TW401373B - Electrolytic ozone generating apparatus - Google Patents

Abstract

The present invention relates to an electrolytic ozone generating apparatus, which mainly comprises an ozone generator, an anode water tank and a cathode water tank, an one-way balanced valve or an on/off type magnetic valve, wherein the ozone generator comprises the following independent elements: a cation exchange membrane, a cathode catalyst membrane, a cathode porous current-collecting plate, an anode catalyst membrane, an anode porous current-collecting plate, flow guiding plates and anticorrosive plates, etc.. The apparatus of the present invention has the advantages of low cost for preparation, feasibility for mass industrialization production, stable operation under pressure and high efficiency of ozone generation.

Description

401373 V. Description of the invention (23) Supplement f

Figure 4 shows the structure of the one-way balance valve 13. The main components are compared with the table 1 water inlet cover 2 water inlet 3 hydrogen outlet 4 cathode water tank 5 reaction medium 6 cathode circulating water pipe 7 anode circulating water pipe 8 ozone generator 9 anode circulating water pipe 10-11 cooling Fan 1 2 Circulating water pipe 13 One-way balancing valve 14 Cathode circulating water pipe 15 Nut 16 Spare water outlet. 17 Isolating pipe 18 Anode water tank 18a Air collecting surface 18b Air duct 19 Water level detecting sealing tube 2 0 Permanent magnet ------- ------------— Order I: -------- line ", (Please read the precautions on the back before filling this page) This paper size applies Yin National Standard ( CNS) A4 specification (210 X 297 mm) -26- 401373 V. Description of the invention (i) Field of the invention The present invention relates to an electrolytic ozone generating device, which is a field of electrochemical technology and ozone application technology. BACKGROUND OF THE INVENTION The advantages of sterilization by ozone method are receiving increasing attention. Currently, high frequency and high voltage corona discharge methods are used to generate ozone ', and research and development of electrochemical methods to generate high concentrations of ozone have attracted widespread attention. The basic principle of electrochemical production of ozone is well known: ozone is produced using deionized water as the raw material. When a DC power supply is applied, the electrochemical reaction formula of the cathode and anode is: Cathodic hydrogen evolution reaction formula: 2H '+ 2e_— Hd ( 1) Cathodic oxygen depolarization reaction formula: 1/2 02 + 21 ^ + 2 6- — Η 2 0 (2) Anode main reaction formula: H2〇—l / 3 〇3 pieces + 2 e- + 2 Η ' (3) The secondary reaction formula of the printed poly anode of the consumer cooperative of the Central Government Bureau of the Ministry of Economic Affairs: Η 2 〇 — 1/2 0 2 + 2 e · + 2 Migration to the cathode through a cation exchange membrane as a water-solvated proton. According to the above electrochemical reaction principle, it can be known that the core part constituting a most basic electrolytic ozone generating device is an electrolytic cell. The electrolytic cell must have -4-(Please read the precautions on the back to complete this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 461375 V. Description of the invention (24 2 1 Float 2 2 2 4 2 5 2 6 2 7 2 8 2 9 3 0 3 1 3 2 3 3 3 4 3 7 3 8 3 9 4 0 4 1 4 2 4 3 4 4 air reed tube micro-hole blocking plate air outlet nut washer Spoiler anticorrosive sheet gasket cathode to frame deflector cathode porous current collector cathode catalyst diaphragm cation exchange membrane anode catalyst diaphragm anode porous current collector anode chamber frame anode heat sink insulation washer bolt drain screw washer cathode water tank interface Anode water tank interface

(Please read the precautions on the back before filling this page) This paper size is applicable to the national standard (CNS) A4 (210 X 297 mm) of the paper size. 5. Description of the invention (2) There are anode, cathode, electrolyte and raw water. The Chinese mainland patent application CN 8 6 1 0 8 7 9 2A describes a solid polymer electrolyte structure including a membrane, a plurality of conductive particles, and a conductive water-permeable substrate member, wherein the conductive particles and the conductive water-permeable substrate (as (Collector plates) are in physical or electrical contact with each other and embedded in the diaphragm 'or combined with the diaphragm. Among these diaphragms, fluorocarbon materials are generally preferred. In order for the conductive and water-permeable substrate to be embedded in the fluorocarbon film, it is preferable that the fluorocarbon is in a thermoplastic state. The conductive water-permeable substrate includes carbon cloth, carbon paper, metal mesh, metal felt, and porous metal sheet. Carbon cloth is preferred. Electrocatalytically active particles can be added to the surface of the membrane using a variety of techniques, including pressurization, mixing with solvents, and blending with powder of the membrane or other polymer. One of the specific methods is to first prepare a thin film composed of electro-catalytically active particles by using a binder such as polytetrafluoroethylene or a membrane in a thermoplastic state, and bonding the material / catalyst composition to It is in the state of porous film. The film can then be laminated between the collector and the diaphragm. The film can be prepared from a thermoplastic ion exchange membrane mix containing 10% (by weight) carbon particles with a particle size of 30 microns and 5% platinum on it. The mixture can be hot-pressed at a temperature of 3 10 ° C and a pressure of 1 ton / inch 2 (155 atmospheres) for 1.25 minutes to prepare a film having a thickness of less than 0.5 mm. The film can be laminated between a carbon cloth collector plate and a diaphragm by a conventional hot pressing technique. Thereafter, the carbon cloth can be embedded in the film sheet 'by the method: 1 2 0. (: Preheat both diaphragm / carbon cloth for 30 seconds under the temperature and atmospheric pressure

In- I t ^ i— n I ^ * ^-4 (Please read the notes on the back f to write this page) This paper size is applicable to China National Standard (CNS) A4 (2 丨 0X297mm) -5- A7 A7

-------------------- Order ---- a ----- line ·--* (谙 Please read the notes on the back before filling this page > _B7 V. Description of the invention (25) 45 Ring-shaped sealing lip 4 6 Anode water tank connection 4 7 Anode water tank connection 4 8 Pressure limiting valve port 4 8a Pressure limiting plug 4 9 Lower check valve body 5 0 Diaphragm 51 Unidirectional Body valve on balance valve 52 Anode water tank connection 52a Obstructed hole The paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -28-V. Description of the invention A7 B7, then at the same temperature and 1- 2 ton / inch 5 5 Consumers ’cooperation with the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China Du printed 3 10 atmospheres of pressure) for 2 2 5 seconds, and then at 2-3 tons / inches 2 (3 1 0 to 4 6 5 atmospheres) Heat under pressure for about 60 seconds. JP, Hei 4-8 8 1 8 2 proposed the use of a perfluorosulfonic acid cation exchange membrane (type 1 17) manufactured by DuPont of the United States, and the suspension (suspension) of commercial ion powder (ion exchange resin powder) was coated on the surface. ) Liquid, apply a pressure of 5kg / cm2, and heat at 180-200 ° C for 30 minutes to form a porous ion exchange resin layer. The surface thickness of this ion exchange resin layer is 100 microns. On the formed ion exchange resin layer, a porous layer was closely arranged with lead oxide to serve as an anode electrode. A nail metal film was formed on the surface of the ion exchange membrane opposite to this porous layer by using electroless plating as a cathode. The specific method for preparing a lead oxide anode is to first apply a coating solution containing 75% titanium and 25% platinum on a plate-shaped substrate made of sintered tantalum powder, and form a