WO2020078266A1

WO2020078266A1 - Membrane electrode electrolytic ozone generator and preparation process therefor

Info

Publication number: WO2020078266A1
Application number: PCT/CN2019/110552
Authority: WO
Inventors: 胡松
Original assignee: 胡松
Priority date: 2018-10-19
Filing date: 2019-10-11
Publication date: 2020-04-23
Also published as: CN108977828B; CN108977828A

Abstract

The present invention provides a membrane electrode electrolytic ozone generator and a preparation process therefor. The membrane electrode electrolytic ozone generator comprises a cation exchange membrane, and a cathode structure and an anode structure respectively provided at two sides of the cation exchange membrane, wherein a sealing ring is provided on a cathode guide-fastening plate; a cathode microporous plate is put into the sealing ring to be tightly attached to the cathode guide-fastening plate; a cathode catalyst is put into the sealing ring to be attached to the cathode microporous plate; the cathode structure, the cation exchange membrane and the anode structure are integrally fastened by means of fastening elements. The cathode catalyst is a cathode catalyst particle layer formed by Ti2O3 particles or Ti2O3 particle and isolate particle mixtures. The material cost of the cathode catalyst of the membrane electrode electrolytic ozone generator is reduced. After the tight pressing with pressure, the contact of the fastened cathode catalyst particle layer and the cation exchange membrane is more uniform. The problem of current distribution non-uniformity of the membrane electrode electrolytic ozone generator is solved. The service life of the membrane electrode electrolytic ozone generator is effectively prolonged.

Description

Membrane electrode electrolytic ozone generator and preparation process thereof

Technical field

The invention belongs to the technical field of electrochemical ozone preparation, and relates to a cathode catalyst structure and process of a membrane electrode electrolytic ozone generator membrane electrode, in particular to a membrane electrode electrolytic ozone generator and a preparation process thereof.

Background technique

Ozone has been used by humans for more than 100 years, and it will be used more widely and deeply by humans in the future.

There are several methods for preparing ozone manually. Generally, there are two types of methods: high-pressure corona method using air or oxygen as raw materials, and electrochemical electrolysis method using deionized water as raw materials.

Membrane electrode electrolytic ozone generator is a specific product of electrochemical electrolysis.

Membrane electrode electrolysis ozone generator uses deionized water as raw material, cathode electrolysis generates hydrogen, anode electrolysis generates oxygen and ozone. The hydrogen, oxygen and ozone formed by electrolysis of raw material deionized water are naturally of high purity and high concentration. Because of this advantage, the ozone produced by the membrane electrode electrolysis method has been widely used and has good development prospects in many aspects such as disinfection, medical treatment, and oxidation processing of large-scale integrated circuits.

Principle of membrane electrode electrolytic ozone generator:

When direct current is input from the outside, under the action of an electric field and a catalyst, H ^{+ of} water (H ₂ O) passes through the sulfonic acid cation chain of the cation exchange membrane and the migration of H ⁺ accompanies the migration of water molecules. The electrochemical reaction formula is:

Cathodic hydrogen evolution reaction ^{^{_{2H + + 2e - → H 2}}} ↑

Cathodic oxygen depolarization _{^{1 / 2O 2 + 2H + +}} e - → H 2 O

The anode of the main reaction _{_{H 2 O → 1 / 3O 3}} ↑ + 2e - + 2H +

The anode side reactions _{_{H 2 O → 1 / 2O 2}} ↑ + 2e - + 2H +

The core component of the membrane electrode electrolytic ozone generator is the membrane electrode. The membrane electrode is made of perfluorosulfonic acid cation exchange membrane (referred to as cation exchange membrane for short) and the cathode and anode catalysts on both sides of the membrane. The cation exchange membrane generally adopts DuPont Nafion ^@ cation exchange membrane. The cathode catalyst generally uses platinum group metals, gold, silver, nickel, ruthenium, or a mixture of metals, and the anode catalyst generally uses platinum-based metals, gold, and lead dioxide.

