Ozone nano-bubble uniform porous aeration material and preparation method thereof

Abstract

Embodiments of the application disclose an ozone nano-bubble uniform porous aeration material and a preparation method thereof. The ozone nano-bubble uniform porous aeration material comprises a silica porous ceramic. The structure of the silica porous ceramic adopts an aeration sheet, the aeration sheet is installed on an aeration disc, and the aeration sheet is provided with aeration holes. Alternatively, the structure of the silica porous ceramic adopts a bifurcated aeration pipe, branch pipes extend from a main body rod of the aeration pipe, and the branch pipes are provided with aeration holes. The preparation method comprises the following steps: mixing UV light-curable printing ink and sol with a silica skeleton structure; after stirring at room temperature, 3D printing and UV light curing are adopted; cold storage and programmed temperature baking treatment are performed; and channel modification and surface modification are performed. The ceramic device can be used to construct a direct aeration ozone nano-bubble generation technology, improve the ozone utilization rate in an advanced oxidation process, and reduce power consumption and operation cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ozone oxidation water treatment technology, which can effectively improve the ozone mass transfer efficiency and the organic matter oxidation removal efficiency, belongs to the field of environmental functional new materials, and specifically relates to an ozone nano-bubble uniform porous aeration material and a preparation method thereof. BACKGROUND

[0002] Ozone oxidation technology is the most widely used wastewater advanced treatment technology in engineering, which can effectively degrade various refractory organic pollutants in secondary biochemical effluent and reduce the COD value of effluent. Since ozone is slightly soluble in water, the mass transfer rate between gas and liquid is slow, and the existing process has problems such as low ozone utilization rate and large dosage, which leads to excessive cost pressure in the actual application process. Therefore, improving the ozone mass transfer efficiency between gas and liquid is very important to reduce the cost of ozone catalytic oxidation.

[0003] Compared with conventional aeration, the specific surface area of nano-bubbles generated by nano-bubble aeration is large, and the internal pressure is high, which increases the driving force of gas mass transfer, and can greatly improve the mass transfer efficiency between gas and liquid. At present, in the actual engineering application of water treatment, the main methods for generating nano-bubbles are dispersion air method and dissolved gas release method, but the nano-bubble device made by these methods will use a low gas-liquid mixing ratio (not more than 10%), if sufficient ozone dosage is required, a large amount of water and gas will be introduced into the device, which will cause problems such as difficult control of gas suction amount, large bubble size dispersion, and fine particles in wastewater hindering the formation of nano-bubbles, etc. The device itself also has problems such as high energy consumption, easy plugging of various fillers in the dissolved gas tank, and easy generation of ozone thermal decomposition to lose strong oxidizing property. Therefore, the existing technology has limited effect on improving the ozone oxidation efficiency by preparing nano-bubbles.

[0004] With the improvement of porous material production technology, the use of porous materials to form micro-bubbles has become a new research hotspot. If the porous material can be used to directly cut the gas outlet of the ozone generator to obtain nano-bubbles, the problems of low gas-liquid mixing ratio and ozone thermal decomposition will not exist. However, the mechanism of generating nano-bubbles by direct aeration of porous materials is complex. According to the Young-Laplace formula, when the aeration pressure is close to the bubble point, the diameter of the generated bubbles is small, but the number is small. If the pressure continues to increase, the number of bubbles will continue to increase, but the size of the bubbles will also increase, which will cause certain difficulties in pressure control. In addition, the outlet pressure of the ozone generator is small, if direct aeration is used to generate nano-bubbles, the porous material needs to have a high porosity, but a high porosity will also cause the phenomenon of bubble coalescence. Therefore, how to accurately control the pore structure and prepare a membrane material that can uniformly generate nano-bubbles is the key to technical breakthrough. SUMMARY

[0005] Therefore, the ozone nanobubble uniform porous aeration material and the preparation method thereof are provided, the film hole structure is accurately controlled through the 3D printing technology, the inorganic nanofiltration membrane with uniform pore diameter, hydrophobic pore channel and hydrophilic surface is prepared by combining surface modification, the nanobubbles are generated through direct aeration, the ozone catalytic oxidation technology can be applied, and the operation cost is greatly reduced.

[0006] In the first aspect, the ozone nanobubble uniform porous aeration material comprises a porous silica ceramic.

