Liquid oxygen catalyst purifier, preparation process and equipment

Abstract

The application discloses a liquid oxygen catalyst purifying agent, a preparation process and equipment, and relates to the technical field of photocatalyst preparation. + reduced to Ag 0 anchored to the oxygen vacancy adjacent site, forming a metal-semiconductor heterojunction, improving the electron transfer efficiency, overcoming the defect that the traditional photocatalyst fails in the lightless or weak light environment, achieving the environmental protection effect, and obtaining a colorless and transparent liquid with neutral pH after the product is filtered through an ultrafiltration membrane and treated by oxygen saturation.

Description

Technical Field

[0001] This invention relates to the field of photocatalyst preparation technology, and in particular to a liquid oxygen catalyst purifier, its preparation process, and equipment. Background Technology

[0002] Indoor air quality is directly related to human health. In particular, the continuous release of chemical pollutants such as formaldehyde, benzene compounds, and total volatile organic compounds (TVOC) in newly renovated homes has become one of the major threats to public health. These pollutants mainly originate from engineered wood products, adhesives, and paints. Therefore, developing an efficient, long-lasting, safe air purification technology that is not limited by the usage environment is of great significance.

[0003] Currently, mainstream indoor air purification technologies are mainly divided into physical adsorption and catalytic oxidation. While physical adsorption can temporarily adsorb some pollutants, it has inherent drawbacks such as easy saturation, secondary pollution, and low purification efficiency for low concentrations of pollutants. Catalytic oxidation, especially photocatalytic technology represented by nano-titanium dioxide, has received widespread attention due to its ability to completely decompose pollutants. However, traditional photocatalytic technology heavily relies on ultraviolet light or specific wavelengths for excitation; its catalytic activity drops sharply or even completely fails in the absence of light or weak light, making it impossible to achieve continuous, all-weather purification of pollutants. To overcome the limitations of photocatalysis, the concept of oxygen catalysts has been proposed. Existing technologies involved include: 1. A photo / oxygen catalyst purifier with publication number CN110917838A, its preparation method and application, which physically mixes metal oxides, peroxides and composite catalysts and uses a gel system as a dispersion medium to achieve partial purification effect under no light conditions. However, due to the addition of gel, the film layer formed on the substrate after spraying may affect the original texture of the substrate. 2. A nano-oxygen catalyst air purifier with publication number CN110756200A is made of metal compounds such as zinc oxide, cadmium sulfide, tungsten trioxide, lead sulfide, silver oxide, zinc sulfide, strontium titanate, zirconium dioxide, antimony oxide, and platinum sulfide. The raw material cost is high, and the cadmium and lead used are both toxic, which can easily pose a threat to human health and the environment.

[0004] Furthermore, in the process of preparing oxygen catalyst using mixing equipment, the reaction system is usually an exothermic reaction. If the local temperature is too high during the raw material addition stage, it will trigger side reactions and affect the quality of the product.

[0005] Some existing mixing equipment only has a cooling structure on the outer wall of the vessel. After the material is added, the heat exchange mainly occurs through contact with the inner wall of the vessel. It is impossible to achieve synchronous cooling during the addition of raw materials. At the same time, the raw materials are generally added to the central area of ​​the reactor, and heat is concentrated at the point where the raw materials land. The temperature of the material near the inner wall of the vessel is relatively low, resulting in a high initial reaction temperature and increasing the difficulty of controlling the subsequent reaction temperature.

[0006] In view of this, we have conducted in-depth research on the above problems and hereby propose a liquid oxygen catalyst purifier, its preparation process, and equipment. Summary of the Invention

[0007] The purpose of this invention is to solve the above-mentioned problems by designing a liquid oxygen catalyst purifier, a preparation process, and equipment. This invention addresses the issues of existing liquid oxygen catalyst purifiers forming a gel film on the substrate surface after spraying, affecting the original texture of the substrate; the use of toxic components such as cadmium and lead in the formulation posing a threat to health and the environment; high raw material costs; and the inability of existing mixing equipment to achieve synchronous and uniform cooling during the raw material addition stage, which easily leads to side reactions due to excessively high local temperatures, making it difficult to control the reaction temperature and resulting in unstable product quality.

[0008] The technical solution of the present invention to achieve the above objectives is as follows: a preparation device for a liquid oxygen catalyst purifier, comprising a vessel, a vessel cover connected to a flange on the vessel, a discharge valve installed at the bottom of the vessel, a first circulation unit installed on the outer wall of the vessel, a circulating cooler movably inserted in the center of the vessel cover, and a central spiral stirrer movably inserted in the center of the circulating cooler. The circulating cold feeder includes a hollow cold feed box, which has a columnar structure and is coaxially arranged with the reactor. The hollow cold feed box is movably inserted into the center of the reactor lid, and a second circulation unit is provided on the hollow cold feed box and the reactor lid. An outer ring spiral agitator is installed on the lower wall of the hollow cold material box, and the bottom end of the outer ring spiral agitator is movably installed on the central spiral agitator. The reactor lid is equipped with a power unit, which is connected to the hollow cold material box and the central spiral agitator. The outer ring spiral stirrer and the central spiral stirrer have a first working state and a second working state. In the first working state, the power unit drives the outer ring spiral stirrer and the central spiral stirrer to rotate in the same direction at the same time. In the second working state, the power unit drives the outer ring spiral stirrer and the central spiral stirrer to rotate in opposite directions at the same time. The hollow cold material box and the kettle lid are evenly distributed with a central spiral agitator as the center. Each feeding unit includes multiple L-shaped discharge pipes. Each L-shaped discharge pipe is inserted into the bottom surface of the hollow cold material box, and the discharge end of each L-shaped discharge pipe is aligned with the inner wall of the kettle.