platinum / An intermediate layer made of molybdenum. An 800 g / l aqueous solution of nitric acid was used as the electrolyte. After adding a small amount of nitric acid, 'heated to 70 ° C, immersed the aforementioned substrate and titanium plate in this electrolyte' with a current density of 1 OA / dm2 in advance. Pre-electrolysis was performed, and then a lead dioxide layer was electrodeposited on the surface of the aforementioned substrate with a current density of 4 A / dm 2 as the anode. The thickness of the surface layer of the lead dioxide layer is 100, and the electrodeposited lead dioxide layer anode is pressed against the ion exchange resin layer side of the ion exchange membrane at a pressure of 1.0 kg / cm2 to form an electrode structure 1? ' Ping 2-43389 and] ?, Ping 2-4339〇 The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) n In Hi---I----I-I · -Η5 "- 1 In K-I. I —II DING Λ """, " (Please read the notes on the back «% write this page first) -6- Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 5. Description of the invention Q) A method for manufacturing an ion exchange resin film and a lead dioxide electrode connecting body is proposed. In this method, an aqueous solution containing a wrong ion is disposed on one side of a cation or anion exchange resin film, and an aqueous solution of hypochlorous acid (or an aqueous solution of bromine) is disposed on the other side, so that lead dioxide is precipitated on one surface of the ion exchange resin film. The coating serves as an anode catalyst for the production of ozone by electrolyzing water. U S 4 9 2 7 8 0 0 introduces an electrode catalyst containing a lead dioxide electrolytic deposition layer and a method for preparing the electrode catalyst. Particles containing / 5-lead dioxide powder are dispersed in a catalyst deposition layer. These particles contain / 3-lead dioxide powder and an optional electrolytic co-catalyst. The electrolytic co-catalyst is one of PTEE (polytetrafluoroethylene), agar, and perfluoro ion exchange resin. This electrode catalyst is useful in the production of ozone by electrolyzing water and the production of peroxides by electrolytic water solutions. The common feature of the above patent applications is that the electrolyte is a solid polymer electrolyte (SPE), usually a perfluorosulfonic acid cation exchange membrane. The cation exchange membrane in the electrolytic cell serves as both the electrolyte and the cathode compartment and the cation. Isolation film. Cathode materials (catalysts) are usually platinum group metals, gold, silver, nickel, ruthenium or mixtures thereof. Anode materials (catalysts) are usually lead-based metals, gold or mixtures thereof, and glassy carbon, dioxide. The above-mentioned method for preparing an electrolytic ozone generator using a solid polymer electrolyte involves the following three technologies: First, the electrode composite membrane is prepared by a hot pressing technique. This technique procedure is complicated, the conditions are severe, and high pressure and pressure are required. The temperature increases the manufacturing cost. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 2 mm) (Please read the precautions on the back #, fill out this I). Order

5. Description of the invention (5). And if the membrane formed by this process cannot be assembled into the whole generator in time, the moisture content of the membrane will change accordingly due to changes in humidity at room temperature and storage space, which will cause deformation of the electrode / membrane assembly. The second is through penetration chemical plating (ie, electroless plating). In this way, an electrocatalyst is deposited on one or both sides of the ion exchange membrane. The concentration of metal ions, oxides or reducing agents used in this method is electroless plating. Changes occur during the process, and it is difficult to protect the uniformity of the membrane / electrode assembly prepared each time. The concentration, temperature, and ρ 各种 of the various components must be strictly maintained, otherwise it is difficult to ensure the quality of the prepared catalyst. Third, the preparation of anode catalyst (such as when using lead dioxide) uses porous titanium as the substrate, and then deposits a layer of anode electrode on this substrate; 0-lead dioxide layer, this plating solution needs to ensure certain lead ions and other additives Concentration (including various components such as / 5-lead dioxide particles, PTFE, agar, perfluoro ion exchange resin, etc. in the above-mentioned dispersion plating method). In this technique, the crystal form of lead dioxide in the coating is also changed when ρ Η 値 is changed. Changes follow. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Γ · # — (Please read the notes on the back to write this page) Therefore, the current technology involves catalysts / ions in electrolytic ozone generators using solid polymer electrolytes. There are disadvantages and deficiencies in the preparation method of the exchange membrane electrode, that is, the preparation process is complicated and the production cost is high. It is not easy to produce on an industrial scale. In addition, the electrochemical reaction (see reaction formulas (3) and (4)) generated in the electrolytic ozone generating device must consume raw water when generating ozone and oxygen; the electrochemical reaction [see reaction formulas (1) and ( 2)] protons are consumed. The protons are produced by the anode reaction and are cationized. The size of this paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm). -8-Α7 Β7 V. Description of the invention) Exchange membrane Migrate to the cathode / cation exchange membrane interface. Proton migration always occurs in the form of water solvation, so as the electrochemical reaction progresses, the amount of raw material water in the field of the electrode decreases and the amount of raw material water in the cathode room gradually increases. The interface generates heat. Without heat dissipation measures, the efficiency of ozone generation will be reduced. OBJECTS OF THE INVENTION The purpose of the present invention is to overcome the disadvantages of the complicated electrode preparation technology in the prior art described above, and to provide an electrolytic ozone generator. The device has a solid polymer electrolyte membrane composite electrode member composed of discrete membranes. The electrode manufacturing technique is simple, the production cost is low, and it is easy to produce on an industrial scale. At the same time, the "automatic balance of raw material water in the anode and anode chambers of the electrolytic ozone generator of the present invention" can output ozone with a pressure higher than atmospheric pressure, and has high ozone production efficiency. Another object of the present invention is to provide a method for preparing an electrolytic ozone generating circuit in the above-mentioned electrolytic ozone generating device. