CN1128759C - Electrolytic ozone generator - Google Patents
Electrolytic ozone generator Download PDFInfo
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- CN1128759C CN1128759C CN97122126A CN97122126A CN1128759C CN 1128759 C CN1128759 C CN 1128759C CN 97122126 A CN97122126 A CN 97122126A CN 97122126 A CN97122126 A CN 97122126A CN 1128759 C CN1128759 C CN 1128759C
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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
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- C25B1/28—Per-compounds
- C25B1/30—Peroxides
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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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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Abstract
The present invention provides an electrolytic ozone generator which mainly comprises the components of an ozone generator, an anode water tank, a cathode water tank, a unidirectional balance valve or make-and-break type electromagnetic valve, etc., wherein the ozone generator comprises independent elements of a cation exchange membrane piece, a cathode catalyst membrane piece, a cathode porous flow collecting piece, an anode catalyst membrane piece, a porous flow collecting piece, a deflector, an anti-corrosive piece, etc. The device has the advantages of low manufacture cost, industrialization large-scale production, stable operation with pressure and high ozone generation efficiency.
Description
Technical field
The present invention relates to a kind of electrolytic ozone generator, it belongs to electrochemical techniques and ozone applied technical field.
Background technology
Adopt the advantage of ozone method sterilization more and more to be subject to people's attention.The corona discharge method of present more employing high-frequency and high-voltage produces ozone, and research and development electrochemical method generation high-concentrated ozone has caused concern widely.The ultimate principle that electrochemical method is produced ozone is well-known: it is raw material that ozone takes place with the deionized water, and when external dc power supply, the electrochemical reaction formula of yin, yang electrode is:
The cathode hydrogen evolution reaction formula:
(1)
Negative electrode oxygen depolarization reaction formula:
(2)
Anode main reaction formula:
(3)
Anode side reaction formula:
(4)
The proton that anodic reaction produces under the DC electric field effect with water-soluble thinner proton form by cationic exchange membrane to cathodic migration.
According to above principle of electrochemical reaction as can be known, the core that constitutes a most basic electrolytic ozone generator partly is an electrolyzer.This electrolyzer must have anode, negative electrode, ionogen and raw water.
Chinese patent application CN86108792A has described a kind of solid polymer electrolyte structure, this structure comprises a diaphragm, many conductive particles and a conduction water-permeable base member, wherein conductive particle and conduction water-permeable matrix (as collector plate) contact with each other and embed in the diaphragm with physics or electrical way, or combine with diaphragm.The general preferred employing fluoro carbon materials of diaphragm wherein.For conduction water-permeable matrix is embedded in the fluorocarbon film, preferably make fluorocarbon be in the thermoplastic state.The permeable matrix of electroconductibility comprises carbon cloth, carbon paper, wire netting, metal felt and porous metal sheet etc., is good with carbon cloth.Use various technology to be added to the electro catalytic activity particle in the membrane surface, comprise pressurization, with solvent and with the powder fusion of diaphragm or other polymkeric substance.Wherein a kind of concrete practice is: a kind of film that the electro catalytic activity particle is combined and formed as the tackiness agent with the tetrafluoroethylene under the thermoplastic state or diaphragm and so on of preparation earlier, the composition of jointing material/catalyzer is as the criterion to be in the porous membrane state.Then, this film can be laminated between collector electrode and the diaphragm.
Film can prepare with a kind of ion exchange membrane sheet compound that is in the thermoplastic state, and containing 10% (weight) granularity in this ion-exchange membrane is 30 microns, and the carbon granule of 5% platinum is arranged on it.This compound can be at 310 ℃ temperature and 1 Tons per Inch
2Hot pressing is 1.25 minutes under the pressure of (155 normal atmosphere), prepares a kind of thickness less than 0.025 millimeter film.This film can be laminated between carbon cloth collector plate and the diaphragm by conventional hot-pressing technique.Thereafter, carbon cloth can be embedded in the diaphragm, its method is: under 120 ℃ temperature and the barometric point with the two preheating about 30 seconds together of diaphragm/carbon cloth, then at same temperature and 1-2 Tons per Inch
2The pressure of (155-310 normal atmosphere) heated 225 seconds down, again at the 2-3 Tons per Inch
2The pressure of (310-465 normal atmosphere) heated about 60 seconds down.
The flat 4-88182 of JP proposes to adopt the perfluorinated sulfonic acid cationic exchange membrane (117 type) of du pont company manufacturing, and suspension (outstanding turbid) liquid at its surface applied commodity ion powder (ion-exchange resin powder) applies 5kg/CM
2Pressure, heating 30 minutes under 180-200 ℃ temperature and form porous matter resinbed, this resinbed skin depth is 100 microns.On the resinbed that forms, closely be configured to plumbous oxide and form a porous aspect as anode electrode.On the face relative of ion-exchange membrane, adopt the method for electroless plating to form the ruthenium metallic membrane as negative electrode with this porous aspect.
Preparation plumbous oxide anodic specific practice is, at first will contain 75% titanium, and the coating liquid of 25% platinum is coated on the panel-shaped base body made from sintering tantalum powder, forms the middle layer that is made of platinum/tantalum in the matrix by thermolysis.The lead nitrate aqueous solution with 800 grams per liters is made electrolytic solution, add a spot of nitric acid after, be heated to 70 ℃, aforesaid matrix and titanium plate are immersed in this electrolytic solution, use 10A/dM in advance
2Current density give electrolysis, and then use 4A/dm
2Current density is galvanic deposit α-titanium dioxide lead layer on aforesaid matrix surface, as anode.This titanium dioxide lead layer skin depth is 100 μ m, with 1.0kg/cm
2Pressure this galvanic deposit titanium dioxide lead layer anode is pressed on resinbed one side of ion-exchange membrane, form electrode assembly.
Flat 2-43389 of JP and JP, flat 2-43390 has proposed the manufacture method of ion exchange resin membrane and lead dioxide electrode linker.This method disposes leaded deionized water solution in a side of positively charged ion or anion-exchange resin membrane, at the opposite side configuration time chlorous acid aqueous solution (the perhaps aqueous solution of bromine), make at a side surface of above-mentioned ion exchange resin membrane and separate out lead dioxide plating coat is made ozone as brine electrolysis anode catalyst.
