A method and apparatus for producing an antibacterial frit doped with zinc oxide and cerium dioxide

Abstract

The application discloses a preparation method and equipment of an antibacterial frit doped with zinc oxide and cerium dioxide, and belongs to the technical field of antibacterial frits. The method comprises the following steps: uniformly mixing raw materials, high-temperature melting and doping, water quenching of the molten liquid, solid-liquid separation and drying, grinding and grading, and product packaging. The innovation lies in that the equal increment method is adopted to mix the raw materials to ensure uniform dispersion, and a water quenching and screening integrated machine is designed. The machine is provided with a mechanical shearing unit and a dehydration unit, and can realize online shearing, particle size control and grading dehydration of the glass particles after water quenching. The application can effectively control the initial particle size of the particles, improve the uniformity of the product, reduce the subsequent grinding energy consumption, realize the synergistic antibacterial effect of zinc oxide and cerium dioxide, and make the antibacterial frit have high-efficiency, stable and persistent antibacterial performance.

Description

Technical Field

[0001] This invention relates to the field of antibacterial frit technology, specifically a method and equipment for preparing an antibacterial frit doped with cerium dioxide using zinc oxide. Background Technology

[0002] Antibacterial frits are widely used in ceramic glazes, coatings, fibers, and building materials due to their advantages such as good heat resistance, long shelf life, and high safety. Their antibacterial mechanism mainly relies on metal ions with antibacterial activity, such as silver, copper, and zinc, which are loaded onto inorganic carriers such as zeolites, phosphates, silica gel, or glass through physical adsorption, ion exchange, or chemical bonding. During use, these ions are slowly released, disrupting the cell structure or enzyme system of microorganisms, thereby achieving long-lasting antibacterial effects.

[0003] In existing technologies, the melt-water quenching method can incorporate antibacterial components into the glass network structure in ionic form, which is considered helpful in improving the stability of the antibacterial components, thereby solving the problems of easy ion detachment and poor antibacterial durability. This has become an important process for preparing high-performance glass-based antibacterial frits. Zinc oxide (ZnO), as a common antibacterial component, contains zinc ions (Zn... 2 + It possesses good antibacterial activity and biosafety. Recent studies have shown that by combining zinc oxide with cerium dioxide (CeO2), which has redox catalytic properties, it is possible to utilize Ce... 4+ / Ce 3+ The cyclic transformation produces reactive oxygen species such as hydroxyl radicals, which react with Zn. 2+ The contact antibacterial effect produces a synergistic effect, which is expected to significantly enhance the broad-spectrum antibacterial and anti-biofilm capabilities of the antibacterial melt.

[0004] However, there are two prominent technical challenges in preparing such composite antibacterial frits using the traditional melt-water quenching method: First, the high-temperature molten glass, after being rapidly cooled by water quenching, will shatter into a large number of loosely structured but highly irregularly shaped glass particles with a very wide particle size distribution due to intense thermal stress. If these initial particles directly enter the subsequent dehydration, drying, and grinding processes, it will not only cause clogging of the dehydration screen and uneven drying, but also severely affect the efficiency of fine grinding and the uniformity of the final powder particle size due to the significant differences in particle size. When these uneven powders are added to ceramic glazes or plastic masterbatches, they are prone to uneven dispersion, affecting the appearance, performance, and stability of the antibacterial effect of the product. Second, in order to control the particle size, existing processes usually involve direct mechanical crushing and prolonged grinding of the dried glass particles after water quenching. This process is energy-intensive and inefficient, and excessive grinding may damage the glass network structure, affecting the stable immobilization of antibacterial ions.

[0005] Therefore, developing a preparation method and dedicated equipment that can effectively control the initial particle size of glass particles after water quenching at the preparation front end and achieve integrated dehydration and preliminary classification is of great practical significance for improving the production efficiency, product uniformity and comprehensive performance of zinc oxide-doped cerium dioxide antibacterial briquettes. Summary of the Invention

[0006] The purpose of this invention is to provide a method and equipment for preparing an antibacterial fused block doped with zinc oxide and cerium dioxide in order to control the initial particle size of glass particles after water quenching.

[0007] A method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide includes the following steps: S1. Raw material mixing and dispersion: The inorganic powder raw materials containing zinc oxide and cerium oxide in the specified proportions are uniformly mixed to obtain a mixture; S2. High-temperature melting and structural doping: The mixture is subjected to high-temperature melting to form a homogeneous glass melt, and functional components are doped into the glass network structure. S3, Melt quenching and vitrification: The glass melt is quenched and rapidly cooled by water to break it up and solidify it into irregular glass particles; S4. Solid-liquid separation and drying: The mixture of glass particles and water obtained after water quenching is separated into solid and liquid by a water quenching and screening machine, and the resulting wet glass particles are dried. S5. Crushing, grinding and particle size classification: The dried glass particles are crushed, finely ground and classified in sequence to obtain a powder semi-finished product with the target particle size distribution. S6. Finished product screening and packaging: The powder semi-finished product is screened to remove impurities and then sealed and packaged to obtain the antibacterial frit finished product.

[0008] Furthermore, in step S1, the inorganic powder raw material includes the basic carrier raw material constituting the silicate glass network, as well as zinc oxide and cerium oxide as functional dopant components.

[0009] Further, in step S1, the inorganic powder raw material includes a basic carrier material constituting the silicate glass network, and zinc oxide and cerium oxide as functional dopant components; the basic carrier material is selected from at least several of feldspar powder, quartz powder, calcite powder, dolomite powder, industrial alumina, barium carbonate, strontium carbonate, boric acid, borax, and zirconium silicate; the composition of the inorganic powder raw material, in terms of oxide weight percentage, is: SiO2: 35-70%; Al2O3: 5-25%; CaO: 5-15%; MgO: 0-7%; K2O: 0-5%; Na2O: 0-13%; ZnO: 2-40%; BaO: 0-10%; Fe2O3: 0-1%; TiO2: 0-1%; SrO: 0-8%; ZrO2: 0-13%; B2O3: 0-21%; CeO2: 0.1-4.5%; The equal-incremental mixing method is used to ensure uniform dispersion of cerium oxide: First, take a base carrier material of equal or several times the mass of cerium oxide and premix it. Then, put the resulting premix and all the remaining raw materials into a high-efficiency mixer and mix for 30-60 minutes.

