Drinking water disinfection device and disinfection method thereof

Abstract

The application discloses a kind of drinking water disinfection device, including disinfection pool, multiple porous self-polarization Xiang pottery are distributed in the disinfection pool;And micro-nano bubble machine, the micro-nano bubble machine is connected with the disinfection pool, and micro-nano bubble is supplied to the disinfection pool;The micro-nano bubble breaks and drives the multiple porous self-polarization Xiang pottery to generate strong local electric field, and the strong local electric field causes microbial cell membrane in situ electroporation and catalyzes to produce reactive oxygen species, the reactive oxygen species enters cell interior, and the metabolite of oxidation microorganism, causes cell death.The disinfection method of the application drinking water disinfection device has the characteristics that strong local electric field can be used to cause microbial cell membrane in situ electroporation and catalyzes to produce reactive oxygen species, the reactive oxygen species enters cell interior, and the metabolite of oxidation microorganism, causes cell death, realizes drinking water disinfection and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to a disinfection device, in particular to a drinking water disinfection device and a disinfection method thereof. BACKGROUND

[0002] Water is the source of life and the basic needs of human beings, but water-borne pathogens cause serious intestinal diseases.

[0003] At present, the traditional technical means for killing water-borne pathogens include chlorine disinfection, ozone disinfection, ultraviolet irradiation disinfection, etc., but there are drawbacks in practical application, such as chlorine disinfection promoting the reproduction of chlorine-resistant bacteria, ozone oxidation leading to the formation of carcinogenic bromate, ultraviolet irradiation allowing pathogenic bacteria to regenerate through enzyme photorepair, etc.

[0004] In addition, the prior art also discloses a drinking water disinfection device, such as a drinking water sterilization and disinfection filtration treatment device disclosed in Chinese Patent Application (CN117566975A). The main purpose is to remove the lead metal contained in underground water. It can be seen that the water-borne pathogens in drinking water cannot be effectively killed.

[0005] Also, such as Chinese Patent Application (CN117645356A) discloses a method for controlling disinfection by-products in drinking water by ozone catalytic oxidation. The method effectively utilizes the high catalytic activity of manganese single atom sites in manganese double single atom carbon-based catalyst, and effectively degrades DOM in water body through specific interface catalytic ozonation, removes the key intermediate of DBPs, effectively reduces the generation amount of C-DBPs and N-DBPs in the chlorination disinfection process, and ensures the safety of drinking water supply. It can be seen that manganese double single atom carbon-based catalyst is used, which means that new impurities are introduced into the drinking water.

[0006] In addition, such as Chinese Patent Application (CN210410759U) discloses an active carbon regeneration device in a drinking water filter, which adopts a structure including a shell and a cleaning chamber, a disinfection chamber and a regeneration chamber connected in sequence arranged in the shell, and a flip cover is arranged on the upper part of the cleaning chamber, the disinfection chamber and the regeneration chamber; the bottom of the cleaning chamber and the bottom of the regeneration chamber are respectively connected with a drain pipe, and a water valve is installed on the drain pipe; an ultraviolet lamp is arranged in the disinfection chamber, an inner barrel is arranged in the regeneration chamber, a metal plate is fixedly arranged at the bottom of the inner barrel, and a piezoelectric ceramic sheet connected with a power source is arranged at the bottom of the metal plate to generate ultrasonic waves for removing impurities. It can be seen that the piezoelectric ceramic sheet is used to generate ultrasonic waves, so that the impurities adsorbed in the micropores of the active carbon are rapidly detached, and the regenerated active carbon can be sterilized and disinfected. However, pure ultrasonic waves cannot completely kill the water-borne pathogens in drinking water.

[0007] In addition, as disclosed in Chinese patent application (CN213506392U), a kind of high-efficiency safe disinfection device of drinking water, including cylinder, the bottom end of the cylinder is installed with several supporting legs, and the bottom of the cylinder is installed with water outlet pipe on one side, the top of the water outlet pipe is installed with switch valve, the top of the cylinder is installed with inlet on one side, and the top of the cylinder is installed with water inlet pipe on the other side, motor is arranged between the water inlet pipe and inlet, the bottom of the cylinder is provided with handle on the other side;Water tank is installed in the inside of the cylinder, and micro-nano bubble generator is installed on the inner wall of the cylinder on both sides, waterproof lampshade is installed on the inner wall of the water tank on both sides, and ultraviolet disinfection lamp is installed on the inner side of the two waterproof lampshades, activated carbon plate is installed in the water inlet pipe, and filter screen one is installed on the inner wall of the water outlet pipe on one side, the top of the motor is installed with stirring rod, and stirring blade is installed on the periphery of the stirring rod, filter screen two is installed on the bottom of the water tank.It can be seen that micro-nano bubble and ultraviolet disinfection lamp are used, and the impact force generated after the micro-nano bubble is broken can break some microorganisms, and then cooperate with the irradiation of ultraviolet disinfection lamp.However, the pathogenic bacteria can be regenerated by enzyme light repair through the ultraviolet irradiation of ultraviolet disinfection lamp.The use efficiency of micro-nano bubble is low, and the role played is small.

[0008] As can be seen above, the existing disinfection technology for drinking water can be further improved to achieve better disinfection. SUMMARY

[0009] The purpose of the present application is to overcome the defects of the prior art and provide a drinking water disinfection device and a disinfection method thereof.

[0010] To achieve the above purpose of the present application, the following technical solutions are adopted:

[0011] A drinking water disinfection device includes a disinfection pool, wherein the disinfection pool is distributed with a plurality of porous self-polarization Nixing pottery, and a micro-nano bubble machine is connected with the disinfection pool to supply micro-nano bubbles to the disinfection pool; the micro-nano bubbles break and drive the plurality of porous self-polarization Nixing pottery to generate a strong local electric field, which causes in-situ electroporation of microbial cell membranes and catalyzes the production of reactive oxygen species, which enter the cell interior to oxidize microbial metabolites, causing cell death.