[0007] The structure of the porous silica ceramic adopts an aeration sheet, the aeration sheet is installed on an aeration disc, and the aeration sheet is provided with aeration holes.

[0008] Alternatively, the structure of the porous silica ceramic adopts a bifurcated aeration pipe, a branch pipe extends from a main rod of the aeration pipe, and the branch pipe is provided with aeration holes.

[0009] The inner wall of the pore channel of the aeration hole is loaded with a layer of super-hydrophobic fluorinated silicon nanoparticles.

[0010] The surface of the porous silica ceramic is loaded with a layer of super-hydrophilic nanometer titanium dioxide particles.

[0011] In combination with the first aspect, the first possible implementation manner of the first aspect is provided, wherein the aeration hole of the porous silica ceramic has a pore diameter distribution of 10-100 nm and a porosity of 50%-70%.

[0012] The super-hydrophobic fluorinated silicon nanoparticles have a particle size distribution of 10-30 nm.

[0013] The super-hydrophilic nanometer titanium dioxide particles have a particle size distribution of 20-40 nm.

[0014] The technical effect lies in that the porous silica ceramic structure has the advantages of uniform and defect-free nanohole structure, high porosity and high strength, can be connected to the gas outlet of an ozone generator, directly generates ozone nanobubbles, controls the bubble diameter at the micro-nanometer level, greatly improves the mass transfer efficiency between ozone and liquid, does not have the problem of low water-gas ratio, and does not have the problems of thermal decomposition of ozone into oxygen and reduction of ozone solubility due to temperature rise.

[0015] In the second aspect, the preparation method of the ozone nanobubble uniform porous aeration material is provided, and the preparation method comprises the following steps.

[0016] The UV light-curable printing ink and the sol with a silica skeleton structure are mixed at a ratio of 80:20-20:80.

[0017] After stirring at room temperature of 25 DEG C, 3D printing ultraviolet light curing is adopted.

[0018] Refrigeration and programmed temperature roasting treatment are carried out.

[0019] Pore modification and surface modification are carried out.

[0020] The technical effects are that the porous aeration material is prepared by using self-assembly, 3D printing and surface modification technology, the preparation process can realize automatic control, has high stability and is conducive to large-scale production.

[0021] In combination with the second aspect, the embodiments of the present application provide a first possible implementation manner of the second aspect, wherein,

[0022] The stirring time at room temperature is 2-10 minutes.

[0023] In combination with the second aspect, the embodiments of the present application provide a second possible implementation manner of the second aspect, wherein,

[0024] The components of the printing ink include aliphatic polyurethane acrylate, epoxy aliphatic acrylate and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, the aliphatic polyurethane acrylate, the epoxy aliphatic acrylate and the 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are mixed in a mass ratio of (5-10):(5-10):1, and constant temperature stirring is carried out at 40-60 DEG C for 0.5-2 h.

[0025] In combination with the second aspect, the embodiments of the present application provide a third possible implementation manner of the second aspect, wherein,

[0026] The sol with a silica skeleton structure is formed by using a polyoxyethylene polyoxypropylene surfactant self-assembly to form an intermediate micelle as a template, and adding a silica gel precursor solution to hydrolyze and condense around the template.

[0027] The silica gel precursor solution includes a polyoxypropylene polyoxyethylene copolymer solution, an ethanol solution and a hydrochloric acid solution, and is uniformly stirred at 30-40 DEG C, cooled to room temperature, then 30%-60% of tetraethyl orthosilicate is added and stirred for 5-30 min to obtain the silica gel precursor solution.

[0028] In combination with the second aspect, the embodiments of the present application provide a fourth possible implementation manner of the second aspect, wherein,

[0029] The refrigeration and programmed temperature roasting treatment includes:

[0030] After 3D printing, the structure is placed in a low-temperature refrigerator and stored at-20 DEG C to-10 DEG C for 3 days.

[0031] The structure is placed in a vacuum drying oven and stored at 30-80 DEG C for 2-5 days.

[0032] Sintering in a muffle furnace, sintering temperature 450-550 DEG C, heating rate 1-3 DEG C / min, holding time 3-5h.

[0033] After rising to 650-750 DEG C at a heating rate of 1-3 DEG C / min, calcining for 2h.

