CN1195643A - Electrolytic ozone generator - Google Patents
Electrolytic ozone generator Download PDFInfo
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- CN1195643A CN1195643A CN97122126A CN97122126A CN1195643A CN 1195643 A CN1195643 A CN 1195643A CN 97122126 A CN97122126 A CN 97122126A CN 97122126 A CN97122126 A CN 97122126A CN 1195643 A CN1195643 A CN 1195643A
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- 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 a kind of electrolytic type ozone generation equipment, mainly including ozone generator, anodic water tank, cathodic water tank and one-way balanced valve or on-off solenoid valve, etc., in which the ozone generator includes the independent elements of cation exchange membrane piece, cathodic catalyst membrane piece, cathode porous collecting piece, anodic catalyst membrane piece, anode porous collecting piece, guide plate and anticorrosion plate. Said invented equipment is low in cost, high in ozone generation efficiency, and can be produced in the industrial scale.
Description
The invention relates to an electrolytic ozone generating device, belonging to the technical field of electrochemistry and ozone application.
The advantages of disinfection and sterilization by an ozone method are more and more taken into consideration by people. At present, a high-frequency high-voltage corona discharge method is adopted to generate ozone, and research and development of an electrochemical method to generate high-concentration ozone have attracted extensive attention. The basic principle of electrochemical methods for producing ozone is well known: the ozone generation takes deionized water as a raw material, and when a direct current power supply is externally added, the electrochemical reaction formula of a cathode and an anode is as follows:
the cathode hydrogen evolution reaction formula: (1)
cathode oxygen depolarization equation: (2)
the anode has a main reaction formula: (3)
the anode side reaction formula: (4)
protons generated by the anode reaction migrate to the cathode through the cation exchange membrane in the form of water-solvated protons under the action of a direct current electric field.
Based on the above electrochemical reaction principle, the core part constituting the most basic electrolytic ozone generator is an electrolytic cell. The cell must have an anode, a cathode, an electrolyte and raw water.
Chinese patent application CN86108792A describes a solid polymer electrolyte structure comprising a membrane, a plurality of conductive particles and a conductive water permeable matrix member, wherein the conductive particles and the conductive water permeable matrix (as current collecting plates) are physically or electrically in contact with each other and embedded in the membrane, or are integrated with the membrane. Wherein fluorocarbon materials are generally preferred for the membrane. In order to embed the electrically conductive, water permeable matrix in the fluorocarbon film, the fluorocarbon is preferably in a thermoplastic state. The conductive water-permeable substrate includes carbon cloth, carbon paper, metal mesh, metal felt, porous metal sheet, etc., preferably carbon cloth. The electrocatalytically-active particles may be incorporated into the surface of the membrane using a variety of techniques, including pressurization, mixing with solvents, and powder blending with the membrane or other polymers. One specific method is as follows: a film is first prepared, for example, by bonding together the electrocatalytically-active particles by means of a binder such as polytetrafluoroethylene or a film in the thermoplastic state, the binder/catalyst combination being in the form of a porous film. The film may then be laminated between the collector and the diaphragm.
The membrane may be prepared from an ion exchange membrane blend in a thermoplastic state containing 10% by weight of carbon particles having a particle size of 30 microns and 5% platinum thereon. The mix may be at a temperature of 310 ℃ and 1 ton/inch2Hot pressing under a pressure of (155 atm) for 1.25 minutes to prepare a film having a thickness of less than 0.025 mm. The membrane may be laminated between the carbon cloth collector plate and the membrane using conventional hot pressing techniques. Thereafter, carbon cloth may be embedded in the membrane by: both the membrane/carbon cloth were preheated together at a temperature of 120 c and atmospheric pressure for about 30 seconds, followed by 1-2 tons/inch at the same temperature2(155-310 atm) for 225 seconds and then 2-3 tons/inch2(310-465 atmospheres) for about 60 seconds.
JP, Hei 4-88182, proposes to apply 5kg/cm of a suspension (suspension) of a commercial ion powder (ion exchange resin powder) to the surface of a perfluorosulfonic acid cation exchange membrane (type 117) manufactured by DuPont, U.S.A.2At a temperature of 180-200 ℃ for 30 minutes to form a porous ion exchange resin layer having a surface layer thickness of 100 μm. Lead oxide is closely arranged on the formed ion exchange resin layer to form a porous layer surface as an anode electrode. On the surface of the ion exchange membrane opposite to the porous layer surface, a ruthenium metal membrane is formed as a cathode by adopting an electroless plating method.
The lead oxide anode was prepared by first coating a coating solution containing 75% titanium and 25% platinum on a plate-like substrate made of sintered tantalum powder and forming an intermediate layer of platinum/tantalum in the substrate by thermal decomposition. Using 800 g/L lead nitrate water solution as electrolyte, adding a small amount of nitric acid,heating to 70 deg.C, immersing the substrate and titanium plate in the electrolyte at a ratio of 10A/dm2Is pre-electrolyzed and then re-electrolyzed at a current density of 4A/dm2Current density A α -lead dioxide layer was electrodeposited as an anode on the surface of the aforementioned substrate, the lead dioxide layer having a surface layer thickness of 100 μm at 1.0kg/cm2The anode of the electrodeposited lead dioxide layer is pressed against the ion exchange resin layer side of the ion exchange membrane by the pressure of (2) to form an electrode structure.
JP, Hei 2-43389 and JP, Hei 2-43390 propose a method for producing an ion exchange resin membrane and a lead dioxide electrode connector. In this method, an aqueous solution containing lead ions is disposed on one side of a cation-or anion-exchange resin membrane, and an aqueous solution of hypochlorous acid (or bromine) is disposed on the other side, so that a lead dioxide plating layer is deposited on one surface of the ion-exchange resin membrane as an anode catalyst for producing ozone by electrolyzing water.
US4927800 describes an electrode catalyst comprising an electrolytically deposited layer of lead dioxide in which particles comprising β -lead dioxide powder are dispersed, the particles comprising β -lead dioxide powder and optionally an electrolytic co-catalyst which is one of PTEE (polytetrafluoroethylene), agar, perfluorinated ion exchange resin, etc., and a process for producing the electrode catalyst.