[0012] As a further improvement of the present application, the micro-nano bubble machine includes a vortex device, one side of the vortex device is provided with a gas inlet, and the other side is provided with a water inlet, and the water inlet is connected with the disinfection pool; wherein the vortex device mixes drinking water entering from the water inlet with air sucked from the gas inlet to produce micro-nano bubble water.

[0013] As a further improvement of the present application, the flow rate of the gas inlet is 90-110 mL / min.

[0014] As a further improvement of the present application, the micro-nano bubble machine has a micro-nano bubble outlet flow rate of 200-220 L / h.

[0015] As a further improvement of the present application, the disinfection tank is provided with an exhaust hole with a hole diameter of 10-15 mm and an inner dustproof screen; the porous self-polarization Nixing pottery is placed at the bottom of the disinfection tank with a placement amount of 4-6 g / L.

[0016] As a further improvement of the present application, the micro-nano bubble machine further comprises a micro-nano bubble conveying pipe and a reflux pipe, the micro-nano bubble machine draws the drinking water in the disinfection tank through the reflux pipe, and the micro-nano bubble machine conveys the reflux drinking water containing a large amount of micro-nano bubbles to the disinfection tank through the micro-nano bubble conveying pipe.

[0017] As a further improvement of the present application, the micro-nano bubble machine further comprises a disinfection tank guide pipe, the disinfection tank guide pipe is installed in the disinfection tank, one end of the disinfection tank guide pipe extends out of the disinfection tank, and the other end of the disinfection tank guide pipe extends to the plurality of porous self-polarization Nixing pottery, and the disinfection tank guide pipe is used to be connected with the micro-nano bubble conveying pipe.

[0018] A porous self-polarization Nixing pottery, a preparation method thereof comprises the following steps:

[0019] S1. Raw material mixing: uniformly mix weathered and crushed Xini and crushed Dongni to obtain a clay material;

[0020] S2. Solid-phase mechanical activation: the clay material and the ball milling medium are added into a mechanical activation reactor, and grinding and activation are carried out under the condition that the rotation speed is 200-500 rpm, the solid-phase mechanical activation time is 2-5 h;

[0021] S3. Wet mechanical activation: water is added, and grinding and activation are carried out under the condition that the rotation speed is 200-400 rpm, the wet mechanical activation time is 6-12 h, the clay slurry and the ball milling medium are separated by screening to obtain the clay slurry;

[0022] S4. Filter pressing and dewatering: the clay slurry is layered after standing, the water in the upper layer is removed, and the lower layer is filter pressed and dewatered to obtain the clay material;

[0023] S5. Vacuum kneading: the clay material is put into a vacuum kneading machine for kneading for 4-24 h;

[0024] S6. Three-stage biological mineralization: the clay material after kneading is put into a biological mineralizer for three-stage biological mineralization, so that silicate minerals with specific crystal structures are generated in the clay material, i.e. the blank;

[0025] S7. Mixing: uniformly mix the blank obtained in step S6 with sugarcane residue and water;

[0026] S8. Molding: Put the mixed mud into a porous mold, and demold after tabletting in a 10-15 MPa tablet press, and the obtained green body is dried;

[0027] S9. High-temperature calcination: Put the green body dried in step S8 into a 1000-1200℃ kiln for 2-3h, and the porous self-polarization Xingxing pottery is obtained after natural cooling.

[0028] As a further improvement of the present application, in step S7, the mass ratio of the green body to bagasse is 1:0.15-0.3, and the mass ratio of the green body to water is 1:0.01-0.03.

[0029] A disinfection method of the above-mentioned drinking water disinfection device, comprising the following steps:

[0030] S1. Pretreatment: Coagulate, sediment and filter raw water to obtain drinking water;

[0031] S2. Drinking water detection: Detect the total bacterial colony count and the number of coliform bacteria group of the drinking water;

[0032] S3. Disinfection: Put the drinking water into a disinfection tank, and start the micro-nano bubble machine, which supplies micro-nano bubbles to the disinfection tank, and the micro-nano bubbles induce the pyroelectric / piezoelectric effect of the porous self-polarization Xingxing pottery through aeration, forming a strong local electric field, which causes in-situ electroporation damage of microbial cell membranes and catalyzes the generation of reactive oxygen species, which enter the cell interior, oxidize the metabolites of microorganisms, and cause cell death;

[0033] S4. Sterilization quantity detection: Calculate the total bacterial colony count and the number of coliform bacteria group of the water after disinfection by plate colony counting method.

[0034] The present application has the following advantages over the prior art:

[0035] 1. The present application uses bagasse as a pore-forming agent and a green body completed by biological mineralization as a raw material, and high-temperature calcination to obtain porous self-polarization Xingxing pottery. The porous structure increases the specific surface area of the self-polarization Xingxing pottery, improves the surface roughness, and reduces the ferroelectric domain. The high specific surface area provides more local electric fields; the rough surface provides more and higher electric dipoles; and the ferroelectric domain reduction improves the polarization strength of the porous self-polarization Xingxing pottery. Therefore, the structure of the porous self-polarization Xingxing pottery makes its pyroelectric / piezoelectric effect more significant, and its ability to convert thermal and mechanical energy into electrical energy stronger.

[0036] 2. The present application uses the local high temperature and high pressure generated by the rupture of micro-nano bubbles to drive the porous self-polarization Xingxing pottery to produce pyroelectric and piezoelectric effects, realize the separation of positive and negative charges, and thus generate 1.9-2.0×10 8Strong local electric field of V / m, positive and negative charges are combined with oxygen and water respectively to generate reactive oxygen species (ROS). In addition, micro-nano bubble aeration increases oxygen, and also converts the charge gathered by the bubble into hydroxyl radicals. Strong local electric field causes in-situ electroporation damage to microbial cell membrane (damage tolerance voltage <10 6 V / m), and active oxygen species (ROS) enter the cell interior, oxidize microbial metabolites, and cause cell death. The present application uses electroporation and ROS oxidation technology to avoid the consumption of oxidants, and significantly improves the disinfection effect of pure chemical oxidation.

