CN1195643A - Electrolytic ozone generator - Google Patents

Abstract

The invention provides an electrolytic ozone generating device, mainly comprising: an ozone generator, an anode water tank, a cathode water tank, a one-way balance valve or an on-off electromagnetic valve and other components. The ozone generator includes cation exchange membrane, cathode catalyst membrane, cathode porous current collector, anode catalyst membrane, anode porous current collector, deflector, anti-corrosion sheet and other independent components. The device has low manufacturing cost, can be produced on an industrial scale, can operate stably under pressure, and has high ozone generation efficiency.

Description

Electrolytic ozone generator

The invention relates to an electrolytic ozone generating device, which belongs to the technical fields of electrochemical technology and ozone application.

The advantages of using the ozone method for disinfection and sterilization have attracted more and more attention. At present, the high-frequency and high-voltage corona discharge method is widely used to generate ozone, and the research and development of electrochemical methods to generate high-concentration ozone has attracted widespread attention. The basic principle of electrochemical method to produce ozone is well known: ozone is generated with deionized water as raw material, and when DC power is applied, the electrochemical reaction formula of cathode and anode electrodes is:

Cathodic hydrogen evolution reaction formula: (1)

Cathodic oxygen depolarization reaction formula: (2)

Anode main reaction formula: (3)

Anode side reaction formula: (4)

The protons produced by the anode reaction migrate to the cathode in the form of water solvated protons through the cation exchange membrane under the action of a direct current electric field.

According to the above electrochemical reaction principle, it can be seen that the core part of the most basic electrolytic ozone generator is an electrolytic cell. The electrolyzer must have an anode, cathode, electrolyte and raw water.

Chinese patent application CN86108792A has described a kind of solid polymer electrolyte structure, and this structure comprises a diaphragm, a lot of conductive particles and a conductive water-permeable matrix member, wherein conductive particle and conductive water-permeable matrix (as collector plate) with physical or electrical ways to contact each other and embedded in the diaphragm, or combined with the diaphragm. Among them, the diaphragm is generally preferably made of fluorocarbon material. In order to embed the conductive water permeable matrix into the fluorocarbon membrane, it is preferable to keep the fluorocarbon in a thermoplastic state. Conductive water-permeable substrates include carbon cloth, carbon paper, metal mesh, metal felt and porous metal sheet, etc., carbon cloth is preferred. Electrocatalytically active particles can be incorporated into the membrane surface using a variety of techniques, including pressurization, mixing with solvents, and blending with membrane or other polymer powders. One of the specific methods is: first prepare a thin film composed of electrocatalytically active particles combined with a binder such as polytetrafluoroethylene or a membrane in a thermoplastic state, and the bonding material/catalyst The composition is in the state of a porous film. This thin film can then be laminated between the collector and diaphragm.

Membranes were prepared from an ion exchange membrane sheet composition in a thermoplastic state containing 10% by weight carbon particles having a particle size of 30 microns and 5% platinum on them. The mixture can be hot-pressed at a temperature of 310° C. and a pressure of 1 ton/in ² (155 atmospheres) for 1.25 minutes to prepare a film with a thickness of less than 0.025 mm. The film can be laminated between the carbon cloth collector plate and the diaphragm by conventional hot pressing technology. Afterwards, the carbon cloth can be embedded in the diaphragm. The method is: preheat the diaphragm/carbon cloth together for about 30 seconds at a temperature of 120°C and atmospheric pressure, and then at the same temperature and 1-2 tons/ In ² (155-310 atm) pressure for 225 seconds, then at 2-3 t/in ² (310-465 atm) for about 60 seconds.

JP, flat 4-88182 proposes to adopt the perfluorinated sulfonic acid cation exchange membrane (type 117) that U.S. Du Pont Company makes, coats the suspension (suspension) liquid of commodity ion powder (ion exchange resin powder) on its surface, applies 5kg/ cm ² pressure, heated at 180-200°C for 30 minutes to form a porous ion exchange resin layer, the surface thickness of the ion exchange resin layer is 100 microns. Lead oxide is closely arranged on the formed ion exchange resin layer to form a porous layer as an anode electrode. On the surface of the ion exchange membrane opposite to the porous layer, a ruthenium metal membrane is formed by electroless plating as a cathode.

The specific method of preparing the lead oxide anode is: firstly, the coating solution containing 75% titanium and 25% platinum is coated on the plate-shaped substrate made of sintered tantalum powder, and the platinum/tantalum in the substrate is formed by thermal decomposition. the middle layer. Use 800 g/L lead nitrate aqueous solution as the electrolyte, add a small amount of nitric acid, heat to 70°C, immerse the aforementioned substrate and titanium plate in the electrolyte, and pre-electrolyze with a current density of 10A/ ^dm2 . Then, a α-lead dioxide layer was electrodeposited on the surface of the aforementioned substrate with a current density of 4A/dm ² as an anode. The thickness of the surface layer of the lead dioxide layer is 100 μm, and the anode of the electrodeposited lead dioxide layer is pressed tightly against the ion exchange resin layer side of the ion exchange membrane with a pressure of 1.0 kg/cm ² to form an electrode structure.

JP, Hei 2-43389 and JP, Hei 2-43390 propose methods for producing ion exchange resin membranes and lead dioxide electrode junctions. In this method, lead-containing ion aqueous solution is disposed on one side of cation or anion exchange resin membrane, and hypochlorous acid aqueous solution (or bromine aqueous solution) is disposed on the other side, so that lead dioxide is precipitated on the surface of one side of above-mentioned ion exchange resin membrane. The coating acts as an anode catalyst for the electrolysis of water to produce ozone.