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -------- Γ · Ben --- (Please read the precautions on the back-write this page on fir soil) Invention 槪 The electrolytic ozone generation of the present invention is required The device includes an electrolytic ozone generator, an anode water tank connected to the anode chamber of the ozone generator through an anode circulating water pipe, and a cathode water tank connected to the cathode chamber of the ozone generator through a cathode circulating water pipe. According to the electrolytic ozone generating device of the present invention, the electrolytic ozone generator includes independent cation exchange membranes, which are respectively close to the cation. The paper is a common Chinese national standard (CNS) A4 specification (210X297 mm) -9- 401373 A7 ________B7_ 5. Description of the invention (7) Independent anode catalyst membrane and independent cathode catalyst membrane on both sides of the exchange membrane, anode porous current collector on the other side of the anode catalyst membrane, and cathode catalyst membrane A cathode porous current collector sheet on the other side of the sheet. The cation exchange membrane is a perfluorosulfonic acid cation exchange resin commonly used in the prior art, and the anode catalyst membrane contains 0.2 to 0.3 mm of polytetrafluoroethylene and lead dioxide. Membrane, said cathode catalyst membrane is a membrane containing polytetrafluoroethylene and rhenium carbon powder with a thickness of 0.1-0.2 mm, said anode porous current collector sheet is coated with a layer containing sodium ' A sintered porous titanium sheet with conductive oxide of antimony, and the cathode porous current collector sheet is a sintered porous titanium sheet. In the electrolytic ozone generating device of the present invention, the position of the cathode water tank is higher than that of the anode water tank, and a one-way balancing valve (or an on-off type solenoid valve) is connected between the cathode water tank and the anode water tank to realize automatic balance of raw water and make This device can output ozone with pressure. The raw water in the anode water tank and the cathode water tank is not only the raw material for generating ozone, but also the circulating coolant of the anode and cathode. The preparation method of the ozone generator in the electrolytic ozone generating device of the present invention includes: printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs a. Platinum carbon powder and polytetrafluoroethylene emulsion containing 5-15% by weight of platinum ( Suspension) and an appropriate amount of twice-distilled water in 8 Ot: left and right water bath to stir into a paste ', and then repeatedly rolled at a temperature of 30-40 ° C into a 0.1-0.2mm thick film, where poly The weight of tetrafluoroethylene accounts for 5-15% of the weight of platinum carbon powder. The rolled membrane is dried at 50-60 ° C and cut to the required size to obtain a cathode catalyst membrane (3 3 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -10- A7 B7 V. Description of the invention (8) b _Put lead dioxide powder and polytetrafluoroethylene emulsion with an appropriate amount of secondary distilled water Stir in a water bath at about 80 ° C to form a paste, and then repeatedly roll it at a temperature of 30 to 40 ° C to a thickness of 0.2-0.3 mm, in which the weight of polytetrafluoroethylene accounts for lead dioxide. 1 to 5% by weight, the rolled membrane is dried at 50 to 6 Ot and cut to a desired size to obtain an anode catalyst Sheet (35); c. The sintered porous titanium sheet is degreased and pre-treated with 50 to 20% by weight of hydrochloric acid, rinsed with secondary distilled water to be free of chloride ions, dried, and then on the surface An organic solution containing lead, thorium and antimony was applied and oxidized in an electric furnace at 500-530 ° C to form a thin layer of a conductive oxide containing platinum, thorium and antimony on the surface to obtain a porous anode current collector. Sheet (3 6) d. The sintered porous titanium sheet is degreased and pre-treated with 5-20% by weight of hydrochloric acid, rinsed with secondary distilled water to be free of chloride ions, and dried to obtain a cathode porous aggregate. Streaming film (3 2). The ozone generator of the present invention is assembled by combining the above independent components with other necessary components well known in the art. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 1. Mj-I-. ^ ϋ i--I n. jn -I • 5, -e-I-(Please read the notes on the back! ^ Write this page) Detailed description of the invention The following is an explanation of the electrolytic ozone generator of the present invention with reference to the drawings. Further detailed description: The electrolytic ozone generating device of the present invention includes an electrolytic odor The generator 8, the anode water tank 18 connected to the anode chamber of the ozone generator 8 through the circulating water pipe 7, and the anode water tank 18 connected to the cathode generator of the ozone generator 8 through the circulating water pipe 6. This paper only applies to Chinese National Standard (CNS) A4 specifications ( 210X297 mm) " ~ " -11-402373 A7 _____B7_ V. Cathode water tank 4 of the invention description (9), one-way balance valve 13, cooling fan 10, 1 1, water level detector 1 9, 2 0, 2 1, 2 2 and isolation tube 1 7. The electrolytic ozone generator 8 includes a cation exchange membrane 34, an anode catalyst membrane 35, an anode porous current collector sheet 36, an anode chamber frame 37, an anode heat sink 3 8, a cathode catalyst membrane 3 3, and a cathode porous Current collecting piece 32, cathode chamber frame 30, deflector 31, anti-corrosion sheet 28 'deflector 27' seal 29 and bolt 40, nut 25 'washer 2 6' 4 2, insulating washer 3 9, drainage screw 4 1 . In the electrolytic ozone generating device of the present invention, the anode water tank 18 has a gas collecting surface 18 a at the upper end, so that the anode gas can be discharged quickly without retention. There is an elongated air guide tube 1 8 b on the gas collecting surface, ozone and oxygen outlets 2 4 on the top of the air guide tube, and a microporous damping plate 2 3 in the air outlet 2 4. The anode water tank is provided with an isolation tube. Printed by a consumer cooperative (please read the note on the back * 45 to write this page) 1 7. It is composed of quartz tube or titanium tube. The anode gas (ozone 'oxygen) and the circulating water produced by the anode reaction are introduced into the anode water tank through this tube. The isolation tube 17 is arranged to reduce the contact and dissolution of ozone and the raw material water in the anode water tank. Ozone and oxygen quickly enter the air duct 18 b through the gas collecting surface 18 a, and the gas / water separation is realized at the upper end of the air duct. The separated ozone and oxygen pass through the microporous damping plate 2 3 and are led out by the ozone and oxygen outlets 2 4. The position of the cathode water tank 4 is higher than that of the anode water tank 18, and the top is provided with a water inlet 2 ', a water inlet cover 1 and a hydrogen outlet 3. The cathode water tank 4 is provided with a water level detector 19 '2 0, 2 1, 2 2'. The water level detector is composed of a reed tube 22, a float 21, and a permanent magnet 20 0 'water level detection sealed tube 19. When the water level in the cathode water tank is too high or too low, a signal is output to stop the generator. This paper size is applicable to China National Standard (C1SS) A4 (210X297 mm) -12- Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 __B7 V. Description of the invention (10) Cathode circulating water pipe 6 The cathode water tank 4 and the cathode The chamber frame 30 is connected to form a water circulation circuit, and the heat generated during the cathode reaction is taken out in time by the water circulation. The anode circulating water pipe 7 connects the anode water tank 18 and the anode chamber frame 37 to form a water circulating circuit ', and the heat generated during the anode reaction is taken out in time by water circulation. According to the electrochemical reaction principle of the electrolytic ozone generator, the production of ozone and oxygen in the anode reaction formulas 3 and 4 requires the consumption of raw water. The protons produced by this reaction migrate to the cathode through the cation exchange membrane in a water-solvated form. When continuing, the raw water in the anode water tank is continuously consumed, while the raw water in the cathode water tank is continuously increasing. The raw material water in the cathode water tank cannot be returned to the anode water tank through the cation exchange membrane in the reverse direction, and the raw water in the anode water tank is completely depleted. In order to solve the above problem, the present invention provides a one-way balancing valve between the cathode water tank and the anode water tank. Referring to Fig. 1 'to Fig. 4, the one-way balancing valve 13 is composed of an upper valve body 51 and a diaphragm 50' and a lower valve body 49. The upper valve body 51 is provided with a cathode water tank interface 4 3, the anode water tank interface 5 2, the interface 5 2 has a damping hole 5 2 a, and a ring-shaped sealing lip 4 5; the unidirectional balanced lower valve body 4 9 is provided with an anode water tank. Connection 47, pressure limiting valve port 48, pressure limiting plug 48a. The cathode water tank interface 43 of the valve body 51 on the one-way balancing valve is connected to the cathode water tank 4, the anode water tank interface 5 2 is connected to the anode water tank 18, and the lower valve body 4 9 of the anode water tank interface 4 7 and the anode water tank 1 8 The size of this paper is applicable to China National Standard (CNS) A4 (210X297 mm) ^ 1---I 'I --- 1--^^ 1 I * ^ vm 1-1 ^ 1-ί I τ » .