[0009] Preferably, the hollow cold material box includes a hollow column, which is movably inserted into the center of the vessel lid. A column box is provided at the bottom of the hollow column, and a box cover is sealed between the top of the column box and the hollow column. Scrapers are installed in a circular array on the outer wall of the column box with the hollow column as the center. The scrapers are movably attached to the inner wall of the vessel, and the bottom of the scrapers is located below the discharge end of the L-shaped discharge pipe.

[0010] Preferably, each feeding unit further includes multiple serpentine tubes, which are connected one-to-one with multiple L-shaped discharge tubes. A connecting tube is installed at the top of each serpentine tube, and a feeding tube is connected to the connecting tube. The feeding tube is inserted into the box cover and the kettle cover, and a first flexible tube is provided on the feeding tube and located between the box cover and the kettle cover.

[0011] Preferably, the outer ring spiral stirrer includes large-diameter spiral blades, which are mounted on the lower wall of the column box. A turntable is mounted at the bottom of the large-diameter spiral blades, and the turntable is movably mounted on the central spiral stirrer.

[0012] Preferably, the second circulation unit includes a second inlet pipe and a second return pipe. Both the second inlet pipe and the second return pipe are inserted into the tank cover and the vessel cover, and the bottom end of the second inlet pipe is fixedly installed on the bottom surface inside the column box. A water passage hole is opened at the bottom end of the second inlet pipe. A second flexible pipe is provided on the second inlet pipe and the second return pipe, and between the tank cover and the vessel cover.

[0013] Preferably, the central spiral stirrer includes a stirring shaft, which is movably inserted into the hollow column and the turntable. Small-diameter spiral blades are installed on the stirring shaft and between the large-diameter spiral blades. The spiral direction of the small-diameter spiral blades is opposite to that of the large-diameter spiral blades. An arc-shaped scraper is installed at the bottom of the stirring shaft and is movably attached to the inner wall of the vessel. A clearance frame extends from the top of the arc-shaped scraper and is correspondingly arranged with the scraper. Multiple shearing blades are provided on the arc-shaped scraper.

[0014] Preferably, the power unit includes a bracket mounted on the upper wall of the vessel lid. A geared motor is mounted on the bracket, and a drive gear is fixedly fitted on the drive end of the geared motor. A driven gear is fixedly fitted on the hollow cold material box, and the drive gear and the driven gear mesh with each other. A high-speed motor is mounted on the bracket, and a drive pulley is mounted on the drive end of the high-speed motor. A driven pulley is fixedly fitted on the stirring shaft, and belts are movably fitted on the drive pulley and the driven pulley.

[0015] Preferably, the first circulation unit includes a jacket, which is fixedly fitted onto the outer wall of the vessel. The jacket is provided with a first water inlet pipe and a first water return pipe, a control unit, and a frame.

[0016] A liquid oxygen catalyst purifier comprises the following raw materials in the following volume ratio: The mixture contains 10 parts soluble manganese salt, 2-3 parts soluble cerium salt, 0.5-1.2 parts soluble silver salt, 2-4 parts structure inducer, 0.8-1.5 parts surface stabilizer, 15-25 parts oxidation aid, and 1000 parts deionized water.

[0017] A preparation process for a liquid oxygen catalyst purifier includes the following steps: Step 1: Under constant temperature of 5℃ and with the aid of the preparation equipment, slowly add a mixed aqueous solution of soluble manganese salt, soluble cerium salt, and soluble silver salt to an alkaline solution. The alkaline solution is a mixture of structure inducer, surface stabilizer, and ammonia water. The pH of the alkaline solution is 10.5±0.3. The addition time is controlled at 40~60 minutes. After the addition is complete, immediately add the oxidizing agent, maintain the temperature at 5-8℃, and continue the reaction for 3 hours to obtain a dark brown translucent sol. Step 2: Transfer the translucent sol to a high-pressure reactor, heat it to 120°C at 1.5°C / min, perform hydrothermal treatment at 120°C and autogenous pressure for 6 hours, and then slowly cool it to room temperature at 0.5°C / min. Mn and Ce are connected to each other through oxygen bridge bonds (Mn—O—Ce) to form mixed-phase composite oxide grains with fluorite structure (CeO type) and / or manganese potassium ore structure (MnOx type). Step 3: The mixed-phase composite oxide crystals are filtered through an ultrafiltration membrane with a molecular cutoff of 3000 Da to obtain a nanocluster solution with free ions and trace agglomerates removed. The conductivity of the nanocluster solution is <10 μS / cm. Then, pure oxygen is introduced into the nanocluster solution for 30 minutes at a flow rate of 0.2 L / min to saturate the oxygen adsorption sites on the surface of the nanoclusters. A quantitative amount of deionized water is then added until the mass fraction of nanoparticles is 3.5%-4.2%, and the pH is adjusted to 7.0±0.2 with sodium hydroxide solution to obtain a colorless, transparent, and odorless liquid oxygen catalyst purifier.