[0037] 3. The disinfection method of the present application has the characteristics of low energy consumption and high efficiency, simple equipment and easy operation, and does not produce toxic by-products during the disinfection process. BRIEF DESCRIPTION OF DRAWINGS

[0038] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed in the specific embodiments or prior art description will be briefly introduced below. In all the drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, each element or part is not necessarily drawn according to the actual scale.

[0039] Figure 1 A structure diagram of a drinking water disinfection device of the present application;

[0040] Figure 2 A SEM diagram of the porous self-polarization Nixing pottery in the present application;

[0041] Figure 3 A BET diagram of the porous self-polarization Nixing pottery in the present application;

[0042] Figure 4 A PFM butterfly curve and local piezoelectric hysteresis loop of the porous self-polarization Nixing pottery in the present application;

[0043] Figure 5 A local electric field fitting diagram of the porous self-polarization Nixing pottery in the present application;

[0044] Figure 6 A graph of the change of the colony density of E. coli with time in Example 8 of the present application;

[0045] Figure 7 SEM diagrams of E. coli with different disinfection treatment times in Example 8 of the present application;

[0046] Figure 8 A graph of the change of the total number of colonies and the total number of E. coli groups with time in Example 9 of the present application;

[0047] The serial numbers in the drawings and the corresponding component names are as follows:

[0048] 1-Micro-nano bubble generator, 2-Air inlet, 3-Water inlet, 4-Micro-nano bubble generator, 5-Power input, 6-Micro-nano bubble delivery pipe, 7-Return pipe, 8-Disinfection tank outlet, 9-Disinfection tank, 10-Porous self-polarizing Nixing pottery, 11-Drinking water, 12-Screw cap, 13-Disinfection tank guide pipe, 14-Exhaust port, 15-Micro-nano bubble, 16-Vortex generator. Detailed Implementation

[0049] To enable those skilled in the art to better understand the technical solutions in this application, the technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and embodiments. Obviously, the described embodiments are only a part of the embodiments in this application. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this application.

[0050] Example 1:

[0051] like Figures 1 to 8 As shown, this embodiment is a drinking water disinfection device, including a disinfection tank 9 and a micro-nano bubble generator 1. The disinfection tank 9 contains multiple porous self-polarizing Nixing pottery 10s; the micro-nano bubble generator 1 is connected to the disinfection tank 9 and supplies micro-nano bubbles 15 to the disinfection tank 9; the micro-nano bubbles 15 rupture and drive the multiple porous self-polarizing Nixing pottery 10s to generate a strong local electric field. This strong local electric field causes in-situ electroporation of the microbial cell membrane and catalyzes the generation of reactive oxygen species. These reactive oxygen species enter the cell interior, oxidize the microbial metabolites, and cause cell death.

[0052] One specification of the micro-nano bubble machine 1 is as follows: installed power: 300W, voltage: 220V, micro-nano bubble flow rate: 200L / h, with power input 5.

[0053] It should be noted that micro- and nanobubbles are bubbles with diameters ranging from nanometers to micrometers, possessing a higher specific surface area than ordinary bubbles. Driven by low buoyancy and high internal pressure, micro- and nanobubbles exhibit excellent liquid-phase residence time and mass transfer efficiency. Furthermore, as charge accumulates at the gas-liquid interface, the size of micro- and nanobubbles shrinks until they disappear completely, resulting in a Zeta potential (potential at the shear surface) with an absolute value reaching tens of millivolts. Micro- and nanobubble aeration is accompanied by transient local hot spots reaching 2300–4600 K and local shear stresses of 100–5000 bar, and generates highly reactive ·OH.

[0054] The localized high temperature and pressure generated by the rupture of micro- and nano-bubbles drive the porous self-polarizing Nixing ceramic to produce pyroelectric and piezoelectric effects, achieving the separation of positive and negative charges, thereby generating 1.9–2.0 × 10⁻⁶ Ω·cm. 8A strong localized electric field of V / m allows positive and negative charges to combine with oxygen and water, respectively, catalyzing the production of reactive oxygen species (ROS). Furthermore, while micro / nanobubbles aerate and oxygenate, they also convert the accumulated charge within the bubbles into hydroxyl radicals. This strong localized electric field causes in-situ electroporation damage to microbial cell membranes (damage withstand voltage <10V). 6 When reactive oxygen species (ROS) enter the cell (V / m), they oxidize the metabolites of microorganisms, causing cell death. Therefore, this invention uses electroporation combined with reactive oxygen species (ROS) oxidation to kill microorganisms, avoiding the consumption of oxidants and significantly outperforming the disinfection effect of simple chemical oxidation.

[0055] The porous structure increases the specific surface area of ​​self-polarizing Nixing ceramics, improves surface roughness, and reduces ferroelectric domains. The high specific surface area provides a larger local electric field; the rough surface provides more and higher electric dipoles; and the reduction in ferroelectric domains increases the polarization intensity of porous self-polarizing Nixing ceramics. Therefore, the structure of porous self-polarizing Nixing ceramics makes its pyroelectric / piezoelectric effect more significant, enhancing its ability to convert thermal and mechanical energy into electrical energy.

[0056] Example 2:

[0057] The only difference from Example 1 is that a structure of a micro / nano bubble machine is provided. For example... Figure 1 As shown, the micro-nano bubble machine 1 includes a vortex 16. One side of the vortex 16 is provided with an air inlet 2 and the other side is provided with a water inlet 3. The water inlet is connected to a disinfection tank 9. The vortex 16 mixes drinking water returning from the disinfection tank 9 that enters from the water inlet 3 with air drawn in from the air inlet 2 to make micro-nano bubble water.