US4927800 introduces an electrode catalyst containing a lead dioxide electrolytic deposition layer and a preparation method of the electrode catalyst. Particles containing β-lead dioxide powder are dispersed in the catalyst deposition layer. These particles contain β-lead dioxide powder and an optional electrolytic co-catalyst, which is one of PTEE (polytetrafluoroethylene), agar, perfluorinated ion exchange resin and the like. This electrode catalyst is very useful in electrolyzing water to prepare ozone and electrolyzing aqueous solution to prepare peroxide.

The common feature of the above-mentioned patent applications is that the electrolytes all use solid polymer electrolytes (SPE), usually perfluorosulfonic acid cation exchange membranes, which are used as both electrolytes in the electrolytic cell and as a space between the cathode chamber and the anode chamber. isolation film.

Cathode materials (catalysts) are usually platinum group metals, gold, silver, nickel, ruthenium or their mixtures.

The anode material (catalyst) usually adopts platinum group metal, gold or its mixture, glassy carbon and lead dioxide.

The preparation method of the electrolytic ozone generator that adopts solid polymer electrolyte as mentioned above relates to following three kinds of processes:

One is to prepare the electrode composite membrane by hot pressing process, which is complicated in procedure, harsh in conditions, requires high pressure and temperature, and increases the manufacturing cost. And if the membrane formed by this process cannot be assembled into the generator as a whole in time, the water content of the membrane will also change accordingly due to changes in room temperature and humidity in the storage space, which will cause deformation of the electrode/membrane assembly.

The second is through permeable electroless plating (that is, electroless plating). This method deposits a layer of electrocatalyst on one or both sides of the ion exchange membrane. There will be changes in the process, and it is difficult to ensure the uniformity of the membrane/electrode assembly prepared each time. It is necessary to strictly ensure the concentration, temperature, and pH value of various components to be constant, otherwise it is difficult to ensure the quality of the prepared catalyst.

Third, the preparation of the anode catalyst (such as when lead dioxide is used) is based on porous titanium, and then anodically electrodeposited a layer of β-lead dioxide on the substrate. It is necessary to ensure certain lead ions and other additives in the electroplating solution. Concentration (including β-lead dioxide particles, PTFE, agar, perfluorinated ion exchange resin and other components in the above-mentioned dispersion plating method), when the pH value changes in this process, the crystal form of lead dioxide in the coating also changes changes.

Therefore, related to the preparation method of catalyst/ion exchange membrane electrode in the electrolytic ozone generator that adopts solid polymer electrolyte in the prior art, there are shortcomings and deficiencies, that is: the preparation process is complex, the production cost is high, and it is not easy for industrial scale Production.

In addition, the electrochemical reaction [see reaction formula (3) and (4)] that takes place in the electrolytic type ozone generating device must consume raw material water when producing ozone and oxygen; Electrochemical reaction [see reaction formula (1) and ( 2)] to consume protons, which are generated by the anode reaction and migrate through the cation exchange membrane to the cathode/cation exchange membrane interface. However, proton migration is always carried out in the form of water solvation, so as the electrochemical reaction proceeds, the amount of raw material water in the anode chamber decreases continuously, while the amount of raw material water in the cathode chamber gradually increases. Heat, if no heat dissipation measures are used, the efficiency of ozone generation will be reduced.

The purpose of the present invention is to overcome the shortcomings of complex electrode preparation process and high production cost in the above-mentioned prior art, and provide an electrolytic ozone generator, which has a solid polymer electrolyte membrane composite electrode member composed of discrete diaphragms, The electrode manufacturing process is simple, the production cost is low, and it is easy to produce on an industrial scale. At the same time, the raw material water in the cathode and anode chambers of the electrolytic ozone generator of the present invention is automatically balanced, and ozone with a pressure higher than atmospheric pressure can be output, and the ozone generation efficiency is high.

Another object of the present invention is to provide a method for preparing the electrolytic ozone generator in the above electrolytic ozone generator.

The electrolytic ozone generating device of the present invention comprises 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 wherein includes an independent cation exchange membrane, an independent anode catalyst membrane and an independent cathode catalyst membrane respectively adjacent to both sides of the cation exchange membrane, The anode porous current collecting sheet is on the other side of the anode catalyst membrane, and the cathode porous current collecting sheet is on the other side of the cathode catalyst membrane.

The cation exchange membrane is a perfluorosulfonic acid cation exchange resin commonly used in the prior art, and the anode catalyst membrane is a film containing polytetrafluoroethylene and lead dioxide with a thickness of 0.2-0.3 mm. The cathode catalyst membrane is a film with a thickness of 0.1-0.2mm containing polytetrafluoroethylene and platinum carbon powder, and the anode porous current collector is coated with a layer of conductive oxide containing platinum, tin and antimony. A sintered porous titanium sheet, 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 balance valve (or on-off electromagnetic valve) is connected between the cathode water tank and the anode water tank to realize the automatic balance of raw water and the use of This device can output ozone under pressure. The raw water in the cathode water tank and the anode water tank is not only the raw material for generating ozone, but also the circulating coolant for the cathode and anode.