US4927800 has introduced a kind of electrode catalyst and kind electrode Preparation of catalysts method that contains the plumbic oxide electrodeposited coating, is dispersed with the particle that contains β-lead dioxide powder in the catalyst deposit layer.Contain the electrolysis co-catalyst that β-lead dioxide powder and can selecting adds in these particles, the electrolysis co-catalyst is PTEE (tetrafluoroethylene), agar, a kind of in the perfluorinated ion exchange resin etc.The kind electrode catalyzer prepares ozone and electrolytic aqueous solution at brine electrolysis and prepares and be very useful aspect the superoxide.
The common feature of above-mentioned patent application is: ionogen all adopts solid polymer electrolyte (SPE), is generally the perfluorinated sulfonic acid cationic exchange membrane, and this cationic exchange membrane had both been made ionogen, the barrier film between double as cathode compartment and the anolyte compartment again in electrolyzer.
What cathode material (catalyzer) adopted usually is platinum metals, gold and silver, nickel, ruthenium or their mixture.
Anode material (catalyzer) adopts platinum metals usually, gold or its mixture and vitreous carbon, plumbic oxide.
The preparation method of the electrolysis type ozone generator of aforesaid employing solid polymer electrolyte relates to following three kinds of technologies:
The one, prepare the electrode composite membrane by heat pressing process, this processing sequence complexity, the condition harshness needs very high pressure and temperature, and manufacturing cost is increased.And as can not in time being assembled into producer integral body, then because the humidity of room temperature and parking space changes, corresponding variation also takes place in the water content of film, can occur the distortion of electrode/membrane molectron like this through the film of this technological forming.
The 2nd, by infiltration type electroless plating (being electroless plating), this mode has eelctro-catalyst at the one or both sides of ion-exchange membrane deposition one deck, the metal ion that this method is used, the concentration of oxygenant or reductive agent can change in the electroless plating process, be difficult to guarantee the even of each film/electrode assembly for preparing, concentration that must the various compositions of strict guarantee, temperature, pH value constant, otherwise be difficult to guarantee to prepare the quality of catalyzer.
The 3rd, anode catalyst preparation (when adopting plumbic oxide) is a matrix with the POROUS TITANIUM, anodic electrodeposition one deck β-titanium dioxide lead layer again on this matrix, need to guarantee the concentration (comprising various compositions such as β-plumbic oxide particle in the above-mentioned dispersion plating method, PTFE, agar, perfluorinated ion exchange resin) of certain lead ion He other additives in this electroplate liquid, when pH value changes in this technology in the coating crystal formation of plumbic oxide also change thereupon.
Therefore, relate to the preparation method of catalyzer/exchange membrane electrode in the electrolysis type ozone generator that adopts solid polymer electrolyte in the prior art, exist shortcoming with not enough, that is: the preparation process complexity, the production cost height is difficult for commercial scale production.
Must consume raw water when in addition, the electrochemical reaction that is taken place [referring to reaction formula (3) and (4)] produces ozone and oxygen in electrolytic ozone generator; Electrochemical reaction will consume proton in [referring to reaction formula (1) and (2)], and this proton is produced by anodic reaction, and migrates to negative electrode/cationic exchange membrane interface through cationic exchange membrane.And always carry out during proton shifting with the form of water-soluble thinner, thereby along with the carrying out of electrochemical reaction, in the anolyte compartment raw material water yield constantly reduce and in the cathode compartment raw material water yield increase gradually, the electrochemical reaction of simultaneous electrode, its reaction interface produces heat, then can reduce the luminous efficiency of ozone as not adopting cooling measure.
Summary of the invention
The objective of the invention is to overcome technology for preparing electrode complexity in the above-mentioned prior art, the shortcoming that production cost is high, a kind of electrolytic ozone generator is provided, this device has the solid polymer electrolyte film composite electrode member of being made up of discrete diaphragm, electrode manufacturing process is simple, production cost is low, be easy to commercial scale production, simultaneously, raw water self-poise in the anode chamber and the cathode chamber of electrolytic ozone generator of the present invention, exportable pressure is higher than atmospheric ozone, the ozone generation efficiency height.
Another object of the present invention provides a kind of method for preparing the electrolysis type ozone generator in the above-mentioned electrolytic ozone generator.
The anode water tank that electrolytic ozone generator of the present invention comprises electrolysis type ozone generator, link to each other with the anolyte compartment of ozonizer by the anode circulating pipe, pass through the negative electrode water tank that the negative electrode circulating pipe links to each other with the cathode compartment of ozonizer.
According to electrolytic ozone generator of the present invention, electrolysis type ozone generator wherein comprise cationic exchange diaphragm independently, respectively be close proximity to the independently anode catalyst diaphragm of cationic exchange diaphragm both sides and independently the cathod catalyst diaphragm, at the anode porous flow collection sheet of anode catalyst diaphragm-operated opposite side, at the negative electrode porous flow collection sheet of cathod catalyst diaphragm-operated opposite side.
Described cationic exchange diaphragm is a perfluorinated sulfonic acid Zeo-karb commonly used in the prior art, described anode catalyst diaphragm is that the thickness that contains tetrafluoroethylene and plumbic oxide is the film of 0.2-0.3mm, described cathod catalyst diaphragm is that the thickness that contains tetrafluoroethylene and platinum carbon dust is the film of 0.1-0.2mm, described anode porous flow collection sheet is the sintered type POROUS TITANIUM sheet of the surface conductive oxide that scribbles one deck platiniferous, tin and antimony, and described negative electrode porous flow collection sheet is a sintered type POROUS TITANIUM sheet.
In electrolytic ozone generator of the present invention, the position of negative electrode water tank is higher than the anode water tank, between negative electrode water tank and anode water tank, be connected unidirectional equilibrium valve (or break-make type magnetic valve), realizing the raw water self-poise and make this install the ozone of exportable band pressure.Raw water in negative electrode water tank and the anode water tank is ozoniferous raw material, is again the dipolar circulating coolant of yin, yang.