[0058] The flow rate of inlet 3 is 90–110 mL / min. The corresponding inlet flow rate can be set as needed, typically 90, 100, or 110 mL / min.

[0059] The flow rate of the micro-nano bubble machine 4 at the micro-nano bubble outlet is 200-220 L / h. Typically, flow rates of 200, 210, or 220 L / h can be selected.

[0060] The disinfection tank can be equipped with an openable screw-on cap. Turning the cap clockwise will attach it to the tank, while turning it counter-clockwise will detach it. In other words, opening the cap allows you to open the tank, add drinking water to be disinfected, and then close the cap to disinfect the water. After disinfection, simply open the cap to remove the disinfected drinking water.

[0061] In order to reduce the air pressure in the disinfection tank, an exhaust hole can be added. The disinfection tank 9 is provided with an exhaust hole 14 with a diameter of 10-15 mm and a dustproof screen. The diameter can be 10, 11, 12, 13, 14 or 15 mm, etc. The dustproof screen can prevent dust and other impurities from entering the disinfection tank through the exhaust hole.

[0062] One specification of the disinfection tank is an inner diameter of 10 cm and a height of 12-15 cm (not limited to this, and the appropriate disinfection tank specification can be selected according to needs). According to this specification of the disinfection tank, the porous self-polarization Nixing pottery can be placed at the bottom of the disinfection tank in an amount of 4-6 g / L. The usual amount is 4, 5 or 6 g / L, etc. It can be understood that the appropriate amount of porous self-polarization Nixing pottery can be selected according to the volume of the disinfection tank.

[0063] Example 3:

[0064] Compared with Examples 1 or 2, the difference is only that a connection structure of the micro-nano bubble machine and the disinfection tank is given, and a micro-nano bubble conveying pipe 6 and a reflux pipe 7 are added. As shown in Figure 1 The micro-nano bubble machine 1 draws the drinking water in the disinfection tank 9 through the reflux pipe 7, and the micro-nano bubble machine 1 conveys the reflux drinking water containing a large number of micro-nano bubbles to the disinfection tank 9 through the micro-nano bubble conveying pipe 6.

[0065] One connection structure of the micro-nano bubble conveying pipe 6: one end of the micro-nano bubble conveying pipe 6 is connected with the micro-nano bubble machine 1, and the other end extends to the disinfection tank 9 and is inserted below the liquid level in the disinfection tank. This can make the micro-nano bubble conveying pipe 6 guide the micro-nano bubbles to the multiple porous self-polarization Nixing pottery in the disinfection tank.

[0066] One connection structure of the reflux pipe: one end of the reflux pipe 7 is connected with the disinfection tank outlet 8 of the disinfection tank 9, and the other end is connected with the water inlet 3 of the micro-nano bubble machine 1.

[0067] One specification of the reflux pipe: the inner diameter of the reflux pipe is 8 mm, and the material is PVC hose. Of course, it is not limited to this, and the appropriate specification can be selected according to actual needs.

[0068] It should be noted that the reflux drinking water containing a large number of micro-nano bubbles is guided to the multiple porous self-polarization Nixing pottery in the disinfection tank, so as to provide sufficient micro-nano bubbles to the multiple porous self-polarization Nixing pottery.

[0069] Example 4:

[0070] The difference compared with example 3 is that only a structure for guiding the micro-nano bubbles into the porous self-polarization Xinxing pottery in the disinfection tank is given, and a disinfection tank guide pipe 13 is additionally installed. The disinfection tank guide pipe 13 is installed in the disinfection tank 9, one end of which extends out of the disinfection tank 9, and the other end of which extends to the plurality of porous self-polarization Xinxing pottery 10 for connection with the micro-nano bubble delivery pipe 6.

[0071] The backflow drinking water containing a large number of micro-nano bubbles generated by the micro-nano bubble machine 1 is delivered to the disinfection tank guide pipe 13 through the micro-nano bubble delivery pipe 6, and the disinfection tank guide pipe 13 guides the backflow drinking water containing a large number of micro-nano bubbles to the plurality of porous self-polarization Xinxing pottery 10 in the disinfection tank. The local high temperature and high pressure generated by the rupture of a large number of micro-nano bubbles around the porous self-polarization Xinxing pottery drive the porous self-polarization Xinxing pottery to generate pyroelectric and piezoelectric effects, forming a strong local electric field, which causes in-situ electroporation damage (damage voltage <10 6 V / m) to the cell membrane of microorganisms and catalyzes the production of reactive oxygen species (ROS), which enter the inside of the cell, oxidize the metabolites of microorganisms, and cause cell death.

[0072] Example 5:

[0073] Compared with any one of examples 1-4, the difference is that only a first preparation method of the porous self-polarization Xinxing pottery is given, which comprises the following steps:

[0074] S1. Raw material mixing: mix the weathered and crushed Xini and the crushed Dongni uniformly to obtain a clay material;

[0075] S2. Solid-phase mechanical activation: add the clay material and the ball milling medium into a mechanical activation reactor, and perform grinding and activation under the condition of a rotation speed of 200 rpm, the solid-phase mechanical activation time being 2 h;

[0076] S3. Wet mechanical activation: add water, and perform grinding and activation under the condition of a rotation speed of 200 rpm, the wet mechanical activation time being 6 h, and the clay slurry and the ball milling medium are separated by screening to obtain the clay slurry;

[0077] S4. Filter pressing and dewatering: stratify the clay slurry, remove the water in the upper layer, and filter press and dewater the lower layer to obtain the clay material;

[0078] S5. Vacuum pugging: put the clay material into a vacuum pug mill for pugging for 4 h;

[0079] S6. Three-stage biological mineralization: put the pugged clay material into a biological mineralizer to perform three-stage biological mineralization, so that silicate minerals with specific crystal structures are generated in the clay material, i.e., the blank;

[0080] S7. Mixing: the blank obtained in step S6 is mixed with bagasse and water uniformly; the mass ratio of the blank to bagasse is 1:0.15, and the mass ratio of the blank to water is 1:0.01. The porous self-polarization Nixing pottery is obtained by high-temperature calcination of the blank with specific crystal structure of silicate minerals generated in the biological mineralization and bagasse as a pore-forming agent. The porous structure increases the specific surface area of the self-polarization Nixing pottery, improves the surface roughness, and reduces the ferroelectric domain.