Membrane electrode preparation methods have used the following processes:

A hot-pressing process is used to prepare the membrane electrode composite. This process presses the anion and anode catalysts on the cation exchange membrane at a temperature of 80-100 ° C. The formed membrane electrode will deform when stored under normal temperature and humidity conditions Not convenient for production use.

Electroless plating is used to form a membrane composite electrode, and a layer of catalyst is electrodeposited on both sides of the ion exchange membrane. The concentration of metal ions, oxidants or reducing agents used in this method must strictly ensure the concentration of the electrolyte during the chemical plating process 、 The temperature and PH value are stable, otherwise it is difficult to ensure the quality of the catalyst.

The Chinese invention patent "Electrolytic Ozone Generator" (Patent No. ZL97122126.X) has made significant improvements to the membrane electrode process: the cathode catalyst and anode catalyst are made into separate membranes. One side of the independent membranes of the anion and anode catalysts is close to the two sides of the cation exchange membrane respectively. On the other side of the anion and anode catalyst membranes, there are mechanical members supporting the anion and anode catalyst membranes, respectively. The cathode structure and anode structure of the membrane electrode electrolytic generator. In the assembly of the membrane electrode electrolytic ozone generator, the cathode structure and anode structure sandwich the cation exchange membrane and merge into one, and then fasten with fastening screws. During the fastening process, the cathode catalyst membrane-cation exchange membrane-anode The catalyst membrane is tightly combined with the membrane electrode, and the electrolytic ozone generator is also assembled (see Figure 1 and Figure 2).

The preparation process of the anode catalyst membrane of the invention patent (patent number ZL97122126.X) is as follows:

Mix lead dioxide powder and polytetrafluoroethylene emulsion with an appropriate amount of deionized water in a 80 ° C water bath to form a paste, and then repeatedly roll to 0.2-0.3mm on a flat plate at a temperature of 30-40 ° C Thick membrane, in which the weight of polytetrafluoroethylene emulsion accounts for 1% -5% of the weight of lead dioxide, the laminated membrane is dried at a temperature of 50-60 ℃, sheared to form a cationic catalyst Diaphragm.

The preparation process of the cathode catalyst membrane is as follows:

Mix platinum carbon powder and polytetrafluoroethylene emulsion containing 5-15% by weight of platinum with appropriate amount of deionized water in a 80 ° C water bath to form a paste, and then at a temperature of 30-40 ° C on a flat plate The film is repeatedly rolled into a 0.1-0.2mm thick film, where the weight of the polytetrafluoroethylene emulsion accounts for 5% -15% of the weight of the platinum carbon powder, and the rolled film is dried at a temperature of 50-60 ℃ , Shear forming to make a cathode catalyst membrane (see Figure 3). In Figures 1-3, a1, cation exchange membrane; a2, anode catalyst membrane a3, cathode catalyst membrane; a4, mechanical member supporting cathode catalyst; a5, mechanical member supporting anode catalyst; a3.1, activated carbon; a3.2, platinum; a3.3, polytetrafluoroethylene emulsion (curing).

The platinum-carbon catalyst is composed of a carrier activated carbon adsorbing platinum metal, and its process is as follows:

A certain amount of 200-mesh sieve carrier activated carbon, put into a certain amount of deionized water and boil for 2 hours, then cool down to use, a certain amount of chloroplatinic acid (H ₂ PtCl ₆ • 6 H ₂ O) dissolved in activated carbon water and fully stirred for 2 hours , And then ultrasonically oscillated. The above aqueous solution is 80-90 ^. C was fully stirred again in the water bath for 2 hours. While stirring, formaldehyde was slowly dropped to reduce platinum ions to platinum element. At this time, the reduced platinum element was embedded in the fine cavity of the carrier activated carbon to form a carbon-supported platinum catalyst.

technical problem

The existing membrane electrode electrolytic ozone generator (invention patent 97122126.X) has the following disadvantages:

1. The cathode catalyst uses precious metal platinum, which has a high material cost. The platinum carbon powder is prepared as an "independent" membrane, which is manually operated. The consistency of the membrane quality is difficult to control; the self-made carbon-supported platinum catalyst process is complicated.