[0034] In combination with the second aspect, the embodiments of the present application provide a fifth possible implementation manner of the second aspect, wherein the pore modification comprises:

[0035] Adopting fluorinated silica sol sealed impregnation.

[0036] The fluorinated silica sol is configured by a mixed solution of tetraethyl orthosilicate, anhydrous ethanol and ammonia water.

[0037] In combination with the second aspect, the embodiments of the present application provide a sixth possible implementation manner of the second aspect, wherein,

[0038] The impregnation degree is 30-70 DEG C, the impregnation time is 24-48h, the sintering temperature after impregnation is 300-800 DEG C, the heating rate is 1-3 DEG C / min, and the holding time is 1-3h.

[0039] In combination with the second aspect, the embodiments of the present application provide a seventh possible implementation manner of the second aspect, wherein the surface modification comprises:

[0040] Adopting titanium dioxide sol coating modification.

[0041] After coating, sintering is performed, the temperature is 300-800 DEG C, the heating rate is 1-3 DEG C / min, and the holding time is 1-3h.

[0042] The titanium dioxide sol is configured by mixing diethanolamine and butyl titanate.

[0043] The technical effect is that the ozone micro-nano bubble technology generated by the device directly aerates, which can effectively improve the ozone utilization rate and the efficiency of ozone oxidation degradation of organic matter in water, reduce power consumption and operation cost, and is an environmentally friendly process method.

[0044] The beneficial effects of the embodiments of the present application are:

[0045] The present application provides a kind of ozone nano bubble uniform porous aeration material and its preparation method, preparation can directly aeration produces ozone nano bubble modified silica porous ceramic device, using this ceramic device can build directly aeration produces ozone nano bubble technology, to improve the ozone utilization rate in advanced oxidation process, effectively promote the application of ozone oxidation in industrial wastewater advanced treatment and sewage resource. BRIEF DESCRIPTION OF DRAWINGS

[0046] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some of the embodiments of the present application, and therefore should not be regarded as a limitation on the scope, and for those skilled in the art, other related drawings can also be obtained without creative labor.

[0047] Fig. 1 Structure diagram of the modified silica porous ceramic aeration sheet for directly aeration ozone nanobubble generation of the present application;

[0048] Fig. 2 Structure diagram of the modified silica porous ceramic aeration pipe for directly aeration ozone nanobubble generation of the present application. DETAILED DESCRIPTION

[0049] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the following will combine the drawings in the embodiments of the present application to make a clear and complete description of the technical solutions in the embodiments of the present application. Obviously, the described embodiments are some of the embodiments of the present application, but not all the embodiments. The components of the embodiments of the present application described and shown in the drawings herein can be arranged and designed in various different configurations.

[0050] Please refer to Figs. 1-2 The first embodiment of the present application provides a kind of ozone nanobubble uniform porous aeration material, wherein, including silica porous ceramic.

[0051] The structure of the silica porous ceramic adopts aeration sheet, the aeration sheet is installed on the aeration disc, and the aeration sheet is provided with aeration holes.

[0052] Alternatively, the structure of the silica porous ceramic adopts a bifurcated aeration pipe, and a branch pipe extends from the main rod of the aeration pipe, and the branch pipe is provided with aeration holes.

[0053] The inner wall of the aeration hole is loaded with a layer of super-hydrophobic fluorinated silicon nanoparticles.

[0054] The surface of the silica porous ceramic is loaded with a layer of super-hydrophilic nanometer titanium dioxide particles.

[0055] The aeration hole diameter distribution of the silica porous ceramic is 10-100 nm, and the porosity is 50%-70%.

[0056] The particle size distribution of the super-hydrophobic fluorinated silicon nanoparticles is 10-30 nm.

[0057] The particle size distribution of the super-hydrophilic nanometer titanium dioxide particles is 20-40 nm.

[0058] The technical effect is that the silica porous ceramic structure has the advantages of uniform and defect-free nano-pore structure, high porosity, high strength, etc., can be connected to the gas outlet of an ozone generator, and directly generates ozone nano-bubbles by aeration, so that the diameter of the bubbles is controlled at the nanometer level, the mass transfer efficiency between ozone and liquid is greatly improved, there is no problem of low water-gas ratio, and problems such as decomposition of ozone into oxygen due to heating, and reduction of ozone solubility due to temperature rise, do not occur.