[0018] The liquid oxygen catalyst purifier, preparation process, and equipment produced using the technical solution of this invention utilize the formation of Mn-O-Ce bridging bonds and oxygen vacancies through the co-precipitation and hydrothermal processes of non-toxic manganese, cerium, and silver salts. This allows oxygen to be spontaneously adsorbed and activated into superoxide free radicals, decomposing pollutants such as formaldehyde without the need for light. Partial Ag... + Restored to Ag 0 Anchored to sites near oxygen vacancies, forming a metal-semiconductor heterojunction, it improves electron transfer efficiency and overcomes the defect of traditional photocatalysts failing in the absence of light or weak light environments. It also achieves environmental protection effects. After ultrafiltration and oxygen saturation treatment, the product is a colorless, transparent, pH-neutral liquid. It does not change the texture and color of the base material after spraying and can penetrate to form a durable purification layer. Compared with existing reactors that rely solely on external wall cooling, by setting up a circular cooler and multiple feeding units in the equipment, the raw materials are pre-cooled before entering the reactor and then added along the inner wall of the reactor. Combined with jacket cooling, it effectively avoids local overheating in the raw material landing area. The outer ring spiral stirrer and the central spiral stirrer have two working states: co-rotation and counter-rotation, which improves mixing uniformity and heat exchange efficiency. Attached Figure Description

[0019] Figure 1 This is a top-view three-dimensional structural diagram of the liquid oxygen catalyst purification agent preparation equipment described in this invention.

[0020] Figure 2 This is a top-view three-dimensional structural diagram of the interior of the vessel in the liquid oxygen catalyst purification agent preparation equipment of the present invention.

[0021] Figure 3 This is a three-dimensional structural diagram of the interior of the vessel in the liquid oxygen catalyst purification agent preparation equipment of the present invention, viewed from below.

[0022] Figure 4 This is a schematic diagram of the internal three-dimensional structure of the hollow cold material box in the liquid oxygen catalyst purification agent preparation equipment of the present invention.

[0023] Figure 5 This is a three-dimensional structural diagram of the feeding unit of the liquid oxygen catalyst purification agent preparation equipment according to the present invention.

[0024] Figure 6 This is a schematic diagram of the main cross-sectional structure of the liquid oxygen catalyst purification agent preparation equipment according to the present invention.

[0025] Figure 7 This is a top cross-sectional view of the liquid oxygen catalyst purification agent preparation equipment described in this invention.

[0026] Figure 8This is a three-dimensional structural diagram of the liquid oxygen catalyst purification agent preparation equipment described in this invention, viewed from a bottom angle.

[0027] In the picture: 1. Kettle / Vat; 11. Discharge Valve; 2. Cauldron cover; 3. Power unit; 31. Bracket; 32. Gear motor; 33. Drive gear; 34. Driven gear; 35. High-speed motor; 36. Drive pulley; 37. Driven pulley; 38. Belt; 4. Central spiral mixer; 41. Mixing shaft; 42. Small diameter spiral blades; 43. Arc-shaped scraper; 44. Clearance frame; 45. Shear blades. 5. Hollow cold material box; 51. Hollow column; 52. Column box; 53. Box cover; 54. Scraper. 6. Outer ring spiral stirrer; 61. Large diameter spiral blades; 62. Rotary disc; 7. Feeding unit; 71. L-shaped discharge pipe; 72. Serpentine pipe; 73. Connecting pipe; 74. Feeding pipe; 75. First flexible pipe; 8. First circulation unit; 81. Jacket; 82. First inlet pipe; 83. First return pipe; 84. Control unit; 85. Frame. 9. Second circulation unit; 91. Second inlet pipe; 92. Second return pipe; 93. Water passage hole; 94. Second flexible pipe. Detailed Implementation

[0028] Example 1: Those skilled in the art should connect all electrical components and their compatible power supplies in this case via wires, and should select appropriate controllers according to actual conditions to meet control requirements. The specific connection and control sequence should refer to the working principle described below, where the electrical components are connected in sequence. The detailed connection methods are well-known in the art. The following mainly introduces the working principle and process, without explaining the electrical control.

[0029] The present invention will now be described in detail with reference to the accompanying drawings, such as... Figure 1-8 As shown, a device for preparing a liquid oxygen catalyst purifier.