-,-, (Please read the precautions on the back before writing this page 4) -13- Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 401373 A7 __ B7 V. Description of the invention (n) Start at the ozone generator During operation, the ozone and oxygen in the anode water tank 18 due to the damping of the micro-orifice damping plate 23 gradually develop a pressure P, which passes through the anode water tank interface 5 2 and the lower valve body of the upper body 51 of the one-way balance valve. 4 9 The anode water tank interface 4 7 is transmitted to both sides of the diaphragm 50. At this time, because there is also the cathode water tank interface 4 3 in the upper valve body 51, the raw material water flows from the anode water tank 18 to the cathode water tank 4. . Water flows through the damping hole 5 2 a of the anode water tank interface 5 2 to generate a pressure drop ΔP. The generation of ΔP causes a pressure difference between the two sides of the diaphragm 50. Under this pressure difference, the diaphragm 50 is biased upwardly toward the valve body 51 until it presses on the annular sealing lip 4 5. At this time, the cathode water tank is cut off. 4 and 8 water flow channels with anode water tank. The diaphragm 50 is maintained in this state by the pressure P in the anode water tank 18 being maintained. At this time, the ozone generator device of the present invention can output ozone and oxygen at a pressure P. When the ozone generation efficiency stops working, the pressure P gradually disappears. If the water level of the cathode water tank 4 is higher than the water level of the anode water tank 18, the diaphragm 50 will be biased downward to the valve body 49 by the water level pressure difference, and the cathode water tank 4 and The positive water tanks 18 and 18 are connected again through a one-way balancing valve. The water levels in the negative and positive water tanks will gradually return to equilibrium. The pressure limiting plug 4 8a of the one-way balance valve will be opened when the pressure in the anode water tank 18 is too high, and it will perform pressure limiting protection. In addition to the one-way balancing valve provided between the cathode water tank 4 and the anode water tank 18, the electrolytic ozone generating device of the present invention can also be provided with an on-off solenoid valve, which can also achieve the purpose of water balance. On-off solenoid valve When the device is started, the channel of the cathode and anode water tank is turned off; when the device is stopped, the paper size is suitable for financial and family protection (CNS) A4 · (2 丨 GX297 mm) '~~' '-14- I- II-II—---II I- 1— 1 --- HI Ding---(Please read the notes on the back to write this page first) A7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _____B7_ V. Description of the invention ( 12) The on-off solenoid valve connects the channels of the cathode and anode water tanks. The cooling fans 10, 11 are installed at the lower part of the electrolytic ozone generator 8, and the cooling air blows upward through the fins 38, the anode water tank 18, and the cathode water tank 4 to assist the heat dissipation. The ozone generator in the present invention is made by cold-pressing the following independent diaphragms prepared through different techniques and 1J. The cation exchange membrane 34 used in the present invention is a perfluorosulfonic acid cation exchange membrane (model 1 1 7) produced by DuPont of the United States. The treatment technology is: 10% hydrogen peroxide is immersed at 80-90 ° C for one hour to remove organic impurities in the membrane. After rinsing with a large amount of secondary distilled water at about 60 ° C, immerse it in sulfuric acid of 2 m ο 1/1 for half an hour to remove a small amount of metal ions, and finally use a large amount of about 60 ° C Rinse the secondary distilled water to neutrality, and store in the secondary distilled water for assembly. The preparation technology of the cathode catalyst membrane 33 is: uranium carbon powder (200 holes sieved) containing 5-15% by weight of lead, and a polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water. Stir in a water bath at about 80 ° C to form a paste, and then repeatedly roll at a temperature of 30 to 40 ° C to a thickness of 0.1 mm to 0.2 mm. The weight of polytetrafluoroethylene is 5 to 15% of the weight of uranium toner. The rolled membrane is dried at 50-60 ° C and cut to the required size for use during assembly. The cathode catalyst membrane produced by this technique has porous conductive properties. Hydrogen generated at the catalyst membrane / cation exchange membrane contact interface and water accompanied by proton migration can smoothly pass through the micropores of the cathode catalyst membrane and enter the cathode chamber. The preparation technique of the anode catalyst membrane 3 5 is: the lead dioxide powder (this paper size applies to China National Standard (CNS) A4 specifications (210 × 297 mm) (please read the precautions on the back to write this page) 4Γ -15 -4Q13T9 A7 B7 V. Description of the invention (13) 1 80 holes sieved) and polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water are stirred into a paste at about 8 Ot. Then rolled at a temperature of 30-40 ° C into a 0.2_0.3mm film. Among them, polytetrafluoroethylene accounts for 1-5% of the weight of lead dioxide powder. After drying the membrane, it will be cut to the required size and stored for use during assembly. The anode catalytic membrane produced by this technology has porous conductivity, and ozone and oxygen generated at the anode catalyst membrane / cation exchange membrane contact interface can smoothly enter the anode chamber through the micropores of the anode catalyst membrane; meanwhile, raw water can pass through the anode chamber. The micropores of the membrane reversely migrate into the anode catalyst membrane / cation exchange membrane reaction interface and participate in the anode reaction. A part of the raw material water moves to the cathode compartment along with the protons through the cation exchange membrane. The preparation technique of printed anode porous current collector sheet 36 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs is: sintered porous titanium sheet (with a maximum pore size of 26 // m and an air permeability of 1 19M3 / m2 · hk P a) After degreasing and pre-treatment with 5-20% by weight of hydrochloric acid, it is rinsed with double distilled water until it is free of chloride ions and then dried. Then the surface is coated with an organic solution containing platinum, rhenium and antimony, and oxidized in an electric furnace at 500-530 ° C to form a thin layer of conductive oxide containing aluminum, tin and antimony on the surface to prevent The porous current collector is passivated when passing through the anode current. The porous current collector made by the above technique has the functions of electrical conduction and gas-liquid conduction (that is, gas products can leave the electrode reaction interface through the current collector; and raw water can enter the electrode reaction