The preparation method of the ozone generator in the electrolytic type ozone generator of the present invention comprises:

a. Stir platinum carbon powder containing 5-15% (weight) platinum and polytetrafluoroethylene emulsion (suspension) with an appropriate amount of double distilled water in a water bath at about 80°C to form a paste, and then heat it at 30-40°C Repeated rolling at high temperature into a 0.1-0.2mm thick diaphragm, in which the weight of polytetrafluoroethylene accounts for 5-15% of the weight of platinum carbon powder, and the rolled diaphragm is dried at 50-60°C and cut Become required size, make cathode catalyst diaphragm (33);

b. Stir lead dioxide powder, polytetrafluoroethylene emulsion and appropriate amount of twice-distilled water in a water bath at about 80°C to form a paste, and then repeatedly roll it into a film with a thickness of 0.2-0.3mm at a temperature of 30-40°C sheet, wherein the weight of polytetrafluoroethylene accounts for 1-5% of the weight of lead dioxide, and the rolled membrane is dried at 50-60°C and cut into required size to obtain an anode catalyst membrane (35 );

c. The sintered porous titanium sheet is degreased and pre-treated with 5-20% (weight) hydrochloric acid etching, rinsed with twice distilled water until there is no chloride ion, and then dried, and then coated with platinum, tin, The organic solution of antimony is oxidized in an electric furnace at 500-530° C. to form a thin layer of conductive oxide containing platinum, tin and antimony on its surface to obtain anode porous current collectors (36);

d. Degrease the sintered porous titanium sheet, pre-treat it with 5-20% (weight) hydrochloric acid, rinse it with double distilled water until it is free of chloride ions, and then dry it to prepare the cathode porous current collector (32).

The ozone generator in the present invention is assembled from the above-mentioned independent components and other necessary components well known in the art.

Fig. 1 is a schematic structural view of the electrolytic ozone generator of the present invention.

Fig. 2 is a schematic diagram of the assembly of the solid polymer electrolyte membrane composite electrode electrolytic ozone generator (8) in Fig. 1 .

FIG. 3 is an expanded view of FIG. 2 .

FIG. 4 is a schematic structural view of the one-way balancing valve 13 .

Below with reference to accompanying drawing, electrolytic type ozone generator of the present invention is described in further detail:

The electrolytic ozone generating device of the present invention comprises an electrolytic ozone generator 8, an anode water tank 18 connected to the anode chamber of the ozone generator 8 through a circulating water pipe 7, and a cathode water tank connected to the cathode chamber of the ozone generator 8 through a circulating water pipe 6 4. One-way balance valve 13, cooling fans 10, 11, water level detectors 19, 20, 21, 22 and isolation pipe 17.

Wherein 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, Cathode chamber frame 30, guide plate 31, anti-corrosion sheet 28, guide plate 27, gasket 29, bolt 40, nut 25, washers 26, 42, insulating washer 39, drainage screw 41.

In the electrolytic ozone generating device of the present invention, the upper end of the anode water tank 18 has a gas collecting surface 18a, so that the anode gas can be discharged quickly without retention. There is a slender air guide tube 18b on the gas collecting surface, ozone and oxygen outlet 24 are arranged on the top of the air guide tube, a microporous damping plate 23 is arranged in the air outlet 24, and an isolation tube 17 is arranged in the anode water tank, which is made of quartz tube or titanium tube. The anode gas (ozone, oxygen) and circulating water produced by the anode reaction are introduced into the anode water tank through this pipe, and the setting of the isolation pipe 17 reduces the contact and dissolution of ozone and the raw material water in the anode water tank. Ozone and oxygen quickly enter the air guide tube 18b through the gas collecting surface 18a, and realize gas/water separation at the upper end of the air guide tube. The separated ozone and oxygen pass through the microporous damping plate 23 and are exported from the ozone and oxygen outlet 24 .

The position of the cathode water tank 4 is higher than that of the anode water tank 18, and a water inlet 2, a water inlet cover 1, and a hydrogen outlet 3 are arranged on the top thereof. Water level detector 19,20,21,22 is housed in cathode water tank 4, and this water level detector is made of reed tube 22, float 21, permanent magnet 20, water level detection sealing 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 from working.

The cathode circulating water pipe 6 connects the cathode water tank 4 and the cathode chamber frame 30 to form a water circulation loop, and the heat generated during the cathode reaction is taken out in time through the water circulation.

The anode circulating water pipe 7 connects the anode water tank 18 and the anode chamber frame 37 into a water circulation loop, and the heat generated during the anode reaction is taken out in time through the water circulation.

According to the electrochemical reaction principle of the electrolytic ozone generator, the generation of ozone and oxygen in the anode reaction formulas 3 and 4 requires the consumption of raw water, and the protons generated in this reaction migrate to the cathode through the cation exchange membrane in the form of water solvation. When continuing, the raw material water in the anode water tank is continuously consumed, while the raw material water in the cathode water tank is continuously increased. The increased raw water in the cathode water tank cannot reversely pass through the cation exchange membrane and return to the anode water tank, eventually resulting in the complete depletion of the raw water in the anode water tank.

In order to solve the above problems, the present invention sets a one-way balance valve between the cathode water tank and the anode water tank.

Referring to Fig. 1, Fig. 4, one-way balance valve 13 is made up of upper valve body 51, diaphragm 50, lower valve body 49. Among them, the upper valve body 51 is provided with a cathode water tank interface 43, an anode water tank interface 52, and the interface 52 has a damping hole 52a and an annular sealing lip 45; the one-way balance lower valve body 49 is provided with an anode water tank interface 47 and a pressure limiting valve port 48 , Pressure limiting plug 48a.