2. In more than ten years of long-term production and practice, it has been found that the "breakdown" phenomenon occurs locally in the cation exchange membrane, and the service life of the generator is relatively short, generally 3000-5000 hours. The reasons for this main disadvantage are as follows:

Under the condition of deionized water, the membrane electrode electrolytic ozone generator must be pressurized by an external power supply to provide direct current. Under the action of an external electric field, H ⁺ has the energy to migrate;

The DC current that the membrane electrode bears is relatively large, up to 2A / cm ² ;

In the operation of the membrane electrode, if the contact between the anion catalyst and the anode catalyst and the cation exchange membrane is uneven, it will cause uneven distribution of current density on the membrane electrode, and the high current will produce high temperature, and the high temperature will damage the ion exchange membrane Wear), so the uniformity of the membrane electrode cathode, anode catalyst and cation exchange membrane is directly related to the service life of the membrane electrode;

Invention patent (patent number ZL97122126.X) The thickness of the anode lead dioxide catalyst membrane is about 0.2mm, the thickness of the cathode catalyst platinum carbon is about 0.1-0.2mm, the thickness of the cation exchange membrane is 0.17mm, and the overall thickness of the membrane electrode is 0.5 -Around 0.6mm, it is extremely difficult to ensure a uniform current distribution in the processing technology on such a thin membrane electrode. Due to the above-mentioned shortcomings, the membrane electrode area of the existing membrane electrode electrolytic ozone generator is also difficult to reach more than 16 cm ² , thereby affecting the product specifications and application scope of the membrane electrode electrolytic ozone generator.

How to design a membrane electrode electrolytic ozone generator and its preparation process, by changing the type of cathode catalyst to achieve the purpose of reducing the cost of materials; by reforming the structure and process of the cathode catalyst, the service life of the membrane electrode electrolytic ozone generator is increased. This is a technical problem to be solved urgently in this technical field.

Technical solution

In view of the above problems in the prior art, the present invention provides a membrane electrode electrolytic ozone generator and a preparation process thereof, which reduces the manufacturing cost of the membrane electrode electrolytic ozone generator and increases the service life of the membrane electrode electrolytic ozone generator.

The object of the present invention is achieved by the following technical solution: a membrane electrode electrolytic ozone generator, including a cation exchange membrane and a cathode structure and an anode structure respectively provided on both sides thereof, characterized in that the cathode structure includes cathode catalyst particles Layer, cathode microwell plate, cathode diversion-fastening plate and sealing ring, the cathode diversion-fastening plate is provided with the sealing ring, and the cathode microwell plate is placed in the sealing ring and The cathode diversion-fastening plate is tightly attached, the cathode catalyst particle layer is placed in the sealing ring and is attached to the cathode microporous plate, and the cathode structure, cation exchange membrane and The anode structure is fastened as a whole, and the cathode catalyst particle layer is at least composed of Ti ₂ O ₃ particles.

Improvement to the above technical solution: Separator particles are added between Ti ₂ O ₃ particles in the cathode catalyst particle layer, and the separator particles are polytetrafluoroethylene particles or quartz particles.

Further improvement to the above technical solution: the particle size of the Ti ₂ O ₃ particles is 50-200 mesh; the particle size of the polytetrafluoroethylene particles or quartz particles is 100-200 mesh, and all the particles in the cathode catalyst particle layer The weight ratio of the weight of the Ti ₂ O ₃ particles to the weight of the polytetrafluoroethylene particles or quartz particles is 100: 0.5-20.

Further improvement to the above technical solution: the ratio of the thickness of the cathode catalyst particle layer to the diameter of its cylindrical circular surface is 4-8: 100, and the minimum thickness is not less than 1 mm.