The common features of the above patent applications are: the electrolyte is a Solid Polymer Electrolyte (SPE), typically a perfluorosulfonic acid cation exchange membrane, which serves both as the electrolyte and as a separator between the cathode and anode chambers in the cell.
Cathode materials (catalysts) are generally employed as platinum group metals, gold, silver, nickel, ruthenium or mixtures thereof.
The anode material (catalyst) is usually platinum group metal, gold or a mixture thereof, glassy carbon, and lead dioxide.
The preparation method of the electrolytic ozone generator using the solid polymer electrolyte as described above involves the following three processes:
firstly, the electrode composite membrane is prepared by a hot pressing process, which has complex process and harsh conditions, needs very high pressure and temperature, and increases the manufacturing cost. Ifthe membrane formed by the process cannot be assembled into a generator whole in time, the moisture content of the membrane also changes correspondingly due to the change of the room temperature and the humidity of the storage space, so that the deformation of the electrode/membrane combination can occur.
Secondly, a layer of electrocatalyst is deposited on one side or two sides of the ion exchange membrane through the permeation type chemical plating (namely electroless plating), the concentration of metal ions, oxidant or reducer used in the method can change in the chemical plating process, the uniformity of the membrane/electrode assembly prepared each time is difficult to ensure, the constancy of the concentration, temperature and PH value of various components must be strictly ensured, otherwise, the quality of the prepared catalyst is difficult to ensure.
Thirdly, the preparation of the anode catalyst (for example, when lead dioxide is adopted) takes porous titanium as a substrate, a β -lead dioxide layer is anodically electrodeposited on the substrate, certain concentrations of lead ions and other additives (including β -lead dioxide particles, PTFE, agar, perfluorinated ion exchange resin and other components in the dispersion electroplating method) need to be ensured in the electroplating solution, and the crystal form of the lead dioxide in the plating layer is changed when the pH value is changed in the process.
Therefore, the prior art relates to a method for preparing a catalyst/ion exchange membrane electrode in an electrolytic ozone generator using a solid polymer electrolyte, which has the following disadvantages and shortcomings: the preparation process is complex, the production cost is high, and the industrial scale production is not easy.
In addition, the electrochemical reaction [ see reaction formulas (3) and (4)]occurring in theelectrolytic ozone generating device must consume raw material water when ozone and oxygen are generated; in the electrochemical reactions [ see equations (1) and (2)]protons are consumed, which are generated by the anodic reaction and migrate through the cation exchange membrane to the cathode/cation exchange membrane interface. However, the proton transfer always proceeds in the form of water solvation, so that the amount of raw material water in the anode chamber is gradually reduced and the amount of raw material water in the cathode chamber is gradually increased as the electrochemical reaction proceeds, and the reaction interface generates heat along with the electrochemical reaction of the electrodes, which reduces the ozone generation efficiency if no heat dissipation measure is taken.
The invention aims to overcome the defects of complex electrode preparation process and high production cost in the prior art, and provides an electrolytic ozone generating device which is provided with a solid polymer electrolyte membrane composite electrode component consisting of separate membranes, has simple electrode manufacturing process and low production cost, is easy for industrial scale production, and simultaneously, raw material water in a cathode chamber and an anode chamber of the electrolytic ozone generating device is automatically balanced, can output ozone with pressure higher than atmospheric pressure, and has high ozone generating efficiency.
Another object of the present invention is to provide a method for preparing the electrolytic ozone generator in the above electrolytic ozone generating device.
The electrolytic ozone generator includes an electrolytic ozone generator, an anode water tank connected to the anode chamber of the ozone generator via an anode circulating water pipe, and a cathode water tank connected to the cathode chamber of the ozone generator via a cathode circulating water pipe.
The electrolytic ozone generator of the present invention includes an independent cation exchange membrane, an independent anode catalyst membrane and an independent cathode catalyst membrane which are respectively close to two sides of the cation exchange membrane, an anode porous current collecting sheet on the other side of the anode catalyst membrane, and a cathode porous current collecting sheet on the other side of the cathode catalyst membrane.
The cation exchange membrane is common perfluorosulfonic acid cation exchange resin in the prior art, the anode catalyst membrane is a membrane with the thickness of 0.2-0.3mm and contains polytetrafluoroethylene and lead dioxide, the cathode catalyst membrane is a membrane with the thickness of 0.1-0.2mm and contains polytetrafluoroethylene and platinum carbon powder, the anode porous current collecting plate is a sintered porous titanium plate, the surface of the sintered porous titanium plate is coated with a layer of conductive oxide containing platinum, tin and antimony, and the cathode porous current collecting plate is a sintered porous titanium plate.
In the electrolytic ozone generator of the present invention, the cathode water tank is higher than the anode water tank, and a one-way balance valve (or on-off type electromagnetic valve) is connected between the cathode water tank and the anode water tank to realize automatic balance of raw material water and make the device capable of outputting pressurized ozone. The raw material water in the cathode water tank and the anode water tank is not only a raw material for generating ozone, but also a circulating coolant of the cathode and the anode.