[0030] A preparation device for a liquid oxygen catalyst purifier includes a vessel 1, a vessel cover 2 connected to a flange on the vessel 1, a discharge valve 11 installed at the bottom of the vessel 1, a first circulation unit 8 installed on the outer wall of the vessel 1, a circulating cooler movably inserted in the center of the vessel cover 2, and a central spiral stirrer 4 movably inserted in the center of the circulating cooler. Specifically, the first circulation unit 8 includes a jacket 81, which is fixedly fitted onto the outer wall of the vessel 1. The jacket 81 is provided with a first water inlet pipe 82 and a first water return pipe 83. The jacket 81 is also provided with a control unit 84 and a frame 85. It should be noted that the equipment is placed at the target location via the frame 85 and connected to the power supply and control unit 84. The control unit 84 can be a control panel with a built-in microcontroller. The microcontroller can be programmed with software, and the control program can be written to control the device. Since this is existing technology, it will not be described in detail here. The lid 2 and the vessel 1 are sealed by a flange connection, and the vessel 1 is equipped with a temperature sensor. The first water inlet pipe 82, the first water return pipe 83 and the circulating cooler are all connected to a medium cooling circulation system. The medium cooling circulation system adopts the mature temperature control scheme of existing reactors. Since this is existing technology, it will not be described in detail here. Specifically, the circulating cold feeder includes a hollow cold feed box 5, which has a columnar structure and is coaxially arranged with the vessel 1. The hollow cold feed box 5 is movably inserted into the center of the vessel cover 2. A second circulation unit 9 is provided on the hollow cold feed box 5 and the vessel cover 2. It should be noted that the second circulation unit 9 is connected to the medium cooling circulation system. The cooled medium enters the hollow cold material box 5, so that the hollow cold material box 5 is filled with low temperature medium. Specifically, an outer ring spiral agitator 6 is installed on the lower wall of the hollow cold material box 5. The bottom end of the outer ring spiral agitator 6 is movably installed on the central spiral agitator 4. A power unit 3 is provided on the lid 2. The power unit 3 is connected to the hollow cold material box 5 and the central spiral agitator 4. It should be noted that, through the operation of the power unit 3, the hollow cold material box 5 and the outer ring spiral agitator 6 can rotate alternately at low speed in both directions, with a rotation angle between 50 and 70 degrees, breaking the streamline of the first working state. Through the operation of the power unit 3, the central spiral agitator 4 can rotate at high speed in the forward direction. Specifically, multiple feeding units 7 are evenly distributed on the hollow cold material box 5 and the lid 2 with the central spiral agitator 4 as the center. Each feeding unit 7 includes multiple L-shaped discharge pipes 71. Each L-shaped discharge pipe 71 is inserted into the bottom surface of the hollow cold material box 5, and the discharge end of each L-shaped discharge pipe 71 is aligned with the inner wall of the lid 1. It should be noted that the feeding unit 7 is connected to the raw material conveying system. The raw materials entering the feeding unit 7 first pass through the hollow cold material box 5. The low-temperature medium in the hollow cold material box 5 lowers the temperature of the raw materials. The cooled raw materials are discharged from the L-shaped discharge pipe 71. The alkaline solution is first added to the reactor 1 through the feeding unit 7. The power unit 3 causes the hollow cold material box 5 and the outer ring spiral agitator 6 to rotate alternately in opposite directions at low speed. Under the action of centrifugal force, other raw materials are thrown onto the inner wall of the reactor 1 from the L-shaped discharge pipe 71 in the feeding unit 7. Since the inner wall of the reactor 1 is continuously cooled by the low-temperature medium in the jacket 81, the raw materials thrown onto the inner wall of the reactor 1 are... Normally kept at a low temperature, the raw materials fall along the inner wall of the vessel 1 until they come into contact with the alkaline solution adhering to the inner wall of the vessel 1. The heat released during the mixing of acid and alkali is carried away by the wall of the vessel 1, realizing the transfer and dispersion of heat. The operation of the hollow cold material box 5 and the raw materials being thrown onto the inner wall of the vessel 1 from the L-shaped discharge pipe 71 in the feeding unit 7 reduces the initial temperature value during the mixing of acid and alkali raw materials, making it easier to control the reaction temperature. When the hollow cold material box 5 and the outer ring spiral stirrer 6 rotate alternately at low speed in both directions, the outer ring spiral stirrer 6 mixes the raw materials, while the central spiral stirrer 4 continues to work to mix the raw materials, resulting in a mixed liquid. Specifically, the outer ring spiral stirrer 6 and the central spiral stirrer 4 have a first working state and a second working state. The first working state is that the outer ring spiral stirrer 6 and the central spiral stirrer 4 rotate in the same direction at the same time. The second working state is that the outer ring spiral stirrer 6 and the central spiral stirrer 4 rotate in opposite directions at the same time. It should be noted that when the power unit 3 causes the hollow cold material box 5 and the outer ring spiral agitator 6 to rotate at a low speed in the forward direction, the outer ring spiral agitator 6 and the central spiral agitator 4 rotate simultaneously in the same direction. This is the first working state. The mixture is pushed by the outer ring spiral agitator 6 and the central spiral agitator 4 together inside the vessel 1, forming a large axial circulation flow, which promotes the overall uniformity of the material along the tank wall and the central area. When the power unit 3 causes the hollow cold material box 5 and the outer ring spiral agitator 6 to rotate at a low speed in the reverse direction, the outer ring spiral agitator 6 and the central spiral agitator 4 rotate simultaneously in opposite directions. This is the second working state. The mixture generates shear and radial convection in the junction area of ​​the outer ring spiral agitator 6 and the central spiral agitator 4, breaking the streamline of the first working state, expanding the flow range of the mixture inside the vessel 1, and improving the mixing quality and mixing