[0010] Further, in step S2, the high-temperature melting treatment is carried out in an air atmosphere or an oxygen atmosphere, and the specific melting regime is: the temperature is programmed to rise to 1500℃ at a heating rate of 5-10℃ / min, and held at 1500℃ for 1.5-2 hours; in step S3, the water quenching is achieved by pouring the glass melt into a high-speed spiral water flow at a constant temperature of 25±5℃; in step S4, the drying conditions are drying at 105±5℃ for 60-90 minutes, so that the water content of the glass particles after drying is less than 0.5wt%.

[0011] An equipment used in the preparation method of antibacterial frit doped with zinc oxide and cerium dioxide includes a water quenching and screening integrated machine used in steps S3 and S4. The water quenching and screening integrated machine includes a high-temperature resistant guide channel. A spiral water channel is provided at one end of the high-temperature resistant guide channel. A water outlet is fixedly connected to the bottom end of the spiral water channel. A water valve is installed on the outer wall of the water outlet. A mounting frame is fixedly connected to the top end of the spiral water channel. A stirring motor is installed at the top end of the mounting frame. A stirring shaft is connected to the output end of the stirring motor. The glass particles discharged from the water outlet are sheared by a mechanical shearing unit. The sheared glass particles are dehydrated by a dehydration unit.

[0012] As a further embodiment of the present invention: the mechanical shearing unit includes a connecting cylinder, which is disposed at the bottom end of the outlet. A discharge pipe is fixedly connected to the bottom end of the connecting cylinder. A filter plate is rotatably connected to the inner wall of the connecting cylinder. A spur gear is fixedly connected to one end of the filter plate. A support frame is fixedly connected to the top end of the connecting cylinder. A variable frequency motor is installed at the top end of the support frame. A square rod is connected to the output end of the variable frequency motor. A square cylinder is slidably connected to the outer wall of the square rod. A shearing plate is fixedly connected to the bottom end of the square cylinder. A displacement frame is rotatably connected to the top outer wall of the square cylinder. A displacement motor is installed at the top end of the support frame, located on one side of the variable frequency motor. A first threaded rod is connected to the output end of the displacement motor. The first threaded rod passes through the displacement frame. A locking block is fixedly connected to the bottom end of the displacement frame. A toothed block is fixedly connected to the outer wall of the displacement frame. The bottom end of the toothed block contacts the spur gear.

[0013] As a further embodiment of the present invention: the dewatering unit includes a base plate, which is disposed below the discharge pipe. A collection groove is formed at the top of the base plate, and a discharge pipe is fixedly connected to the bottom end of the base plate. A support spring is fixedly connected to the top of the base plate, and a vibration frame is fixedly connected to the top of the support spring. Three collection boxes are provided at one end of the base plate, and an L-shaped frame is fixedly connected to the other end of the base plate. A vibration motor is installed on the outer wall of the L-shaped frame, and a rotating disk is connected to the output end of the vibration motor. A protrusion is fixedly connected to the outer wall of the rotating disk.

[0014] As a further embodiment of the present invention: the dewatering unit further includes three guide plates, the guide plates being fixedly connected to one end of the vibrating frame, the inner wall of the vibrating frame being fixedly connected to three rows of support rods, the inner wall of the vibrating frame being slidably connected to the top of the support rods, the outer wall of the guide plate being fixedly connected to the end facing the sieve plate being a connecting plate, the outer wall of the connecting plate being fixedly connected to an insert plate, the sieve plate being provided with a slot at the end facing the guide plate, the vibrating frame being symmetrically fixedly connected to a side plate at the end away from the guide plate, the outer wall of the side plate being rotatably connected to a rotating column, a second threaded rod being fixedly connected between the two rotating columns, and a positioning plate being symmetrically slidably connected to the outer wall of the second threaded rod.

[0015] As a further embodiment of the present invention: the outer wall of the square rod is in contact with the inner wall of the square cylinder; the top of the displacement frame has a first threaded hole, which matches the first threaded rod.

[0016] As a further embodiment of the present invention: the outer wall of the tooth block is provided with a tooth groove, the tooth groove meshes with the spur gear, and the bottom outer wall of the locking block engages with the spur gear.

[0017] As a further embodiment of the present invention: the inner wall of the slot is in contact with the outer wall of the insert plate; the outer wall of the second threaded rod is symmetrically provided with external threads, and the outer wall of the positioning plate is provided with a second threaded hole, which matches the external threads.

[0018] Compared with the prior art, the beneficial effects of the present invention are: 1. The method for preparing antibacterial frit doped with zinc oxide and cerium dioxide of the present invention, by adopting an equal-incremental premixing and a high-temperature melting process under a specific oxidizing atmosphere, allows zinc oxide and cerium oxide to be uniformly and stably doped into the glass network structure, effectively avoiding the aggregation and loss of functional components, thereby ensuring that the obtained antibacterial frit has a long-lasting and stable ion-releasing ability and excellent broad-spectrum antibacterial durability.

[0019] 2. The method for preparing antibacterial frits doped with zinc oxide and cerium dioxide of the present invention, by precisely controlling the water quenching temperature, drying parameters and graded grinding targets, not only obtains loose glass particles with high surface activity, but also flexibly adjusts the particle size distribution and physical state of the product according to different application requirements, significantly improving the dispersion adaptability, batch stability and final application performance of the product in different substrates.

[0020] 3. The water quenching and screening integrated machine of the present invention, by setting up a mechanical shearing unit, allows water and glass particles to enter the connecting cylinder through the water outlet. The filter plate filters the glass particles, leaving larger glass particles at the top of the filter plate. At this time, the variable frequency motor is started, and the operation of the variable frequency motor drives the square rod to rotate. The rotation of the square rod drives the square cylinder to rotate, and the rotation of the square cylinder drives the shearing plate to rotate. The rotating shearing plate comes into contact with the glass particles and impacts and shears the glass particles, so that the glass particles can pass through the filter plate and be discharged along the discharge pipe, which makes it easier to control the initial particle size of the glass particles after water quenching.