[0059] Please refer to Figs. 1-2 The second embodiment of the present application provides a preparation method of the ozone nano-bubble uniform porous aeration material as described above, wherein the preparation method comprises the following steps:

[0060] The UV light-curable printing ink and the sol with a silica skeleton structure are mixed at a ratio of 80:20 to 20:80.

[0061] After stirring at 25 DEG C, the 3D printer is used for UV light curing at 385 nm.

[0062] Refrigeration and programmed temperature calcination are performed.

[0063] Channel modification and surface modification are performed.

[0064] The technical effect is that the porous aeration material is prepared by using self-assembly, 3D printing and surface modification technology, the preparation process can realize automatic control, has high stability, and is conducive to large-scale production.

[0065] The ratio of the UV light-curable printing ink to the sol with a silica skeleton structure is 80:20 to 20:80.

[0066] The stirring time at room temperature is 5 minutes.

[0067] The light intensity of the light curing is 30 mW / cm2, the exposure time is 6 s, and the exposure layer thickness is 200 microns.

[0068] In combination with the second aspect, the embodiments of the present application provide a second possible implementation manner of the second aspect, wherein the preparation method comprises the following steps:

[0069] The components of the printing ink include aliphatic polyurethane acrylate, epoxy aliphatic acrylate and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, the aliphatic polyurethane acrylate, the epoxy aliphatic acrylate and the 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are mixed at a mass ratio of 48.5:48.5:6, and constant temperature stirring is performed at 40-60 DEG C for 1 h.

[0070] The ratio of the UV light-curable printing ink to the sol with a silica skeleton structure is 80:20 to 20:80.

[0071] The sol with the silica skeleton structure uses a polyoxyethylene polyoxypropylene surfactant to self-assemble an intermediate micelle as a template, and a silica gel precursor solution is added to hydrolyze and condense around the template.

[0072] The silica gel precursor solution includes 14wt% of a polyoxypropylene polyoxyethylene copolymer solution, 33wt% of an ethanol solution, and 1wt% of a hydrochloric acid solution, is cooled to 25℃ after stirring for 1 minute at 30-40℃, and 45wt% of tetraethyl orthosilicate is added and stirred for 15 minutes to obtain the silica gel precursor solution.

[0073] The refrigeration and programmed temperature calcination process includes:

[0074] The 3D printed structure is placed in a low-temperature refrigerator and stored at -20℃ to -10℃ for 3 days.

[0075] It is placed in a vacuum drying oven and stored at 50℃ for three days.

[0076] Sintering in a muffle furnace, sintering temperature 450-550℃, heating rate 1℃ / min, holding time 4h.

[0077] Set the heating rate to 1℃ / min to rise to 650-750℃, and calcine for 2h.

[0078] The pore modification includes:

[0079] The fluorinated silica sol is sealed and immersed.

[0080] The fluorinated silica sol is prepared using a mixed solution of tetraethyl orthosilicate, anhydrous ethanol, and 0.02mol / L of ammonia water.

[0081] 1wt% hydrochloric acid solution is added to adjust the pH value, and stirred at room temperature for 2h, and then left standing for 24h.

[0082] 1wt% fluorosilane ethanol solution is added, and left standing at 50-60℃ for 12h, and then purified to obtain a uniform fluorinated silica sol.

[0083] The immersion temperature is 30-70℃, the immersion time is 24-48h, the sintering temperature after immersion is 500℃, the heating rate is 2℃ / min, and the holding time is 120min.

[0084] The surface modification includes:

[0085] Titanium dioxide sol is used for coating modification.

[0086] Sintering after coating, temperature 500℃, heating rate 2℃ / min, holding time 120min.

[0087] The titanium dioxide sol is prepared by mixing diethanolamine and butyl titanate.

[0088] wherein,

[0089] After mixing the diethanolamine and butyl titanate, they are dissolved in anhydrous ethanol solution, and stirred in a water bath at room temperature for 15 min.

[0090] Add ice acetic acid and a mixed solution of PVB and HPC to the mixed solution, add ethanol as a solvent, and stir in a water bath, and the temperature of the water bath is set to 30-50 DEG C.

[0091] After the temperature of the solution rises to the set temperature, deionized water is added dropwise at a rate of 1 drop / s, and the stirring in the water bath is continued for 2 h, to obtain a transparent and clear titanium dioxide sol.