efficiency. Specifically, the hollow cold material box 5 includes a hollow column 51, which is movably inserted into the center of the vessel cover 2. A column box 52 is provided at the bottom of the hollow column 51. A box cover 53 is sealed between the top of the column box 52 and the hollow column 51. Scrapers 54 are installed in a circular array on the outer wall of the column box 52 with the hollow column 51 as the center. The scrapers 54 are movably attached to the inner wall of the vessel 1. The bottom of the scrapers 54 is located below the discharge end of the L-shaped discharge pipe 71. It should be noted that the hollow column 51 and the column box 52 are an integral structure. The hollow column 51 and the vessel cover 2 are connected by a bearing. The cover 53 is used to seal and block the opening between the column box 52 and the hollow column 51, so that the low temperature medium flows in the hollow cold material box 5. When the power unit works, the weak acid raw material is thrown onto the inner wall of the vessel 1 and falls to contact the alkaline solution. At the same time, the scraper 54 rotates with the column box 52 to disperse and stir the raw material mixing part in time to ensure the mixing quality. Specifically, each feeding unit 7 also includes multiple serpentine tubes 72, which are connected one-to-one with multiple L-shaped discharge tubes 71. A connecting tube 73 is installed at the top of the multiple serpentine tubes 72, and a feeding tube 74 is connected to the connecting tube 73. The feeding tube 74 is inserted into the box cover 53 and the kettle cover 2. A first flexible tube 75 is provided on the feeding tube 74 and between the box cover 53 and the kettle cover 2. It should be noted that the first flexible tube 75 provides a certain amount of movement for the rotation of the hollow cold material box 5. The top of the feed pipe 74 is connected to the raw material conveying system. The raw material enters the connecting pipe 73 from the feed pipe 74 through the first flexible tube 75, and then disperses into multiple serpentine tubes 72. The multiple serpentine tubes 72 are equivalent to diverting the raw material to ensure the cooling quality of the raw material by the cooling medium. The serpentine tubes 72 are used to extend the time of the raw material in the cooling medium to ensure the cooling quality. Specifically, the outer ring spiral stirrer 6 includes a large-diameter spiral blade 61, which is installed on the lower wall of the column box 52. A turntable 62 is installed at the bottom of the large-diameter spiral blade 61, and the turntable 62 is movably installed on the central spiral stirrer 4. It should be noted that when the hollow cold material box 5 rotates, the large-diameter spiral blade 61 and the turntable 62 rotate simultaneously to mix the raw materials; Specifically, the second circulation unit 9 includes a second water inlet pipe 91 and a second water return pipe 92. Both the second water inlet pipe 91 and the second water return pipe 92 are inserted into the box cover 53 and the vessel cover 2. The bottom end of the second water inlet pipe 91 is fixedly installed on the inner bottom surface of the column box 52. A water passage hole 93 is opened at the bottom end of the second water inlet pipe 91. A second flexible pipe 94 is provided on the second water inlet pipe 91 and the second water return pipe 92, and between the box cover 53 and the vessel cover 2. It should be noted that the second inlet pipe 91 and the second return pipe 92 are connected to the medium cooling circulation system. The cooling medium enters the second inlet pipe 91, flows into the column box 52 through the water inlet 93, and then flows back to the medium cooling circulation system through the second return pipe 92 to realize the medium cooling circulation. Specifically, the central spiral stirrer 4 includes a stirring shaft 41, which is movably inserted into the hollow column 51 and the turntable 62. Small diameter spiral blades 42 are installed on the stirring shaft 41 and between the large diameter spiral blades 61. The spiral direction of the small diameter spiral blades 42 is opposite to that of the large diameter spiral blades 61. An arc-shaped scraper 43 is installed at the bottom of the stirring shaft 41. The arc-shaped scraper 43 is movably attached to the inner wall of the vessel 1. A clearance frame 44 extends from the top of the arc-shaped scraper 43. The clearance frame 44 is correspondingly arranged with the scraper 54. Multiple shearing blades 45 are provided on the arc-shaped scraper 43. It should be noted that the stirring shaft 41 is movably connected to the hollow column 51 and the turntable 62 through bearings. The movable connection between the turntable 62 and the stirring shaft 41 can make the large-diameter spiral blade 61 rotate stably, prevent jumping, and avoid damage to the vessel 1 and the central spiral stirrer 4. The power unit drives the stirring shaft 41 to rotate, and the stirring shaft 41 drives the small-diameter spiral blade 42, the arc-shaped scraper 43, the clearance frame 44 and multiple shear blades 45 to rotate, shearing and mixing the raw materials. The arc-shaped scraper 43 is used to scrape off the material on the inner wall of the vessel 1. Specifically, the power unit 3 includes a bracket 31, which is mounted on the upper wall of the vessel lid 2. A geared motor 32 is mounted on the bracket 31. A drive gear 33 is fixedly mounted on the drive end of the geared motor 32. A driven gear 34 is fixedly mounted on the hollow cold material box 5. The drive gear 33 and the driven gear 34 mesh with each other. A high-speed motor 35 is mounted on the bracket 31. A drive pulley 36 is mounted on the drive end of the high-speed motor 35. A driven pulley 37 is fixedly mounted on the stirring shaft 41. A belt 38 is movably mounted on the drive pulley 36 and the driven pulley 37. It should be noted that the bracket 31 is used to install the geared motor 32 and the high-speed motor 35. When the geared motor 32 works, the driving gear 33 drives the driven gear 34 to rotate. The pitch circle diameter of the driving gear 33 is smaller than that of the driven gear 34 to achieve the purpose of speed reduction. The driven gear 34 thus drives the hollow cold material box 5 to rotate. When the high-speed motor 35 works, the driving pulley 36 drives the driven pulley 37 to rotate through the belt 38, so that the stirring shaft 41 rotates at high speed. Example 2: A liquid oxygen catalyst purifier comprises the following raw materials in the following volume ratio: The mixture contains 10 parts soluble manganese salt, 2-3 parts soluble cerium salt, 0.5-1.2 parts soluble silver salt, 2-4 parts structure inducer, 0.8-1.5 parts surface stabilizer, 15-25 parts oxidation aid, and 1000 parts deionized water.