The preparation method of the ozone generator in the electrolytic ozone generating device comprises the following steps:
a. stirring platinum carbon powder containing 5-15 wt% of platinum and polytetrafluoroethylene emulsion (suspension) with a proper amount of secondary distilled water in a water bath at about 80 ℃ to form paste, repeatedly rolling the paste into a membrane with the thickness of 0.1-0.2mm at the temperature of 30-40 ℃, wherein the weight of polytetrafluoroethylene accounts for 5-15% of the weight of the platinum carbon powder, drying the rolled membrane at the temperature of 50-60 ℃, and cutting the membrane into required sizes to obtain a cathode catalyst membrane (33);
b. lead dioxide powder, polytetrafluoroethylene emulsion and a proper amount of secondary distilled water are stirred into paste in a water bath at the temperature of about 80 ℃, then the paste is repeatedly rolled into a membrane with the thickness of 0.2 to 0.3mm at the temperature of 30 to 40 ℃, wherein the weight of the polytetrafluoroethylene accounts for 1 to 5 percent of the weight of the lead dioxide, and the rolled membrane is dried and cut into required size at the temperature of 50 to 60 ℃ to prepare an anode catalyst membrane (35);
c. degreasing the sintered porous titanium sheet, etching the sintered porous titanium sheet by 5-20 wt% hydrochloric acid, rinsing the sintered porous titanium sheet by secondary distilled water until no chloride ions exist, drying the sintered porous titanium sheet, coating an organic solution containing platinum, tin and antimony on the surface of the sintered porous titanium sheet, and oxidizing the organic solution in an electric furnace at the temperature of 500-;
d. the sintered porous titanium sheet is degreased and etched by 5-20 wt% hydrochloric acid, rinsed by secondary distilled water until no chloride ion exists, and dried to obtain the cathode porous current collecting sheet (32).
The ozone generator of the present invention is assembled from the above-described individual components in combinationwith other necessary components well known in the art.
FIG. 1 is a schematic view showing the structure of an electrolytic ozone generator of the present invention.
FIG. 2 is a schematic view showing the assembly of the solid polymer electrolyte membrane composite electrode electrolytic ozone generator (8) of FIG. 1.
Fig. 3 is an expanded view of fig. 2.
Fig. 4 is a schematic structural view of the check balance valve 13.
The electrolytic ozone generator of the present invention will be described in further detail with reference to the accompanying drawings:
the electrolytic ozone generator of the invention comprises an electrolytic ozone generator 8, an anode water tank 18 connected with an anode chamber of the ozone generator 8 through a circulating water pipe 7, a cathode water tank 4 connected with a cathode chamber of the ozone generator 8 through a circulating water pipe 6, a one-way balance valve 13, cooling fans 10 and 11, water level detectors 19, 20, 21 and 22 and an isolation pipe 17.
The electrolytic ozone generator 8 comprises a cation exchange membrane 34, an anode catalyst membrane 35, an anode porous current collector 36, an anode chamber frame 37, an anode cooling fin 38, a cathode catalyst membrane 33, a cathode porous current collector 32, a cathode chamber frame 30, a flow guide plate 31, an anti-corrosion plate 28, a flow guide clamping plate 27, a sealing gasket 29, a bolt 40, a nut 25, gaskets 26 and 42, an insulating gasket 39 and a drainage screw 41.
The electrolytic ozone generator of the present invention has a gas collecting surface 18a at the upper end of the anode water tank 18, so that the anode gas can be discharged quickly without retention. The gas collecting surface is provided with a slender gas guide tube 18b, the top of thegas guide tube is provided with an ozone and oxygen outlet 24, a micropore damping plate 23 is arranged in the gas outlet 24, and the anode water tank is internally provided with an isolating tube 17 which is composed of a quartz tube or a titanium tube. The anode gas (ozone, oxygen) and the circulating water generated by the anode reaction are led into the anode water tank through the pipe, and the arrangement of the isolating pipe 17 reduces the contact dissolution of the ozone and the raw material water in the anode water tank. Ozone and oxygen rapidly enter the gas-guide tube 18b through the gas-collecting surface 18a, and gas/water separation is realized at the upper end of the gas-guide tube. The separated ozone and oxygen permeate the microporous damping plate 23 and are led out from the ozone and oxygen outlet 24.
The cathode water tank 4 is higher than the anode water tank 18, and the top of the cathode water tank is provided with a water filling port 2, a water filling port cover 1 and a hydrogen outlet 3. The cathode water tank 4 is internally provided with water level detectors 19, 20, 21, 22 which are composed of a reed pipe 22, a float 21, a permanent magnet 20, and a water level detection sealing pipe 19. When the water level in the cathode water tank is too high or too low, a signal is output to stop the generator.
The cathode water tank 4 and the cathode chamber frame 30 are connected by the cathode circulating water pipe 6 to form a water circulation loop, and heat generated during the cathode reaction is timely taken out through water circulation.
The anode circulating water pipe 7 connects the anode water tank 18 and the anode chamber frame 37 to a water circulation loop, and the heat generated during the anode reaction is timely taken out through water circulation.
According to the electrochemical reaction principle of the electrolyticozone generator, raw material water is consumed for the generation of ozone and oxygen in the anode reaction formulas 3 and 4, protons generated by the reaction migrate to the cathode through a cation exchange membrane in a water solvation form, and when the electrolytic reaction continues, the raw material water in the anode water tank is continuously consumed, and the raw material water in the cathode water tank is continuously increased. The raw material water added in the cathode water tank can not reversely return to the anode water tank through the cation exchange membrane, and finally the result that the raw material water in the anode water tank is completely exhausted is caused.
In order to solve the problems, the invention arranges a one-way balance valve between the cathode water tank and the anode water tank.
Referring to fig. 1 and 4, the check balance valve 13 is composed of an upper valve body 51, a diaphragm 50, and a lower valve body 49. Wherein the upper valve body 51 is provided with a cathode water tank interface 43 and an anode water tank interface 52, a damping hole 52a and an annular sealing lip 45 are arranged in the interface 52; the unidirectional balance lower valve body 49 is provided with an anode water tank interface 47, a pressure limiting valve port 48 and a pressure limiting plug 48 a.
The cathode water tank interface 43 of the one-way balance valve upper valve body 51 is connected with the cathode water tank 4, the anode water tank interface 52 is connected with the anode water tank 18, and the anode water tank interface 47 of the lower valve body 49 is connected with the anode water tank 18.