[0021] 4. The water-quenching and screening integrated machine is equipped with a dewatering unit. Glass particles fall onto the screen plate, and smaller glass particles fall through the holes in the screen plate, allowing glass particles of different sizes to slide along different screen plates and enter the guide plate. They then enter different collection boxes for collection. Vibration shakes the water off the glass particles, and the water falls into the collection tank for collection and is discharged through the discharge pipe, facilitating the dewatering and particle size classification of the glass particles. At the same time, the screen plates can be quickly installed and disassembled, allowing for the replacement of screen plates with different apertures according to different needs. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the integrated water quenching and screening machine of the present invention; Figure 2 This is a schematic diagram of the spiral water tank of the water quenching and screening integrated machine of the present invention; Figure 3 This is a schematic diagram of the internal structure of the connecting cylinder of the integrated water quenching and screening machine of the present invention; Figure 4 This is a schematic diagram of the displacement frame of the water quenching and screening integrated machine described in this invention; Figure 5 This is a schematic diagram of the connection structure between the displacement frame and the square cylinder of the water quenching and screening integrated machine described in this invention; Figure 6 This is a schematic diagram of the structure of the vibrating frame of the water quenching and screening integrated machine described in this invention; Figure 7 This is a schematic diagram of the internal structure of the vibrating frame of the water quenching and screening integrated machine described in this invention; Figure 8 This is a schematic diagram of the insert plate of the water quenching and screening integrated machine described in this invention; Figure 9 This is a schematic diagram of the positioning plate of the water quenching and screening integrated machine of the present invention.

[0023] In the diagram: 1. High-temperature resistant guide channel; 2. Spiral water channel; 3. Outlet; 4. Water valve; 5. Mounting bracket; 6. Agitator motor; 7. Agitator shaft; 8. Mechanical shearing unit; 801. Connecting cylinder; 802. Discharge pipe; 803. Filter plate; 804. Spur gear; 805. Support frame; 806. Variable frequency motor; 807. Square rod; 808. Square cylinder; 809. Shearing plate; 810. Displacement motor; 811. First threaded rod; 812. Displacement frame; 813. Tooth block; 814. 901. Locking block; 902. Dehydration unit; 903. Base plate; 904. Collection trough; 905. Discharge pipe; 906. Support spring; 907. Vibrating frame; 908. L-shaped frame; 909. Vibrating motor; 9000. Rotating disc; 910. Protrusion; 911. Collection box; 912. Guide plate; 913. Support rod; 914. Screen plate; 915. Connecting plate; 916. Insert plate; 917. Slot; 918. Side plate; 919. Rotating column; 920. Second threaded rod; 911. Positioning plate. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating orientation or positional relationships, are based on the orientation or positional relationships shown in the accompanying drawings and are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance. In the description of this invention, it should be noted that unless otherwise explicitly specified and limited, the terms "installed," "connected," "linked," and "set up" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal communication of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances. The following describes embodiments of the invention based on its overall structure. Example 1

[0026] Please see Figures 1 to 9 In this embodiment of the invention, a method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide includes the following specific steps: S1. Raw Material Selection, Weighing, and Uniform Mixing: Select quartz powder (providing SiO2), feldspar powder (providing SiO2, Al2O3, K2O, and Na2O), calcite powder (providing CaO), industrial alumina, zinc oxide, cerium oxide, and boric acid (providing B2O3) as raw materials. The final oxide weight percentages are: SiO2: 67%; Al2O3: 16%; CaO: 10%; Na2O: 4%; ZnO: 2.0%; CeO2: 0.1%; B2O3: 0.9%. Weigh accurately. Add all powder raw materials to a high-efficiency mixer. To ensure uniform dispersion of the trace component CeO2, an equal-incremental feeding method is adopted: first, take quartz powder of the same mass as cerium oxide and premix it in a small mixer for 10 minutes until the color is uniform (the mixture is visually free of color difference or clumping). Then, put this premixed material together with all the remaining raw materials into a high-efficiency mixer and mix for 40 minutes to obtain a mixture with uniform color and no visible lumps.

[0027] S2. High-Temperature Melting and Doping: The mixture is transferred to a high-temperature silicon molybdenum rod electric furnace and heated to 1500°C at a programmed heating rate of 5°C / min under air atmosphere. After reaching the temperature, it is held for 1.5 hours. During this process, all raw materials are fully melted and homogenized into a clear, bubble-free glass melt. Zinc oxide and cerium oxide are firmly doped into the formed silicate glass network structure in ionic form.

[0028] S3. Meltwater Quenching and Vitrification: The high-temperature molten glass is rapidly introduced into the high-temperature resistant guide tank 1 of the integrated water quenching and screening machine, where it undergoes rapid water quenching and cooling in a high-speed spiral water flow at 25°C. Upon contact with water, the high-temperature molten glass instantly shatters and solidifies into irregular glass particles with a loose structure and high activity due to intense thermal stress.

[0029] S4. Dehydration and Drying of Water-Quenched Particles: The mixture of water-quenched glass particles and water is conveyed to the mechanical shearing unit 8 of the integrated water-quenching and screening machine for shearing and crushing. First, the mixture enters the connecting cylinder 801 through the water outlet, where the filter plate 803 (1.5mm aperture) filters the glass particles. The variable frequency motor 806 is started, driving the shearing plate 809 to rotate via the square rod 807 and square cylinder 808, impacting and shearing large particles stuck at the top of the filter plate 803, allowing them to pass through the filter plate 803. Subsequently, the mixture of particles and water flows into the vibrating screen plate 913 (apertures from top to bottom are 1.2mm, 0.6mm, and 0.3mm respectively) of the dehydration unit 9. Driven by the vibrating motor 907, the particles are dehydrated and initially separated according to different particle size ranges, and the water is collected in the collection tank 902 and discharged. Wet glass particles were collected using a collection box with a particle size of 910 and then sent to a forced-air drying oven to be dried at 105°C for 60 minutes to obtain dried glass particles with a water content of less than 0.5 wt%.