The cathode water tank interface 43 of the upper valve body 51 of the one-way balance valve 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 oxygen in the anode water tank 18 gradually form a pressure P due to the damping of the microporous damping plate 23, and the pressure P passes through the anode water tank interface 52 of the upper valve body 51 of the one-way balance valve and the lower valve. The anode water tank interface 47 of the body 49 is transmitted to both sides of the diaphragm 50. At this time, because there is also a cathode water tank interface 43 in the upper valve body 51, the flow of raw water from the anode water tank 18 to the cathode water tank 4 is formed. The water flows through the orifice 52a of the anode water tank interface 52 to generate a pressure drop ΔP. The generation of ΔP creates a pressure difference on both sides of the diaphragm 50, and the diaphragm 50 is biased towards the upper valve body 51 under the action of the pressure difference until it is pressed against the annular sealing lip 45, at this time the cathode water tank 4 and the anode water tank 18 are cut off. of water flow channels. The diaphragm 50 maintains this state due to the maintenance of the pressure P within the anode water tank 18 . At this time, the ozone generator device of the present invention can output ozone and oxygen at the pressure P.

After the ozone generating device 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 is biased towards the lower valve body 49 by the water level pressure difference, and the cathode water tank 4 and the anode water tank 18 The one-way balance valve is connected again, and the water levels in the cathode and anode water tanks will gradually restore balance.

The pressure limiting plug 48a of the one-way balance valve will be pressed open when the pressure in the anode water tank 18 is too high, so as to play the role of pressure limiting protection.

The electrolytic type ozone generating device of the present invention can also be provided with an on-off type solenoid valve except that a one-way balance valve is set between the cathode water tank 4 and the anode water tank 18, which can also realize the purpose of water balance. When the device is started, the channels of the cathode and anode water tanks are shut off; when the device stops working, the on-off electromagnetic valve connects the channels of the cathode and anode water tanks.

Cooling fan 10,11 is installed in the bottom of electrolytic type ozone generator 8, and its cooling wind upwards blows through radiator fin 38, anode water tank 18 and cathode water tank 4 and plays auxiliary cooling effect.

The ozone generator in the present invention is made by cold-pressing the following independent diaphragms prepared separately through different processes.

The cation exchange membrane 34 used in the present invention is a perfluorosulfonic acid cation exchange membrane (model 117) produced by DuPont, USA. The treatment process is as follows: soaking with 10% hydrogen peroxide at 80-90°C for one hour to remove organic impurities in the film. After rinsing with a large amount of double-distilled water at about 60°C, put it into 2mol/l sulfuric acid at 80-90°C for half an hour to remove a small amount of metal ions, and finally rinse it with a large amount of double-distilled water at about 60°C until it is neutral. Used in double distilled water for assembly.

The preparation process of the cathode catalyst membrane 33 is: the platinum carbon powder (200 mesh sieve) containing 5-15% (weight) platinum, the polytetrafluoroethylene emulsion (suspension) and an appropriate amount of twice distilled water are placed in a water bath at about 80°C Stir in a medium to form a paste, and then repeatedly roll it into a 0.1-0.2mm thick membrane at a temperature of 30-40°C. Wherein the weight of polytetrafluoroethylene accounts for 5-15% of the weight of platinum carbon powder. Dry the rolled diaphragm at 50-60°C, and cut it into the required size for assembly. The cathode catalyst membrane produced by this process has porous and conductive properties, and the hydrogen gas and water accompanied by proton migration at the contact interface of the catalyst membrane/cation exchange membrane can smoothly enter the cathode chamber through the micropores of the cathode catalyst membrane.

The preparation process of the anode catalyst membrane 35 is: stirring lead dioxide powder (180 mesh sieve), polytetrafluoroethylene emulsion (suspension) and appropriate amount of double distilled water at about 80° C. to form a paste. Then it is rolled into a membrane of 0.2-0.3mm at a temperature of 30-40°C. Wherein polytetrafluoroethylene accounts for 1-5% of lead dioxide powder weight. The membrane is dried at 50-60°C and then cut into the required size for storage until assembly. The anode catalytic membrane made by this process has porous conductivity, and the ozone and oxygen generated at the contact interface of the anode catalyst membrane/cation exchange membrane can smoothly enter the anode chamber through the micropores of the anode catalyst membrane; at the same time, the raw water can pass through the The micropores of the membrane reversely migrate into the anode catalyst membrane/cation exchange membrane reaction interface to participate in the anode reaction. Part of the feed water migrates to the cathode compartment along with the protons through the cation exchange membrane.

The preparation process of the anode porous current collector 36 is: the sintered porous titanium sheet (maximum pore size is 26 μm, air permeability is 119M ³ /m ² .hkPa) is degreased and etched with 5-20% (weight) hydrochloric acid After pretreatment, rinse with double distilled water until there is no chloride ion and then dry it. Then apply an organic solution containing platinum, tin, and antimony on its surface, and oxidize it in an electric furnace at 500-530°C to form a thin layer of conductive oxide containing platinum, tin, and antimony on the surface to prevent the porous current collector from Passivation occurs when an anodic current is passed. The porous current collector made by the above process has the function of conduction and gas-liquid conduction (that is, the gas product can leave the electrode reaction interface through the current collector; and the raw material water can enter the electrode reaction interface through the current collector). Wherein said containing platinum, tin, the percentage by weight of the organic solution of antimony is composed of:

Concentrated hydrochloric acid 3-9%; H ₂ P _t Cl ₆ .6H ₂ O 1-2%; S _n Cl ₄ .5H ₂ O 5-10%; S _b Cl ₃ 0.5-1.5%; C ₄ H ₉ OH 60 -90%.