interface through the current collector). The weight percentage of the organic solution containing platinum, tin, and antimony described herein is: concentrated hydrochloric acid S — I-2% This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -16- Economic 'Qiu Printed by A7 B7, Consumer Cooperatives of the Central Bureau of Standards 5. Description of Invention (14): S „c 1 4 · 5 Η 2 0 5-1 0% ·· S». C 1 3 0.5 -1 · 5%; C4H9〇 H 60-90%. The preparation technique of cathode porous current collector 32 is: sintered porous titanium plate (maximum pore size is 26, air permeability is 1 1 9M3 / m2.hkPa), after degreasing, use 5-20% (Weight) hydrochloric acid etching, rinse with distilled water until no chloride ions, dry, save, and use when assembled. The porous current collector has electrical conductivity and gas-liquid conduction function. The deflector 31 is a metal titanium plate, The parts formed with longitudinal and horizontal grooves after processing are shown in Fig. 3. The deflectors are respectively assembled in the cathode, and the anode frame constitutes the cathode and the anode. The faces with the longitudinal and horizontal grooves face the cathode respectively, and the anode is porous. Flow piece. The vertical and horizontal grooves of the deflector 31 can contain raw water, and the raw water and gas products convect in the groove. The deflector has a conductive cooling function. The anode chamber frame 37 is made of Teflon material and processed into independent components, as shown in Figure 3. The frame is provided with upper and lower gas nozzles, and is connected with the anode water tank 1 respectively. The 8 phases are connected to form the raw material water circulation circuit in the anode room. With the rise of the gas (ozone, oxygen) generated by the anode reaction and the temperature difference between the raw material water temperature in the anode room and the temperature of the anode water tank as the power, the automatic water circulation is formed. Cooling effect. The cathode chamber frame 30 is made of organic glass or ABS plastic, as shown in Figure 3. The frame is provided with upper and lower gas nozzles, and is connected to the cathode water tank 4, respectively, to form a raw material water circulation circuit in the cathode chamber. The gas (hydrogen) rising force generated by the cathode reaction and the temperature of the raw material water in the cathode chamber are higher than the paper standard. The Chinese National Standard (CNS) A4 specification (210 × 297 mm) is applied. (Please read the precautions on the back and fill in this page first.) , '1T' -17- Α7 Β7 V. Description of the invention U) The temperature difference of the water temperature of the cathode water tank is used as the power to form an automatic circulation of water and play a cooling role. It is made of silicon rubber material, which ensures the sealing of the gas and raw water produced in the yin and yang rooms. Anti-corrosion sheet 2 8 Choose the metal titanium material to prevent the deflector splint from corrosion. The deflector splint 2 7 is made of hard alloy aluminum plate. The ozone and anode electrodes of the generator are connected with an external DC power source. The ozone generator of the present invention is made of the above components by cold pressing assembly method, and the assembly sequence is: IW pole heat sink 3 8, deflector 2 7, anticorrosive sheet 2 8, gasket 29, deflector 3 1, anode chamber frame 37, gasket 29, anode porous current collector sheet 36, anode catalyst membrane 35, cation exchange membrane 3 4 'cathode catalyst membrane 3 3 'cathode porous current collecting sheet 3 2, gasket 2 9' deflector 3 1 'cathode chamber frame 3 〇, gasket 2 9, anticorrosive sheet 28, deflector splint 27, and then use bolts, nuts, washers, insulation The washer is tightened. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back to write this page) The electrolytic ozone generator of the present invention has simple preparation technology and easy assembly. Compared with the prior art ozone generator, The cost of the device 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 of the present invention can be automatically balanced, and can output ozone higher than atmospheric pressure of 0.1 MPa. The device can perform stably for a long time, and the ozone production efficiency is high. The following table is a comparison of the ozone production efficiency of the device of the present invention and some electrolytic ozone generation devices of the prior art: This paper is suitable for financial institutions (CNS) A4 ^ (2iqx297 (Gongchu) -18- 401373 at ___B7 V. Description of the invention (16) Reference voltage (V) (A / cm2) (%) Reference voltage of the tank voltage and current density ozone generation The present invention 3.5 1.5 18-20 Prior art 1 3.6 1.0 16 US4927800 Existing technology 2 4.0 8 JP43390 / 90 Existing technology 3 3.3 1.0 13 JP20488 / 91 Existing technology 4 4.0 7 JP43389 / 90 Existing technology 5 1.0 13-16 US5203972 Example: Example 1: Preparation of an electrolytic ozone generator (8) (Please read the notes on the back first to write this page) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs a. Preparation of cation exchange membrane (34): 117 type perfluorosulfonic acid cation exchange membrane (product of DuPont) % Hydrogen peroxide is immersed at 90 ° C for one hour to remove organic impurities in the membrane, rinsed with a large amount of secondary distilled water at 60 ° C and then immersed in 80 ° C 2mo 1/1 sulfuric acid for half an hour Remove a small amount of metal ions, and finally rinsed to neutral with a large number of secondary 6 0 ° C distilled water, distilled water, when the secondary assembly to be stored. b. Preparation of cathode catalyst diaphragm (3 3): platinum carbon powder (200 holes sieved) containing 6% (weight) platinum with polytetrafluoroethylene emulsion (suspension) and appropriate amount of secondary distilled water at 8 The film was stirred in a water bath at about 0 ° C to form a paste, and then repeatedly rolled at a temperature of 3 5 ° C to a thickness of 0.1 mm. Among them, the weight of polytetrafluoroethylene accounts for 10% of the weight of uranium carbon powder. The rolled diaphragm is dried at 60 ° C and cut to the required size for use during assembly. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -19- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (17) C. Anode catalyst membrane (3 5) Preparation: Mix / 3-lead dioxide powder (180 holes sieved) with polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water at about 80 ° C to form a paste. It was then rolled into a 0.2mm film at 40 ° C. Among them, polytetrafluoroethylene accounts for 2% of the weight of lead dioxide powder. The membrane is dried at 5 5 ° C and cut to the required size for storage before use in assembly. d. Preparation of anode porous current collector sheet (3 6): sintered porous titanium sheet (maximum pore size is 2 6 " m, air permeability is 1 1 9M3 / m2 • hk P a), degreased and treated with 1 〇 After etching with% hydrochloric acid, rinse with secondary distilled water until there is no chloride ion, and then dry. Then the surface is coated with an organic solution containing platinum, tin, and antimony, and oxidized in an electric furnace at 520 ° C to form a thin layer of conductive oxide containing uranium, tin, and antimony on the surface. The weight percentage of the organic solution containing uranium, tin, and antimony described therein is: concentrated hydrochloric acid 1%; S „C 1 4 · 5 H a 0 8%: S. ≫ C 1 3 1.0%; C 4 H 9 〇 H 8 5%. E. Preparation of cathode porous current collector sheet (32): sintered porous titanium sheet (with a maximum pore size of 26 and an air permeability of 1 1 9M3 / m2 · hk P a) is used after degreasing Etching with 10% hydrochloric acid, rinsing with distilled water until there are no chloride ions, drying it, storing it, and using it after assembly. Cut the five components prepared above into 8 c m2 squares, cooperate with other components, and