When the ozone generator starts to work, the ozone and the oxygen in the anode water tank 18 are damped by the micropore damping plate 23, pressure P is gradually formed, the pressure P is transmitted to two sides of the diaphragm 50 through the anode water tank interface 52 of the one-way balance valve upper valve body 51 and the anode water tank interface 47 of the lower valve body 49, at this time, the cathode water tank interface 43 is formed in the upper valve body 51, and therefore, the raw water flows from the anode water tank 18 to the cathode water tank 4. The water flow passes through the orifice 52a of the anode tank port 52 to create a pressure drop Δ P. The generation of Δ P creates a pressure difference across the diaphragm 50, and the diaphragm 50 is biased toward the upper valve body 51 by the pressure difference until it presses against the annular sealing lip 45, at which time the water flow paths of the cathode water tank 4 and the anode water tank 18 are cut off. The diaphragm 50 maintains this state due to the maintenance of the pressure P within the anode water tank 18. The ozone generator device of the present invention can now output ozone and oxygen at a pressure P.
When the ozone generator stops working, the pressure P disappears gradually, if the water level of the cathode water tank 4 is higher than that of the anode water tank 18, the diaphragm 50 is biased to the direction of the lower valve body 49 under the action of the water level pressure difference, the cathode water tank 4 is communicated with the anode water tank 18 through the one-way balance valve, and the water levels in the cathode water tank and the anode water tank can be gradually restored to be balanced.
The pressure limiting plug 48a of the one-way balance valve is pressed open when the pressure in the anode water tank 18 is too high, so that the pressure limiting protection effect is achieved.
The electrolytic ozone generating device of the invention can be provided with an on-off type electromagnetic valve besides a one-way balance valve between the cathode water tank 4 and the anode water tank 18, and can also realize the purpose of water balance, and theon-off type electromagnetic valve cuts off the channel of the cathode water tank and the anode water tank when the device is started; when the device stops working, the on-off type electromagnetic valve is communicated with the channels of the cathode water tank and the anode water tank.
The cooling fans 10 and 11 are installed at the lower part of the electrolytic ozone generator 8, and the cooling wind blows upwards through the heat sink 38, the anode water tank 18 and the cathode water tank 4 to play a role of auxiliary heat dissipation.
The ozone generator of the present invention is cold pressed with the following independent membranes prepared by different processes.
The cation exchange membrane 34 used in the present invention is a perfluorosulfonic acid cation exchange membrane (model 117) manufactured by dupont, usa. The treatment process comprises the following steps: the membrane was digested with 10% hydrogen peroxide at 80-90 ℃ for one hour to remove organic impurities. Rinsing with a large amount of secondary distilled water at about 60 deg.C, soaking in 80-90 deg.C 2mol/l sulfuric acid for half an hour to remove a small amount of metal ions, rinsing with a large amount of secondary distilled water at about 60 deg.C to neutral, and storing in secondary distilled water for assembly.
The preparation process of the cathode catalyst membrane 33 is as follows: platinum carbon powder (200 mesh sieve) containing 5-15 wt% of platinum, polytetrafluoroethylene emulsion (suspension) and a proper amount of secondary distilled water are stirred into paste in a water bath at about 80 ℃, and then repeatedly rolled into a film with the thickness of 0.1-0.2mm at the temperature of 30-40 ℃. Wherein the weight of the polytetrafluoroethylene accounts for 5-15% of the weight of the platinum carbon powder. Drying the rolled membrane at 50-60 deg.C, and cutting into required size for assembly. The cathode catalyst membrane prepared by the process has porous conductive property, and hydrogen generated at the contact interface of the catalyst membrane and the cation exchange membrane and water accompanied with proton migration can smoothly pass through the micropores of the cathode catalyst membrane to enter a cathode chamber.
The preparation process of the anode catalyst membrane 35 is as follows: lead dioxide powder (sieved by a 180-mesh sieve), polytetrafluoroethylene emulsion (suspension) and a proper amount of secondary distilled water are stirred into paste at about 80 ℃. Then rolling into 0.2-0.3mm film at 30-40 deg.C. Wherein the polytetrafluoroethylene accounts for 1 to 5 percent of the weight of the lead dioxide powder. The membrane is dried at 50-60 ℃ and then cut into required size for storage, and is used in assembly. The anode catalytic membrane prepared by the process has porous conductivity, and ozone and oxygen generated at the contact interface of the anode catalyst membrane and the cation exchange membrane can smoothly enter the anode chamber through the micropores of the anode catalyst membrane; meanwhile, raw material water can reversely migrate through the micropores of the membrane to enter an anode catalyst membrane/cation exchange membrane reaction interface to participate in an anode reaction. A portion of the feed water migrates with the protons through the cation exchange membrane to the cathode compartment.
The preparation process of the anode porous current collecting sheet 36 is as follows: sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2hkPa) is subjected to degreasing and pretreatment by etching with 5 to 20% by weight of hydrochloric acid, rinsed with secondary distilled water until no chloride ion is present, and dried. Then coating a layer containing platinum,The organic solution of tin and antimony is oxidized in an electric furnace at the temperature of 500-530 ℃ to form a thin layer of conductive oxide containing platinum, tin and antimony on the surface of the organic solution, so that the porous current collecting piece is prevented from being passivated when passing through anode current. The porous current collector prepared by the process has the functions of electric conduction and gas-liquid conduction (namely, gas products can leave the electrode reaction interface through the current collector, and raw material water can enter the electrode reaction interface through the current collector). Wherein the organic solution containing platinum, tin and antimony comprises the following components in percentage by weight:
3-9% of concentrated hydrochloric acid; h2PtCl6.6H2O 1-2％；SnCl4.5H2O 5-10％；SbCl30.5-1.5％；C4H9OH 60-90％。
The preparation process of the cathode porous current collecting sheet 32 is as follows: sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2hkPa) is degreased, etched with 5-20 wt% hydrochloric acid, rinsed with secondary distilled water until no chloride ion is present, dried, stored, and ready for assembly. The porous collectorThe flow sheet has the functions of electric conduction and gas-liquid conduction.
The guide plate 31 is a metal titanium plate, and is machined to form a part with longitudinal and transverse grooves, as shown in fig. 3. The guide plate is respectively assembled in the cathode frame and the anode frame to form a cathode chamber and an anode chamber. The surfaces with longitudinal and transverse grooves are respectively opposite to the cathode and anode porous current collecting plates. The vertical and horizontal grooves of the guide plate 31 canaccommodate raw material water, and the raw material water and the gaseous product are convected and diffused in the grooves. The guide plate has a conductive cooling function.