The preparation process of the cathode porous current collector 32 is: degreasing the sintered porous titanium sheet (the maximum pore size is 26 μm, and the air permeability is 119M ³ /m ² .hkPa) and then etching it with 5-20% (weight) hydrochloric acid. Rinse with double distilled water until there is no chloride ion, dry it, save it, and use it when assembling. The porous current collector has the functions of conduction and gas-liquid conduction.

The deflector 31 is a metal titanium plate, which is processed to form parts with vertical and horizontal grooves, as shown in FIG. 3 . The deflector is respectively assembled in the frame of the cathode and the anode to form two chambers of the cathode and the anode. The surfaces with vertical and horizontal grooves respectively face the cathode and anode porous current collectors. The vertical and horizontal grooves of the deflector 31 can accommodate raw water, and the raw water and gas products convect and diffuse in the grooves. The deflector has a conductive cooling function.

The anode chamber frame 37 is made of polytetrafluoroethylene material and processed into independent components, as shown in FIG. 3 . The frame is provided with upper and lower air nozzles, which are respectively connected with the anode water tank 18 to form a raw material water circulation loop in the anode chamber. With the help of the gas (ozone, oxygen) rising force generated by the anode reaction and the temperature difference of the raw material water temperature in the anode chamber higher than the water temperature in the anode water tank as the power, the automatic circulation of water is formed to play a cooling role.

The cathode chamber frame 30 is selected from plexiglass or ABS plastic for processing and molding, as shown in FIG. 3 . The frame is provided with upper and lower air nozzles, which are respectively connected with the cathode water tank 4 to form a raw material water circulation loop in the cathode chamber. With the help of the rising force of the gas (hydrogen) generated by the cathode reaction and the temperature difference of the raw material water temperature in the cathode chamber higher than the water temperature in the cathode water tank as the power, the automatic circulation of water is formed to play a cooling role.

Sealing pad 29 selects the silicon rubber material to make, and it guarantees the sealing of the gas and raw material water produced in the Yin and Yang chambers.

The anti-corrosion sheet 28 is made of titanium metal to prevent corrosion of the guide splint. The deflector splint 27 is made of hard alloy aluminum plate, and is connected with an external DC power supply as the cathode and anode electrodes of the generator.

Ozone generator of the present invention is to adopt cold press assembly method to make by above-mentioned each element, and its assembly sequence is:

Anode heat sink 38, diversion splint 27, anticorrosion sheet 28, gasket 29, diversion plate 31, anode chamber frame 37, gasket 29, anode porous current collector 36, anode catalyst membrane 35, cation exchange membrane 34, Cathode catalyst membrane 33, cathode porous collector sheet 32, sealing gasket 29, deflector 31, cathode chamber frame 30, sealing gasket 29, anticorrosion sheet 28, deflector splint 27, then use bolts, nuts, washers, insulating washers fasten.

The electrolysis type ozone generating device of the present invention has simple preparation process and convenient assembly, and compared with the prior art ozone generating device, the cost of the device of the present invention can be reduced by 30-50%. Moreover, the raw material water in the cathode and anode water tanks of the electrolytic ozone generator of the present invention can be automatically balanced, and the highest output ozone is 0.1MPa higher than the atmospheric pressure. The device can run stably for a long time, and the ozone generating efficiency is high. The following table is a comparison of the ozone generating efficiency between the device of the present invention and some electrolytic ozone generating devices in the prior art:

      Cell Voltage   Current Density   Ozone Generation Efficiency   References

(v) (A/cm ² ) (%) The present invention 3.5 1.5 18-20 prior art 1 3.6 1.0 16 US4927800 prior art 2 4.0 8 JP43390/90 prior art 3 3.3 1.0 13 JP20488/91 prior art 4 4.0 7 JP43389/90 Prior Art 5 1.0 13-16 US5203972 Example: Example 1: Preparation of Electrolytic Ozone Generator (8)

a. Preparation of cation-exchange membrane (34): 117 type perfluorosulfonic acid cation-exchange membranes (DuPont products) were soaked for one hour at 90°C with 10% hydrogen peroxide to remove organic impurities in the membrane. Rinse with double distilled water at 60°C, then soak in 2mol/l sulfuric acid at 80°C for half an hour to remove a small amount of metal ions, and finally rinse with a large amount of double distilled water at 60°C until neutral, and store in double distilled water To be used when assembling.

b. the preparation of cathode catalyst membrane (33): the platinum carbon powder (200 mesh sieves) containing 6% (weight) platinum and polytetrafluoroethylene emulsion (suspension) and appropriate amount of double distilled water are in a water bath at about 80 ℃ Stir in a medium to form a paste, and then repeatedly roll it into a 0.1mm thick membrane at a temperature of 35°C. Wherein the weight of polytetrafluoroethylene accounts for 10% of the weight of the platinum carbon powder. The laminated membranes were dried at 60°C and cut into required sizes for assembly.

c. Preparation of the anode catalyst membrane (35): Stir β-lead dioxide powder (180-mesh sieve), polytetrafluoroethylene emulsion (suspension) and appropriate amount of double distilled water at about 80°C to form a paste. Then it is rolled into a 0.2 mm membrane at a temperature of 40°C. Wherein polytetrafluoroethylene accounts for 2% of lead dioxide powder weight. The diaphragm is dried at 55°C and then cut into the required size for storage until assembly.