The above technical solution is further improved: the cathode diversion_fastening plate is provided with a through hole in the middle, the cathode microporous plate is a titanium microporous plate, and the pores of the titanium microporous plate are 40-80 μm.

The above technical solution is further improved: the sealing ring is an annular body with a rectangular cross-sectional shape, the material of the sealing ring is fluororubber or silicone rubber, the cation exchange membrane is circular, and the cathode catalyst particle layer It is cylindrical, the titanium microporous plate is circular, the diversion_fastening plate is circular, the outer diameters of the cathode catalyst particle layer and the titanium microporous plate are all circular with the middle of the sealing ring The inner diameter is the same, the thickness of the titanium microporous plate is 0.8-2mm, the thickness of the sealing ring is equal to the thickness of the titanium microporous plate and the thickness of the cathode catalyst particle layer, and the diversion_fastening plate is provided in the middle A circular concave surface, the sealing ring is embedded in the circular concave surface.

A preparation process of the above-mentioned membrane electrode electrolytic ozone generator is characterized in that it includes the following steps:

(1) A sealing ring 4 is provided on the concave surface of the cathode diversion_fastening plate 3, a cathode microporous plate is provided in the sealing ring 4, and Ti ₂ O ₃ particles or a mixture of Ti ₂ O ₃ particles and separator particles is filled in On the cathode microwell plate in the seal ring, scrape the accumulated Ti ₂ O ₃ particles or the mixture of Ti ₂ O ₃ particles and separator particles to form a cathode catalyst particle layer, which is flush with the top surface of the seal ring;

(2) Under the parallel downward pressure of the press, the cathode catalyst particles are laminated to a strength of 100-200 N / cm ² ;

(3) Then, lay a cation exchange membrane on the sealing ring to make the cation exchange membrane adhere to the surface of the cathode catalyst particle layer;

(4) Laminate the anode structure and the cation exchange membrane on the cathode structure, and fasten the cathode structure, cation exchange membrane, and anode structure together with fasteners, and the fastening strength is 200- 300N / cm ² .

Improvement of the above technical solution: After the tightening strength reaches 200-300N / cm ² according to the step (4), the cathode catalyst particle layer is completely infiltrated with deionized water, and the second pressing with the tightening screw is performed at a pressure of 400-700N / cm ² makes the particle distribution in the cathode catalyst particle layer more uniform, and its contact with the cation exchange membrane is more uniform.

Beneficial effect

Compared with the prior art, the present invention has the following advantages and positive effects:

1. The cathode catalyst of the membrane electrode electrolysis ozone generator of the present invention uses Ti ₂ O _{3 to} replace the existing precious metal—platinum, which reduces the material cost.

2. The preparation process of the cathode catalyst structure of the present invention makes the particle distribution of the cathode catalyst layer more uniform and the contact with the cation exchange membrane more uniform. The problem of uneven distribution of the membrane electrode current of the electrolytic ozone generator is solved, and the service life of the membrane electrode electrolytic ozone generator is effectively improved. The batch test results show that the continuous service life can reach 20,000 hours; the membrane electrode electrolytic ozone generator of the present invention uses a mixture of Ti ₂ O ₃ particles and separator particles to form a cathode catalyst particle layer, which is infiltrated with deionized water With the method of secondary tightening, the continuous service life has exceeded 36000 hours.

BRIEF DESCRIPTION

1 is a schematic diagram of the structure of a prior art membrane electrode electrolytic ozone generator;

Figure 2 is a schematic diagram of the cathode structure of the prior art membrane electrode electrolytic ozone generator;

3 is an enlarged schematic diagram of the microstructure of the cathode membrane of the prior art membrane electrode electrolytic ozone generator;

4 is a schematic diagram of the cathode structure of a membrane electrode electrolytic ozone generator of the present invention;

5 is a microscopic schematic view of an embodiment of a cathode structure of a membrane electrode electrolytic ozone generator of the present invention;