The anode chamber frame 37 is made of teflon and is fabricated as a separate element, as shown in fig. 3. The frame is provided with an upper air water nozzle and a lower air water nozzle, and is respectively connected with an anode water tank 18 to form a raw material water circulation loop in an anode chamber. The gas (ozone and oxygen) lifting force generated by the anode reaction and the temperature difference of the water temperature of the raw material in the anode chamber higher than the water temperature of the anode water tank are used as power to form automatic circulation of water so as to play a cooling role.
The cathode chamber frame 30 is formed from plexiglass or ABS plastic, as shown in FIG. 3. The frame is provided with an upper air water nozzle and a lower air water nozzle, and is respectively connected with the cathode water tank 4 to form a cathode indoor raw material water circulation loop. The gas (hydrogen) lifting force generated by the cathode reaction and the temperature difference of the water temperature of the raw material in the cathode chamber higher than the water temperature of the cathode water tank are used as power to form automatic circulation of water so as to play a cooling role.
The gasket 29 is made of a silicone rubber material, which ensures sealing between the gas generated in the male and female chambers and the raw material water.
The corrosion-resistant sheet 28 is made of metal titanium material to prevent the diversion clamp plate from being corroded. The diversion clamp plate 27 is made of hard alloy aluminum plate and is connected with an external direct current power supply as a cathode and an anode of the generator.
The ozone generator of the invention is made by the components by adopting a cold pressing assembly method, and the assembly sequence is as follows:
the anode cooling fins 38, the diversion clamp plate 27, the corrosion prevention sheet 28, the sealing gasket 29, the diversion plate 31, the anode chamber frame 37, the sealing gasket 29, the anode porous current collecting sheet 36, the anode catalyst membrane 35, the cation exchange membrane 34, the cathode catalyst membrane 33, the cathode porous current collecting sheet 32, the sealing gasket 29, the diversion plate 31, the cathode chamber frame 30, the sealing gasket 29, the corrosion prevention sheet 28 and the diversion clamp plate 27 are fastened by bolts, nuts, gaskets and insulating gaskets.
The electrolytic ozone generating device has simple preparation process and convenient assembly, and compared with the ozone generating device in the prior art, the electrolytic ozone generating device has the advantage that the cost can be reduced by 30-50%. In addition, the raw material water in the cathode and anode water tanks of the electrolytic ozone generating device can be automatically balanced, and the ozone with the maximum output pressure higher than the atmospheric pressure by 0.1MPa can be output. The device can stably run for a long time, the ozone generating efficiency is high, and the following table shows the comparison of the ozone generating efficiency of the device of the invention and some electrolytic ozone generating devices in the prior art:
cell voltage current density ozone generation efficiency reference
(v) (A/cm2) (%) inventive 3.51.518-20 Prior Art 13.61.016 US4927800 prior art 24.08 JP43390/90 prior art 33.31.013 JP20488/91 prior art 44.07 JP43389/90 prior art 51.013-16 US5203972 example: example 1: preparation of electrolytic ozone generator (8)
a. Preparation of cation exchange membrane (34): a117 type perfluorinated sulfonic acid cation exchange membrane (a product of DuPont company) is soaked and boiled for one hour at 90 ℃ by 10 percent hydrogen peroxide to remove organic impurities in the membrane, the membrane is rinsed by a large amount of 60 ℃ secondary distilled water and then is soaked and boiled in 80 ℃ 2mol/l sulfuric acid for half an hour to remove a small amount of metal ions, and finally the membrane is rinsed to be neutral by a large amount of 60 ℃ secondary distilled water and is stored in the secondary distilled water for use during assembly.
b. Preparation of cathode catalyst membrane (33): platinum carbon powder (200 mesh sieve) containing 6 wt% platinum, polytetrafluoroethylene emulsion (suspension) and appropriate amount of redistilled water are stirred into paste in water bath at about 80 ℃, and then repeatedly rolled into film with thickness of 0.1mm at 35 ℃. Wherein the weight of the polytetrafluoroethylene accounts for 10 percent of the weight of the platinum carbon powder. The rolled film is dried at 60 ℃ and cut to the required size to be used for assembly.
c. The preparation of anode catalyst diaphragm (35) is that β -lead dioxide powder (180 mesh sieve), polytetrafluoroethylene emulsion (suspension) and proper amount of secondary distilled water are stirred into paste at about 80 ℃, then the paste is rolled into 0.2mm diaphragm at 40 ℃, wherein, the polytetrafluoroethylene accounts for 2% of the weight of the lead dioxide powder, and the diaphragm is cut into required size after being dried at 55 ℃ and stored for use when being assembled.
d. Preparation of anode porous current collector sheet (36): sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2hkPa) is subjected to degreasing and etching with 10% hydrochloric acid, and then rinsed with secondary distilled waterAnd drying the product till no chloride ions exist. Then coating organic solution containing platinum, tin and antimony on the surface of the substrate, and oxidizing the substrate in an electric furnace at 520 ℃ to form a thin layer of conductive oxide containing platinum, tin and antimony on the surface of the substrate. Wherein the organic solution containing platinum, tin and antimony comprises the following components in percentage by weight:
5% of concentrated hydrochloric acid; h2PtCl6.6H2O 1％；SnCl4.5H2O 8％；SbCl31.0％；C4H9OH 85％。
e. Preparation of cathode porous current collector (32): sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2Hhpa) is degreased and then etched with 10% hydrochloric acid, rinsed with secondary distilled water until no chloride ions are present, dried, stored, and ready for assembly.