[0081] S8. Molding: the mixed mud is placed in a porous mold plate, and the blank body is obtained after the tablet is pressed in a 10 MPa tablet press and demolded, and then the blank body is dried. One specification of the porous mold plate can be a 16-hole mold plate with a hole radius of 2.7 mm and a depth of 3.5 mm.

[0082] S9. High-temperature calcination: the blank body dried in step S8 is placed in a 1000℃ kiln for 2h, and the porous self-polarization Nixing pottery is obtained after natural cooling.

[0083] Example 6:

[0084] Compared with any one of examples 1-4, the difference is only that a second preparation method of the porous self-polarization Nixing pottery is given, and the second preparation method comprises the following steps:

[0085] S1. Raw material mixing: the weathered and crushed Xini and the crushed Dongni are mixed uniformly to obtain mud;

[0086] S2. Solid-phase mechanical activation: the mud and the ball milling medium are added to the mechanical activation reactor, and the grinding and activation are carried out under the condition that the rotation speed is 500 rpm, and the solid-phase mechanical activation time is 5h;

[0087] S3. Wet mechanical activation: water is added, and the grinding and activation are carried out under the condition that the rotation speed is 400 rpm, and the wet mechanical activation time is 12h, and the mud slurry and the ball milling medium are separated by screening to obtain the mud slurry;

[0088] S4. Filter pressing and dewatering: the mud slurry is layered by standing, the upper layer of water is removed, and the lower layer is dewatered by filter pressing to obtain the mud;

[0089] S5. Vacuum pugging: the mud is put into the vacuum pug mill for 24h;

[0090] S6. Three-stage biological mineralization: the pugged mud is placed in the biological mineralizer for three-stage biological mineralization, so that silicate minerals with specific crystal structures are generated in the mud, i.e. the blank;

[0091] S7. Mixing: the blank obtained in step S6 is mixed with bagasse and water uniformly; the mass ratio of the blank to bagasse is 1:0.3, and the mass ratio of the blank to water is 1:0.03. The porous self-polarization Nixing pottery is obtained by high-temperature calcination of the blank with specific crystal structure of silicate minerals generated in the bagasse as a pore-forming agent and the blank with completed biomineralization as a raw material. The porous structure increases the specific surface area of the self-polarization Nixing pottery, improves the surface roughness, and reduces the ferroelectric domain.

[0092] S8. Molding: the mixed mud is placed in a porous mold plate, and the blank body is obtained after demolding after tabletting in a 15 MPa tablet press and then dried. One specification of the porous mold plate can be a 16-hole mold plate with a hole radius of 2.7 mm and a depth of 3.5 mm.

[0093] S9. High-temperature calcination: the blank body dried in step S8 is placed in a 1200℃ kiln for 3h, and the porous self-polarization Nixing pottery is obtained after natural cooling.

[0094] Example 7:

[0095] Compared with any one of examples 1-4, the difference is only that a third preparation method of the porous self-polarization Nixing pottery is given, and the third preparation method comprises the following steps:

[0096] S1. Raw material mixing: the weathered and crushed Xini and the crushed Dongni are mixed uniformly to obtain mud;

[0097] S2. Solid-phase mechanical activation: the mud and the ball milling medium are added to the mechanical activation reactor, and the grinding and activation are carried out under the condition that the rotation speed is 350 rpm, and the solid-phase mechanical activation time is 3.5h;

[0098] S3. Wet mechanical activation: water is added, and the grinding and activation are carried out under the condition that the rotation speed is 300 rpm, and the wet mechanical activation time is 9h, and the mud slurry and the ball milling medium are separated by screening to obtain the mud slurry;

[0099] S4. Filter pressing and dewatering: the mud slurry is layered after standing, the upper layer of water is removed, and the lower layer is dewatered by filter pressing to obtain the mud;

[0100] S5. Vacuum pugging: the mud is put into the vacuum pug mill for 14h;

[0101] S6. Three-stage biomineralization: the pugged mud is put into the biomineralization device for three-stage biomineralization, so that silicate minerals with specific crystal structures are generated in the mud, i.e. the blank;

[0102] S7. Mixing: the blank obtained in step S6 is mixed with bagasse and water uniformly; the mass ratio of the blank to bagasse is 1:0.225, and the mass ratio of the blank to water is 1:0.02. The porous self-polarization Nixing pottery is obtained by calcining the blank prepared by the biological mineralization and the bagasse as a pore-forming agent. The porous structure increases the specific surface area of the self-polarization Nixing pottery, improves the surface roughness, and reduces the ferroelectric domain.

[0103] S8. Molding: the mixed mud is placed in a porous mold plate, and the blank body is obtained after the tablet is pressed in a 12.5 MPa tablet press and demolded, and then the blank body is dried.

[0104] S9. High-temperature calcination: the blank body dried in step S8 is placed in a 1100 DEG C kiln for 2.5 h, and the porous self-polarization Nixing pottery is obtained after natural cooling.