6 is a microscopic schematic view of another embodiment of the cathode structure of a membrane electrode electrolytic ozone generator of the present invention;

7 is a schematic diagram of the scraping process of the cathode catalyst particle layer of a membrane electrode electrolytic ozone generator of the present invention;

8 is a schematic view of the process of using a press to act on the cathode catalyst particle layer of the present invention;

9 is a schematic diagram of a membrane electrode electrolytic ozone generator assembly process of the present invention;

10 is a schematic diagram of deionized water injection of the present invention;

11 is a schematic diagram of Embodiment 1 of a cathode structure of a membrane electrode electrolytic ozone generator of the present invention;

12 is a schematic diagram of Embodiment 2 of a cathode structure of a membrane electrode electrolytic ozone generator of the present invention.

In the figure, 1. Cathode catalyst particle layer; 2. Cathode microwell plate; 3. Cathode diversion-fastening plate; 4. Sealing ring; 5. Cation exchange membrane; 6. Fastening screw; 7. Insulation pad.

Embodiments of the invention

The present invention will be further described in detail below with reference to the drawings:

4 to 10, an embodiment of a membrane electrode electrolytic ozone generator of the present invention includes a cation exchange membrane 5 and a cathode structure and an anode structure respectively provided on both sides thereof. The cathode structure includes a cathode catalyst particle layer 1 、 Cathode microplate 2, cathode diversion-fastening plate 3, sealing ring 4. A sealing ring 4 is provided on the cathode diversion-fastening plate 3, and the cathode microwell plate 2 is placed in the sealing ring 4 to be in close contact with the cathode diversion-fastening plate 3. Cathode microplate 2 is attached, and the cathode structure, cation exchange membrane 5 and anode structure are fastened together with fasteners (such as fastening screws 6), and the cathode catalyst particle layer is made of at least Ti ₂ O ₃ particles. As shown in FIG. 9, an insulating pad 7 is provided at the anode structure corresponding to the fastening screw 6.

In an embodiment shown in FIG. 5, the cathode catalyst particle layer 1 contains only Ti ₂ O ₃ particles 1.1.

In another embodiment shown in FIG. 6, separator particles 1.2 are added between the Ti ₂ O ₃ particles 1.1 in the cathode catalyst particle layer 1, and the separator particles 1.2 are polytetrafluoroethylene particles or quartz particles. The particle size of the ₂ O ₃ particles 1.1 is 50 to 200 mesh; the particle size of the polytetrafluoroethylene particles or quartz particles 1.2 is 100 to 200 meshes; the weight of the Ti ₂ O ₃ particles 1.1 in the cathode catalyst particle layer 1 is The weight ratio of vinyl fluoride particles or quartz particles 1.2 is 100: 0.5-20.

Further, the above-mentioned cathode catalyst particle layer 1 is cylindrical, and the ratio of the thickness of the cylindrical cathode catalyst particle layer 1 to the diameter of the circular surface of its cylinder is 4-8: 100, and the thickness is not less than 1 mm.

A through hole 3.1 is provided in the middle of the cathode diversion_fastening plate 3, and the through hole 3.1 is used for hydrogen gas, water and process water injection. The cathode microporous plate 2 is a titanium microporous plate, and the pores of the titanium microporous plate 2 are 40-80 μm.

Preferably, the sealing ring 4 is an annular body with a rectangular cross-sectional shape, the material of the sealing ring 4 is fluororubber or silicone rubber, the cation exchange membrane 5 is circular, the titanium microwell plate 2 is circular, and the guide The flow_fastening plate 3 has a circular shape, and the outer diameters of the cathode catalyst particle layer 1 and the titanium microporous plate 2 are consistent with the circular inner diameter in the middle of the sealing ring 4. The thickness of the titanium microporous plate 2 is 0.8 to 2 mm, the thickness of the sealing ring 4 is equal to the thickness of the titanium microporous plate 2 and the thickness of the cathode catalyst particle layer 1, and a circular concave surface is provided in the middle of the diversion_fastening plate 3. The sealing ring 4 is embedded in the circular concave surface.