Five elements prepared as described above were cut to 8cm2The square block of the size is matched with other elements, and is arranged in sequence according to an anode radiating fin (38), a flow guide clamping plate (27), an anti-corrosion sheet (28), a sealing gasket (29), a flow guide plate (31), an anode chamber frame (37), a sealing gasket (29), an anode porous current collecting sheet (36), an anode catalyst membrane (35), a cation exchange membrane (34), a cathode catalyst membrane (33), a cathode porous current collecting sheet (32), a sealing gasket (29), a flow guide plate (31), a cathode chamber frame (30), a sealing gasket (29), an anti-corrosion sheet (28) and a flow guide clamping plate (27), wherein the flow guide plate (31) is processed and manufactured by a metal titanium plate with the thickness of 10mm, and 7 grooves with the width of 2.5mm and the depth of 6 mm; the cathode chamber frame (30) is formed by injection molding of organic glass material, and the inside of the frame is 31 multiplied by 9mm3The inner diameter of the upper and lower air-water connecting nozzles is 4 mm; the anode chamber frame (37) is made of polytetrafluoroethylene, and the shape, the size and the inner volume of the anode chamber frame are completely consistent with those of the cathode chamber frame (30); the corrosion-resistant sheets (28) are all made of industrial pure titanium, the thickness is 0.8mm, and the area is 40 multiplied by 40mm2(ii) a The diversion splint (27) is made of hard alloy aluminum material, the thickness is 8mm, and the area isIs 60 x 60mm2(ii) a Then fastening by bolts (40), nuts (25), washers (26, 42) and insulating washers (39) to obtain the electrolytic ozone generator (8). Example 2: electrolytic ozone generatorPreparation of the raw vessel (8)
a. Preparation of cation exchange membrane (34): a117 type perfluorinated sulfonic acid cation exchange membrane (a product of DuPont company) is soaked and boiled for one hour at 80 ℃ by 10 percent hydrogen peroxide to remove organic impurities in the membrane, the membrane is rinsed by a large amount of 60 ℃ secondary distilled water and then is soaked and boiled in 80 ℃ 2mol/l sulfuric acid for half an hour to remove a small amount of metal ions, and finally the membrane is rinsed to be neutral by a large amount of 60 ℃ secondary distilled water and is stored in the secondary distilled water for use during assembly.
b. Preparation of cathode catalyst membrane (33): platinum carbon powder (200 mesh sieve) containing 12 wt% platinum, polytetrafluoroethylene emulsion (suspension) and appropriate amount of redistilled water are stirred into paste in water bath at about 80 deg.C, and then repeatedly rolled into film with thickness of 0.2mm at 40 deg.C. Wherein the weight of the polytetrafluoroethylene accounts for 15 percent of the weight of the platinum carbon powder. The rolled film is dried at 60 ℃ and cut to the required size to be used for assembly.
c. Preparation of anode catalyst membrane (35): lead dioxide powder (sieved by a 180-mesh sieve), polytetrafluoroethylene emulsion (suspension) and a proper amount of secondary distilled water are stirred into paste at about 80 ℃. Then rolled into 0.2mm film pieces at a temperature of 35 ℃. Wherein the polytetrafluoroethylene accounts for 1 percent of the weight of the lead dioxide powder. The membrane is dried at 60 ℃ and then cut into required size for storage, and is used during assembly.
d. Preparation of anode porous current collector sheet (36): sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2Hfpa) was subjected to degreasing and etching with 10% hydrochloric acid, rinsed with secondary distilled water until no chloride ion was present, and dried. Then coating organic solution containing platinum, tin and antimony on the surface of the substrate, and oxidizing the substrate in an electric furnace at 500 ℃ to form a thin layer of conductive oxide containing platinum, tin and antimony on the surface of the substrate. Wherein the organic solution containing platinum, tin and antimony comprises the following components in percentage by weight:
9% of concentrated hydrochloric acid; h2PtCl6.6H2O 2％；SnCl4.5H2O 10％；SbCl31.0％；C4H9OH 78％。
e. Preparation of cathode porous current collector (32): sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2Hhpa) is degreased and then etchedwith 10% hydrochloric acid, rinsed with secondary distilled water until no chloride ions are present, dried, stored, and ready for assembly.
The element thus obtained was assembled with other elements in the same manner as in example 1 to form an electrolytic ozone generator (8) of the present invention. Example 3: preparation of electrolytic ozone generator (8)
a. Preparation of cation exchange membrane (34): a117 type perfluorinated sulfonic acid cation exchange membrane (a product of DuPont company) is soaked and boiled for one hour at 85 ℃ by 10 percent hydrogen peroxide to remove organic impurities in the membrane, the membrane is rinsed by a large amount of 60 ℃ secondary distilled water and then is soaked and boiled in 80 ℃ 2mol/l sulfuric acid for half an hour to remove a small amount of metal ions, and finally the membrane is rinsed to be neutral by a large amount of 60 ℃ secondary distilled water and is stored in the secondary distilled water for use during assembly.
b. Preparation of cathode catalyst membrane (33): platinum carbon powder (200 mesh sieve) containing 10 wt% platinum, polytetrafluoroethylene emulsion (suspension) and appropriate amount of redistilled water are stirred into paste in water bath at about 80 deg.C, and then repeatedly rolled into film with thickness of 0.1mm at 30 deg.C. Wherein the weight of the polytetrafluoroethylene accounts for 5 percent of the weight of the platinum carbon powder. The rolled film is dried at 60 ℃ and cut to the required size to be used for assembly.
c. The preparation of anode catalyst diaphragm (35) is that β -lead dioxide powder (180 mesh sieve), polytetrafluoroethylene emulsion (suspension) and proper amount of secondary distilled water are stirred into paste at about 80 ℃, then rolled into 0.3mm diaphragm at 30 ℃, wherein, the polytetrafluoroethylene accounts for 1.5% of the weight of the lead dioxide powder,and the diaphragm is cut into required size after being dried at 60 ℃ and stored for use in assembly.
d. Preparation of anode porous current collector sheet (36): sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2Hfpa) was subjected to degreasing and etching with 10% hydrochloric acid, rinsed with secondary distilled water until no chloride ion was present, and dried. Then coating organic solution containing platinum, tin and antimony on the surface of the substrate,oxidizing in an electric furnace at 520 deg.C to form a thin layer containing Pt, Sn and SbA conductive oxide. Wherein the organic solution containing platinum, tin and antimony comprises the following components in percentage by weight:
3% of concentrated hydrochloric acid; h2PtCl6.6H2O 1.5％；SnCl4.5H2O 5％；SbCl30.5％；C4H9OH90％。
e. Preparation of cathode porous current collector (32): sintering type porous titanium sheet (maximum aperture is 26 μ M, air permeability is 119M)3/m2Hhpa) is degreased and then etched with 10% hydrochloric acid, rinsed with secondary distilled water until no chloride ions are present, dried, stored, and ready for assembly.