d. Preparation of the anode porous current collector (36): After the sintered porous titanium sheet (maximum pore diameter is 26 μm, air permeability is 119M ³ /m ² .hkPa) is degreased and pre-treated by etching with 10% hydrochloric acid, Rinse with double distilled water until free of chloride ions and dry. Then apply an organic solution containing platinum, tin, and antimony on its surface, and oxidize it in an electric furnace at 520°C to form a thin layer of conductive oxide containing platinum, tin, and antimony on its surface. Wherein said containing platinum, tin, the percentage by weight of the organic solution of antimony is composed of:

Concentrated hydrochloric acid 5%; H ₂ P _t Cl ₆ .6H ₂ O 1%; S _n Cl ₄ .5H ₂ O 8%; S _b Cl ₃ 1.0%; C ₄ H ₉ OH 85%.

e. Preparation of the cathode porous current collector (32): degrease the sintered porous titanium sheet (the maximum pore size is 26 μm, and the air permeability is 119M ³ /m ² .hkPa) and etch it with 10% hydrochloric acid, and use twice distilled water Rinse until free of chloride ions, dry, and store until assembly.

Cut the five components prepared above into squares with a size of 8 cm ² , and cooperate with other components, according to the anode cooling fin (38), deflector splint (27), anti-corrosion sheet (28), sealing gasket (29), deflector (31), anode chamber frame (37), gasket (29), anode porous current collector (36), anode catalyst membrane (35), cation exchange membrane (34), cathode catalyst membrane (33), cathode The sequential arrangement of the porous collector sheet (32), sealing gasket (29), deflector (31), cathode chamber frame (30), sealing gasket (29), anti-corrosion sheet (28), and deflector splint (27), The deflector (31) is made of a 10mm thick metal titanium plate, and seven grooves with a width of 2.5mm and a depth of 6mm are evenly distributed on one side; the cathode chamber frame (30) is injection molded with plexiglass material, and the frame There is a space of 31 × 31 × 9mm in ^the interior, and the inner diameter of the upper and lower air-water connection nozzles is 4mm; the anode chamber frame (37) is processed with polytetrafluoroethylene, and its shape, size and internal volume are exactly the same as those of the cathode chamber frame (30). Consistent; anticorrosion sheet (28) adopts industrial pure titanium, thickness is 0.8mm, area is 40 * 40mm ² ; diversion splint (27) is hard alloy aluminum material, thickness is 8mm, area is 60 * 60mm ² ; Then Fasten with bolts (40), nuts (25), washers (26, 42) and insulating washers (39), to obtain the electrolytic ozone generator (8) of the present invention. Embodiment 2: the preparation of electrolytic type ozone generator (8)

a. Preparation of cation-exchange membrane (34): 117 type perfluorosulfonic acid cation-exchange membranes (DuPont products) were soaked for one hour at 80°C with 10% hydrogen peroxide to remove organic impurities in the membrane. Rinse with double distilled water at 60°C, then soak in 2mol/l sulfuric acid at 80°C for half an hour to remove a small amount of metal ions, and finally rinse with a large amount of double distilled water at 60°C until neutral, and store in double distilled water To be used when assembling.

b. the preparation of cathode catalyst diaphragm (33): the platinum carbon powder (200 mesh sieves) containing 12% (weight) platinum and polytetrafluoroethylene emulsion (suspension) and appropriate amount of twice distilled water are in a water bath at about 80 ℃ Stir it into a paste, and then roll it repeatedly at a temperature of 40°C to form a 0.2mm thick membrane. Wherein the weight of polytetrafluoroethylene accounts for 15% of the weight of platinum carbon powder. The laminated membranes were dried at 60°C and cut into required sizes for assembly.

c. Preparation of the anode catalyst membrane (35): Stir lead dioxide powder (180-mesh sieve), polytetrafluoroethylene emulsion (suspension) and appropriate amount of double distilled water at about 80°C to form a paste. Then it was rolled into a 0.2mm film at a temperature of 35°C. Wherein polytetrafluoroethylene accounts for 1% of lead dioxide powder weight. The diaphragm is dried at 60°C and then cut into the required size for storage until assembly.

d. Preparation of the anode porous current collector (36): After the sintered porous titanium sheet (maximum pore diameter is 26 μm, air permeability is 119M ³ /m ² .hkPa) is degreased and pre-treated by etching with 10% hydrochloric acid, Rinse with double distilled water until free of chloride ions and dry. Then apply an organic solution containing platinum, tin, and antimony on its surface, and oxidize it in an electric furnace at 500°C to form a thin layer of conductive oxide containing platinum, tin, and antimony on its surface. Wherein said containing platinum, tin, the percentage by weight of the organic solution of antimony is composed of:

Concentrated hydrochloric acid 9%; H ₂ P _t Cl ₆ .6H ₂ O 2%; S _n Cl ₄ .5H ₂ O 10%; S _b Cl ₃ 1.0%; C ₄ H ₉ OH 78%.

e. Preparation of the cathode porous current collector (32): degrease the sintered porous titanium sheet (the maximum pore size is 26 μm, and the air permeability is 119M ³ /m ² .hkPa) and etch it with 10% hydrochloric acid, and use twice distilled water Rinse until free of chloride ions, dry, and store until assembly.