Referring to FIGS. 4-10, an embodiment of the preparation process of the above-mentioned membrane electrode electrolytic ozone generator of the present invention includes the following steps:

(1) A sealing ring 4 is provided on the concave surface of the cathode diversion_fastening plate 3, and a cathode microporous plate 2 is provided in the sealing ring 4 to separate Ti ₂ O ₃ particles 1-a or Ti ₂ O ₃ particles 1.1 from The mixture of material particles 1.2 is filled into the cathode microplate 2 in the sealing ring 4, and the stacked Ti ₂ O ₃ particles 1.1 or the Ti ₂ O ₃ particles 1.1 and the separator particle mixture 1.2 are scraped to form the cathode catalyst particle layer 1, And flush with the top surface of the sealing ring 4 (as shown in Figure 7);

(2) Under the action of parallel downward pressure of the press, the cathode catalyst particle layer 1 is pressured to 100-200 N / cm ² to form a cathode catalyst particle layer (as shown in FIG. 8);

(3) Then, the cation exchange membrane 5 is laid on the sealing ring 4 to make the cation exchange membrane 5 adhere to the surface of the cathode catalyst particle layer 1;

(4) The manufactured anode structure is bonded to the cation exchange membrane 5 on the cathode structure, and the cathode structure, the cation exchange membrane 5 and the anode structure are fastened together with a fastening screw 6, and the fastening strength 200-300N / cm ² .

Further, the specific process of the above step (2): the cathode catalyst particle layer 1 is first pressed by a press for preliminary shaping, and then, deionized water is injected through the through hole 3.1 in the middle of the cathode diversion-fastening plate 3 As shown in FIG. 10, the cathode catalyst particle layer 1 is completely infiltrated with deionized water and pressed a second time with the fastening screw 6, so that the cathode catalyst particles 1 are more evenly distributed, and the cathode catalyst layer 1 is in contact with the cation exchange membrane 5 More evenly. The problem of uneven distribution of the membrane electrode current of the electrolytic ozone generator is solved, and the service life of the membrane electrode electrolytic ozone generator is effectively improved.

Referring to FIG. 11, Embodiment 1 of a membrane electrode electrolytic ozone generator of the present invention:

Preparation of cathode structure: a sealing ring 4 is provided on the cathode diversion_fastening plate 3, and a sealing ring 4 (φ39 mm (outer diameter) × φ34 mm (inner diameter) × 3 mm (thickness)) made of fluororubber is provided with a cathode The outer diameter of the microplate 2, the cathode microplate 2 (such as titanium microplate) is equal to the inner diameter of the seal ring 4. Fill the 180 mesh Ti ₂ O ₃ particles 1.1 into the sealing ring 4, scrape it out and make it equal to the sealing ring 4 (Figure 7). Under the parallel downward pressure of the press (Figure 8), the pressure of the cathode catalyst particle layer 1 reaches 100-200 N / cm ² , and the cathode catalyst particle layer 1 is basically formed. The cathode microplate 2 is a titanium microplate, and the pores of the titanium microplate are 40-80 μm.

Then, the cation exchange membrane 5 (eg Dupont Nafion ^@ 117 membrane) is laid on the pressed cathode catalytic particle layer 1 and the sealing ring 4 (Figure 9).