[0030] S5. Fine grinding and classification of glass particles: The dried glass particles were first initially crushed using a jaw crusher. Then, the crushed particles were fed into a zirconia ball mill jar and ball-milled for 6 hours using ethanol as the medium. After drying the slurry, the powder was classified using an air classifier, and the powder with D50 ≤ 5μm was collected as a semi-finished product. In this embodiment, the D50 was measured to be 4.5μm.

[0031] S6. Finished Product Screening and Packaging: The graded semi-finished powder is screened through an 800-mesh ultrasonic vibrating screen to remove any individual coarse particles or mechanical impurities. Finally, the qualified antibacterial frit powder is sealed and packaged in a dry environment with a humidity of 25% to obtain the finished antibacterial frit.

[0032] It should be noted that in S1, taking several times the mass of the basic carrier raw material and premixing it with cerium oxide means taking 2 times, 3 times, or other integer multiples of the mass of the basic carrier raw material and premixing it with cerium oxide.

[0033] Please refer to this carefully. Figures 1 to 2The equipment used in the preparation method of antibacterial frit doped with zinc oxide and cerium dioxide includes a water quenching and screening integrated machine used in steps S3 and S4. The water quenching and screening integrated machine includes a high-temperature resistant guide channel 1, a spiral water channel 2 is provided at one end of the high-temperature resistant guide channel 1, a water outlet 3 is fixedly connected to the bottom end of the spiral water channel 2, a water valve 4 is installed on the outer wall of the water outlet 3, a mounting frame 5 is fixedly connected to the top end of the spiral water channel 2, a stirring motor 6 is installed at the top end of the mounting frame 5, a stirring shaft 7 is connected to the output end of the stirring motor 6, the glass particles discharged from the water outlet 3 are sheared by a mechanical shearing unit 8, and the sheared glass particles are dehydrated by a dehydration unit 9.

[0034] In this embodiment: the high-temperature glass melt enters the spiral water tank 2 from the high-temperature resistant guide tank 1. The stirring motor 6 drives the stirring shaft 7 to rotate. The rotation of the stirring shaft 7 forms a high-speed vortex water flow field in the spiral water tank 2, ensuring that the melt and cooling water are fully contacted in a very short time. A variable frequency speed-regulating mechanical shearing unit 8 is added to the bottom of the outlet 3 to actively control the initial particle size of the glass particles after water quenching. Then, the broken glass particles and cooling water enter the dewatering unit 9 together for particle size classification and screening.

[0035] Please refer to this carefully. Figures 3 to 5 The mechanical shearing unit 8 includes a connecting cylinder 801, which is located at the bottom of the outlet 3. A discharge pipe 802 is fixedly connected to the bottom of the connecting cylinder 801. A filter plate 803 is rotatably connected to the inner wall of the connecting cylinder 801. A spur gear 804 is fixedly connected to one end of the filter plate 803. A support frame 805 is fixedly connected to the top of the connecting cylinder 801. A variable frequency motor 806 is mounted on the top of the support frame 805. A square rod 807 is connected to the output end of the variable frequency motor 806. A square cylinder 804 is slidably connected to the outer wall of the square rod 807. 08. A shearing plate 809 is fixedly connected to the bottom end of the square cylinder 808. A displacement frame 812 is rotatably connected to the top outer wall of the square cylinder 808. A displacement motor 810 is installed on the top of the support frame 805 on one side of the frequency converter motor 806. A first threaded rod 811 is connected to the output end of the displacement motor 810. The first threaded rod 811 passes through the displacement frame 812. A locking block 814 is fixedly connected to the bottom end of the displacement frame 812. A toothed block 813 is fixedly connected to the outer wall of the displacement frame 812. The bottom end of the toothed block 813 is in contact with the spur gear 804.

[0036] In this embodiment: the bottom end of the locking block 814 engages with the spur gear 804, fixing the spur gear 804 and thus fixing the filter plate 803; water and glass particles enter the connecting cylinder 801 through the outlet 3, the filter plate 803 filters the glass particles, leaving larger glass particles at the top of the filter plate 803, at this time the variable frequency motor 806 is started, the variable frequency motor 806 drives the square rod 807 to rotate, the square rod 807 drives the square cylinder 808 to rotate, the square cylinder 808 drives the shearing plate 809 to rotate, the shearing plate 809 rotates and contacts the glass particles, impacting and shearing the glass particles, so that the glass particles can pass through the filter plate 803 and be discharged along the discharge pipe 802; when the outlet 3 no longer discharges liquid, the displacement motor 810 is started, the displacement motor 810 drives the first The threaded rod 811 rotates, causing the displacement frame 812 to move. The displacement frame 812 moves the square cylinder 808 and the shearing plate 809 upwards simultaneously. The shearing plate 809 moves upwards and separates from the filter plate 803. At the same time, the displacement frame 812 moves the locking block 814 and separates from the spur gear 804, thus removing the fixation on the filter plate 803. This continues until the displacement frame 812 moves the toothed block 813 and contacts the spur gear 804, causing the spur gear 804 to rotate. The rotation of the spur gear 804 causes the filter plate 803 to rotate. The filter plate 803 rotates vertically, causing the glass particles adhering to the edge of the filter plate 803 to fall off and be discharged along the discharge pipe 802, avoiding waste and facilitating control of the initial particle size of the glass particles after water quenching.