The preparation method of the ozonizer in the electrolytic ozone generator of the present invention comprises:
The platinum carbon dust that a. will contain 5-15% (weight) platinum and ptfe emulsion (suspension) become pasty state with an amount of stirred in water bath of redistilled water about 80 ℃, under 30-40 ℃ of temperature, be rolled into the thick diaphragm of 0.1-0.2MM then repeatedly, wherein tetrafluoroethylene weight accounts for the 5-15% of platinum carbon dust weight, the diaphragm that is rolled is dried and cut into desired size under 50-60 ℃, make cathod catalyst diaphragm 33;
B. titanium dioxide lead powder and ptfe emulsion are become pasty state with an amount of stirred in water bath of redistilled water about 80 ℃, under 30-40 ℃ of temperature, be rolled into the thick diaphragm of 0.2-0.3MM then repeatedly, wherein tetrafluoroethylene weight accounts for the 1-5% of plumbic oxide weight, the diaphragm that is rolled is dried and cut into desired size under 50-60 ℃, make anode catalyst diaphragm 35;
C. sintered type POROUS TITANIUM sheet is given processing through degreasing with the salt acid etch of 5-20% (weight), do not dry after having chlorion with the second distillation water rinse, the organic solution that contains platinum, tin, antimony then in its surface applied, oxidation in 500-530 ℃ of electric furnace, make its surface form the conductive oxide of skim platiniferous, tin, antimony, make anode porous flow collection sheet 36;
D. sintered type POROUS TITANIUM sheet is given processing through degreasing with the salt acid etch of 5-20% (weight), after having chlorion, do not dry, make negative electrode porous flow collection sheet 32 with the second distillation water rinse.
Ozonizer among the present invention is assembled with other indispensable element well-known in the art by above-mentioned independent component cooperation.
Description of drawings
Fig. 1 is the structural representation of electrolytic ozone generator of the present invention.
Fig. 2 is the assembling synoptic diagram of solid polymer electrolyte film composite electrode electrolysis type ozone generator 8 among Fig. 1.
Fig. 3 is the stretch-out view of Fig. 2.
Fig. 4 is the structural representation of unidirectional equilibrium valve 13.
Embodiment
Followingly electrolytic ozone generator of the present invention is described in further detail with reference to accompanying drawing:
The anode water tank 18 that electrolytic ozone generator of the present invention comprises electrolysis type ozone generator 8, link to each other with the anolyte compartment of ozonizer 8 by anode circulating pipe 7, pass through negative electrode water tank 4, unidirectional equilibrium valve 13, cooling blower 10,11, level switch 19,20,21,22 and isolated tube 17 that negative electrode circulating pipe 6 links to each other with the cathode compartment of ozonizer 8.
Wherein electrolysis type ozone generator 8 comprises cationic exchange diaphragm 34, anode catalyst diaphragm 35, anode porous flow collection sheet 36, anolyte compartment's framework 37, anode radiator 38, cathod catalyst diaphragm 33, negative electrode porous flow collection sheet 32, cathode compartment framework 30, flow deflector 31, anticorrosion 28, water conservancy diversion clamping plate 27, gasket 29 and bolt 40, nut 25, packing ring 26,42, insulating washer 39, drainage screw 41.
There is gas collection face 18a anode water tank 18 upper ends in the electrolytic ozone generator of the present invention, make anodic gas not have the discharge of delay rapidly.Elongated airway 18b is arranged on the gas collection face, and ozone and oxygen outlet 24 are arranged at the airway top, and micropore damping sheet 23 is arranged in the air outlet 24, are provided with isolated tube 17 in the anode water tank, are made of silica tube or titanium pipe.Anodic gas (ozone, oxygen) that anodic reaction produces and recirculated water are managed thus and are imported the anode water tank, and being provided with of this isolated tube 17 reduced the contact lysis of ozone and the interior raw water of anode water tank.Ozone and oxygen enter airway 18b rapidly through gas collection face 18a, and have realized gas/water sepn in the airway upper end.Ozone after the separation and oxygen see through micropore damping sheet 23, are derived by ozone, oxygen outlet 24.
The position of negative electrode water tank 4 is higher than anode water tank 18, and filler 2, filler cap 1, hydrogen outlet 3 are arranged at its top.Level switch 19,20,21,22 is housed in the negative electrode water tank 4, and this level switch is made of reed capsule 22, float 21, permanent magnet 20, water level detecting sealed tube 19.When water level was too high or too low in the negative electrode water tank, output signal quit work producer.
Negative electrode circulating pipe 6 connects to water-flow circuit with negative electrode water tank 4 and cathode compartment framework 30, and the heat that produces during with cathodic reaction by water cycle is in time taken out of.
Anode circulating pipe 7 connects to water-flow circuit with anode water tank 18 and anolyte compartment's framework 37, and the heat that produces during with anodic reaction by water cycle is in time taken out of.
According to the electrolysis type ozone generator principle of electrochemical reaction, the generation of ozone and oxygen need consume raw water in the anodic reaction formula 3 and 4, the proton that this reaction produces with the form of water-soluble thinner by cationic exchange membrane to cathodic migration, when electrolytic reaction is proceeded, raw water constantly is consumed in the anode water tank, and raw water constantly increases in the negative electrode water tank.The raw water that increases in the negative electrode water tank can not reversely return the anode water tank by cationic exchange membrane, the result who finally causes the raw water of anode water tank to exhaust fully.
In order to address the above problem, the present invention is provided with a unidirectional equilibrium valve between negative electrode water tank and anode water tank.
Referring to Fig. 1, Fig. 4, unidirectional equilibrium valve 13 is made up of upper valve body 51, diaphragm 50, following valve body 49.Wherein upper valve body 51 is provided with negative electrode water tank interface 43, and anode water tank interface 52 has damper hole 52a in the interface 52, annular seal lip 45; Valve body 49 is provided with anode water tank interface 47, pressure limiting valve port 48, pressure limiting plug 48a under the unidirectional balance.
The negative electrode water tank interface 43 of unidirectional equilibrium valve upper valve body 51 is connected with negative electrode water tank 4, and anode water tank interface 52 is connected with anode water tank 18, and anode water tank interface 47 of valve body 49 is connected with anode water tank 18 under it.
When ozonizer is started working, ozone in the anode water tank 18 and oxygen are because the damping of micropore damping sheet 23, form pressure P gradually, this pressure P is delivered to diaphragm 50 both sides by the anode water tank interface 52 of unidirectional equilibrium valve upper valve body 51 and the anode water tank interface 47 of following valve body 49, at this moment, upper valve body 51 is interior owing to also having negative electrode water tank interface 43, so form raw water flowing from anode water tank 18 to negative electrode water tank 4.Current flow through anode water tank interface 52 damper hole 52a and produce a pressure and fall △ P.The generation of △ P makes diaphragm 50 both sides form pressure difference, and diaphragm 50 is partial to upper valve body 51 directions under this pressure difference effect, until being pressed onto on the annular seal lip 45, has cut off the water stream channel of negative electrode water tank 4 with anode water tank 18 this moment.Diaphragm 50 is owing to the maintenance of the pressure P in the anode water tank 18 keeps this state.This moment, ozonizer device of the present invention can be exported ozone and oxygen with pressure P.