Place the prepared anode structure on the cation exchange membrane 5, so that the catalyst (lead dioxide) in the anode structure contacts the cation exchange membrane 5, and tighten the screw 6 to tighten the force, then conduct the flow from the cathode_tighten The through hole 3.1 in the middle of the plate 3 is filled with deionized water (Figure 10) until the cathode catalyst particle layer 1 is completely wetted, and the tightening screw 6 is continued until the cathode catalyst particle layer 1-cation exchange membrane 5-catalyst 2 in the anode structure The pressure between the lead oxides reaches 600N / cm ² . Practice has proved that the cathode structure of Example 1 of the present invention greatly improves the service life of the membrane electrode electrolytic ozone generator, and the continuous service life can reach 20,000 hours. When the continuous use time exceeds 20,000 hours, it is found that the cathode catalyst particle layer 1 containing only Ti ₂ O ₃ particles 1.1 has a phenomenon of “consolidation” locally, which affects the passage of water and gas. Therefore, the particles of Ti ₂ O ₃ having a certain particle size and the separator particles having a certain particle size are mixed in proportion to constitute a cathode catalyst particle layer having a certain thickness, as the main improvement point of Example 2.

Referring to FIG. 12, Embodiment 2 of a membrane electrode electrolytic ozone generator of the present invention:

Preparation of cathode structure: a sealing ring 4 is provided on the cathode diversion_fastening plate 3, and a sealing ring 4 (φ39 mm (outer diameter) × φ34 mm (inner diameter) × 3 mm (thickness)) made of fluororubber The outer diameter of the microwell plate 2 and the cathode microwell plate 2 is equal to the inner diameter of the sealing ring 4. After the 180 mesh Ti ₂ O ₃ particles 1.1 and the 180 mesh polytetrafluoroethylene particles 1.2 are evenly mixed at a ratio of 100: 5, fill them into the sealing ring 4, scrape it out and level with the sealing ring 4 (Figure 7). Under the parallel downward pressure of the press (Figure 8), the pressure of the cathode catalyst particle layer 1 reaches 100-200 N / cm ² , and the cathode catalyst particle layer 1 is basically formed. The cathode microplate 2 is a titanium microplate, and the pores of the titanium microplate are 40-80 μm.

Then, the cation exchange membrane 5 (such as DuPont Nafion ^@ 117 membrane) is laid on the pressed cathode catalytic particle layer 1 and the sealing ring 4 (Figure 9).

Place the prepared anode structure on the cation exchange membrane 5, so that the catalyst (lead dioxide) in the anode structure contacts the cation exchange membrane 5, and tighten the screw 6 to tighten the force, then conduct the flow from the cathode_tighten The through hole 3.1 in the middle of the plate 3 is filled with deionized water (Fig. 10) until the cathode catalyst particle layer 1 is completely infiltrated. The pressure between the lead oxides reaches 600N / cm ² .

The batch test results show that the continuous service life of the membrane electrode electrolytic ozone generator of Example 2 of the present invention has exceeded 36000 hours.

Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Those of ordinary skill in the art, within the essential scope of the present invention, make changes, modifications, additions or replacements should also It belongs to the protection scope of the present invention.