[0037] Please refer to this carefully. Figures 6 to 9The dewatering unit 9 includes a base plate 901, which is located below the discharge pipe 802. A collection trough 902 is formed at the top of the base plate 901. A discharge pipe 903 is fixedly connected to the bottom of the base plate 901. A support spring 904 is fixedly connected to the top of the base plate 901, and a vibrating frame 905 is fixedly connected to the top of the support spring 904. Three collection boxes 910 are provided at one end of the base plate 901, and an L-shaped frame 906 is fixedly connected to the other end of the base plate 901. A vibrating motor 907 is mounted on the outer wall of the L-shaped frame 906. A rotating disk 908 is connected to the output end of the vibrating motor 907, and a protrusion 909 is fixedly connected to the outer wall of the rotating disk 908. The dewatering unit 9 also includes three guide plates 911. The guide plates 911 are fixed... Connected to one end of the vibrating frame 905, the inner wall of the vibrating frame 905 is fixedly connected with three rows of support rods 912, and the inner wall of the vibrating frame 905 is slidably connected to the top of the support rods 912. The outer wall of the guide plate 911 facing the end of the sieve plate 913 is fixedly connected to a connecting plate 914, and the outer wall of the connecting plate 914 is fixedly connected to an insert plate 915. The end of the sieve plate 913 facing the guide plate 911 is provided with a slot 916. The end of the vibrating frame 905 away from the guide plate 911 is symmetrically fixedly connected to a side plate 917, and the outer wall of the side plate 917 is rotatably connected to a rotating column 918. A second threaded rod 919 is fixedly connected between the two rotating columns 918, and a positioning plate 920 is symmetrically slidably connected to the outer wall of the second threaded rod 919.

[0038] In this embodiment: the aperture size of the three sieve plates 913 decreases from top to bottom. When the vibration motor 907 is started, the vibration motor 907 drives the rotating disk 908 to rotate. The rotating disk 908 drives the protrusion 909 to move in a circular motion. During the displacement, the protrusion 909 comes into contact with the vibration frame 905 and impacts the vibration frame 905, causing the vibration frame 905 to vibrate. Glass particles fall onto the sieve plates 913. Smaller glass particles fall through the holes on the sieve plates 913, so that glass particles of different sizes slide along different sieve plates 913 into the guide plate 911 and enter different collection boxes 910 for collection. The vibration shakes the water off the glass particles, and the water falls into the collection tank 902 for collection and is discharged through the discharge pipe 903, which facilitates the dehydration and particle size classification of the glass particles.

[0039] When installing the sieve plate 913, move the sieve plate 913 into the inner wall of the vibration frame 905 and slide it along the top of the support rod 912 until one end of the sieve plate 913 contacts the connecting plate 914. Insert the insertion plate 915 into the insertion slot 916 to position the sieve plate 913. Then rotate the rotating column 918. The rotation of the rotating column 918 drives the second threaded rod 919 to rotate. The rotation of the second threaded rod 919 drives the two positioning plates 920 to move in opposite directions. The displacement of the positioning plates 920 contacts the other end of the sieve plate 913, thereby fixing the sieve plate 913. When disassembling, rotate the rotating column 918 to drive the positioning plates 920 to separate from the sieve plate 913. Then push the sieve plate 913 to move and displace the sieve plate 913 out of the vibration frame 905. This design can facilitate the rapid installation and disassembly of the sieve plate 913, so that sieve plates 913 with different pore diameters can be replaced according to different needs.

[0040] Please refer particularly to Figures 3 to 5 , the outer wall of the square rod 807 fits with the inner wall of the square cylinder 808.

[0041] In this embodiment: The variable-frequency motor 806 operates to drive the square rod 807 to rotate. The rotation of the square rod 807 drives the square cylinder 808 to rotate. The rotation of the square cylinder 808 drives the shear plate 809 to rotate. When the displacement frame 812 moves, the square cylinder 808 can slide up and down on the outer wall of the square rod 807.

[0042] Please refer particularly to Figures 3 to 5 , a first threaded hole is opened at the top of the displacement frame 812, and the first threaded hole matches the first threaded rod 811.

[0043] In this embodiment: The displacement motor 810 operates to drive the first threaded rod 811 to rotate. The rotation of the first threaded rod 811 drives the displacement frame 812 to move.

[0044] Please refer particularly to Figures 3 to 5 , tooth grooves are formed on the outer wall of the tooth block 813, and the tooth grooves mesh with the spur gear 804. The bottom outer wall of the clamping block 814 engages with the spur gear 804.

[0045] In this embodiment: The bottom end of the clamping block 814 engages with the spur gear 804 to fix the spur gear 804, thereby fixing the filter plate 803. When the displacement frame 812 moves upward, it drives the clamping block 814 to move. The displacement of the clamping block 814 separates from the spur gear 804, canceling the fixation of the filter plate 803 until the displacement frame 812 moves to drive the tooth block 813 to move. The displacement of the tooth block 813 contacts the spur gear 804, driving the spur gear 804 to rotate. The rotation of the spur gear 804 drives the filter plate 803 to rotate.

[0046] Please refer particularly to Figures 6 to 9 , the inner wall of the slot 916 fits against the outer wall of the insertion plate 915.

[0047] In this embodiment: Move the sieve plate 913 into the inner wall of the vibrating frame 905 and slide along the top of the support rod 912 until one end of the sieve plate 913 contacts the connecting plate 914. Insert the insertion plate 915 into the slot 916 to position the sieve plate 913.

[0048] Please refer particularly to Figures 6 to 9 , external threads are symmetrically provided on the outer wall of the second threaded rod 919, and second threaded holes are formed on the outer wall of the positioning plate 920. The second threaded holes match the external threads.

[0049] In this embodiment: Rotate the rotating column 918. The rotation of the rotating column 918 drives the second threaded rod 919 to rotate, and the rotation of the second threaded rod 919 drives the two positioning plates 920 to displace in opposite directions. Embodiment 2

[0050] A preparation method of an antibacterial frit doped with zinc oxide in cerium dioxide is as follows: S1. Selection, weighing and uniform mixing: Select quartz powder, feldspar powder, calcite powder, dolomite powder (providing MgO), industrial alumina, barium carbonate (providing BaO), zinc oxide, cerium dioxide, boric acid, borax as raw materials. By weight percentage of the final oxides: SiO2: 55%; Al2O3: 15%; CaO: 8%; MgO: 2%; Na2O: 6%; ZnO: 12%; CeO2: 1.0%; BaO: 0.5%; B2O3: 0.5%; conduct precise weighing. Use the equal increment method for mixing: First, premix cerium dioxide with industrial alumina powder of the same mass evenly, and then put this premixed material and all other raw materials into a high-efficiency mixer and mix for 50 minutes to obtain a uniform mixture.