follow the anode Heat sink (3 8) 'Flow guide plate (2 7 This paper size applies to China National Standard (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back side first write this page) " ° -20- 40f37 fluorine V. Description of the invention (18)) 'Anticorrosive sheet (28)' Seal (29), deflector (31) 'Anode chamber frame (37)' Seal (29), anode porous current collector (Please read the precautions on the back first and write this page) Sheet (36) 'Anode catalyst membrane (3 5), Cation exchange membrane (34)' Cathode catalyst membrane (3 3), negative Porous current collector sheet (32) 'Seal (29), deflector (31), cathode chamber frame (30), seal (29), anticorrosive sheet (28), deflector (2 7) Arrangement, where the deflector (31) is made of 丄 0mm thick metal titanium plate, which has 7 grooves with a width of 2.5mm and a depth of 6mm evenly distributed on the surface: the cathode chamber frame is made of plexiglass Material injection molding, there is a space of 3 1 X 3 1 X 9 mm 3 in the frame 'the inner diameter of the upper and lower air and water connection nozzles is 4 mm; the anode chamber frame (printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed by 3 7) Tetrafluoroethylene storage processing is made into 'the shape, size and inner volume are completely consistent with the cathode chamber frame (30); the anticorrosive sheet (2 8) is made of industrial pure titanium', the thickness is 0.8mm, the area is 40x40mm2; the guide splint (2 7) is a hard alloy aluminum material with a thickness of 8mm and an area of 60x60mm2; and then fastened with bolts (40), nuts (25), washers (26, 42) and insulating washers (39) to obtain the invention Electrolytic ozone generator (8). Example 2: Preparation of electrolytic ozone generator (8) a. Production of cation exchange membrane (34) Preparation: The 117 type perfluorosulfonic acid cation exchange membrane (product of DuPont) was soaked with 10% hydrogen peroxide at 80 ° C for one hour to remove organic impurities in the membrane, and after a large amount of 60 ° C for two times After rinsing with distilled water, put it at 80 ° C 2 m ο 1/1 of the sulphur paper standard applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -21-觎 ma? 'B7 1. Description of the invention (19) Soak in acid for half an hour to remove a small amount of metal ions. Finally, rinse with a large amount of secondary distilled water at 6 ◦ ° C to neutrality, and store in secondary distilled water for assembly. b. Preparation of cathode catalyst membrane (33): platinum carbon powder (200 holes sieved) containing 12% (weight) platinum and polytetrafluoroethylene emulsion (suspension) and appropriate amount of secondary distilled water at 80 In a water bath at about ° C, stir into a paste, and then repeatedly roll at a temperature of 40 ° C to form a 0.2 mm thick film. The weight of polytetrafluoroethylene accounts for 15% of the weight of uranium toner. The rolled membrane is dried at 6 and cut to the required size, and 0 C is used for assembly. Preparation of anode catalyst membrane (35): sieving lead dioxide powder (180 holes) Stir with polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water at about 80 ° C to form a paste. It is then rolled at a temperature of 35 ° C into a membrane of 0 · 2 mm. Among them, polytetrafluoroethylene accounts for 1% of the weight of lead dioxide powder. After drying, the membrane is cut to the required size and stored for use during assembly. d. Preparation of anode porous current collector sheet (3 6): sintered porous titanium sheet (maximum pore size is 2 6 // m, air permeability is 1 1 9M3 / m2 • hk P a) after degreasing and using 1 0 After etching with% hydrochloric acid, rinse with secondary distilled water until there is no chloride ion, and then dry. Then the surface is coated with an organic solution containing platinum, tin, and antimony, and oxidized in an electric furnace at 500 ° C to form a thin layer of conductive oxide containing uranium 'tin' antimony on its surface. The weight of the organic solution containing uranium, tin, and chains is divided into: (Please read the precautions on the back and fill in this page first) Order the staff of the Central Standards Bureau of the Ministry of Economic Affairs Standard (CNS) A4 specification (210X297 mm) -22- 0% 2% 20 0% 2% 20 V. Description of the invention (concentrated hydrochloric acid 9%; H2ptc 16.6Η2〇snc 1 ^. 5 Η 2 〇 10 0%; S b C 1 3 c > H 9 Ο H 7 8%. E. Preparation of cathode porous current collecting sheet (3 2): sintered porous sheet (maximum pore size is 2 6 # m, air permeability is 1 1 9M3 / m2.hk P a) After degreasing, it is etched with 0% hydrochloric acid, rinsed with distilled water until no chloride ions, dried, stored, and used until assembly. According to the same method as in Example 1, the The assembly of the above-mentioned components and other components into the electrolytic ozone generator (8) of the invention. Example 3: Preparation of an electrolytic ozone generator (8) a. Preparation of a cation exchange membrane (34): 1 sulfonic acid Cation exchange membrane (product of DuPont) was immersed in 10% at 85 ° C for one hour to remove organic impurities in the membrane, ° After rinsing with C in distilled water, immerse it in 80 ° C 2 m 〇 acid for half an hour to remove a small amount of metal ions. Finally, rinse in distilled water at ° C to neutrality, and store it in secondary distillation. b. Preparation of cathode catalyst membrane (33): paste (weight) uranium lead carbon powder (200 holes sieved) with polytetra (suspension) and appropriate amount of secondary distilled water at 80 ° C And then repeatedly rolled into 0.1 pieces at a temperature of 30 ° C. Among them, the weight of polytetrafluoroethylene accounts for 5% of the weight of uranium toner. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the notes on the back first to write this page). 3 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 1 Type 7 perfluorinated hydrogen peroxide. A large amount of 6 0 1/1 of sulfur is used in a large amount of 60. 10% vinyl fluoride emulsion was stirred into a mm-thick film. The rolled -23- Central Standard of the Ministry of Economy 扃 Staff Consumer Cooperative Cooperative Printing Shaft 75-V. Description of the invention (21) The film was baked at 60 ° C Dry and cut to the required size for use during assembly. C · Preparation of anode catalyst membrane (3 5): Θ — Stirred dioxide powder (sieved with 180 holes), polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water are stirred into a paste at about 80 ° C. Then rolled at 3 ° C to 0 · 3mm film. Polytetrafluoroethylene accounts for 1.5% of the weight of the powder. This film is dried after being cut to the required size and stored for use in assembly. d. Preparation of anode porous current collector sheet (3 6): sintered porous titanium sheet (maximum pore size is 2 6 # m, air permeability is 1 1 9 M 3 / m 2 • hk P a) after degreasing and using After 10% hydrochloric acid is etched and pre-treated, it is rinsed with secondary distilled water to be free of chloride ions and then dried. Then, the surface is coated with an organic solution containing uranium'tin and antimony, and oxidized in an electric furnace at 520 ° C, so that a thin layer of conductive oxide containing ferrite, tin, and antimony is formed on the surface. The weight percent of the organic solution containing platinum, tin, and antimony described therein is: concentrated hydrochloric acid 1.5%; S n C 1 1 · 5 Η 2 0 5%; S, > C 1 3 0.5%: C 4 H 9 0 H 90%. e · Preparation of cathode porous current collector sheet (3 2): sintered porous titanium sheet (maximum pore size is 2 6 and air permeability is 1 1 9M3 / m2 · hk P a) is etched with 10% hydrochloric acid after degreasing , Rinse with double distilled water until there is no chloride ion, dry it, store it, and use it for assembly. According to the same method as in Example 1, the above-prepared element and its paper size were applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1 ^ m-----1 1 ^ 1 n I mi In ^^ 1-.