[0105] In the embodiments 5-7 of the present application, it should be noted that the Nixing pottery clay used in the present application is collected without processing and keeps the original state, so the main components of the Nixing pottery clay of the present application include SiO2, Al2O3, Fe2O3, MgO, CaO, K2O, Na2O, etc., in addition to the above, it also contains minerals, humus, protease and water, part of the inorganic ions are dissolved in the water, and most of the protease is adsorbed on the surface of the humus and minerals. The Nixing pottery raw material is derived from coastal mud, which contains special marine biological organic matter and mineral components, which are related to the mineral phase and crystal structure characteristics.

[0106] It should also be noted that the Nixing pottery clay is divided into east mud and west mud, and the east mud is generally stored in a closed state, and the west mud is taken back and exposed to sunlight and rain for more than four to six months to make it crumble, dissolve and oxidize to reach the weathered state, and then the soil is crushed to obtain the "weathered and crushed west mud". It can be seen that the east mud is directly stored and used, and the minerals, humus, protease and other substances in the soil still exist. Therefore, the biological mineralization in step S6 of the preparation method of the porous self-polarization Nixing pottery of the present application can be smoothly realized.

[0107] The present application adopts a mechanical activation reaction system combining solid-phase method and wet method to activate and pretreat the Nixing pottery clay. In the solid-phase mechanical activation process, the crystalline substances in the Nixing pottery mud produce plastic deformation and various types of defects such as lattice distortion, crystal crystallinity reduction and even amorphization while producing cracks, so that part of the mechanical energy is converted into internal energy of the substance, thereby improving the reaction activity of the solid. The mechanical activation changes the crystal structure of the mineral components, forms amorphous structure and lattice defects to activate the mineral components, and activates the organic matter at the same time. It can be seen that the main purpose of the solid-phase mechanical activation in the present application is to activate and pretreat the Nixing pottery clay and activate the organic matter in the Nixing pottery clay.

[0108] It is also necessary to point out that in the process of wet mechanical activation, the addition of water makes the activation of the whole system more uniform, the mineral structure of the clay is destroyed, and the surface of the mineral crystal is activated to increase the energy, which makes a large number of inorganic ions dissolved in the water (when the water in the clay evaporates, the inorganic ions contained in the water will not evaporate with it, but will be adsorbed on the clay, and after adding water again, the inorganic ions can be dissolved in water again, so there is no need to add acid and alkali), and a large amount of dissolved or dispersed in water after the enzyme is detached from the mineral. At this time, the inorganic ions in the water are in a high-energy supersaturated state.

[0109] At the same time, the dispersed protease in water contains a large number of negatively charged amino and carboxyl groups, which become natural biological mineralization chelation sites for metal ions, and are tightly chelated with Ca 2+ , Al 3+ and other metal ions dissolved in water, and then the inorganic negative ions combine with the metal ions to form Ca4Al3Si4O 16 (OH)4nuclei. Because the system is in a metastable state, the crystal nucleus around the enzyme protein grows around the nucleation site, effectively reducing the Gibbs free energy of the system. Then the activated Nixing clay is biomineralized to reorganize its phase and crystal structure, and in the biomineralization device, the organic matter is used as a template agent to control the humidity, temperature and other factors to control the mineralization to generate specific crystal structure silicate minerals, and in the high temperature sintering process, the silicate mineral Ca4Al3Si4O 16 (OH)4with ring structure is formed through high temperature solidification and isomorphism development. The space group of Ca4Al3Si4O 16 (OH)4is P63, which belongs to one of the 10 types of asymmetric center crystals, and has spontaneous polarization.

[0110] This crystal is embedded in Nixing pottery, and there is a positive and negative charge accumulation at both ends of the crystal c-axis. Due to the spontaneous polarization effect of the crystal, the crystal has multiple properties: (1) emitting far infrared rays: with a slight change in pressure or temperature, the crystal lattice constituting the crystal will be severely distorted and stretched, causing some ions and groups to be excited to a higher energy level, and when they jump to a lower energy level, the excess energy is released in the form of far infrared rays; (2) releasing negative oxygen ions: the potential difference existing at both ends of the crystal under slight changes in temperature and pressure is sufficient to ionize the surrounding air, and the electrons hit attach to adjacent water and oxygen molecules and convert them into air negative ions. In addition, the electrostatic field of the crystal promotes the electrolysis of water molecules to form H + and OH - , which form active molecules H3O + and (H3O2) -(3) Pyroelectricity and piezoelectricity: the pyroelectricity of eco-functional Xingtong at different temperatures is mainly due to the change of the inherent electric dipole moment of the polyhedron dominated by [SiO4] tetrahedron along the c-axis, resulting in the generation of equal number and opposite sign of electric charges at the two ends of the crystal along its c-axis. This pyroelectricity is asymmetric and anharmonic vibration, and the pyroelectricity coefficient p changes nonlinearly with temperature. Simply speaking, the pyroelectricity and spontaneous polarization strength ΔP can be expressed as follows:

[0111] ΔP s = pΔT;

[0112] p and ΔT are pyroelectricity coefficient (C cm -2 K -1 ) and temperature change (K) respectively. The pyroelectric Xingtong is also piezoelectric, that is, when the material is mechanically deformed, the electric charge on the surface of the material will change.

[0113] It can be understood that the eco-functional Xingtong of the application can occur biological mineralization process and generate silicate minerals with specific crystal structure through mechanical activation method in the preparation process.

[0114] Example 8:

[0115] Compared with any one of examples 1-7, the difference is only that the application gives a drinking water disinfection method, the specific steps are as follows:

[0116] S1. Pretreatment and simulated drinking water detection: Escherichia coli is dispersed in 0.85% wt / vol sterilized normal saline to obtain simulated drinking water with a bacterial number of 10 7 cfu / mL.