[0051] S2. High-temperature melting and doping: Under an air atmosphere, program the temperature to rise to 1500 °C at a rate of 8 °C per minute and hold at this temperature for 2 hours to obtain a homogeneous glass melt.

[0052] S3. Melt water quenching and vitrification: Pour the melt into a high-speed spiral water flow at a constant temperature of 25 °C for water quenching.

[0053] S4. Dehydration and drying of water-quenched particles: Use a water quenching and screening integrated machine (filter plate pore size 2.0 mm) for shearing, dehydration and preliminary classification. Dry the wet particles at 105 °C for 75 minutes.

[0054] S5. Fine grinding and classification of glass particles: After primary crushing by a jaw crusher, grind to the target particle size using a vibration mill, and collect the powder with D50 ≤ 2 μm as a semi-finished product using an air classifier.

[0055] S6. Finished product screening and packaging: After screening through an 800-mesh ultrasonic vibrating screen, it is hermetically packaged in an environment with a humidity of 25%.

[0056] The preparation devices such as the water quenching and screening integrated machine used are the same as those in Example 1 and will not be elaborated here. Example 3

[0057] A preparation method of an antibacterial frit doped with zinc oxide and cerium dioxide is as follows: S1. Raw material selection, weighing and uniform mixing: Select quartz powder, feldspar powder, calcite powder, industrial alumina, zinc oxide, cerium dioxide, zirconium silicate (providing ZrO2), and boric acid as raw materials. By the weight percentage of the final oxides: SiO2: 38%; Al2O3: 10%; CaO: 5%; ZnO: 40%; CeO2: 4.5%; ZrO2: 1.5%; B2O3: 1.0%; conduct accurate weighing. Use the equal increment method for mixing: First premix cerium dioxide, and then put all raw materials into a high-efficiency mixer and mix for 60 minutes to obtain a uniform mixture.

[0058] S2. High-temperature melting and doping: Under an oxygen atmosphere, the temperature is programmed to rise to 1500 °C at a rate of 10 °C per minute and held for 2 hours to obtain a melt (to promote the doping of high-content ZnO and CeO2, a stronger oxidation atmosphere is used).

[0059] S3. Melt water quenching and vitrification: Pour the melt into a high-speed spiral water flow at a constant temperature of 25 °C for water quenching.

[0060] S4. Dehydration and drying of water-quenched particles: Use a water quenching and screening integrated machine (filter plate pore diameter 2.5 mm) for treatment, and dry the wet particles at 108 °C for 90 minutes.

[0061] S5. Fine grinding and classification of glass particles: After primary crushing, use a jet mill for fine grinding, and use a classifier to collect the powder with D50 ≤ 1 μm as the semi-finished product.

[0062] S6. Finished product screening and packaging: After screening through a 1000-mesh ultrasonic vibrating screen, it is hermetically packaged in an environment with a humidity of 20%.

[0063] The preparation devices such as the water quenching and screening integrated machine used are the same as those in Example 1 and will not be elaborated here. Comparative Example 1

[0064] In this comparative example, the preparation method of the antibacterial frit is as follows: S1. Raw material selection, weighing and uniform mixing: This step is exactly the same as S1 in Example 2.

[0065] S2. High-temperature melting and doping: This step is exactly the same as S2 in Example 2.

[0066] S3. Melting solution water quenching and vitrification: This step is exactly the same as S3 in Example 2.

[0067] S4. Solid-liquid separation and drying: The mixture of glass particles and water obtained after water quenching is directly transported to a common linear vibrating screen for solid-liquid separation. The separated wet glass particles are sent to a drying device and dried at 105 °C for 75 minutes. Online shearing and pre-sizing of the particles cannot be performed during this process.

[0068] S5. Crushing, grinding and particle size classification: The glass particles with a very wide particle size distribution after drying are directly fed into a jaw crusher for crushing, and then into a vibrating mill for long-time grinding (the total time-consuming is about 2.5 times that of Example 2), and repeatedly separated by an air classifier. Finally, a semi-finished powder with a D50 of about 2.1 μm is obtained.

[0069] S6. Finished product screening and packaging: This step is the same as S6 in Example 2.

[0070] The preparation devices such as the water quenching and screening integrated machine used are the same as those in Example 1 and will not be elaborated here. Comparative Example 2

[0071] In this comparative example, the preparation method of the antibacterial frit is as follows: S1. Raw material selection, weighing and uniform mixing: On the basis of the formula in Example 2, cerium oxide (CeO2) is removed, and its 1.0% weight percentage is supplemented by an equal amount of silicon dioxide (SiO2). That is, the formula is adjusted to: SiO2: 56.0%; Al2O3: 15%; CaO: 8%; MgO: 2%; Na2O: 6%; ZnO: 12%; BaO: 0.5%; B2O3: 0.5%. After accurate weighing according to this formula, the same equal increment method and mixing parameters as S1 in Example 2 are used for uniform mixing.

[0072] S2. High-temperature melting and doping: This step is exactly the same as S2 in Example 2.

[0073] S3. Melting solution water quenching and vitrification: This step is exactly the same as S3 in Example 2.

[0074] S4. Dehydration and drying of water-quenched particles: Use a water quenching and screening integrated machine (filter plate aperture 2.0 mm) for shearing, dehydration and preliminary classification. The wet particles are dried at 105 °C for 75 minutes.

[0075] S5. Fine grinding and classification of glass particles: After primary crushing by a jaw crusher, it is ground to the target particle size by a vibrating mill, and the powder with D50 ≤ 2 μm is collected by an air classifier as a semi-finished product.

[0076] S6, Finished product screening and packaging: After screening through an 800-mesh ultrasonic vibrating screen, it is hermetically packaged in an environment with a humidity of 25%.

