coli bacteria group summary by constant-temperature fluorescence detector.Result shows, after disinfection function resume module three
The flora sum in Escherichia coli solution is planted well below the Monitoring lower-cut of instrument.As can be seen here, what the present invention was provided kills
Bacterium chlorination equipment can be killed ideally by the cell wall damage of Escherichia coli and by bacillus, therefore, can be used for swimming-pool water
Purified treatment.Disinfection function electrode combination part is immersed directly in the water of swimming pool, sterilizing work is carried out after energization
Make.
Claims (10)
1. a kind of electrolysis-type sterilization and disinfection device, it is characterised in that：It includes several disinfection function modules, and described kills
Bacterium sterilizing function module includes dc source and disinfection function electrode combination part；Described disinfection function electrode group
Closing part includes anode electrode and cathode electrode, and described anode electrode is functional electrode, and described cathode electrode is function electricity
Pole or stainless steel mesh electrode, described functional electrode have the metal electrode of nano composite ceramic coating for surface, and nanometer is multiple
The thickness for closing ceramic coating is more than 2 μm；
The functional electrode is adopted and prepared with the following method：
（1）By chloro-iridic acid, cobalt chloride, cobalt oxide, citric acid and ethylene glycol in molar ratio 0.1~0.5：0.01~0.2：0.01~
0.2：0.3~0.7：12~20 are well mixed, and obtain compound solution；
（2）With step（1）The compound solution for obtaining is masking liquid, is evenly applied to the surface of metal electrode board, then toasted；
（3）Repeat step（2）Masking liquid coating, baking procedure 15~20 times, then sintered treatment, obtain the functional electrode.
2. a kind of electrolysis-type sterilization and disinfection device according to claim 1, it is characterised in that：Described disinfection function
Module, its disinfection function electrode combination part is fixed by hollow out outer cover and side cover；DC power output voltage is 24~36
Volt.
3. a kind of electrolysis-type sterilization and disinfection device according to claim 1 and 2, it is characterised in that：Described sterilizing
Functional electrode combiner includes base plate, stainless steel anode screw rod and stainless steel cathode screw rod；The positive and negative output end of dc source
It is connected with anode tap and cathode terminal on base plate respectively, the anode tap and cathode terminal on base plate pass through stainless steel anode screw rod respectively
Connected with anode electrode and cathode electrode with stainless steel cathode screw rod；The exhausted of a hollow out is provided between anode electrode and cathode electrode
Edge separation layer.
4. a kind of electrolysis-type sterilization and disinfection device according to claim 3, it is characterised in that：Anode electrode and cathode electrode
The upper axis hole opened up respectively at two electrical connection circular holes and an axle center, two electrical connection circular holes are by screw respectively by anode electricity
Pole and cathode electrode are fixed with stainless steel anode screw rod and stainless steel cathode screw rod, and insulation locating dowel passes through axis hole.
5. a kind of preparation method of the functional electrode of electrolysis-type sterilization and disinfection device, it is characterised in that comprise the following steps：
（1）By chloro-iridic acid, cobalt chloride, cobalt oxide, citric acid and ethylene glycol in molar ratio 0.1~0.5：0.01~0.2：0.01~
0.2：0.3~0.7：12~20 are well mixed, and obtain compound solution；
（2）With step（1）The compound solution for obtaining is masking liquid, is evenly applied to the surface of metal electrode board, then toasted；
（3）Repeat step（2）Masking liquid coating, baking procedure 15~20 times, then sintered treatment, obtain a kind of with nano combined
Ceramic coating, the functional electrode for electrolysis-type sterilization and disinfection device.
6. the preparation method of a kind of electrolysis-type sterilization and disinfection device functional electrode according to claim 5, it is characterised in that：
The mol ratio of chloro-iridic acid, cobalt chloride, cobalt oxide, citric acid and ethylene glycol is：0.12 : 0.01：0.02 : 0.5 : 16.
7. the preparation method of a kind of electrolysis-type sterilization and disinfection device functional electrode according to claim 5, it is characterised in that：
Described metal electrode board is titanium net electrode, and the mesh physical dimension of electrode is less than 3mm × 6mm, and mesh number is 20~100 mesh.
8. the preparation method of a kind of electrolysis-type sterilization and disinfection device functional electrode according to claim 5, it is characterised in that：
Baking process temperature is 100~200 DEG C, and the time is 10~15 minutes.
9. the preparation method of a kind of electrolysis-type sterilization and disinfection device functional electrode according to claim 5, it is characterised in that：
Sintering process temperature is 500~650 DEG C, and the time is 10~120 minutes.
10. a kind of a kind of application of electrolysis-type sterilization and disinfection device as claimed in claim 1, it is characterised in that：By several
Disinfection function electrode combination part is immersed directly in the water of swimming pool, and sterilizing is carried out to water body after connecting direct current.
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| CN105565467B (en) * | 2016-03-08 | 2018-10-26 | 辛煜 | A kind of sterilization sterilizer |
| CN107043154A (en) * | 2017-06-16 | 2017-08-15 | 福州金慧健康科技有限公司 | A kind of free radical generation device |
| CN110453243A (en) * | 2018-05-08 | 2019-11-15 | 罗民雄 | A kind of general electrolyte electrode modular method |
| CO2019005182A1 (en) * | 2019-05-21 | 2020-05-29 | Volta Em Sas | High voltage electrostatic field emitting electrode device in liquid sterilization |
| CN114656075A (en) * | 2022-04-01 | 2022-06-24 | 江苏济冠通环保科技股份有限公司 | Filtering and sterilizing method for swimming pool |
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| JPH0633280A (en) * | 1992-07-21 | 1994-02-08 | Japan Carlit Co Ltd:The | Method for disinfecting drink water |
| WO2000068153A1 (en) * | 1999-05-06 | 2000-11-16 | Japan Science And Technology Corporation | Apparatus for oxidatively destructing trace injurious substance |
| CN101020590B (en) * | 2006-02-14 | 2010-08-11 | 北京国力源高分子科技研发中心 | Process of treating refractory organic effluent with free radical |
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