After this ozone generating-device quits work, pressure P fades away, if the water level of negative electrode water tank 4 is higher than the water level of anode water tank 18, diaphragm 50 is subjected to water level differential pressure action deflection valve body 49 directions down, negative electrode water tank 4 is communicated with again by unidirectional equilibrium valve with anode water tank 18, and water level can restore balance gradually in cathode and anode two water tanks.
The pressure limiting plug 48a of unidirectional equilibrium valve when anode water tank 18 internal pressures are too high, will be pressed off, and plays the voltage-limiting protection effect.
Electrolytic ozone generator of the present invention is except being provided with between negative electrode water tank 4 and anode water tank 18 the unidirectional equilibrium valve, one break-make type magnetic valve also can be set, can realize isorrheic purpose equally, break-make type magnetic valve turn-offs the passage of cathode and anode water tank when this device starts; When this device quit work, break-make type magnetic valve was connected the passage of cathode and anode water tank.
Cooling blower 10,11 is installed in the bottom of electrolysis type ozone generator 8, and its cooling air is upwards blown over radiator element 38, anode water tank 18 and negative electrode water tank 4 and played the auxiliary heat dissipation effect.
Ozonizer among the present invention is to adopt the following independent diaphragm cold compaction for preparing respectively through different process to become.
The preparation technology of cathod catalyst diaphragm 33 is: the platinum carbon dust (200 orders sieve) that will contain 5-15% (weight) platinum becomes pasty state with an amount of redistilled water 80 ℃ of left and right sides stirred in water bath with ptfe emulsion (suspension), is rolled into the thick diaphragm of 0.1-0.2MM then under 30-40 ℃ of temperature repeatedly.Wherein tetrafluoroethylene weight accounts for the 5-15% of platinum carbon dust weight.The diaphragm that rolled through 50-60 ℃ of oven dry, and is cut into required size, use when to be assembled.The cathod catalyst diaphragm made of technology has porous, electrically conductive character thus, the hydrogen that produces at this catalyzer diaphragm/cationic exchange membrane contact interface and follow the water of proton shifting to enter cathode compartment by cathod catalyst diaphragm micropore smoothly.
The preparation technology of anode catalyst diaphragm 35 is: titanium dioxide lead powder (180 orders sieve) and ptfe emulsion (suspension) and an amount of redistilled water are stirred into pasty state about 80 ℃.Under 30-40 ℃ of temperature, be rolled into the diaphragm of 0.2-0.3MM then.Wherein tetrafluoroethylene accounts for the 1-5% of plumbic oxide grain weight amount.This diaphragm is cut into required size preserve after 50-60 ℃ of oven dry, use when to be assembled.The anode-catalyzed diaphragm made of technology has porous, electrically conductive thus, and the ozone and the oxygen that produce at anode catalyst diaphragm/cationic exchange membrane contact interface can enter the anolyte compartment by anode catalyst diaphragm micropore smoothly; Raw water can enter anode catalyst diaphragm/cationic exchange membrane reaction interface by this diaphragm micropore backward transfer simultaneously, participates in anodic reaction.Part raw water follows proton to migrate to cathode compartment by cationic exchange membrane.
The preparation technology of anode porous flow collection sheet 36 is: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with the POROUS TITANIUM sheet of sintered type
3/ m
2.hkPa) through after degreasing and giving processing, after having chlorion, do not dry with the second distillation water rinse with the salt acid etch of 5-20% (weight).The organic solution that contains platinum, tin, antimony then in its surface applied, oxidation in 500-530 ℃ electric furnace makes its surface form the conductive oxide of skim platiniferous, tin, antimony, prevents that the porous flow collection sheet from passivation taking place by anodic current the time.The porous flow collection sheet of making through above-mentioned technology has conduction and gas-liquid conducting function (is that gaseous product can leave the electrode reaction interface by this flow collection sheet; And raw water can enter the electrode reaction interface by this flow collection sheet).The wherein said weight percent that contains the organic solution of platinum, tin, antimony consists of:
Concentrated hydrochloric acid 3-9%; H
2P
tCl
6.6H
2O 1-2%; S
nCl
4.5H
2O 5-10%; S
bCl
30.5-1.5%; C
4H
9OH 60-90%.
The preparation technology of negative electrode porous flow collection sheet 32 is: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with sintered type POROUS TITANIUM sheet
3/ m
2.hkPa) the salt acid etch of usefulness 5-20% (weight) after degreasing, is dried to there not being chlorion with the second distillation water rinse, preserves, and uses when to be assembled.This porous flow collection sheet has conduction and gas-liquid conducting function.
Anolyte compartment's framework 37 adopts polytetrafluoroethylmaterial material, is processed into independent component, as shown in Figure 3.This framework is provided with upper and lower gas-water tap, and is connected with anode water tank 18 respectively, constitutes raw water circulation loop in the anolyte compartment.Gas (ozone, the oxygen) raising force that produces by anodic reaction and be power with the temperature difference that raw material water temperature in the anolyte compartment is higher than anode water tank water temperature forms the automated cycle of water and plays cooling effect.
Cathode compartment framework 30 is selected synthetic glass or ABS plastic machine-shaping, as shown in Figure 3.This framework is provided with upper and lower gas-water tap, and is connected with negative electrode water tank 4 respectively, constitutes raw water circulation loop in the cathode compartment.Gas (hydrogen) raising force that produces by cathodic reaction and be power with the temperature difference that raw material water temperature in the cathode compartment is higher than negative electrode water tank water temperature forms the automated cycle of water and plays cooling effect.
Select the metal titanium material for anticorrosion 28, prevent the corrosion of water conservancy diversion clamping plate.Water conservancy diversion clamping plate 27 adopt the Wimet aluminium sheet to make, and are connected with external direct current power supply as producer yin, yang electrode.