According to the same method as in Example 1, the above-mentioned components and other components were assembled into the electrolytic ozone generator (8) of the present invention. Embodiment 3: the preparation of electrolytic type ozone generator (8)

a. Preparation of cation-exchange membrane (34): 117 type perfluorosulfonic acid cation-exchange membranes (products of DuPont) were soaked with 10% hydrogen peroxide for one hour at 85° C. to remove organic impurities in the membrane. After rinsing with double distilled water at 60°C, put it into 80°C 2mol/l sulfuric acid for half an hour to remove a small amount of metal ions, and finally rinse with a large amount of double distilled water at 60°C until neutral, and store in double distilled water To be used when assembling.

b. the preparation of cathode catalyst diaphragm (33): the platinum carbon powder (200 mesh sieves) containing 10% (weight) platinum and polytetrafluoroethylene emulsion (suspension) and appropriate amount of twice distilled water are in a water bath at about 80 ℃ Stir in a medium to form a paste, and then repeatedly roll it into a 0.1mm thick membrane at a temperature of 30°C. Wherein the weight of polytetrafluoroethylene accounts for 5% of the weight of platinum carbon powder. The laminated membranes were dried at 60°C and cut into required sizes for assembly.

c. Preparation of the anode catalyst membrane (35): Stir β-lead dioxide powder (180-mesh sieve), polytetrafluoroethylene emulsion (suspension) and appropriate amount of double distilled water at about 80°C to form a paste. Then it was rolled into a 0.3mm membrane at a temperature of 30°C. Wherein polytetrafluoroethylene accounts for 1.5% of lead dioxide powder weight. The diaphragm is dried at 60°C and then cut into the required size for storage until assembly.

d. Preparation of the anode porous current collector (36): After the sintered porous titanium sheet (maximum pore diameter is 26 μm, air permeability is 119M ³ /m ² .hkPa) is degreased and pre-treated by etching with 10% hydrochloric acid, Rinse with double distilled water until free of chloride ions and dry. Then apply an organic solution containing platinum, tin, and antimony on its surface, and oxidize it in an electric furnace at 520°C to form a thin layer of conductive oxide containing platinum, tin, and antimony on its surface. Wherein said containing platinum, tin, the percentage by weight of the organic solution of antimony is composed of:

Concentrated hydrochloric acid 3%; H ₂ P _t Cl ₆ .6H ₂ O 1.5%; S _n Cl ₄ .5H ₂ O 5%; S _b Cl ₃ 0.5%; C ₄ H ₉ OH 90%.

e. Preparation of the cathode porous current collector (32): degrease the sintered porous titanium sheet (maximum pore diameter of 26 μm, air permeability of 119M ³ /m ² .hkPa) and etch it with 10% hydrochloric acid, and use twice distilled water Rinse until free of chloride ions, dry, and store until assembly.

According to the same method as in Example 1, the above-mentioned components and other components were assembled into the electrolytic ozone generator (8) of the present invention. Embodiment 4: Assembly and application of the electrolytic ozone generator of the present invention

Adopt the electrolytic type ozone generator (8) that embodiment 1 makes and following element:

1500 ml cathode water tank (4), 1200 ml 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 detection Devices (19, 20, 21, 22) and isolation tubes (17) are installed according to methods known in the art to form the electrolytic ozone generator of the present invention.

When the electrolytic ozone generating device of this embodiment operates at a current density of 1.5A/ ^cm2 , the voltage of the generator tank is 3.5±0.1V, and when the ambient temperature is about 25°C, it operates continuously for 24 hours, and the cathode and anode water tanks The temperature of the raw material water in the tank can be maintained at about 30°C, and the ozone generation efficiency is 18%.

Ozone at a pressure of 0.08Mpa higher than atmospheric pressure can be output from the anode water tank.

Claims (25)