[0077] The preparation devices such as the water quenching and screening integrated machine used are the same as those in Example 1, and will not be elaborated here. Comparative Example 3

[0078] In this comparative example, the preparation method of the antibacterial frit is as follows: S1, Raw material selection, weighing and uniform mixing: On the basis of the formula in Example 2, the content of CeO2 is increased to 8.0%, and the content of SiO2 is correspondingly reduced. The adjusted formula is: SiO2: 47.0%; Al2O3: 15%; CaO: 8%; MgO: 2%; Na2O: 6%; ZnO: 12%; CeO2: 5.0%; BaO: 0.5%; B2O3: 0.5%. After accurate weighing according to this formula, the equal increment method and mixing parameters the same as those in S1 of Example 2 are used for uniform mixing.

[0079] S2, High-temperature melting and doping: This step is exactly the same as S2 in Example 2.

[0080] S3, Molten liquid water quenching and vitrification: This step is exactly the same as S3 in Example 2.

[0081] S4, Dehydration and drying of water-quenched particles: Use a water quenching and screening integrated machine (filter plate pore size 2.0 mm) for shearing, dehydration and preliminary classification. The wet particles are dried at 105 °C for 75 minutes.

[0082] S5, Fine grinding and classification of glass particles: After primary crushing by a jaw crusher, it is ground to the target particle size by a vibration mill, and the powder with D50≤2 μm is collected by an air classifier as a semi-finished product.

[0083] S6, Finished product screening and packaging: After screening through an 800-mesh ultrasonic vibrating screen, it is hermetically packaged in an environment with a humidity of 25%.

[0084] The preparation devices such as the water quenching and screening integrated machine used are the same as those in Example 1, and will not be elaborated here.

[0085] Analysis and testing

[0086] The following performance tests and analyses are carried out on the products obtained above: 1. Particle size distribution: Use a Malvern Mastersizer 3000 laser particle size analyzer to measure the volume average particle size (D50) and particle size distribution span ((D90 - D10) / D50) of the powder, with anhydrous ethanol as the medium.

[0087] 2. Microscopic Morphology and Element Distribution: The morphology of the particles was observed using a Zeiss Sigma300 scanning electron microscope (SEM), and combined with an Oxford X-MaxN80 energy dispersive spectrometer (EDS) for surface scanning analysis to characterize the uniformity of the distribution of Zn and Ce elements at the micron scale.

[0088] 3. Antibacterial Performance: Referring to the standard of 《GB / T21866-2008》, Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538) were selected as the test strains. The antibacterial powder was uniformly dispersed in the molten agar medium at a ratio of 1.0 wt%, and poured into a plate. Using the film close contact method, after inoculating the bacterial solution, it was cultured at 37 °C for 24 hours, and the antibacterial rate was calculated.

[0089] 4. Ion Release Behavior: Accurately weigh Ⅰ.00 g of the antibacterial frit powder and place it in 100 mL of deionized water, and oscillate it in a constant temperature oscillator at 37 °C and 120 rpm. Samples were taken on the 1st, 3rd, and 7th days respectively. After the solution was filtered through a 0.22 μm filter membrane, the concentration of Zn in the solution was measured using a PerkinElmer Optima8300 inductively coupled plasma emission spectrometer (ICP-OES). 2+ concentration.

[0090] 5. Process Energy Consumption Evaluation: Use an electric energy meter to record the actual power consumption of the entire crushing, grinding, and classification process from the end of S4 drying (i.e., obtaining dried glass particles) to the completion of S5 to obtain qualified semi-finished product powder, and convert it into the energy consumption (kWh / kg) of the qualified semi-finished product powder per unit mass.

[0091] The performance test results of the products prepared in the above examples and comparative examples are shown in Table 1 below:

[0092] Table 1 - Comparison Table of Product Performance Test Results between Examples and Comparative Examples

[0093] The above test data comprehensively show that: In Examples 1-3, a water quenching and screening integrated machine was used, and the particle size distribution span (1.1 - 1.3) was significantly narrower than that of Comparative Example 1 (2.9), proving that the equipment achieved effective online control and pre-classification of water quenched particles. This directly led to a significant reduction in the subsequent grinding energy consumption (the unit power consumption of the examples was 0.8 - 1.1 kWh / kg, only 35% - 48% of that of Comparative Example 1), demonstrating the core advantages of the present invention in improving production efficiency and product physical homogeneity.

[0094] Comparative Example 2 (without CeO2) in Zn 2+The antibacterial rate is the lowest (about 85%) in the case of the highest release amount, while the antibacterial rate of Example 2 containing CeO2 is as high as over 99.5%. This conclusively proves that the synergistic antibacterial effect of ZnO and CeO2 surpasses simple ion dissolution. The local enrichment phenomenon occurring in Comparative Example 3 (excessive CeO2) supports the reasonable setting of the content range of the active components (such as CeO2: 0.1-4.5%) in the claims from a process perspective.

[0095] In summary, through the combination of the special equipment of the water quenching and screening integrated machine and the optimized ZnO / CeO2 synergistic system formula, the present invention synchronously solves the technical problems of low production efficiency, poor product uniformity, and antibacterial performance relying on high ion release in the traditional process.

[0096] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes, should be covered within the protection scope of the present invention.