The element thus obtained was assembled with other elements in the same manner as in example 1 to form an electrolytic ozone generator (8) of the present invention. Example 4: assembly and application of the electrolytic ozone generator of the invention
The electrolytic ozone generator (8) prepared in example 1 and the following elements were used:
1500 ml of cathode water tank (4), 1200 ml of anode water tank (18), one-way balance valve (13), cooling fans (10, 11), anode circulating water pipe (7), cathode circulating water pipe (6), water level detectors (19, 20, 21, 22) and isolating pipe (17) are installed according to the method known in the art to form the electrolytic ozone generating device.
The electrolytic ozone generator of this embodiment is operated at 1.5A/cm2When the current density of the generator is operated, the voltage of the generator groove is 3.5 +/-0.1V, when the ambient temperature is about 25 ℃, the generator groove is continuously operated for 24 hours, the water temperature of raw materials in the cathode water tank and the anode water tank can be maintained at about 30 ℃, and the ozone generation efficiency is 18 percent.
Ozone with pressure higher than atmospheric pressure by 0.08Mpa can be output from the anode water tank.
Claims (25)
1. An electrolytic ozone generating device, comprising an electrolytic ozone generator (8), an anode water tank (18) connected with an anode chamber of the ozone generator (8) through an anode circulating water pipe (7), and a cathode water tank (4) connected with a cathode chamber of the ozone generator (8) through a cathode circulating water pipe (6), characterized in that:
the electrolytic ozone generator (8) comprises an independent cation exchange membrane (34), an independent anode catalyst membrane (35) and an independent cathode catalyst membrane (33) which are respectively abutted against two sides of the cation exchange membrane (34), an anode porous current collecting sheet (36) on the other side of the anode catalyst membrane (35), and a cathode porous current collecting sheet (32) on the other side of the cathode catalyst membrane (33).
2. The electrolytic ozone generator of claim 1, wherein: the cathode catalyst membrane (33) in the electrolytic ozone generator (8) contains platinum carbon powder and polytetrafluoroethylene, wherein the platinum carbon powder contains 5-15 percent (by weight) of platinum, and the polytetrafluoroethylene accounts for 5-15 percent (by weight) of the platinum carbon powder.
3. The electrolytic ozone generator of claim 2, wherein: the particle size of the platinum carbon powder in the cathode catalyst membrane (33) is less than 200 meshes.
4. The electrolytic ozone generator of claim 2, characterized in that the cathode catalyst membrane (33) has a thickness of 0.1-0.2 mm.
5. The electrolytic ozone generator of claim 1, wherein: the anode catalyst membrane (35) in the electrolytic ozone generator (8) contains lead dioxide and polytetrafluoroethylene.
6. The electrolytic ozone generator of claim 5, characterized in that the weight of the polytetrafluoroethylene in the anode catalyst membrane (35) is 1-5% of the weight of the lead dioxide.
7. The electrolytic ozone generator of claim 5 or 6, characterized in that: the particle size of the lead dioxide used in the anode catalyst membrane (35) is less than 180 meshes.
8. The electrolytic ozone generator as claimed in claim 5 or 6, wherein the lead dioxide used in the anode catalyst membrane (35) is β -lead dioxide.
9. The electrolytic ozone generator as claimed in claim 7, wherein the lead dioxide used in the anode catalyst membrane (35) is β -leaddioxide.
10. The electrolytic ozone generator of claim 5 or 6, characterized in that the anode catalyst membrane (35) has a thickness of 0.2-0.3 mm.
11. The electrolytic ozone generator of claim 8, characterized in that the anode catalyst membrane (35) has a thickness of 0.2-0.3 mm.
12. The electrolytic ozone generator of claim 9, characterized in that the anode catalyst membrane (35) has a thickness of 0.2-0.3 mm.
13. The electrolytic ozone generator of claim 1, wherein: the anode porous current collecting sheet (36) in the electrolytic ozone generator (8) is a sintered porous titanium sheet coated with a layer of conductive oxide containing platinum, tin and antimony on the surface.
14. The electrolytic ozone generator of claim 1, characterized in that the electrolytic ozone generator (8) further comprises a baffle made of titanium metal and provided with grooves on one side.
15. The electrolytic ozone generator of claim 1, wherein:
the upper end of the anode water tank (18) is provided with an air collecting surface (18a), the air collecting surface is provided with a slender air guide pipe (18b), the top of the air guide pipe (18b) is provided with an ozone and oxygen outlet (24), a micropore damping plate (23) is arranged in the ozone and oxygen outlet (24), an isolation pipe (17) is arranged in the anode water tank (18), and the anode water tank (18) is connected with an anode chamber frame (37) through an anode circulating pipe (7) to form a water circulation loop;
16. the electrolytic ozone generator of claim 1, wherein: the cathode water tank (4) is higher than the anode water tank (18), the top of the cathode water tank is provided with a water filling port (2), a water filling port cover (1) and a hydrogen outlet (3), water level detectors (19, 20, 21 and 22) are arranged in the cathode water tank (4), and the cathode water tank (4) is connected with a cathode chamber frame (30) through a cathode circulating pipe (6) to form a water circulating loop.
17. The electrolytic ozone generator of claim 1, wherein:
a one-way balance valve (13) is arranged between the cathode water tank (4) and the anode water tank (18), and the one-way balance valve (13) consists of an upper valve body (51), a diaphragm (50) and a lower valve body (49); wherein the upper valve body (51) is provided with a cathode water tank interface (43), an anode water tank interface (52), a damping hole (52a) and an annular sealing lip (45) are arranged in the anode water tank interface (52); the unidirectional balance lower valve body (49) is provided with an anode water tank interface (47), a pressure limiting valve port (48) and a pressure limiting plug (48 a).