[0092] Age for 1-3 days.

[0093] The technical effect lies in that the direct aeration ozone micro-nano bubble technology established by the device can effectively improve the ozone utilization rate and the efficiency of ozone oxidation degradation of organic matters in water, reduces the power consumption and operation cost, and is an environmentally friendly process method.

[0094] The third embodiment of the present application provides a specific preparation method of the ozone nano bubble uniform porous aeration material, comprising:

[0095] (1) Preparation of 3D printing precursor gel: 10ml of 14wt% polyoxypropylene polyoxyethylene copolymer solution is dissolved in 40ml of 33wt% ethanol solution. Then 5ml of 1wt% hydrochloric acid solution is added, stirred at 30 DEG C for 1 min, and then cooled to 25 DEG C to form an intermediate micelle by self-assembly. Finally, 20ml of 45wt% tetraethyl orthosilicate is added, and stirred for 15 min to obtain a sol with a specified concentration of a silica skeleton structure.

[0096] (2) Preparation of ink solution: aliphatic polyurethane diacrylate, epoxy aliphatic acrylate and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are mixed at a mass ratio of 48.5:48.5:6, and stirred at 40 DEG C for 1 h to obtain a homogeneous UV-curable stretchable ink solution.

[0097] (3) Preparation of 3D printing precursor solution by mixing: the sol and the ink solution are mixed at a mass ratio of 80:20 at room temperature of 25 DEG C for 5 min to obtain a 3D printing precursor solution.

[0098] (4) Setting of printing, refrigeration and temperature rising procedures: in the setting of the 3D printer, a UV LED light source (wavelength 385nm) is used, and the light intensity is 30mW / cm 2The exposure time is set to 6 seconds, the exposure layer thickness is set to 200 microns, and then the pre-imported CAD model is 3D printed. In the cold storage temperature and temperature rising program setting after printing, the structure after 3D printing is put into a low temperature refrigerator and stored at-10 DEG C for 3 days. Then it is put into a vacuum drying oven and stored at 50 DEG C for three days. Then, sintering in a muffle furnace, sintering temperature 450 DEG C, temperature rising rate 1 DEG C / min, holding time 4h. Finally, set the temperature rising rate to 1 DEG C / min, rise to 650 DEG C, and calcine for 2h.

[0099] (5) Surface coating modification: 7.5g diethanolamine and 10g butyl titanate are dissolved in 10g anhydrous ethanol solution, water bath stirring at room temperature for 15min, then 5g glacial acetic acid and 2g 0.2wt% PVB and 2g 0.0025wt% HPC solution are added to the mixed solution, 60g anhydrous ethanol is added as solvent, continue water bath stirring, set the water bath temperature to 30 DEG C, when the temperature rises to the set temperature, 4g of deionized water is measured, and is added dropwise at a speed of 1 drop per second, continue water bath stirring for 2h to obtain transparent and clear TiO2 sol, after aging for 1 day, the surface of the ozone exposure material is uniformly coated. Titanium dioxide sol is used for surface coating modification, and the final sintering temperature is 300 DEG C, the temperature rising rate is 1 DEG C / min, and the holding time is 120min.

[0100] (6) Nanopore sealing and impregnation modification: 6g tetraethyl orthosilicate, 12g anhydrous ethanol and 8g 0.02mol / L ammonia solution are mixed uniformly, 2ml 1wt% hydrochloric acid solution is added, stirred at room temperature for 2h, then static for 24h, 5ml 1wt% fluorosilane ethanol solution is added, static for 12h at 50 DEG C, after filtration and alcohol washing, uniform fluorosilicon sol is obtained, and the pore of the ozone exposure material is sealed and impregnated. Fluorosilicon sol is used for sealing and impregnation modification, and the final sintering temperature of the modification is 300 DEG C, the temperature rising rate is 1 DEG C / min, and the holding time is 120min.

[0101] The fourth embodiment of the present application provides a specific preparation method of ozone nano-bubble uniform porous aeration material, comprising:

[0102] (1) Configuration of 3D printing precursor gel: 20ml 14wt% polyoxypropylene polyoxyethylene copolymer solution is dissolved in 50ml 33wt% ethanol solution. Then 10ml 1wt% hydrochloric acid solution is added, stirred at 35 DEG C for 1min, then cooled to 25 DEG C, self-assembled to form an intermediate micelle. Finally, 30ml 45wt% tetraethyl orthosilicate is added, stirred for 15min to obtain a sol with a specified concentration of silica skeleton structure.