Ozonizer of the present invention is to adopt the assembly method of colding pressing to make by above-mentioned each element, and its erection sequence is:
The preparation technology of electrolytic ozone generator of the present invention is simple, easy to assembly, compares with the ozone generating-device of prior art, and the cost of apparatus of the present invention can reduce 30-50%.But and raw water self-poise in the anode and cathode water tank of electrolytic ozone generator of the present invention, the highest exportable ozone that is higher than normal atmosphere 0.1MPa.Device can steady in a long-term move, the ozone generation efficiency height, and following table is the comparison of ozone generation efficiency of some electrolytic ozone generators of device of the present invention and prior art:
| Bath voltage (v) | Current density (A/cm 2) | Ozone generation efficiency (%) | Reference | |
| The present invention | 3.5 | 1.5 | 18-20 | |
| Prior art 1 | 3.6 | 1.0 | 16 | US4927800 |
| Prior art 2 | 4.0 | 8 | JP43390/90 | |
| Prior art 3 | 3.3 | 1.0 | 13 | JP20488/91 |
| Prior art 4 | 4.0 | 7 | JP43389/90 | |
| Prior art 5 | 1.0 | 13-16 | US5203972 |
EXAMPLE Example 1: the preparation of electrolysis type ozone generator 8
A. the preparation of cationic exchange diaphragm 34: with the hydrogen peroxide of 117 type perfluorinated sulfonic acid cationic exchange membranes (E.I.Du Pont Company's product) with 10% 90 ℃ of digestions one hour to remove organic impurities in the striping, sulfuric acid digestion half an hour of putting into 80 ℃ of 2mol/l behind a large amount of 60 ℃ second distillation water rinses again is to remove a spot of metal ion, use a large amount of 60 ℃ second distillation water rinses to neutral at last, be stored in the redistilled water and use when to be assembled.
B. the preparation of cathod catalyst diaphragm 33: the platinum carbon dust (200 orders sieve) that will contain 6% (weight) platinum becomes pasty state with an amount of redistilled water 80 ℃ of left and right sides stirred in water bath with tetrafluoroethylene emulsion (suspension), is rolled into the thick diaphragm of 0.1MM then under 35 ℃ of temperature repeatedly.Wherein tetrafluoroethylene weight accounts for 10% of platinum carbon dust weight.The diaphragm that is rolled is in 60 ℃ of oven dry, and cuts into required size, uses when to be assembled.
C. the preparation of anode catalyst diaphragm 35: β-titanium dioxide lead powder (180 orders sieve) and tetrafluoroethylene emulsion (suspension) and an amount of redistilled water are stirred into pasty state about 80 ℃.Under 40 ℃ of temperature, be rolled into the diaphragm of 0.2MM then.Wherein tetrafluoroethylene accounts for 2% of plumbic oxide grain weight amount.This diaphragm cuts into required size and preserves after 55 ℃ of oven dry, use when to be assembled.
D. the preparation of anode porous flow collection sheet 36: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with the POROUS TITANIUM sheet of sintered type
3/ m
2.hkPa) through after degreasing and giving processing, after having chlorion, do not dry with the second distillation water rinse with 10% salt acid etch.The organic solution that contains platinum, tin, antimony then in its surface applied, oxidation in 520 ℃ electric furnace makes its surface form the conductive oxide of skim platiniferous, tin, antimony.The wherein said weight percent that contains the organic solution of platinum, tin, antimony consists of:
Concentrated hydrochloric acid 5%; H
2P
tCl
6.6H
2O 1%; S
nCl
4.5H
2O 8%; S
bCl
31.0%; C
4H
9OH 85%.
E. the preparation of negative electrode porous flow collection sheet 32: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with sintered type POROUS TITANIUM sheet
3/ m
2.hkPa) after degreasing with 10% salt acid etch,, dry to there not being chlorion with the second distillation water rinse, preserve, use when to be assembled.
Five elements of above-mentioned preparation are cut into 8CM
2The square of size, cooperate other element, according to anode radiator 38, water conservancy diversion clamping plate 27, anticorrosion 28, gasket 29, flow deflector 31, anolyte compartment's framework 37, gasket 29, anode porous flow collection sheet 36, anode catalyst diaphragm 35, cationic exchange membrane 34, cathod catalyst diaphragm 33, negative electrode porous flow collection sheet 32, gasket 29, flow deflector 31, cathode compartment framework 30, gasket 29, anticorrosion 28, water conservancy diversion clamping plate 27, series arrangement, flow deflector 31 wherein, adopt the thick metallic titanium plate processing of 10mm, 7 wide 2.5mm of its uniform distribution, the degree of depth is the groove of 6mm; Cathode compartment framework 30 has 31 * 31 * 9mm with the pmma material injection moulding in the framework
3The space, its up and down air water connection internal diameter be 4mm; Anolyte compartment's framework 37 is processed into tetrafluoroethylene, and its shape size and internal volume and cathode compartment framework 30 are in full accord; All adopt industrially pure titanium for anticorrosion 28, thickness is 0.8mm, and area is 40 * 40mm
2Water conservancy diversion clamping plate 27 are the Wimet aluminium, and thickness is 8mm, and area is 60 * 60mm
2Use bolt 40, nut 25, packing ring 26,42 and insulating washer 39 fastening then, promptly obtain electrolysis type ozone generator 8 of the present invention.Embodiment 2: the preparation of electrolysis type ozone generator 8
A. the preparation of cationic exchange diaphragm 34: with the hydrogen peroxide of 117 type perfluorinated sulfonic acid cationic exchange membranes (E.I.Du Pont Company's product) with 10% 80 ℃ of digestions one hour to remove organic impurities in the striping, sulfuric acid digestion half an hour of putting into 80 ℃ of 2mol/l behind a large amount of 60 ℃ second distillation water rinses again is to remove a spot of metal ion, use a large amount of 60 ℃ second distillation water rinses to neutral at last, be stored in the redistilled water and use when to be assembled.
B. the preparation of cathod catalyst diaphragm 33: the platinum carbon dust (200 orders sieve) that will contain 12% (weight) platinum becomes pasty state with an amount of redistilled water 80 ℃ of left and right sides stirred in water bath with tetrafluoroethylene emulsion (suspension), is rolled into the thick diaphragm of 0.2MM then under 40 ℃ of temperature repeatedly.Wherein tetrafluoroethylene weight accounts for 15% of platinum carbon dust weight.The diaphragm that is rolled is in 60 ℃ of oven dry, and cuts into required size, uses when to be assembled.
C. the preparation of anode catalyst diaphragm 35: titanium dioxide lead powder (180 orders sieve) and tetrafluoroethylene emulsion (suspension) and an amount of redistilled water are stirred into pasty state about 80 ℃.Under 35 ℃ of temperature, be rolled into the diaphragm of 0.2MM then.Wherein tetrafluoroethylene accounts for 1% of plumbic oxide grain weight amount.This diaphragm cuts into required size and preserves after 60 ℃ of oven dry, use when to be assembled.