¾., I (please read the precautions on the back first ^ write this page) -24-A7 ________B7 V. Description of the invention (22) Its component assembly cost is the electrolytic ozone generator (8) of the invention. Embodiment 4: The assembly and application of the electrolytic ozone generating device of the present invention uses the electrolytic ozone generator (8) prepared in Example 1 and the following components: a cathode water tank (4) of 1500 ml, 1200 Milliliter anode water tank (1 8) 'one-way balance valve (1 3), cooling fan (1 0 '11)' anode circulating water pipe (7), cathode circulating water pipe (6), water level detector (1 9, 2 0 2 1, 2 2) and the isolation tube (1 7) are installed according to methods known in the art to form the electrolytic ozone generating device of the present invention. When the electrolytic ozone generating device of this embodiment is performed at a current density of 1.5 A / cm2, the generator tank voltage is 3.5 ± 0. IV, and the ambient temperature is about 2 5 ° C, which is continuously performed for 2 4 The temperature of the raw material water in the anode and anode water tanks can be maintained at about 30 ° C, and the ozone generation efficiency is 18%. The anode water tank can output a pressure higher than the atmospheric pressure of 0.08MPa. The ozone printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first to write this page). Brief description of the drawings: FIG. 1 is a schematic structural diagram of an electrolytic ozone generating device according to the present invention. Fig. 2 is an assembly schematic diagram of the electrolytic ozone generating device (8) of the solid polymer electrolyte membrane composite electrode in Fig. 1. FIG. 3 is a developed view of FIG. 2. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -25- 401373 V. Description of the invention (23) Supplement f

Figure 4 shows the structure of the one-way balance valve 13. The main components are compared with the table 1 water inlet cover 2 water inlet 3 hydrogen outlet 4 cathode water tank 5 reaction medium 6 cathode circulating water pipe 7 anode circulating water pipe 8 ozone generator 9 anode circulating water pipe 10-11 cooling Fan 1 2 Circulating water pipe 13 One-way balancing valve 14 Cathode circulating water pipe 15 Nut 16 Spare water outlet. 17 Isolating pipe 18 Anode water tank 18a Air collecting surface 18b Air duct 19 Water level detecting sealing tube 2 0 Permanent magnet ------- ------------— Order I: -------- line ", (Please read the precautions on the back before filling this page) This paper size applies Yin National Standard ( CNS) A4 specification (210 X 297 mm) -26- 461375 V. Description of the invention (24 2 1 Float 2 2 2 4 2 5 2 6 2 7 2 8 2 9 3 0 3 1 3 2 3 3 3 4 3 7 3 8 3 9 4 0 4 1 4 2 4 3 4 4 Reed tube micro hole obstruction plate air outlet nut washer baffle plate anticorrosive sheet gasket cathode to frame deflector cathode porous current collector cathode cathode membrane cation exchange membrane Sheet anode catalyst diaphragm anode porous current collecting sheet anode chamber frame anode heat sink insulating washer bolt drainage Screw washer Cathode water tank connection Anode water tank connection

(Please read the precautions on the back before filling out this page) The paper size applies the national standard (CNS) A4 (210 X 297 mm) -27- A7 A7

-------------------- Order ---- a ----- line ·--* (谙 Please read the notes on the back before filling this page > _B7 V. Description of the invention (25) 45 Ring-shaped sealing lip 4 6 Anode water tank connection 4 7 Anode water tank connection 4 8 Pressure limiting valve port 4 8a Pressure limiting plug 4 9 Lower check valve body 5 0 Diaphragm 51 Unidirectional Body valve on balance valve 52 Anode water tank connection 52a Obstructed hole The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -28-

Claims (1)

No. 86117241 Patent Application Chinese Patent Application Amendment (please read the notes on the back before filling out this page) Republic of China 88 / > Month Amendment 1 · An electrolytic ozone generator, including electrolytic ozone generator (8) An anode water tank (18) connected to the anode chamber of the ozone generator (8) through the anode circulating water pipe (7), and a cathode water tank (4) connected to the cathode chamber of the ozone generator (8) through the anode circulating water pipe (6). Among them, the electrolytic ozone generator (8) includes independent cation exchange membranes (34), independent anode catalyst membranes (35) adjacent to the sides of the cation exchange membrane (34), and independent Cathode catalyst diaphragm (33), anode porous current collector (36) on the other side of anode catalyst diaphragm (35), cathode porous current collector (3) on the other side of cathode catalyst diaphragm (33) 2 ). 2. The electrolytic ozone generating device according to item 1 of the scope of patent application, wherein the cathode catalyst membrane (33) in the electrolytic ozone generator (8) contains uranium carbon powder and polytetrafluoroethylene, Among them, uranium carbon powder contains 5-15% by weight of platinum, and the weight of polytetrafluoroethylene accounts for 5-15% of the weight of platinum carbon powder. 3. The electrolytic ozone generating device according to item 2 of the scope of patent application, wherein the particle size of the platinum carbon powder in the cathode catalyst membrane (33) is less than 200 holes. _ 4. The electrolytic ozone generating device according to item 2 of the scope of the patent application, wherein the thickness of the cathode catalyst membrane (3 3) is 0.1. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) No. 86117241 Patent Application Chinese Patent Application Amendment (please read the notes on the back before filling out this page) Republic of China 88 / > Month Amendment 1 · An electrolytic ozone generator, including electrolytic ozone generator (8) An anode water tank (18) connected to the anode chamber of the ozone generator (8) through the anode circulating water pipe (7), and a cathode water tank (4) connected to the cathode chamber of the ozone generator (8) through the anode circulating water pipe (6). Among them, the electrolytic ozone generator (8) includes independent cation exchange membranes (34), independent anode catalyst membranes (35) adjacent to the sides of the cation exchange membrane (34), and independent Cathode catalyst diaphragm (33), anode porous current collector (36) on the other side of anode catalyst diaphragm (35), cathode porous current collector (3) on the other side of cathode catalyst diaphragm (33) 2 ). 2. The electrolytic ozone generating device according to item 1 of the scope of patent application, wherein the cathode catalyst membrane (33) in the electrolytic ozone generator (8) contains uranium carbon powder and polytetrafluoroethylene, Among them, uranium carbon powder contains 5-15% by weight of platinum, and the weight of polytetrafluoroethylene accounts for 5-15% of the weight of platinum carbon powder. 3. The electrolytic ozone generating device according to item 2 of the scope of patent application, wherein the particle size of the platinum carbon powder in the cathode catalyst membrane (33) is less than 200 holes. _ 4. The electrolytic ozone generating device according to item 2 of the scope of the patent application, wherein the thickness of the cathode catalyst membrane (3 3) is 0.1. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) A8 B8 C8 ______ D8 6. Scope of patent application-0 · 2 mm. 5. The electrolytic ozone generating device according to item 1 of the scope of the patent application, wherein the anode catalyst membrane (35) in the electrolytic ozone generator (8) contains lead dioxide and polytetrafluoroethylene. 6. The electrolytic ozone generating device according to item 5 of the scope of the patent application, wherein 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 generating device according to item 5 or 6 of the scope of the patent application, wherein the particle size of the lead dioxide used in the anode catalyst membrane (35) is less than 180 holes. 