[0103] (2) Inks solution preparation: Aliphatic polyurethane diacrylate, epoxy aliphatic acrylate and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide were mixed in a mass ratio of 48.5:48.5:6, and stirred at 50°C for 1h to obtain a homogeneous UV-curable stretchable ink solution.

[0104] (3) Mixing to obtain 3D printing precursor solution: the sol and ink solution were mixed in a mass ratio of 50:50 at room temperature for 5min to obtain a 3D printing precursor solution.

[0105] (4) Setting of printing, refrigeration and temperature rising procedures: in the setting of the 3D printer, a UV LED light source (wavelength 385nm) was used, the light intensity was 30mW / cm 2 , the exposure time was set to 6s, the exposure layer thickness was set to 200 microns, and then the 3D printing of the pre-imported CAD model was performed. In the setting of the refrigeration temperature and temperature rising procedures after printing, the 3D printed structure was placed in a low-temperature refrigerator and stored at -15°C for 3 days. Then it was placed in a vacuum drying oven and stored at 50°C for 3 days. Then, sintering was performed in a muffle furnace, the sintering temperature was 500°C, the temperature rising rate was 5°C / min, and the holding time was 4h. Finally, the temperature rising rate was set to 5°C / min to rise to 700°C, and calcination was performed for 2h.

[0106] (5) Surface coating modification: 6g of diethanolamine and 12g of butyl titanate were dissolved in 10g of anhydrous ethanol solution, and stirred in a water bath at room temperature for 15min. Then 4g of glacial acetic acid, 1g of 0.2wt% PVB and 3g of 0.0025wt% HPC solution were added to the mixed solution, 60g of anhydrous ethanol was added as a solvent, and water bath stirring was continued, with the water bath temperature set to 30°C. When the temperature rose to the set temperature, 8g of deionized water was measured and added dropwise at a rate of 1 drop / s. After 2h of continuous water bath stirring, a transparent and clear TiO2 sol was obtained. After aging for 2 days, the surface of the ozone-exposed material was uniformly coated. Titanium dioxide sol was used for surface coating modification, and the final sintering temperature was 500°C, the temperature rising rate was 2°C / min, and the holding time was 120min.

[0107] (6) Nanopore sealing and impregnation modification: 8g of tetraethyl orthosilicate, 12g of anhydrous ethanol and 8g of 0.02mol / L ammonia solution were mixed uniformly, 2ml of 1wt% hydrochloric acid solution was added, stirred at room temperature for 2h, and then left standing for 24h. 4ml of 1wt% fluorosilane ethanol solution was added, and the mixture was left standing at 55°C for 12h. After filtration and alcohol washing, a uniform fluorosilicon sol was obtained, and the pores of the ozone-exposed material were subjected to sealing and impregnation modification. Fluorosilicon sol was used for sealing and impregnation modification, and the final sintering temperature was 500°C, the temperature rising rate was 2°C / min, and the holding time was 120min.

[0108] The fifth embodiment of the present application provides a specific preparation method of ozone nanobubble uniform porous aeration material, comprising:

[0109] (1) Configuration of 3D printing precursor gel: 30 ml of 14 wt% polyoxypropylene polyoxyethylene copolymer solution is dissolved in 60 ml of 33 wt% ethanol solution. Then 15 ml of 1 wt% hydrochloric acid solution is added. After stirring at 40°C for 1 minute, it is cooled to 25°C to self-assemble into intermediate micelles. Finally, 40 ml of 45 wt% tetraethyl orthosilicate is added and stirred for 15 min to obtain a sol with a specified concentration of silica skeleton structure.

[0110] (2) Configuration of ink solution: aliphatic polyurethane diacrylate, epoxy aliphatic acrylate and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are mixed at a mass ratio of 48.5:48.5:6, and stirred at 60°C for 1 h to obtain a homogeneous UV-curable stretchable ink solution.

[0111] (3) Mixing to obtain 3D printing precursor solution: the sol and ink solution are mixed at a mass ratio of 20:80 and stirred at room temperature for 5 min to obtain a 3D printing precursor solution.