D. the preparation of anode porous flow collection sheet 36: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with the POROUS TITANIUM sheet of sintered type
3/ m
2.hkPa) through after degreasing and giving processing, after having chlorion, do not dry with the second distillation water rinse with 10% salt acid etch.The organic solution that contains platinum, tin, antimony then in its surface applied, oxidation in 500 ℃ electric furnace makes its surface form the conductive oxide of skim platiniferous, tin, antimony.The wherein said weight percent that contains the organic solution of platinum, tin, antimony consists of:
Concentrated hydrochloric acid 9%; H
2P
tCl
6.6H
2O 2%; S
nCl
4.5H
2O 10%; S
bCl
31.0%; C
4H
9OH 78%.
E. the preparation of negative electrode porous flow collection sheet 32: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with sintered type POROUS TITANIUM sheet
3/ m
2HkPa) after degreasing with 10% salt acid etch,, dry to there not being chlorion with the second distillation water rinse, preserve, use when to be assembled.
Method according to identical with embodiment 1 is assembled into electrolysis type ozone generator 8 of the present invention with the above-mentioned element that makes and other element.Embodiment 3: the preparation of electrolysis type ozone generator 8
A. the preparation of cationic exchange diaphragm 34: with the hydrogen peroxide of 117 type perfluorinated sulfonic acid cationic exchange membranes (E.I.Du Pont Company's product) with 10% 85 ℃ of digestions one hour to remove organic impurities in the striping, sulfuric acid digestion half an hour of putting into 80 ℃ of 2mol/l behind a large amount of 60 ℃ second distillation water rinses again is to remove a spot of metal ion, use a large amount of 60 ℃ second distillation water rinses to neutral at last, be stored in the redistilled water and use when to be assembled.
B. the preparation of cathod catalyst diaphragm 33: the platinum carbon dust (200 orders sieve) that will contain 10% (weight) platinum becomes pasty state with an amount of redistilled water 80 ℃ of left and right sides stirred in water bath with tetrafluoroethylene emulsion (suspension), is rolled into the thick diaphragm of 0.1MM then under 30 ℃ of temperature repeatedly.Wherein tetrafluoroethylene weight accounts for 5% of platinum carbon dust weight.The diaphragm that is rolled is in 60 ℃ of oven dry, and cuts into required size, uses when to be assembled.
C. the preparation of anode catalyst diaphragm 35: β-titanium dioxide lead powder (180 orders sieve) and tetrafluoroethylene emulsion (suspension) and an amount of redistilled water are stirred into pasty state about 80 ℃.Under 30 ℃ of temperature, be rolled into the diaphragm of 0.3MM then.Wherein tetrafluoroethylene accounts for 1.5% of plumbic oxide grain weight amount.This diaphragm cuts into required size and preserves after 60 ℃ of oven dry, use when to be assembled.
D. the preparation of anode porous flow collection sheet 36: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with the POROUS TITANIUM sheet of sintered type
3/ m
2.hkPa) through after degreasing and giving processing, after having chlorion, do not dry with the second distillation water rinse with 10% salt acid etch.The organic solution that contains platinum, tin, antimony then in its surface applied, oxidation in 520 ℃ electric furnace makes its surface form the conductive oxide of skim platiniferous, tin, antimony.The wherein said weight percent that contains the organic solution of platinum, tin, antimony consists of:
Concentrated hydrochloric acid 3%; H
2P
tCl
6.6H
2O 1.5%; S
nCl
4.5H
2O 5%; S
bCl
30.5%; C
4H
9OH 90%.
E. the preparation of negative electrode porous flow collection sheet 32: (maximum diameter of hole is 26 μ M, and air penetrability is 119M with sintered type POROUS TITANIUM sheet
3/ m
2.hkPa) after degreasing with 10% salt acid etch,, dry to there not being chlorion with the second distillation water rinse, preserve, use when to be assembled.
Method according to identical with embodiment 1 is assembled into electrolysis type ozone generator 8 of the present invention with the above-mentioned element that makes and other element.Embodiment 4: the assembling of electrolytic ozone generator of the present invention and application
The electrolysis type ozone generator 8 and the following element that adopt embodiment 1 to make:
The anode water tank 18 that 1500 milliliters negative electrode water tank is 4,1200 milliliters, unidirectional equilibrium valve 13, cooling blower 10 and 11, anode circulating pipe 7, negative electrode circulating pipe 6, level switch 19,20,21,22 and isolated tube 17 are installed according to method well known in the art and are formed electrolytic ozone generator of the present invention.
The electrolytic ozone generator of present embodiment is with 1.5A/cm
2Current density when operation, the producer bath voltage is 3.5 ± 0.1V, when envrionment temperature is 25 ℃ of left and right sides, moves 24 hours continuously, the raw material water temperature in the cathode and anode water tank can maintain about 30 ℃, ozone generation efficiency is 18%.
Can export the ozone that is higher than normal atmosphere 0.08MPa pressure from the anode water tank.
Claims (25)
1, a kind of electrolytic ozone generator, the anode water tank (18) that comprises electrolysis type ozone generator (8), links to each other with the anolyte compartment of ozonizer (8) by anode circulating pipe (7), pass through negative electrode circulating pipe (6) and the negative electrode water tank (4) that the cathode compartment of ozonizer (8) links to each other, it is characterized in that:
Negative electrode water tank (4) position is higher than anode water tank (18), and a unidirectional equilibrium valve (13) is set between negative electrode water tank (4) and anode water tank (18),
Electrolysis type ozone generator wherein (8) comprise cationic exchange diaphragm (34) independently, respectively be close proximity to the independently anode catalyst diaphragm (35) of cationic exchange diaphragm (34) both sides and independently cathod catalyst diaphragm (33), at the anode porous flow collection sheet (36) of the opposite side of anode catalyst diaphragm (35), at the negative electrode porous flow collection sheet (32) of the opposite side of cathod catalyst diaphragm (33).
2, electrolytic ozone generator according to claim 1, it is characterized in that: the cathod catalyst diaphragm (33) in the described electrolysis type ozone generator (8) contains platinum carbon dust and tetrafluoroethylene, wherein contain the platinum of 5-15 weight % in the platinum carbon dust, the weight of tetrafluoroethylene accounts for the 5-15% of platinum carbon dust weight.
3, electrolytic ozone generator according to claim 2 is characterized in that: the particle size of the platinum carbon dust in the described cathod catalyst diaphragm (33) is less than 200 orders.
4, electrolytic ozone generator according to claim 2 is characterized in that, the thickness of described cathod catalyst diaphragm (33) is 0.1-0.2mm.