1, a kind of electrolytic type ozone generator, comprise electrolytic type ozone generator (8), the anode water tank (18) that links to each other with the anode chamber of ozone generator (8) by anode circulation water pipe (7), pass through cathode circulation water pipe ( 6) the cathode water tank (4) that links to each other with the cathode chamber of ozone generator (8), it is characterized in that: Wherein the electrolytic ozone generator (8) comprises an independent cation exchange membrane (34), an independent anode catalyst membrane (35) and an independent cathode catalyst membrane which are respectively close to the both sides of the cation exchange membrane (34) sheet (33), 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 according to claim 1, characterized in that: the cathode catalyst diaphragm (33) in the electrolytic ozone generator (8) contains platinum carbon powder and polytetrafluoroethylene, wherein The platinum carbon powder contains 5-15% (weight) of platinum, and the weight of polytetrafluoroethylene accounts for 5-15% of the weight of the platinum carbon powder. 3. The electrolytic ozone generator according to claim 2, characterized in that the particle size of the platinum carbon powder in the cathode catalyst membrane (33) is less than 200 mesh. 4. The electrolytic ozone generator according to claim 2, characterized in that the thickness of the cathode catalyst membrane (33) is 0.1-0.2 mm. 5. The electrolytic odor generating device according to claim 1, characterized in that: the anode catalyst membrane (35) in the electrolytic ozone generator (8) contains lead dioxide and polytetrafluoroethylene. 6. The electrolytic ozone generator according to claim 5, characterized in that the weight of polytetrafluoroethylene in the anode catalyst membrane (35) accounts for 1-5% of the weight of lead dioxide. 7. The electrolytic ozone generator according to claim 5 or 6, characterized in that the particle size of the lead dioxide used in the anode catalyst membrane (35) is smaller than 180 mesh. 8. The electrolytic ozone generator according to claim 5 or 6, characterized in that the lead dioxide used in the anode catalyst membrane (35) is β-lead dioxide. 9. The electrolytic ozone generator according to claim 7, characterized in that the lead dioxide used in the anode catalyst membrane (35) is β-lead dioxide. 10. The electrolytic ozone generator according to claim 5 or 6, characterized in that the thickness of the anode catalyst membrane (35) is 0.2-0.3 mm. 11. The electrolytic ozone generator according to claim 8, characterized in that the thickness of the anode catalyst membrane (35) is 0.2-0.3 mm. 12. The electrolytic ozone generator according to claim 9, characterized in that the thickness of the anode catalyst membrane (35) is 0.2-0.3 mm. 13. The electrolytic ozone generator according to claim 1, characterized in that: the anode porous current collector (36) in the electrolytic ozone generator (8) is coated with a layer containing platinum, tin and Sintered porous titanium sheet of conductive oxide of antimony. 14. The electrolytic ozone generator according to claim 1, characterized in that the electrolytic ozone generator (8) further comprises a guide plate made of metal titanium with grooves evenly arranged on one side. 15. The electrolytic ozone generator according to claim 1, characterized in that: The upper end of the anode water tank (18) has a gas-collecting surface (18a), an elongated air duct (18b) is arranged on the gas-gathering surface, and ozone and oxygen outlets (24) are arranged on the top of the air duct (18b), and ozone and oxygen outlets ( 24) There is a microporous damping plate (23) inside, an isolation tube (17) is inside the anode water tank (18), and the anode water tank (18) is connected to the anode chamber frame (37) through the anode circulation pipe (7) to form a water circulation loop; 16. The electrolytic ozone generator according to claim 1, characterized in that: the cathode water tank (4) is located higher than the anode water tank (18), and has a water inlet (2) and a water inlet cover (1 ), hydrogen outlet (3), water level detectors (19, 20, 21, 22) are housed in the cathode water tank (4), and the cathode water tank (4) is connected to the cathode chamber frame (30) through the cathode circulation pipe (6) to form a water cycle circuit. 17. The electrolytic ozone generator according to claim 1, characterized in that: A one-way balance valve (13) is set 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), a lower valve body ( 49) composition; wherein the upper valve body (51) is provided with a cathode water tank interface (43), an anode water tank interface (52), and a damping hole (52a) is arranged in the anode water tank interface (52), and an annular sealing lip (45); single The lower valve body (49) is provided with an anode water tank interface (47), a pressure limiting valve port (48) and a pressure limiting plug (48a) towards the balance lower valve body. 18. The electrolytic ozone generator according to claim 1, characterized in that an on-off solenoid valve is set between the cathode water tank (4) and the anode water tank (18). 19. A method for preparing an electrolytic ozone generator (8) as claimed in claim 1, comprising: a. Stir platinum carbon powder containing 5-15% (weight) platinum and polytetrafluoroethylene emulsion with an appropriate amount of double distilled water in a water bath at about 80°C to form a paste, then repeatedly grind at a temperature of 30-40°C Press into a 0.1-0.2mm thick membrane, in which the weight of polytetrafluoroethylene accounts for 5-15% of the weight of platinum carbon powder, dry the rolled membrane at 50-60°C and cut it into the required size , making a cathode catalyst membrane (33); b. Stir lead dioxide powder, polytetrafluoroethylene emulsion and appropriate amount of twice-distilled water in a water bath at about 80°C to form a paste, and then repeatedly roll it into a film with a thickness of 0.2-0.3mm at a temperature of 30-40°C sheet, wherein the weight of polytetrafluoroethylene accounts for 1-5% of the weight of lead dioxide, and the rolled membrane is dried at 50-60°C and cut into required size to obtain an anode catalyst membrane (35 ); c. The sintered porous titanium sheet is degreased and pre-treated with 5-20% (weight) hydrochloric acid etching, rinsed with twice distilled water until there is no chloride ion, and then dried, and then coated with platinum, tin, The organic solution of antimony is oxidized in an electric furnace at 500-530° C. to form a thin layer of conductive oxide containing platinum, tin and antimony on its surface to obtain anode porous current collectors (36); d. Degrease the sintered porous titanium sheet, pre-treat it with 5-20% (weight) hydrochloric acid, rinse it with double distilled water until it is free of chloride ions, and then dry it to prepare the cathode porous current collector (32). 20. The preparation method of the ozone generator according to claim 19, characterized in that the particle size of the platinum carbon powder used in the preparation of the cathode catalyst membrane (33) is less than 200 mesh. 21. The preparation method of the ozone generator according to claim 19, characterized in that the particle size of the lead dioxide used in the preparation of the anode catalyst membrane (35) is less than 180 mesh. 22. The preparation method of the ozone generator according to 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 for preparing an ozone generator according to claim 19, characterized in that the weight percent of the organic solution containing platinum, tin and antimony used in the preparation of the porous anode current collector (36) is composed of : concentrated hydrochloric acid 3-9%; H ₂ PtCl ₆ .6H ₂ O 1-2%; S _n Cl ₄ .5H ₂ O 5-10%; S _b Cl ₃ 0.5-1.5%; C ₄ H ₉ OH 60- 90%. 24. The preparation method of the ozone generator as claimed in claim 19, characterized in that the maximum pore diameter of the sintered porous titanium sheet used in the preparation of the anode porous current collector (36) is 26 μm, and the air permeability is 119M ³ /m ² .h.kPa. 25. The preparation method of an ozone generator as claimed in claim 19, characterized in that the maximum pore diameter of the sintered porous titanium sheet used in the preparation of the cathode porous current collector (32) is 26 μm, and the air permeability is 119M ³ /m ² .h.kPa.

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