18. The electrolytic ozone generator of claim 1, wherein: an on-off type electromagnetic valve is arranged between the cathode water tank (4) and the anode water tank (18).
19. A method of making an electrolytic ozone generator (8) as claimed in claim 1, comprising:
a. stirring platinum carbon powder containing 5-15 wt% of platinum and polytetrafluoroethylene emulsion with a proper amount of secondary distilled water in a water bath at about 80 ℃ to form paste, repeatedly rolling the paste into a membrane with the thickness of 0.1-0.2mm at the temperature of 30-40 ℃, wherein the weight of polytetrafluoroethylene accounts for 5-15% of the weight of the platinum carbon powder, drying the rolled membrane at 50-60 ℃ and cutting the membrane into required size to obtain a cathode catalyst membrane (33);
b. lead dioxide powder, polytetrafluoroethylene emulsion and a proper amount of secondary distilled water are stirred into paste in a water bath at the temperature of about 80 ℃, then the paste is repeatedly rolled into a membrane with the thickness of 0.2 to 0.3mm at the temperature of 30 to 40 ℃, wherein the weight of the polytetrafluoroethylene accounts for 1 to 5 percent of the weight of the lead dioxide, and the rolled membrane is dried and cut into required size at the temperature of 50 to 60 ℃ to prepare an anode catalyst membrane (35);
c. degreasing the sintered porous titanium sheet, etching the sintered porous titanium sheet by 5-20 wt% hydrochloric acid, rinsing the sintered porous titanium sheet by secondary distilled water until no chloride ions exist, drying the sintered porous titanium sheet, coating an organic solution containing platinum, tin and antimony on the surface of the sintered porous titanium sheet, and oxidizing the organic solution in an electric furnace at the temperature of 500-;
d. the sintered porous titanium sheet is degreased and etched by 5-20 wt% hydrochloric acid, rinsed by secondary distilled water until no chloride ion exists, and dried to obtain the cathode porous current collecting sheet (32).
20. The method for preparing an ozone generator as claimed in claim 19, wherein the particle size of the platinum carbon powder used in preparing the cathode catalyst membrane (33) is less than 200 mesh.
21. The method of claim 19 wherein the lead dioxide used in preparing said anode catalyst membrane (35) has a particle size of less than 180 mesh.
22. The method for the preparation of an ozone generator as claimed in claim 19 or 21, characterized in that the lead dioxide used in the preparation of the anode catalyst membrane (35) is β -lead dioxide.
23. The method of claim 19 wherein said porous anode assembly is preparedThe weight percentage of the organic solution containing platinum, tin and antimony used in the flow sheet (36) is as follows: 3-9% of concentrated hydrochloric acid; h2PtCl6.6H2O 1-2％；SnCl4.5H2O 5-10％；SbCl30.5-1.5％；C4H9OH 60-90％。
24. The method of claim 19, wherein the sintered porous titanium sheet used in the preparation of said anode porous current collector sheet (36) has a maximum pore size of 26 μ M and an air permeability of 119M3/m2.h.kPa。
25. The method of claim 19, wherein the sintered porous titanium sheet used in the preparation of said cathode porous current collector sheet (32) has a maximum pore size of 26 μ M and an air permeability of 119M3/m2.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 | 1997-03-07 | ||
| CN97209412.1 | 1997-11-19 | ||
| CN97122126A CN1128759C (en) | 1997-03-07 | 1997-11-19 | Electrolytic ozone generator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1195643A true CN1195643A (en) | 1998-10-14 |
| CN1128759C 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) |
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| WO2007009313A1 (en) * | 2005-07-20 | 2007-01-25 | Yantai United Ozonetec Corporation | Thin membrane type one-way valves used in an ozone/ozone-water return line |
| WO2007009311A1 (en) * | 2005-07-20 | 2007-01-25 | Yantai United Ozonetec Corporation | An anode structure for electrolysis-type ozone generator |
| CN100364882C (en) * | 2004-02-25 | 2008-01-30 | 东芝三菱电机产业系统株式会社 | Ozone generator and ozone generating method |
| WO2009146653A1 (en) * | 2008-06-04 | 2009-12-10 | Hsu Mingyung | An anode with fastening spring pressure plate for electrolytic ozone generator |
| 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 |
| WO2010091569A1 (en) * | 2009-02-11 | 2010-08-19 | Hsu Mingyung | Electrolytic ozone generator with a membrane electrode |
| CN102560525A (en) * | 2011-04-12 | 2012-07-11 | 周美荣 | Electrolytic ozone generating device for recycling cathode water |
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| JP2001181876A (en) * | 1999-12-22 | 2001-07-03 | Teeiku Wan Sogo Jimusho:Kk | Ozone generating electrolytic cell and its manufacturing method |
| HUP0501204A2 (en) | 2005-12-23 | 2007-07-30 | Thales Rt | Ozone generating electrolytic cell |
| CN201746592U (en) * | 2010-06-22 | 2011-02-16 | 刘迅 | Water electrolysis device |
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| 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 WO PCT/CN1998/000030 patent/WO1998040535A1/en active Application Filing
- 1998-03-04 AU AU62884/98A patent/AU6288498A/en not_active Abandoned
- 1998-03-09 JP JP10057071A patent/JP3025473B2/en not_active Expired - Fee Related
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| CN100364882C (en) * | 2004-02-25 | 2008-01-30 | 东芝三菱电机产业系统株式会社 | Ozone generator and ozone generating method |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO1998040535A8 (en) | 1999-06-10 |
| CN1128759C (en) | 2003-11-26 |
| AU6288498A (en) | 1998-09-29 |
| TW401373B (en) | 2000-08-11 |
| JP3025473B2 (en) | 2000-03-27 |
| WO1998040535A1 (en) | 1998-09-17 |
| JPH111789A (en) | 1999-01-06 |
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