[0031] Example 3: A preparation process for a liquid oxygen catalyst purifier includes the following steps: Step 1: Low-temperature co-precipitation of precursors Under constant temperature of 5℃ and with the aid of the preparation equipment, a mixed aqueous solution of soluble manganese salt, soluble cerium salt, and soluble silver salt was slowly added dropwise to an alkaline solution. The alkaline solution was a mixture of structure inducer, surface stabilizer, and ammonia water, with a pH of 10.5±0.3. The addition time was controlled at 40~60 minutes. After the addition was completed, an oxidizing agent was added immediately, and the temperature was maintained at 5-8℃. The reaction was continued for 3 hours to obtain a dark brown translucent sol.

[0032] It should be noted that the soluble manganese salt is manganese acetate, the soluble cerium salt is cerium nitrate, the soluble silver salt is silver nitrate, the structure inducing agent is trisodium citrate, the surface stabilizer is polyvinylpyrrolidone, the oxidizing agent is hydrogen peroxide solution, and a low temperature environment of 5°C can inhibit excessive crystal nucleus growth. Under weakly alkaline conditions and in the presence of hydrogen peroxide, some silver ions (Ag) can be oxidized. + Reduced to zero-valent silver Ag 0 And uniformly dispersed on the surface of Mn, Ce hydroxide or oxide precursors, through Ag 0 The contact between the metal and the Mn and Ce oxide semiconductors forms a tiny metal-semiconductor heterojunction, in which electrons can flow from the Mn and Ce oxides to the Ag. 0 Or from Ag 0 The electron-hole separation, which requires ultraviolet light to complete in photocatalysis, is achieved at room temperature by flowing to Mn and Ce oxides, thus providing a structural basis for subsequent lightless activation of oxygen.

[0033] Step 2: Hydrothermal Controlled Crystallization and Oxygen Vacancy Construction The translucent sol was transferred to a high-pressure reactor and heated to 120°C at a rate of 1.5°C / min. It was then subjected to hydrothermal treatment at 120°C and autogenous pressure for 6 hours, and then slowly cooled to room temperature at a rate of 0.5°C / min. Mn and Ce were interconnected through oxygen bridges Mn—O—Ce, forming mixed-phase composite oxide grains with fluorite CeO type and / or manganese potassium ore MnOx type structures.

[0034] It should be noted that during the hydrothermal crystallization process at 120℃, manganese ions enter the cerium oxide lattice or cerium ions enter the manganese oxide lattice, forming a Mn—O—Ce bridging bond structure through oxygen atoms. Because Mn... 4+ / Mn 3+ With Ce 4+ / Ce 3+ The presence of variable valence states allows for efficient electron transfer within the structure, endowing the catalyst with extremely strong redox capabilities. Simultaneously, the doping of manganese ions and the valence state changes introduce oxygen vacancies into the crystal lattice, causing oxygen molecules (O2) from the air to spontaneously adsorb onto these vacancies and separate from the neighboring Mn atoms. 3+ or Ce 3+ It gains electrons and is activated into a superoxide radical (·O2). -This allows for the direct capture and activation of oxygen under light-free conditions; furthermore, the Ag generated in step 1... 0 or Ag + During the hydrothermal process, the particles are anchored at sites near oxygen vacancies, which further promotes the transfer of electrons from oxides to adsorbed oxygen, thereby improving oxygen activation efficiency. The silver atoms themselves can also act as active sites to directly participate in the adsorption and bond breaking of organic matter. At the same time, by controlling the temperature gradient and reaction time, the particle size is locked at 3.2-4.8 nm, and the surface is rich in hydroxyl groups, making it highly hydrophilic.