[0117] S2. Disinfection: the simulated drinking water 11 is placed in the disinfection tank 9, the simulated drinking water 11 enters the vortex device 16 from the water outlet 8 of the disinfection tank along the reflux pipe 7, and the air enters from the air inlet 2, and the micro-nano bubble water is formed after the gas-liquid mixing, and the micro-nano bubble water is guided to the multiple porous self-polarization Xingtong 10 in the disinfection tank 9 from the water outlet of the micro-nano bubble machine 4 along the micro-nano bubble conveying pipe 6 through the disinfection tank guide pipe 13, the micro-nano bubbles 15 continuously generate local high temperature and high pressure by aeration, induce the multiple porous self-polarization Xingtong 10 in the disinfection tank 9 to generate pyroelectric / piezoelectric effect, form a strong local electric field, the strong local electric field causes in-situ electroporation damage (damage voltage <10 6 V / m) of microbial cell membrane and catalyzes the generation of reactive oxygen species (ROS), and the reactive oxygen species (ROS) enters the cell interior, oxidizes the metabolites of microorganisms, and causes cell death. The simulated drinking water 11 is disinfected.

[0118] S3. Sterilization quantity test: The total number of Escherichia coli colonies was counted using the plate count method.

[0119] like Figure 6 The figure shows the relationship between Escherichia coli colony density and time. It can be seen that Escherichia coli is completely inactivated after 45 minutes of disinfection, which confirms that the disinfection method of the present invention has excellent sterilization performance.

[0120] Example 9:

[0121] Compared with any of Examples 1-7, the only difference is that another method for disinfecting drinking water according to the present invention is provided, the specific steps of which are as follows:

[0122] S1. Pretreatment: The actual lake water is coagulated, settled, and filtered to obtain filtered water.

[0123] S2. Filtered water testing: The total number of colonies and the total number of Escherichia coli colonies in the filtered water were counted using the plate count method.

[0124] S3. Disinfection: Filtered water is placed in disinfection tank 9. The filtered water enters the vortex generator 16 from the disinfection tank outlet 8 along the return pipe 7 through the inlet 3 of the micro-nano bubble generator 4. It mixes with the air entering from the air inlet 2 to form micro-nano bubble water. This water is then guided from the outlet of the micro-nano bubble generator 4 along the micro-nano bubble delivery pipe 6 through the disinfection tank guide pipe 13 to multiple porous self-polarizing Nixing ceramics 10 in disinfection tank 9. The continuous aeration of the micro-nano bubbles 15 generates local high temperature and high pressure, inducing the porous self-polarizing Nixing ceramics 10 to generate pyroelectric / piezoelectric effects, forming a strong local electric field. This strong local electric field causes in-situ electroporation damage to the microbial cell membrane (damage resistance voltage <10). 6 The process involves the generation of reactive oxygen species (ROS) through a process involving V / m (volume / m). These ROS enter the cells, oxidize the metabolites of microorganisms, and cause cell death. This process disinfects the filtered water.

[0125] S4. Sterilization Quantity Detection: The total number of colonies and the total number of Escherichia coli colonies in the filtered water during the disinfection process were counted using the plate count method.

[0126] like Figure 8 As shown in the figure, the total number of colonies and the total number of Escherichia coli changes over time. It can be seen that 10 min and 3 min respectively achieve complete inactivation of the total colonies and Escherichia coli colonies in the actual lake water, which confirms that the disinfection method of the present invention has broad-spectrum sterilization properties and excellent disinfection performance in actual water bodies.

[0127] Characterization analysis

[0128] (1) SEM analysis of porous self-polarizing Nixing ceramics

[0129] like Figure 2The figure shows a SEM image of the porous self-polarizing Nixing ceramic of the present invention. As can be seen from the figure, the porous self-polarizing Nixing ceramic consists of a dense mesoporous structure (Figure a) and macropores of tens of micrometers (Figure b). The abundant secondary porous structure provides a high specific surface area and polarization dipole moment.

[0130] (2) Analysis of porous self-polarizing Nixing ceramics

[0131] The specific surface area and pore size distribution of the porous self-polarizing Nixing ceramic of Example 1 of this invention were characterized by nitrogen isotherm adsorption-desorption curves. The results are as follows: Figure 3 As shown in the figure, the pore structure of the porous self-polarizing Nixing ceramic is mainly composed of mesopores with a pore size of about 21 nm, and its specific surface area is 0.669 m². 2 / g.

[0132] (3) PFM analysis of porous self-polarizing Nixing ceramics

[0133] The pyroelectric / piezoelectric effect of the porous self-polarizing Nixing ceramic of Example 1 of the present invention was characterized by piezoelectric microscopy. The results are as follows: Figure 4 As shown, under a ±10V DC bias field, the phase angle changes by approximately 180°, confirming the emergence of local polarization switching in the electric field; the measured amplitude curve is a typical butterfly shape, with a maximum value of 11.7nm, which also verifies the excellent local ferroelectric / piezoelectric response of porous self-polarizing Nixing ceramic.

[0134] (4) Fitting the local electric field of porous self-polarizing Nixing pottery

[0135] The local electric field of the porous self-polarizing Nixing ceramic of Embodiment 1 of the present invention was further simulated using COMSOL Multiphysics software, and the results are as follows: Figure 5 As shown, a porous self-polarizing Nixing ceramic surface with a diameter of 1.92 × 10⁻⁶ was constructed under the induction of continuous bursting of micro / nanobubbles (MNB). 8 Local electric field V / m (>10 6 V / m), which is sufficient to cause electroporation damage to microbial cell membranes.