5, electrolytic ozone generator according to claim 1 is characterized in that: the anode catalyst diaphragm (35) in the described electrolysis type ozone generator (8) contains plumbic oxide and tetrafluoroethylene.
6, electrolytic ozone generator according to claim 5 is characterized in that, the weight of tetrafluoroethylene accounts for the 1-5% of plumbic oxide weight in the described anode catalyst diaphragm (35).
7, according to claim 5 or 6 described electrolytic ozone generators, it is characterized in that: the particle size of the plumbic oxide that uses in the described anode catalyst diaphragm (35) is less than 180 orders.
8, according to claim 5 or 6 described electrolytic ozone generators, it is characterized in that: used plumbic oxide is β-plumbic oxide in the described anode catalyst diaphragm (35).
9, electrolytic ozone generator according to claim 7 is characterized in that: used plumbic oxide is β-plumbic oxide in the described anode catalyst diaphragm (35).
According to claim 5 or 6 described electrolytic ozone generators, it is characterized in that 10, the thickness of described anode catalyst diaphragm (35) is 0.2-0.3mm.
11, electrolytic ozone generator according to claim 8 is characterized in that, the thickness of described anode catalyst diaphragm (35) is 0.2-0.3mm.
12, electrolytic ozone generator according to claim 9 is characterized in that, the thickness of described anode catalyst diaphragm (35) is 0.2-0.3mm.
13, electrolytic ozone generator according to claim 1 is characterized in that: the anode porous flow collection sheet (36) in the described electrolysis type ozone generator (8) is the sintered type POROUS TITANIUM sheet of the surface conductive oxide that scribbles one deck platiniferous, tin and antimony.
14, electrolytic ozone generator according to claim 1 is characterized in that, described electrolysis type ozone generator (8) comprises that also the one side of being made by metal titanium evenly is provided with fluted flow deflector.
15, electrolytic ozone generator according to claim 1 is characterized in that:
There is gas collection face (18a) described anode water tank (18) upper end, elongated airway (18b) is arranged on the gas collection face, ozone, oxygen outlet (24) are arranged at airway (18b) top, in ozone, the oxygen outlet (24) micropore damping sheet (23) is arranged, isolated tube (17) is arranged in the anode water tank (18), and anode water tank (18) is connected to form water-flow circuit by anode circulation pipe (7) and anolyte compartment's framework (37);
16, electrolytic ozone generator according to claim 1, it is characterized in that: filler (2), filler cap (1), hydrogen outlet (3) are arranged at the top of described negative electrode water tank (4), level switch (19,20,21,22) is housed in the negative electrode water tank (4), and negative electrode water tank (4) is connected to form water-flow circuit by cathode circulating tube (6) and cathode compartment framework (30).
17, electrolytic ozone generator according to claim 1 is characterized in that:
Described unidirectional equilibrium valve (13) is made up of upper valve body (51), diaphragm (50), following valve body (49); Wherein upper valve body (51) is provided with negative electrode water tank interface (43), and anode water tank interface (52) has damper hole (52a) in the anode water tank interface (52), annular seal lip (45); Valve body under the unidirectional balance (49) is provided with anode water tank interface (47), pressure limiting valve port (48) and pressure limiting plug (48a).
18, electrolytic ozone generator according to claim 1 is characterized in that: a break-make type magnetic valve is set between negative electrode water tank (4) and anode water tank (18).
19, a kind of preparation method of the electrolysis type ozone generator (8) described in claim 1 comprising:
The platinum carbon dust that a. will contain 5-15 weight % platinum and ptfe emulsion become pasty state with an amount of stirred in water bath of redistilled water about 80 ℃, under 30-40 ℃ of temperature, be rolled into the thick diaphragm of 0.1-0.2mm then repeatedly, wherein tetrafluoroethylene weight accounts for the 5-15% of platinum carbon dust weight, the diaphragm that is rolled is dried and cut into desired size under 50-60 ℃, make cathod catalyst diaphragm (33);
B. titanium dioxide lead powder and ptfe emulsion are become pasty state with an amount of stirred in water bath of redistilled water about 80 ℃, under 30-40 ℃ of temperature, be rolled into the thick diaphragm of 0.2-0.3mm then repeatedly, wherein tetrafluoroethylene weight accounts for the 1-5% of plumbic oxide weight, the diaphragm that is rolled is dried and cut into desired size under 50-60 ℃, make anode catalyst diaphragm (35);
C. sintered type POROUS TITANIUM sheet is given processing through degreasing with the salt acid etch of 5-20 weight %, do not dry after having chlorion with the second distillation water rinse, the organic solution that contains platinum, tin, antimony then in its surface applied, oxidation in 500-530 ℃ of electric furnace, make its surface form the conductive oxide of skim platiniferous, tin, antimony, make anode porous flow collection sheet (36);
D. sintered type POROUS TITANIUM sheet is given processing through degreasing with the salt acid etch of 5-20 weight %, after having chlorion, do not dry, make negative electrode porous flow collection sheet (32) with the second distillation water rinse.
20, the preparation method of ozonizer as claimed in claim 19 is characterized in that, the particle size of the platinum carbon dust that uses in the described cathod catalyst diaphragm of preparation (33) is less than 200 orders.
21, the preparation method of ozonizer as claimed in claim 19 is characterized in that, the particle size of the plumbic oxide that uses in the described anode catalyst diaphragm of preparation (35) is less than 180 orders.
As the preparation method of claim 19 or 21 described ozonizers, it is characterized in that 22, used plumbic oxide is β-plumbic oxide in the described anode catalyst diaphragm of preparation (35).
23, the preparation method of ozonizer as claimed in claim 19 is characterized in that, the weight percent of the used organic solution that contains platinum, tin, antimony consists of in the described anode porous flow collection sheet of preparation (36): concentrated hydrochloric acid 3-9%; H
2PtCl
6.6H
2O 1-2%; SnCl
4.5H
2O 5-10%; SbCl
30.5-1.5%; C
4H
9OH 78-90%.
24, the preparation method of ozonizer as claimed in claim 19 is characterized in that, the maximum diameter of hole of used sintered type POROUS TITANIUM sheet is 26 μ m in the described anode porous flow collection sheet of preparation (36), and air penetrability is 119M
3/ m
2.h.kPa.