Claims

A membrane electrode electrolytic ozone generator, comprising a cation exchange membrane and a cathode structure and an anode structure provided on both sides thereof, characterized in that the cathode structure includes a cathode catalyst particle layer, a cathode microwell plate, and a cathode diversion- A fastening plate and a sealing ring, the sealing ring is provided on the cathode diversion-fastening plate, and the cathode micro-well plate is placed in the sealing ring to be in close contact with the cathode diversion-fastening plate, The cathode catalyst particle layer is placed in the sealing ring and attached to the cathode microwell plate, and the cathode structure, the cation exchange membrane and the anode structure are fastened together by a fastening connector, and the cathode The catalyst particle layer is composed of at least Ti 2 O 3 particles.
The membrane electrode electrolytic ozone generator according to claim 1, wherein separator particles are added between the Ti 2 O 3 particles in the cathode catalyst particle layer, and the separator particles are polytetrafluoroethylene particles or Quartz particles.
The membrane electrode electrolytic ozone generator according to claim 2, wherein the particle size of the Ti 2 O 3 particles is 50-200 mesh; the particle size of the polytetrafluoroethylene particles or quartz particles is 100-200 mesh. The weight ratio of the weight of the Ti 2 O 3 particles in the cathode catalyst particle layer to the weight of the polytetrafluoroethylene particles or quartz particles is 100: 0.5-20.
The membrane electrode electrolytic ozone generator according to any one of claims 1 to 3, characterized in that the ratio of the thickness of the cathode catalyst particle layer to the diameter of its cylindrical circular surface is 4-8: 100, and the thickness is the lowest Not less than 1mm.
The membrane electrode electrolytic ozone generator according to any one of claims 1 to 3, characterized in that a through hole is provided in the middle of the cathode diversion_fastening plate, and the cathode microplate is a titanium microplate, The pores of the titanium microporous plate are 40-80 μm.
The membrane electrode electrolytic ozone generator according to claim 4, wherein a through hole is provided in the middle of the cathode diversion_fastening plate, the cathode micro-well plate is a titanium micro-well plate, and the titanium micro-hole The pores of the plate are 40-80 μm.
The membrane electrode electrolytic ozone generator according to any one of claims 1 to 3, wherein the sealing ring is an annular body with a rectangular cross-sectional shape, and the material of the sealing ring is fluororubber or silicone rubber , The cation exchange membrane is circular, the cathode catalyst particle layer is cylindrical, the titanium microporous plate is circular, the diversion_fastening plate is circular, the cathode catalyst particle layer and titanium The outer diameter of the micro-well plate is consistent with the circular inner diameter in the middle of the sealing ring, the thickness of the titanium micro-well plate is 0.8-2 mm, and the thickness of the sealing ring is equal to that of the titanium micro-well plate and the cathode catalyst particles With the sum of the thicknesses of the layers, a circular concave surface is provided in the middle of the diversion_fastening plate, and the sealing ring is embedded in the circular concave surface.
The membrane electrode electrolytic ozone generator according to claim 6, wherein the sealing ring is an annular body with a rectangular cross-sectional shape, the material of the sealing ring is fluorine rubber or silicone rubber, and the cation exchange The membrane is circular, the cathode catalyst particle layer is cylindrical, the titanium microwell plate is circular, the diversion_fastening plate is circular, the cathode catalyst particle layer and the outer surface of the titanium microwell plate The diameters are consistent with the circular inner diameter in the middle of the sealing ring, the thickness of the titanium microwell plate is 0.8 to 2 mm, and the thickness of the sealing ring is equal to the sum of the thicknesses of the titanium microwell plate and the cathode catalyst particle layer , A circular concave surface is provided in the middle of the diversion_fastening plate, and the sealing ring is embedded in the circular concave surface.
A process for preparing a membrane electrode electrolytic ozone generator according to claim 8, characterized in that it includes the following steps;

(1) A sealing ring 4 is provided on the concave surface of the cathode diversion_fastening plate 3, a cathode microporous plate is provided in the sealing ring 4, and Ti 2 O 3 particles or a mixture of Ti 2 O 3 particles and separator particles is filled in On the cathode microwell plate in the seal ring, scrape the accumulated Ti 2 O 3 particles or the mixture of Ti 2 O 3 particles and separator particles to form a cathode catalyst particle layer, which is flush with the top surface of the seal ring;

(2) Under the parallel downward pressure of the press, the cathode catalyst particles are laminated to a strength of 100-200 N / cm 2 ;

(3) Then, lay a cation exchange membrane on the sealing ring to make the cation exchange membrane adhere to the surface of the cathode catalyst particle layer;

(4) Laminate the anode structure and the cation exchange membrane on the cathode structure, and fasten the cathode structure, cation exchange membrane, and anode structure together with fasteners, and the fastening strength is 200- 300N / cm 2 .
The preparation process of the membrane electrode electrolytic ozone generator according to claim 9, characterized in that after the tightening strength reaches 200-300 N / cm 2 according to the step (4), the cathode catalyst particle layer is completely deionized water Infiltrate and press for the second time with fastening screws at a pressure of 400-700 N / cm 2 to make the particle distribution in the cathode catalyst particle layer more uniform and its contact with the cation exchange membrane more uniform.