[0136] (5) SEM analysis of Escherichia coli

[0137] In Example 8 of this invention, E. coli samples with different disinfection times were washed with 0.85% wt / vol physiological saline, fixed with glutaraldehyde fixative for 12 h, then dehydrated with a gradient of ethanol and observed by scanning electron microscopy. The results are as follows: Figure 7 As shown. By Figure 7 (a) It can be seen that fresh E. coli have an intact structure and are full of bacteria; Figure 7(b) It can be seen that the E. coli cell membrane ruptured after 15 min sterilization, which is the in-situ electroporation damage of cell membrane caused by pyroelectric / piezoelectric generated local electric field; from Figure 7 (c) It can be seen that the E. coli cell membrane ruptured at one end and a large amount of residual material was outside the cell after 30 min sterilization, which is due to the active oxygen species (ROS) entering the cell interior from the broken hole of the cell membrane to cause deep oxidation, resulting in the outflow of cell contents; from Figure 7 (d) It can be seen that the E. coli has been completely destroyed and inactivated after 45 min sterilization, which benefits from the high efficiency of the sterilization method of drinking water based on porous self-polarization pottery.

[0138] Obviously, the above examples are only examples for clearly illustrating but not limiting the embodiments. Based on the above description, other different forms of changes or variations can also be made by those skilled in the art. Here, it is not necessary and also impossible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A drinking water disinfecting device, characterized by: The disinfection tank is provided with a plurality of porous self-polarization Xinxing pottery; and The micro-nano bubble machine is connected with the disinfection tank and supplies micro-nano bubbles to the disinfection tank. The micro-nano bubbles break and drive the plurality of porous self-polarization Xinxing pottery to generate a strong local electric field, which causes in-situ electroporation of microbial cell membranes and catalyzes the generation of reactive oxygen species, which enter the cell interior, oxidize the metabolites of microorganisms, and cause cell death. The micro-nano bubble machine comprises a vortex device, one side of the vortex device is provided with an air inlet, the other side is provided with a water inlet, and the water inlet is connected with the disinfection tank.

2. The device for disinfecting drinking water according to claim 1, characterized in that: The vortex device mixes the drinking water entering from the water inlet with the air sucked from the air inlet to produce micro-nano bubble water. The air inlet flow rate is 90-110 mL / min.

3. The drinking water disinfection device of claim 2, wherein: The micro-nano bubble machine has a micro-nano bubble water outlet flow rate of 200-220 L / h.

4. The drinking water disinfection device of claim 2, wherein: The disinfection tank is provided with an air exhaust hole with a diameter of 10-15 mm and an inner dustproof screen.

5. The drinking water disinfecting device of claim 1, wherein: The plurality of porous self-polarization Xinxing pottery is placed at the bottom of the disinfection tank, and the placement amount is 4-6 g / L. It also includes a micro-nano bubble delivery pipe and a return pipe, the micro-nano bubble machine draws the drinking water in the disinfection tank through the return pipe, and the micro-nano bubble machine delivers the return drinking water containing a large number of micro-nano bubbles to the disinfection tank through the micro-nano bubble delivery pipe.

6. The drinking water disinfecting device of claim 1, wherein: It also includes a disinfection tank guide pipe, which is installed in the disinfection tank, one end of which extends out of the disinfection tank, and the other end of which extends to the plurality of porous self-polarization Xinxing pottery, for connection with the micro-nano bubble delivery pipe.

7. A drinking water disinfection device according to claim 6, characterized in that: The preparation method of the porous self-polarization Xinxing pottery comprises the following steps:

8. A drinking water disinfection device according to any one of claims 1-7, characterized in that S1. Raw material mixing: mix weathered and crushed Xini with crushed Dongni uniformly to obtain a mud material; S2. Solid-phase mechanical activation: add the mud material and ball milling medium into a mechanical activation reactor, and grind and activate under the condition of a rotation speed of 200-500 rpm, the solid-phase mechanical activation time is 2-5 h; S3. Wet mechanical activation: add water and grind and activate under the condition of a rotation speed of 200-400 rpm, the wet mechanical activation time is 6-12 h, and the mud slurry and ball milling medium are separated by screening to obtain a mud slurry; S4. Filter pressing and dewatering: stratify the mud slurry, remove the water in the upper layer, and dewater the lower layer by filter pressing to obtain a mud material; S5. Vacuum mud conditioning: put the mud material into a vacuum mud conditioning machine for mud conditioning for 4-24 h; S6. Three-stage biological mineralization: put the mud material after mud conditioning into a biological mineralizer for three-stage biological mineralization, so that silicate minerals with specific crystal structures are generated in the mud material, i.e. a blank material; S7. Mixing: mix the blank material obtained in step S6 with sugarcane residue and water uniformly; S8. Molding: place the mixed mud material in a porous mold, press the tablet in a 10-15 MPa tablet press, and then demold, and the obtained blank body is air dried; S9. High-temperature calcination: put the blank body after air drying in step S8 into a 1000-1200℃ kiln for 2-3 h, and naturally cool to obtain the porous self-polarization Xinxing pottery. ​ 9. A drinking water disinfection device according to claim 8, characterized in that: The mass ratio of the blank to bagasse is 1:0.15-0.3, and the mass ratio of the blank to water is 1:0.01-0.

03.

10. A method of disinfecting a drinking water disinfection device as claimed in any one of the claims 1-9, characterized in that, The method comprises the following steps: S1. Pretreatment: coagulating, precipitating and filtering raw water to obtain drinking water; S2. Drinking water detection: detecting the total bacterial colony count and the number of coliform bacteria group of the drinking water; S3. Disinfection: placing the drinking water in a disinfection tank, starting the micro-nano bubble machine, and supplying micro-nano bubbles to the disinfection tank; the micro-nano bubbles induce the pyroelectric / piezoelectric effect of the porous self-polarization Nixing pottery through aeration, form a strong local electric field, cause in-situ electroporation damage of the cell membrane of microorganisms and catalyze the generation of reactive oxygen species, the reactive oxygen species enter the inside of the cell, oxidize the metabolites of the microorganisms, and cause cell death; S4. Sterilization quantity detection: calculating the total bacterial colony count and the number of coliform bacteria group of the water after disinfection by using the plate colony counting method.

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