25, the preparation method of ozonizer as claimed in claim 19 is characterized in that, the maximum diameter of hole of used sintered type POROUS TITANIUM sheet is 26 μ m in the described negative electrode porous flow collection sheet of preparation (32), and air penetrability is 119M
3/ m
2.h.kPa.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW086117241A TW401373B (en) | 1997-03-07 | 1997-11-17 | Electrolytic ozone generating apparatus |
| CN97122126A CN1128759C (en) | 1997-03-07 | 1997-11-19 | Electrolytic ozone generator |
| PCT/CN1998/000030 WO1998040535A1 (en) | 1997-03-07 | 1998-03-04 | Electrolytic ozone-generating apparatus and the process for manufacturing the same |
| AU62884/98A AU6288498A (en) | 1997-03-07 | 1998-03-04 | Electrolytic ozone-generating apparatus and the process for manufacturing the s ame |
| JP10057071A JP3025473B2 (en) | 1997-03-07 | 1998-03-09 | Electrolytic ozone generator and method for making it |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97209412.1 | 1997-03-07 | ||
| CN97209412 | 1997-03-07 | ||
| CN97122126A CN1128759C (en) | 1997-03-07 | 1997-11-19 | Electrolytic ozone generator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1195643A CN1195643A (en) | 1998-10-14 |
| CN1128759C true CN1128759C (en) | 2003-11-26 |
Family
ID=25744409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122126A Expired - Fee Related CN1128759C (en) | 1997-03-07 | 1997-11-19 | Electrolytic ozone generator |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3025473B2 (en) |
| CN (1) | CN1128759C (en) |
| AU (1) | AU6288498A (en) |
| TW (1) | TW401373B (en) |
| WO (1) | WO1998040535A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011160446A1 (en) * | 2010-06-22 | 2011-12-29 | Liu Xun | Water electrolytic device |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001181876A (en) | 1999-12-22 | 2001-07-03 | Teeiku Wan Sogo Jimusho:Kk | Ozone generating electrolytic cell and its manufacturing method |
| TW200528390A (en) * | 2004-02-25 | 2005-09-01 | Toshiba Mitsubishi Elec Inc | Apparatus and method of producing ozone gas |
| CN1900367A (en) * | 2005-07-20 | 2007-01-24 | 徐名勇 | Anode structure of electrolytic ozone generator |
| CN2854261Y (en) * | 2005-07-20 | 2007-01-03 | 徐名勇 | Thin-film check valve used in ozone/ozone water loop |
| HUP0501204A2 (en) | 2005-12-23 | 2007-07-30 | Thales Rt | Ozone generating electrolytic cell |
| CN101250710B (en) * | 2008-03-28 | 2010-06-09 | 陕西科技大学 | Electrolytic ozone generator and preparation technique for cathode catalysis layer thereof |
| CN101289749B (en) * | 2008-06-04 | 2010-10-06 | 徐伟钧 | Spring bearer plate structure for fastening anodic of electrolytic ozone generator |
| CN101698942B (en) * | 2009-02-11 | 2011-08-10 | 徐名勇 | Ozone generator for use in membrane electrode electrolysis |
| CN102181879A (en) * | 2011-04-12 | 2011-09-14 | 周美荣 | Electrolytic ozone generating device capable of recycling cathode water |
| CN103498954B (en) * | 2013-10-11 | 2015-07-08 | 苏州竞立制氢设备有限公司 | Double-system balance valve |
| CN104032326B (en) * | 2014-03-03 | 2017-02-01 | 上海维埃姆环保科技有限公司 | Titanium steel guide plate and generator adopting the guide plate |
| CN103981532A (en) * | 2014-05-30 | 2014-08-13 | 李欣 | Novel membrane electrode electrolysis ozone generator |
| CN107441543A (en) * | 2017-09-29 | 2017-12-08 | 深圳欧威奇科技有限公司 | Air purifying and sterilizing machine |
| CN107469121A (en) * | 2017-09-29 | 2017-12-15 | 深圳欧威奇科技有限公司 | A kind of air purifying and sterilizing machine |
| CN108301013B (en) * | 2018-02-14 | 2020-05-12 | 中氧科技（广州）有限公司 | Preparation method of modified lead dioxide anode for ozone |
| CN108977828B (en) * | 2018-10-19 | 2023-11-03 | 胡松 | Membrane electrode electrolytic ozone generator and preparation process thereof |
| CN109338399A (en) * | 2018-11-19 | 2019-02-15 | 武汉威蒙环保科技有限公司 | A kind of built-in gas water cyclic electrolysis formula ozone generating-device |
| CN112744903A (en) * | 2019-10-30 | 2021-05-04 | 无锡维邦工业设备成套技术有限公司 | Electrolyzed water ozone-making type purified water sterilization system |
| CN114293211B (en) * | 2021-12-30 | 2023-09-05 | 深圳康诚博信科技有限公司 | Ozone generator with rapid disassembly and assembly structure and preparation method of cathode prefabricated film of ozone generator |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4316782A (en) * | 1980-05-29 | 1982-02-23 | Regents Of The University Of California | Electrolytic process for the production of ozone |
| JP2840753B2 (en) * | 1989-03-31 | 1998-12-24 | 株式会社ササクラ | Ozone electrolytic production method |
| JPH0320488A (en) * | 1989-06-19 | 1991-01-29 | Permelec Electrode Ltd | Method for generating ozone by water electrolysis |
| US5460705A (en) * | 1993-07-13 | 1995-10-24 | Lynntech, Inc. | Method and apparatus for electrochemical production of ozone |
| CN2229460Y (en) * | 1993-11-24 | 1996-06-19 | 武汉大学 | Solid polymer electrolyte film electrode electrolytic ozonator |
| JPH07157301A (en) * | 1993-12-08 | 1995-06-20 | Hitachi Maxell Ltd | Ozone generator |
-
1997
- 1997-11-17 TW TW086117241A patent/TW401373B/en not_active IP Right Cessation
- 1997-11-19 CN CN97122126A patent/CN1128759C/en not_active Expired - Fee Related
-
1998
- 1998-03-04 AU AU62884/98A patent/AU6288498A/en not_active Abandoned
- 1998-03-04 WO PCT/CN1998/000030 patent/WO1998040535A1/en active Application Filing
- 1998-03-09 JP JP10057071A patent/JP3025473B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011160446A1 (en) * | 2010-06-22 | 2011-12-29 | Liu Xun | Water electrolytic device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998040535A8 (en) | 1999-06-10 |
| JP3025473B2 (en) | 2000-03-27 |
| CN1195643A (en) | 1998-10-14 |
| TW401373B (en) | 2000-08-11 |
| JPH111789A (en) | 1999-01-06 |
| WO1998040535A1 (en) | 1998-09-17 |
| AU6288498A (en) | 1998-09-29 |
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