8. The electrolytic ozone generating device according to item 5 or 6 of the scope of the patent application, wherein the lead dioxide used in the anode catalyst membrane (3 5) is / 3-lead dioxide. 9. The electrolytic ozone generating device according to item 7 of the scope of the patent application, wherein the lead dioxide used in the anode catalyst membrane (35) is point-point lead dioxide. 10. The electrolytic ozone generating device according to item 5 or 6 of the scope of the patent application, wherein the thickness of the anode catalyst membrane (3 5) is 0.2 to 0.3 mm. 1 1. The electrolytic ozone generating device according to item 8 of the scope of patent application, wherein the thickness of the anode catalyst membrane (3 5) is 0 · 2 — ◦. 3 mm. 12. The electrolytic ozone generating device according to item 9 in the scope of the patent application, wherein the thickness of the anode catalyst membrane (3 5) is -------- order ------- -Line * 丨 (Please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 * 297 mm) -2- 401373 έΙ C8 D8 _ VI. Application scope 0 2-0.3 mm. 13. The electrolytic ozone generating device according to item 1 of the scope of the patent application, wherein the anode porous current collector (3 6) in the electrolytic ozone generator (8) is coated with a layer containing platinum, And antimony conductive oxide sintered porous titanium sheet. 14. The electrolytic ozone generator (1) according to item 1 of the scope of the patent application, wherein the electrolytic ozone generator (8) further comprises a deflector made of metal titanium and uniformly provided with grooves on one side. 1 5 · The electrolytic ozone generating device according to item 1 of the scope of patent application, wherein the anode water tank (18) has a gas collecting surface (18a) on the upper end, and an elongated air guiding tube (18b) on the gas collecting surface. The top of the gas pipe (18b) is ozone, oxygen outlet (24), ozone, oxygen outlet (24) has a microporous damping plate (23), an anode water tank (18) has an isolation tube (17), and the anode water tank (18) passes The anode circulation pipe (7) is connected with the anode chamber frame (37) to form a water circulation circuit. 16. The electrolytic ozone generating device according to item 1 of the scope of patent application, wherein the position of the cathode water tank (4) is higher than that of the anode water tank (18), and the top has a water inlet (2) and a water inlet cover (1) The hydrogen outlet (3), the cathode water tank (4) is equipped with a water level detector (19, 20, 21, 22), and the cathode water tank (4) is connected to the cathode chamber frame (30) through the cathode circulation pipe (6). Form a water circulation loop. 17. The electrolytic ozone generating device as described in item 1 of the scope of patent application, in which the paper size applies to the Chinese national standard (CNSM4 specification (210 * 297 public love) -3------------ -/ A -------- Order -------- Hand (Please read the precautions on the back before filling this page) A8 B8 C8 ______ D8 _ VI. The scope of patent application is in the cathode water tank (4 ) And the anode water tank (18) are provided with a one-way balancing valve (13), the one-way balancing valve (13) is composed of an upper valve body (51), a diaphragm (50), and a lower valve body (49); The upper valve body (51) is provided with a cathode water tank interface (43), an anode water tank interface (52), a damping hole (52a) in the anode water tank interface (52), and a ring-shaped sealing lip (45): a unidirectionally balanced lower valve body (49) An anode water tank interface (47), a pressure limiting valve port (48) and a pressure limiting plug (48a) are provided. 18. The electrolytic ozone generating device according to item 1 of the scope of patent application, wherein the cathode water tank ( 4) An on-off solenoid valve is provided between the anode water tank (1 8) and 19. A method for preparing an electrolytic ozone generator (8) according to item 1 of the patent application scope, comprising: a. Platinum carbon powder and polytetrafluoroethylene emulsion containing 5-15% by weight of rhenium and an appropriate amount of secondary distilled water are stirred into a paste in a water bath at about 80 ° C, and then repeatedly milled at a temperature of 30-40 ° C Compressed into a film with a thickness of 0.1 to 0.2mm, in which the weight of polytetrafluoroethylene accounts for 5 to 15% of the weight of platinum carbon powder. The rolled film is dried at 50 to 60 ° C and dried. Cut to the required size to prepare the cathode catalyst membrane (33); b. Stir the lead dioxide powder and polytetrafluoroethylene emulsion with an appropriate amount of secondary distilled water in a water bath at about 80 ° C, Then repeatedly rolled at a temperature of 30 _ 40 ° C to a thickness of 0.2-2. 3mm film, wherein the weight of polytetrafluoroethylene accounts for 1-15% of the weight of lead dioxide, the rolled film Dry at 5 0 — 6 0 ° C and cut to the required size to produce — — — — — — — — — — — IIIII —1 ^ * 11 — — — — — — — (F Read the notes on the reverse side and fill in this page) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm). 4-A8B8C8D8 4013T3 Catalyst film (3 5); · c. The sintered porous titanium sheet is degreased and pre-treated with 5-20% by weight of hydrochloric acid, rinsed with twice distilled water to be free of chloride ions, and dried. The surface is coated with an organic solution containing platinum, thorium, and antimony, and oxidized in an electric furnace at 500-530 ° C to form a thin layer of a conductive oxide containing platinum '钖' antimony on the surface, thereby making the anode porous. Current collecting sheet (36); d. The sintered porous titanium sheet is degreased and pretreated with 5-20% by weight of hydrochloric acid, rinsed with secondary distilled water to be free of chloride ions, and dried to obtain a cathode. Porous current collector (3 2). 20. The method for preparing an ozone generator according to item 19 of the scope of the patent application, wherein the particle size of the platinum carbon powder used in preparing the cathode catalyst membrane (33) is less than 200 holes. . 21. The method for preparing an ozone generator according to item 19 of the scope of patent application, wherein the particle size of the lead dioxide used in preparing the anode catalyst membrane (35) is less than 180 holes. 2 2. The method for preparing an ozone generator according to item 19 or 21 in the scope of the patent application, wherein the lead dioxide used in preparing the anode catalyst membrane (35) is lead dioxide. . 2 3. The method for preparing an ozone generator according to item 19 of the scope of patent application, wherein the organic solution containing platinum, tin and antimony used in preparing the anode porous current collector sheet (36) is The weight percentages are: concentrated hydrochloric acid 3-9%; H2PtC 16.6H2〇L-2%; S «C 1 4 · 5 Η 2 Ο 5-10%; S b C 1 3 0.5- 1 · 5%; C 4 H 9 Ο H 60-90%. This paper size applies to China National Standard (CNS) A4 (210 x 297 cm) -5-(Please read the precautions on the back before filling this page)--II ΙΊ ^ · 1ΙΙΙΙΙΙΙ ^ A8 B8 C8 D8 VI. The scope of patent application 24. The method for preparing an ozone generator according to item 19 of the scope of patent application, wherein the maximum pore size of the sintered porous decoction pieces used in preparing the anode porous current collector sheet (36) It is 2 6 and the air permeability is 119M3 / m2.hkPa. 25. The method for preparing an ozone generator according to item 19 in the scope of the patent application, wherein the maximum pore diameter of the sintered porous titanium sheet used in preparing the cathode porous current collector sheet (3 2) is 2 6 ym, air permeability is 1 19M3 / m2 · hkPa. (Please note on the back of Μίι before filling out this page) ------- II Order ---------- Line i Bud Paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) -6-