[0035] Step 3: Purification, activation, and preparation of saturated solutions The mixed-phase composite oxide crystals were filtered through an ultrafiltration membrane with a molecular cutoff of 3000 Da to obtain a nanocluster solution with free ions and trace agglomerates removed. The conductivity of the nanocluster solution was <10 μS / cm. Then, pure oxygen was introduced into the nanocluster solution for 30 minutes at a flow rate of 0.2 L / min to saturate the oxygen adsorption sites on the surface of the nanoclusters. A quantitative amount of deionized water was then added until the mass fraction of nanoparticles was 3.5%-4.2%, and the pH was adjusted to 7.0±0.2 with sodium hydroxide solution to obtain a colorless, transparent, and odorless liquid oxygen catalyst purifier.

[0036] It should be noted that ultrafiltration membrane filtration removes free ions and trace aggregates, exposing oxygen vacancies on the surface of the mixed-phase composite oxide crystals. This avoids impurities interfering with the catalytic reaction and ensures long-term solution stability and prevents sedimentation. Pure oxygen is then introduced into the filtrate to saturate the oxygen adsorption sites on the nanoclusters, generating superoxide radicals (·O2). - This allows the product to decompose pollutants such as formaldehyde immediately after spraying without waiting. By adjusting the nano-cluster content to 3.5%-4.2%, a colorless and transparent liquid is obtained, which is suitable for spraying operations and does not affect the appearance quality of the substrate. Furthermore, the pH is adjusted to neutral to avoid corrosion of the substrate. At the same time, the nano-cluster surface is rich in hydroxyl groups, which are highly hydrophilic and can penetrate into the interior of the material to form a long-lasting purification layer, which is beneficial for adsorbing polar formaldehyde molecules.

[0037] The above technical solutions only embody the preferred technical solutions of the present invention. Any modifications that may be made by those skilled in the art to certain parts therein embody the principles of the present invention and fall within the protection scope of the present invention.

Claims

1. A preparation apparatus for a liquid oxygen catalyst purifier, comprising a vessel (1), a vessel cover (2) connected to a flange on the vessel (1), a discharge valve (11) installed at the bottom of the vessel (1), and a first circulation unit (8) installed on the outer wall of the vessel (1), characterized in that, The center of the lid (2) is equipped with a rotating cooler, and the center of the rotating cooler is equipped with a central spiral stirrer (4). The circulating cold feeder includes a hollow cold feed box (5), which is a columnar structure and is coaxially arranged with the vessel (1). The hollow cold feed box (5) is movably inserted into the center of the vessel lid (2). A second circulation unit (9) is provided on the hollow cold feed box (5) and the vessel lid (2). The lower wall of the hollow cold material box (5) is equipped with an outer ring spiral agitator (6), and the bottom end of the outer ring spiral agitator (6) is movably installed on the central spiral agitator (4). A power unit (3) is provided on the lid (2), and the power unit (3) is connected to the hollow cold material box (5) and the central spiral agitator (4); The outer ring spiral stirrer (6) and the central spiral stirrer (4) have a first working state and a second working state. The first working state is that the power unit (3) drives the outer ring spiral stirrer (6) and the central spiral stirrer (4) to rotate in the same direction at the same time. The second working state is that the power unit (3) drives the outer ring spiral stirrer (6) and the central spiral stirrer (4) to rotate in opposite directions at the same time. Multiple feeding units (7) are evenly distributed on the hollow cold material box (5) and the lid (2) with the central spiral stirrer (4) as the center. Each feeding unit (7) includes multiple L-shaped discharge pipes (71). Each L-shaped discharge pipe (71) is inserted into the bottom surface of the hollow cold material box (5), and the discharge end of each L-shaped discharge pipe (71) is aligned with the inner wall of the vessel (1). The hollow cold material box (5) includes a hollow column (51), which is movably inserted into the center of the vessel cover (2). A column box (52) is provided at the bottom of the hollow column (51). A box cover (53) is sealed between the top of the column box (52) and the hollow column (51). Scrapers (54) are installed in a circular array on the outer wall of the column box (52) with the hollow column (51) as the center. The scrapers (54) are movably attached to the inner wall of the vessel (1). The bottom of the scrapers (54) is located below the discharge end of the L-shaped discharge pipe (71). Each of the feeding units (7) also includes multiple serpentine tubes (72), which are connected one-to-one with multiple L-shaped discharge tubes (71). A connecting tube (73) is installed at the top of each of the multiple serpentine tubes (72), and a feed tube (74) is connected to the connecting tube (73). The feed tube (74) is inserted into the box cover (53) and the kettle cover (2). A first flexible tube (75) is provided on the feed tube (74) and between the box cover (53) and the kettle cover (2).