[0112] (4) Setting of printing, refrigeration and temperature rising procedures: in the setting of the 3D printer, a UV LED light source (wavelength 385 nm) is used, the light intensity is 30 mW / cm 2 , the exposure time is set to 6 seconds, the exposure layer thickness is set to 200 microns, and then the CAD model is 3D printed. In the setting of the refrigeration temperature and temperature rising procedures after printing, the structure after 3D printing is placed in a low-temperature refrigerator and stored at -20°C for 3 days. Then it is placed in a vacuum drying oven and stored at 50°C for 3 days. Then, sintering is carried out in a muffle furnace, the sintering temperature is 500°C, the temperature rising rate is 10°C / min, and the holding time is 4 h. Finally, the temperature rising rate is set to 10°C / min to rise to 700°C, and calcination is carried out for 2 h.

[0113] (5) Surface coating modification: 4.5 g of diethanolamine and 14 g of butyl titanate are dissolved in 10 g of anhydrous ethanol solution, and stirred in a water bath at room temperature for 15 min, then 5 g of glacial acetic acid, 0.5 g of 0.2wt% PVB and 3.5 g of 0.0025wt% HPC solution are added to the mixed solution, 60 g of anhydrous ethanol is added as a solvent, and the water bath is continued to be stirred, and the water bath temperature is set to 50℃, when the temperature rises to the set temperature, 12 g of deionized water is measured, and added dropwise at a speed of 1 drop per second, and the water bath is continued to be stirred for 2 h to obtain a transparent and clear TiO2 sol, and the surface of the ozone exposure material is uniformly coated after aging for 3 days. The surface is coated with titanium dioxide sol, and the final sintering temperature is 800℃, the heating rate is 3℃ / min, and the holding time is 120 min.

[0114] (6) Nanopore sealing and impregnation modification: 10 g of tetraethyl orthosilicate, 12 g of anhydrous ethanol and 8 g of 0.02 mol / L ammonia solution are mixed uniformly, 2 ml of 1wt% hydrochloric acid solution is added, stirred at room temperature for 2 h, and then static for 24 h, 3 ml of 1wt% fluorosilane ethanol solution is added, and static at 60℃ for 12 h, and then filtered and washed with alcohol to obtain a uniform fluorosilicon sol, and the pores of the ozone exposure material are sealed and impregnated. The fluorosilicon sol is used for sealing and impregnation modification, and the final sintering temperature of the modification is 800℃, the heating rate is 3℃ / min, and the holding time is 120 min.

[0115] The embodiment of the present application aims to protect a kind of ozone nano bubble uniform porous aeration material and its preparation method, with the following effects:

[0116] 1. The modified silica porous ceramic device of the application can be connected to the gas outlet of an ozone generator to directly generate ozone nano bubbles, and the device has uniform and defect-free nanopore structure, high porosity and high strength, and has two structures of aeration sheet and aeration pipe. The aeration material is prepared by self-assembly, 3D printing and surface modification technology, and the preparation process is advanced and feasible. The direct aeration ozone micro-nano bubble technology established by the device can effectively improve the ozone utilization rate and the efficiency of ozone oxidation degradation of organic matter in water, and reduce the power consumption and operating cost.

[0117] 2. The modified silica porous ceramic device of the present application can be connected to the gas outlet of an ozone generator to directly generate ozone nanobubbles, with the bubble diameter controlled at the nanometer level. This can greatly improve the mass transfer efficiency between ozone and liquid, and there is no problem of low water-gas ratio, nor problems of thermal decomposition of ozone into oxygen, reduced solubility of ozone due to increased temperature, etc. This technology will have very promising applications. As an important part of ozone (catalytic) oxidation, it will greatly improve the utilization rate of ozone in the reactor, effectively reduce the ozone dosage and operating cost, and promote the application of ozone (catalytic ozone) oxidation in industrial wastewater deep treatment and wastewater resource utilization. It also has important significance for alleviating the contradiction between water supply and demand, reducing water pollution, and ensuring water ecological safety.