Claims

1. A method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide, characterized in that... Includes the following steps: S1. Raw material mixing and dispersion: The inorganic powder raw materials containing zinc oxide and cerium oxide in the specified proportions are uniformly mixed to obtain a mixture; S2. High-temperature melting and structural doping: The mixture is subjected to high-temperature melting to form a homogeneous glass melt, and functional components are doped into the glass network structure. S3, Melt quenching and vitrification: The glass melt is quenched and rapidly cooled by water to break it up and solidify it into irregular glass particles; S4. Solid-liquid separation and drying: The mixture of glass particles and water obtained after water quenching is separated into solid and liquid phases using a water quenching and screening machine, and the resulting wet glass particles are dried. S5. Crushing, grinding and particle size classification: The dried glass particles are crushed, finely ground and classified in sequence to obtain a powder semi-finished product with the target particle size distribution. S6. Finished product screening and packaging: The powder semi-finished product is screened to remove impurities and then sealed and packaged to obtain the antibacterial frit finished product. The water quenching and screening integrated machine includes a high temperature resistant guide channel (1), a spiral water tank (2) is provided at one end of the high temperature resistant guide channel (1), a water outlet (3) is fixedly connected to the bottom end of the spiral water tank (2), a water valve (4) is installed on the outer wall of the water outlet (3), a mounting frame (5) is fixedly connected to the top end of the spiral water tank (2), a stirring motor (6) is installed at the top end of the mounting frame (5), a stirring shaft (7) is connected to the output end of the stirring motor (6), the glass particles discharged from the water outlet (3) are sheared by a mechanical shearing unit (8), and the sheared glass particles are dehydrated by a dehydration unit (9). The mechanical shearing unit (8) includes a connecting cylinder (801), which is located at the bottom end of the outlet (3). A discharge pipe (802) is fixedly connected to the bottom end of the connecting cylinder (801). A filter plate (803) is rotatably connected to the inner wall of the connecting cylinder (801). A spur gear (804) is fixedly connected to one end of the filter plate (803). A support frame (805) is fixedly connected to the top end of the connecting cylinder (801). A variable frequency motor (806) is installed at the top end of the support frame (805). A square rod (807) is connected to the output end of the variable frequency motor (806). A square cylinder (808) is slidably connected to the outer wall of the square rod (807). The bottom end of the square tube (808) is fixedly connected to a shearing plate (809), and the top outer wall of the square tube (808) is rotatably connected to a displacement frame (812). The top of the support frame (805) is located on one side of the variable frequency motor (806) and a displacement motor (810) is installed. The output end of the displacement motor (810) is connected to a first threaded rod (811), which passes through the displacement frame (812). The bottom end of the displacement frame (812) is fixedly connected to a locking block (814), and the outer wall of the displacement frame (812) is fixedly connected to a toothed block (813). The bottom end of the toothed block (813) is in contact with the spur gear (804). The outer wall of the square rod (807) is in contact with the inner wall of the square tube (808). The top of the displacement frame (812) has a first threaded hole, which matches the first threaded rod (811). The outer wall of the tooth block (813) is provided with a tooth groove, which meshes with the spur gear (804), and the bottom outer wall of the locking block (814) is engaged with the spur gear (804).

2. The method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide according to claim 1, characterized in that, In step S1, the inorganic powder raw material includes a basic carrier material constituting the silicate glass network, and zinc oxide and cerium oxide as functional dopant components; the basic carrier material is selected from at least several of feldspar powder, quartz powder, calcite powder, dolomite powder, industrial alumina, barium carbonate, strontium carbonate, boric acid, borax, and zirconium silicate; the composition of the inorganic powder raw material, in terms of oxide weight percentage, is: SiO2: 35-70%; Al2O3: 5-25%; CaO: 5-15%; MgO: 0-7%; K2O: 0-5%; Na2O: 0-13%; ZnO: 2-40%; BaO: 0-10%; Fe2O3: 0-1%; TiO2: 0-1%; SrO: 0-8%; ZrO2: 0-13%; B2O3: 0-21%; CeO2: 0.1-4.5%; The equal-incremental mixing method is used to ensure uniform dispersion of cerium oxide: First, take the base carrier raw material with the same mass or several times the mass of cerium oxide and premix it. Then, put the resulting premix and all the remaining raw materials into a high-efficiency mixer and mix for 30-60 minutes.

3. The method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide according to claim 1, characterized in that, In step S2, the high-temperature melting treatment is carried out in an air atmosphere or an oxygen atmosphere. The specific melting regime is as follows: the temperature is raised to 1500°C at a heating rate of 5-10°C / minute, and held at 1500°C for 1.5-2 hours. In step S3, the water quenching is achieved by pouring the molten glass into a high-speed spiral water flow at a constant temperature of 25±5℃. In step S4, the drying conditions are 105±5℃ for 60-90 minutes, so that the water content of the glass particles after drying is less than 0.5wt%.

4. The method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide according to claim 1, characterized in that, The dehydration unit (9) includes a base plate (901) located below the discharge pipe (802). A collection trough (902) is provided at the top of the base plate (901). A discharge pipe (903) is fixedly connected to the bottom of the base plate (901). A support spring (904) is fixedly connected to the top of the base plate (901). A vibration frame (905) is fixedly connected to the top of the support spring (904). Three collection boxes (910) are provided at one end of the base plate (901). An L-shaped frame (906) is fixedly connected to the other end of the base plate (901). A vibration motor (907) is installed on the outer wall of the L-shaped frame (906). A rotating disk (908) is connected to the output end of the vibration motor (907). A protrusion (909) is fixedly connected to the outer wall of the rotating disk (908).

5. The method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide according to claim 4, characterized in that, The dewatering unit (9) also includes three guide plates (911), which are fixedly connected to one end of the vibrating frame (905). Three rows of support rods (912) are fixedly connected to the inner wall of the vibrating frame (905). A sieve plate (913) is slidably connected to the top of the support rods (912) on the inner wall of the vibrating frame (905). A connecting plate (914) is fixedly connected to the outer wall of the guide plate (911) facing the sieve plate (913). The outer side of the connecting plate (914)... A plate (915) is fixedly connected to the wall. A slot (916) is provided at one end of the screen plate (913) facing the guide plate (911). A side plate (917) is symmetrically fixedly connected to one end of the vibrating frame (905) away from the guide plate (911). A rotating column (918) is rotatably connected to the outer wall of the side plate (917). A second threaded rod (919) is fixedly connected between the two rotating columns (918). A positioning plate (920) is symmetrically slidably connected to the outer wall of the second threaded rod (919).

6. The method for preparing an antibacterial briquette doped with zinc oxide and cerium dioxide according to claim 5, characterized in that, The inner wall of the slot (916) fits against the outer wall of the insert plate (915); the outer wall of the second threaded rod (919) is symmetrically provided with external threads, and the outer wall of the positioning plate (920) is provided with a second threaded hole, which matches the external threads.

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