2. The equipment for preparing a liquid oxygen catalyst purifier according to claim 1, characterized in that, The outer ring spiral stirrer (6) includes a large diameter spiral blade (61), which is installed on the lower wall of the column box (52). A turntable (62) is installed at the bottom of the large diameter spiral blade (61), and the turntable (62) is movably installed on the central spiral stirrer (4).

3. The equipment for preparing a liquid oxygen catalyst purifier according to claim 1, characterized in that, The second circulation unit (9) includes a second inlet pipe (91) and a second return pipe (92). The second inlet pipe (91) and the second return pipe (92) are both inserted into the box cover (53) and the kettle cover (2). The bottom end of the second inlet pipe (91) is fixedly installed on the inner bottom surface of the column box (52). A water passage hole (93) is opened at the bottom end of the second inlet pipe (91). A second flexible pipe (94) is provided on the second inlet pipe (91) and the second return pipe (92) and between the box cover (53) and the kettle cover (2).

4. The equipment for preparing a liquid oxygen catalyst purifier according to claim 1, characterized in that, The central spiral stirrer (4) includes a stirring shaft (41), which is movably inserted into the hollow column (51) and the turntable (62). Small diameter spiral blades (42) are installed on the stirring shaft (41) and between the large diameter spiral blades (61). The spiral direction of the small diameter spiral blades (42) is opposite to that of the large diameter spiral blades (61). An arc-shaped scraper (43) is installed at the bottom of the stirring shaft (41). The arc-shaped scraper (43) is movably attached to the inner wall of the vessel (1). A clearance frame (44) extends from the top of the arc-shaped scraper (43). The clearance frame (44) is correspondingly arranged with the scraper (54). Multiple shearing blades (45) are provided on the arc-shaped scraper (43).

5. The equipment for preparing a liquid oxygen catalyst purifier according to claim 4, characterized in that, The power unit (3) includes a bracket (31), which is mounted on the upper wall of the vessel lid (2). A geared motor (32) is mounted on the bracket (31). A drive gear (33) is fixedly mounted on the drive end of the geared motor (32). A driven gear (34) is fixedly mounted on the hollow cold material box (5). The drive gear (33) and the driven gear (34) mesh with each other. A high-speed motor (35) is mounted on the bracket (31). A drive pulley (36) is mounted on the drive end of the high-speed motor (35). A driven pulley (37) is fixedly mounted on the stirring shaft (41). A belt (38) is movably mounted on the drive pulley (36) and the driven pulley (37).

6. The equipment for preparing a liquid oxygen catalyst purifier according to claim 1, characterized in that, The first circulation unit (8) includes a jacket (81), which is fixedly fitted on the outer wall of the vessel (1). The jacket (81) is provided with a first water inlet pipe (82) and a first water return pipe (83). The jacket (81) is provided with a control unit (84) and a frame (85).

7. A liquid oxygen catalyst purifier, applied to the preparation equipment as described in any one of claims 1-6, characterized in that, Raw materials including the following volume ratios: 10 parts soluble manganese salt, 2-3 parts soluble cerium salt, 0.5-1.2 parts soluble silver salt, 2-4 parts structure inducer, 0.8-1.5 parts surface stabilizer, 15-25 parts oxidation aid, and 1000 parts deionized water; The following steps are included: Step 1: Under constant temperature of 5℃ and with the aid of the preparation equipment, slowly add a mixed aqueous solution of soluble manganese salt, soluble cerium salt, and soluble silver salt to an alkaline solution. The alkaline solution is a mixture of structure inducer, surface stabilizer, and ammonia water. The pH of the alkaline solution is 10.5±0.

3. The addition time is controlled at 40~60 minutes. After the addition is complete, immediately add the oxidizing agent, maintain the temperature at 5-8℃, and continue the reaction for 3 hours to obtain a dark brown translucent sol. Step 2: Transfer the translucent sol to a high-pressure reactor, heat it to 120°C at 1.5°C / min, perform hydrothermal treatment at 120°C and autogenous pressure for 6 hours, and then slowly cool it to room temperature at 0.5°C / min. Mn and Ce are connected to each other through oxygen bridge bonds Mn-O-Ce to form mixed-phase composite oxide grains with fluorite CeO type and / or manganese potassium ore MnOx type. Step 3: Filter the mixed-phase composite oxide crystals through an ultrafiltration membrane with a molecular cutoff of 3000 Da to obtain a nanocluster solution with free ions and trace agglomerates removed. The conductivity of the nanocluster solution is <10 μS / cm. Then, pure oxygen is introduced into the nanocluster solution for 30 minutes at a flow rate of 0.2 L / min to saturate the oxygen adsorption sites on the surface of the nanoclusters. Then, a quantitative amount of deionized water is added until the mass fraction of nanoparticles is 3.5%-4.2%, and the pH is adjusted to 7.0±0.2 with sodium hydroxide solution to obtain a colorless, transparent, and odorless liquid oxygen catalyst purifier.

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