[0118] Finally, it should be noted that the above-described embodiments are merely specific implementations of the present application, which are used to illustrate the technical solutions of the present application, but not to limit it. The protection scope of the present application is not limited thereto. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that any person skilled in the art can modify or easily think of changes to the technical solutions described in the foregoing embodiments, or make equivalent replacements to some technical features, within the technical scope disclosed by the present application. Such modifications, changes or replacements do not cause the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application, and should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A uniform porous aeration material for ozone nanobubbles, characterized in that, This includes porous silica ceramics, which are prepared by 3D printing. The porous silica ceramic structure adopts an aeration plate, which is installed on an aeration disc and has aeration holes. Alternatively, the porous silica ceramic may be constructed with a bifurcated aeration pipe, with branch pipes extending from the main body of the aeration pipe and aeration holes provided on the branch pipes. The inner wall of the aeration pore is loaded with superhydrophobic silicon fluoride nanoparticles. The surface of the porous silica ceramic is loaded with superhydrophilic nano-titanium dioxide particles. The aeration pores of the silica porous ceramic have a pore size distribution of 10~100 nm and a porosity of 50%~70%. The particle size distribution of the superhydrophobic silicon fluoride nanoparticles is 10~30nm; The particle size distribution of the superhydrophilic nano-titanium dioxide particles is 20~40 nm.

2. A method for preparing the ozone nanobubble uniform porous aeration material according to claim 1, characterized in that, include: Mix UV-curable printing ink and sol with a silica framework structure in a ratio of 80:20 to 20:

80. After stirring at room temperature, it is then 3D printed and cured with ultraviolet light. The process involves refrigeration and programmed temperature roasting. Pore ​​modification and surface modification are carried out.

3. The method for preparing the ozone nanobubble uniform porous aeration material according to claim 2, characterized in that, Stirring at room temperature takes 2 to 10 minutes.

4. The method for preparing the ozone nanobubble uniform porous aeration material according to claim 2, characterized in that, The printing ink consists of aliphatic polyurethane acrylate, epoxy aliphatic acrylate and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The aliphatic polyurethane acrylate, epoxy aliphatic acrylate and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are mixed in a mass ratio of (5~10):(5~10):1 and stirred at a constant temperature of 40~60℃ for 0.5~2h.

5. The method for preparing the ozone nanobubble uniform porous aeration material according to claim 2, characterized in that, The sol with a silica framework structure is formed by self-assembly of intermediate micelles of polyoxyethylene and polyoxypropylene surfactants as templates, and hydrolysis and condensation of silica precursor solution around the templates. The silica precursor solution comprises a polyoxypropylene-polyoxyethylene copolymer solution, an ethanol solution, and a hydrochloric acid solution. The mixture is rapidly stirred and mixed at 30-40°C, cooled to room temperature, and then 30%-60% tetraethyl orthosilicate is added and stirred for another 5-30 minutes to obtain the product.

6. The method for preparing the ozone nanobubble uniform porous aeration material according to claim 2, characterized in that, The refrigeration and programmed temperature roasting process includes: The 3D-printed structure was placed in a low-temperature freezer and stored at -20°C to -10°C for 3 days. Place it in a vacuum drying oven and store it at 30~80°C for 2~5 days; Sintering is carried out in a muffle furnace at a sintering temperature of 450~550℃, a heating rate of 1~3℃ / min, and a holding time of 3~5h. Then, set the heating rate to 1~3℃ / min and raise it to 650~750℃, then calcine for 1~3 hours.

7. The method for preparing the ozone nanobubble uniform porous aeration material according to claim 2, characterized in that, The channel modification includes: The process involves sealed impregnation with fluorinated silicon sol. The fluorinated silica sol is prepared using a mixed solution of tetraethyl orthosilicate, anhydrous ethanol, and ammonia.

8. The method for preparing the ozone nanobubble uniform porous aeration material according to claim 7, characterized in that, The impregnation temperature is 30~70℃, the impregnation time is 24~48h, the sintering temperature after impregnation is 300~800℃, the heating rate is 1~3℃ / min, and the holding time is 1~3h.

9. The method for preparing the ozone nanobubble uniform porous aeration material according to claim 2, characterized in that, The surface modification includes: Modification was achieved by titanium dioxide sol-coating; After coating, sintering is carried out at a temperature of 300~800℃, a heating rate of 1~3℃ / min, and a holding time of 1~3h. The titanium dioxide sol is prepared by mixing diethanolamine and tetrabutyl titanate.

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